CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

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Review

Carbon surface functionalities and SEI formation

during Li intercalation
a,1 a,1
John Collins , Gerald Gourdin , Michelle Foster a, Deyang Qu b,*

a
Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Blvd., Boston, MA 02135, United States
b
Department of Mechanical Engineering, University of Wisconsin Milwaukee, 3200 N Cramer St., Milwaukee, WI 53211, United States

A R T I C L E I N F O A B S T R A C T

Article history: This review aims to (1) briefly summarize the use of carbon as intercalation materials in
Received 14 January 2015 electrochemical energy storage and the development of the solid electrolyte interphase
Accepted 4 April 2015 (SEI) layer on the surface of the carbon electrode, (2) discuss the impacts of surface func-
Available online 9 April 2015 tional groups on the physical and electronic properties of carbon materials and the perfor-
mance of electrochemical energy storage devices, (3) analyze the specific contributions that
the most abundant oxygen and nitrogen carbon-surface functionality, in particular surface
functional group hybridization and the influence that Lewis basicity/acidity, have towards
promoting Li-ion charge storage and (4) examine the impact that those heteroatom func-
tionalities have on the formation of the SEI layer.
 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction and scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194

1.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
1.2. Beyond lithium ion batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
1.3. Scope of the review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2. Intercalation energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2.1. Lithium ion batteries (LIB). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2.2. Lithium ion capacitors (LIC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
2.3. Sodium ion batteries (NaIB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3. SEI layer formation and composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1. Layer composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.2. Formation of layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
4. Carbon surface functionalization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
4.1. Surface oxygen group (SOG) functionalization of carbon surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206

* Corresponding author: Fax: +1 414 229 6958.

E-mail address: qud@uwm.edu (D. Qu).
1
Equal contribution as first authors.
http://dx.doi.org/10.1016/j.carbon.2015.04.007
0008-6223/ 2015 Elsevier Ltd. All rights reserved.
194 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

4.1.1. Basic and acidic SOG functionalities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206

4.1.2. Control of SOG distribution and passivation of active surface area. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.1.3. Acidic SOGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
4.1.4. Basic SOGs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.1.5. Capacitance-promoting basic SOGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
4.2. Surface nitrogen group (SNG) functionalization of carbon surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
4.2.1. SNGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
4.2.2. Nitrogen and nitrogen/oxide doped nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
4.2.3. Nitrogen and nitrogen/oxide doped graphene oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
4.2.4. Nitrogen doping by pyrrole deposition/carbonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
4.2.5. Combined nitrogen and oxygen co-doping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.2.6. Combining acidic/basic surface character with sp2/sp3 hybridized SOGs and SNGs . . . . . . . . . . . . . . . . 224
5. Impact of surface functionality on SEI layer development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.1. Reactive sites for functionalization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
5.2. Reversible redox reactions – increase in storage capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
5.3. Irreversible redox reactions – increase in irreversible capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235

1. Introduction and scope

1.1. Fundamentals
Energy storage devices can be classified based on the amount of
energy that can be stored (i.e. energy density) and on how
rapidly that energy can be accessed (i.e. power density). Both
attributes are important for determining a particular device’s
specific application and devices can be compared based on
those attributes using a Ragone plot, as is shown in Fig. 1.
Towards the higher end of the energy density scale of a
Ragone plot (Fig. 1) are batteries. The higher energy storage
density of batteries arises out of the significant chemical
changes that the two electrode materials undergo during
charge and discharge operations. These changes are redox
processes and as the device releases its stored electrical
energy, the spontaneous redox reactions results in the elec-
trode materials undergoing bulk chemical and structural
changes. In general, these processes are multi-electron redox
processes and, as would be expected, the changes in the elec-
trode materials are slow, yet the deeper level of changes is
what gives rise to the very high-energy storage density that
is associated with these devices.
There are two properties of lithium metal that first made it
attractive as a potential anode material: it is both the most
electronegative and the lightest metal. These properties gives
lithium a negative potential that translates into a high cell
voltage, when matched with the appropriate cathodes, and

Capacitors

Electrochemical Capacitors Li-ion Capacitors

Hybrid Capacitors
Li-ion Batteries

Fuel Cells
Batteries
(Pb-acid, Ni-MH)

Fig. 1 – Ragone plot. The Ragone plot illustrates the relationship between energy density and power density among different
energy storage devices. (A color version of this figure can be viewed online.)
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
makes it an anode of high specific capacity (3.86 Ah g1) [1,2].
However, the application of lithium chemistry in rechargeable
technology encountered significant difficulties in terms of
cycle life and safety. During charging of a battery, dendritic
(needlelike) lithium can develop on the lithium metal anode
surface. Because these formations could become electrically
isolated due to non-uniform dissolution rates across their sur-
faces, the loss of lithium results in a decrease in energy den-
sity. However, a more serious concern is the hazard that the
dendrites pose. While they may be electrochemically inactive,
they are still chemically reactive and dendrite growth could
continue enough to pierce the separator that could then result
in an internal short and thermal runaway.
These insurmountable issues prompted a search for mate-
rials that could avoid the formation of dendrites while still
achieving the benefits of lithium metal anodes (i.e. high cell
potential, energy density). The focus of the research then
turned toward ‘intercalation’- or ‘insertion’-type materials
for electrodes, which had already been exploited as cathode
materials for lithium batteries [1,3,4]. The structure of an
intercalation material is such that the material allows for
the insertion and deinsertion of ‘guest’ ions without the ions
undergoing any Faradaic changes. The redox reactions that
occur during injection or extraction of electrons take place
on the host lattice. For cathodes, the majority of the inter-
calation materials are transition metal oxides or chalco-
genides. Initially, lithiated oxides were employed as
intercalation anodes but there was a substantial penalty in
terms of the cell’s energy density, which limited the commer-
cial potential of those devices [1,5,6]. The breakthrough
occurred when researchers exploited the concept of using
carbonaceous materials as the anode intercalation host. Just
as with materials used for cathodes, the intercalated lithium
is stored in the carbon matrix in its ionic form, which, during
normal operations of the devices, eliminates the possibility
for the formation of dendritic lithium [1,7].
Furthermore, the use of ion intercalation materials, such
as carbons for anodes and/or transition-metal oxides for
cathodes, incurs an additional advantage in regards to cycle
life. One of the factors that limits the cycle life of non-inter-
calation electrode materials is that the physical changes that
the material undergoes during charge/discharge adds strain
to the structure of the material. This strain ultimately results
in permanent damage. On the other hand, ion intercalation
materials possess a two-dimensionally stable (i.e. ‘low strain’)
structure with volume changes during intercalation/deinter-
calation 6 10%. This added stability greatly adds to the
longer cycle life attributed to intercalation devices [8].
1.2. Beyond lithium ion batteries
The application of carbon-based intercalation materials has
also recently been extended to other energy storage devices
besides lithium ion batteries (LIB), including lithium ion
capacitors (LIC) and sodium ion batteries (NaIB). In all cases,
carbon materials have been employed as the negative elec-
trode. However, due to the low intercalation/deintercalation
potential of these materials, the operating potential of these
devices will exceed the decomposition potential of the elec-
trolytes employed in these devices. At certain cell potentials
195
during the lithium, or sodium, intercalation process, compo-
nents of the electrolyte react at active sites on the carbon sur-
face and will reductively decompose. This reduction of the
electrolyte initiates a process that eventually decomposes
those components into soluble and gaseous byproducts, and
insoluble products that form a three-dimensional layer on
the surface of the electrode surface. This solid interphase
between the electrode and the electrolyte is commonly
referred to as the solid electrolyte interphase (SEI) layer [9,10].
In addition, the type and distribution of surface functionality
on the carbon materials will have an impact on the formation
of the SEI layer.
1.3. Scope of the review
The intention of this review is fourfold: (1) provide a summary
of the electrochemical energy storage that utilize intercalation
materials as the means of storing electrical energy and discuss
the formation of the passivation layer that is a necessary devel-
opment for the viable operation of these devices, (2) discuss the
types of surface functional groups that naturally occur or can
be introduced to carbon-based intercalation materials and
how those groups alter the physical and electronic properties
of the materials, (3) analyze the specific contribution of the
most abundantly concentrated (natural or synthetically pre-
sent) oxygen and/or nitrogen carbon-surface-residing func-
tionality, particularly hybridization and the functionality’s
influence on Lewis basicity/acidity, in promoting Li-ion charge
storage and (4) correlate how the heteroatom functionality
impacts the formation of the passivation (SEI) layer. While
non-carbon intercalation materials may also be used as the
negative electrode, their insertion potential is significantly
above the insertion potential of carbon materials, thereby
reducing the degree of electrolyte decomposition, as non-car-
bon intercalation materials typically lack the surface func-
tionality that can enhance or diminish SEI layer formation. It
should be pointed out, however, that those non-carbon inter-
calation materials might be employed as the positive electrode,
which means that they will likely operate above the stable
potential range of the electrolytes. However, the formation of
an SEI layer that results from oxidative decomposition on
non-carbon materials is outside the scope of this review.
2. Intercalation energy storage
2.1. Lithium ion batteries (LIB)
The primary example of an energy storage device that
employs intercalation materials as the means for storing
energy are lithium ion batteries. Lithium ion batteries gener-
ally consist of a lithiated transition metal oxide as the cath-
ode and a carbon (graphite) anode. During the charging
process, the cathode material (negative) electrode will gener-
ate lithium ions that then migrate and intercalate into the
matrix of the anode (positive) electrode and where the mate-
rial accepts the transferred electron, as shown below.
Cathode (negative) electrode: LiMy Oz ! Li1x My Oz þ
þ 
xLi þ xe
196 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

þ
Anode (positive) electrode: xLi þ xe þ 6C ! Lix C6 Capacitors utilize capacitive forms of charge storage that
allows for such devices to charge and discharge at rates sig-
During the discharging process, lithium ions de-in- nificantly much higher than any battery. In addition, capaci-
tercalate out of the anode material (negative) electrode, which tors enjoy a much longer cycle life than batteries, since the
then migrate and recombine with the material of the cathode electrode materials of capacitors are not required to undergo
(positive) electrode in the following process. repeated physical and chemical changes as part of their
operation. However, even with the use of high surface area
þ
Anode (negative) electrode: Lix C6 ! xLi þ xe þ 6C materials as the electrodes like in electrochemical capacitors,
Cathode (positive) electrode: Li1x My Oz þ the energy densities of capacitors are at least two or more
þ orders of magnitude smaller than those that can be obtained
xLi þ xe ! LiMy Oz
by batteries. To overcome this limitation, one avenue of
research is focused toward the development of high perfor-
The overall reaction is: LiMy Oz þ 6C ¢ Li1x My Oz þ Lix C6
mance lithium ion hybrid capacitors. These devices combine
where M is a transition metal oxide, such as Co (y = 1, z = 2)
a lithium intercalation electrode with a capacitive charge
or Mn (y = 2, z = 4). A diagram that illustrates the process is
storage electrode in order to achieve higher power densities
shown in Fig. 2 where the transition metal oxide is LiCoO2.
than rechargeable batteries (e.g. Li-ion batteries) while
The solvent components of a lithium ion battery elec-
increasing the energy density relative to supercapacitors
trolyte are susceptible to reactions with the charged carbon
[15–19]. Such a hybrid device has been referred to as a Li ion
surface and the surface functional groups on lithium ion
capacitor (LIC).
intercalation electrodes. These components will undergo
In Li ion batteries, both the negative and positive elec-
decomposition reactions during the primary lithium inter-
trodes are intercalation materials and so a hybrid capacitor
calation process and over the first few charge/discharge
could theoretically utilize an intercalation material either as
cycles. This results in the formation of a solid electrolyte
the negative electrode (anode) or as the positive electrode
interphase (SEI) layer, an important component in the opera-
(cathode). The operation of an example LIC is illustrated in
tion of ion insertion-based energy storage systems like
Fig. 3.
lithium ion batteries and lithium ion capacitors [11–14]. This
During charging of an LIC, the Li ions are stored in the
developed layer passivates the active sites of the graphitic
matrix of the intercalation material electrode, while at the
material and halts further electrolyte decomposition while
same time the counter ions (anions) establish a double-layer
still allowing for the conductance of Li ions through the layer.
at the interface of the capacitive electrode. During discharge,
A more detailed discussion covering the formation of the SEI
the intercalation material loses electrons and the Li ions de-
layer and its impact on the performance of these devices will
intercalate while the double layer is broken at the positive
be provided in Section 3.
electrode. The intercalation materials that have been
exploited as anodes include hydroxides [21], transition metal
2.2. Lithium ion capacitors (LIC)
oxides [22–26], polyanions [27,28], and graphitic carbons
[29,30], whereas cathode materials include layered oxides
Dielectric and electrochemical capacitors dominate the high
[31,32], spinels [33,34], phosphates [35,36], and silicates [37].
power density scale of the Ragone plot (see Fig. 1).
In a very recent and comprehensive article, Aravindan et al.

Positive Electrode Negative Electrode

Charge

Li+
Co
O

Li

Li+

Discharge
LiCoO2
Graphite

Fig. 2 – Lithium ion battery charge and discharge processes. (A color version of this figure can be viewed online.)
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
Fig. 3 – Charge and discharge mechanisms for a typical lithium ion capacitor. Li ions from the electrolyte are consumed to
form the SEI layer during the initial charging of the device. Adapted from Ref. [20]. (A color version of this figure can be viewed
online.)
have provided an excellent review covering the variety of
intercalation materials that have been or can be used in
lithium ion capacitors [38]. In order to maintain the focus of
this review, we will only briefly discuss a few examples.
In the first reported instance of such a hybrid device,
Amatucci et al. constructed a device where the positive elec-
trode stored charge through either reversible nonfaradaic or
pseudocapacitive reactions and the negative electrode was
nano-structured Li4Ti5O12, a lithium intercalation material
[15]. The authors compared the performance of graphitic
and activated carbons in both lithium half-cells and full cells
with the Li4Ti5O12 negative electrode. With the graphite posi-
tive electrodes, charge was stored through the intercalation of
the anions from the electrolyte whereas the activated carbon
stored the charge through the formation of a double layer at
the electrode/electrolyte interface, which provided the high-
est rate capability. The authors concluded that the hybrid cell
utilizing the activated carbon positive electrode exhibited
a > 400% increase in the energy density with respect to non-
aqueous double-layer capacitors while maintaining a long
cycle life.
In the work by Hao at al., an activated carbon was
employed as the negative electrode with Li2Mn4O9, a cation-
deficient intercalation material, as the positive electrode
[39]. The authors were able to achieve an energy density of
53 Wh kg1 at a power density of 276 W kg1 with their aque-
ous hybrid supercapacitor over a potential range of 0–1.4 V
(vs. SHE). Furthermore, the hybrid supercapacitor was able
to deliver a maximum discharge specific capacitance of
54.6 F g1 in 1 M LiNO3 electrolyte at a current density of
100 mA g1.
One disadvantage to the use of metal oxides as the inter-
calation material for the negative electrode is the relatively
high intercalation–de-intercalation potential. With Li4Ti5O12-
based materials, for example, the associated potential is
around 1.5 V vs. Li. In such conditions, the hybrid capacitor
197
could be only charged/discharged between 1.2 and 3.2 V, lead-
ing to under utilization of the positive electrode. However, the
use of a carbon-based negative electrode (insertion–deinser-
tion potential 0.2 V vs. Li) allows for substantially extending
the operating voltage, and the corresponding energy density,
for this kind of hybrid capacitor. This advantage was
exploited by Raymundo-Pinero et al. in their hybrid gra-
phite/activated carbon capacitor [40]. They demonstrated a
hybrid system with an organic electrolyte that used graphite
and activated carbon as the negative and positive electrode
materials, respectively. They found that that the hybrid
device could be optimized for working in a potential range
from 1.5 V up to 4.5 V and that the capacitance of the hybrid
capacitor was greater than 2 times higher than that typically
obtained for a symmetric double–layer capacitor. They con-
cluded that gravimetric and volumetric energy densities as
high as 103.8 Wh kg1 and 111.8 Wh L1 could be obtained in
such a hybrid capacitor, while maintaining very good cyclabil-
ity within that operating potential range.
Due to the larger crystallite domains that allows for signifi-
cant intercalation capacity, graphitic carbons are the typical
carbon of choice for the negative electrode in lithium ion bat-
teries. The random orientation of those same domains in
more amorphous carbons limits their capacity for the inter-
calation/insertion of ions. However, intercalation into gra-
phite is a relatively slower process due to the much smaller
accessible surface area and the phase change/ordering pro-
cess that the material undergoes during ion intercalation,
which could have a negative impact on the high rate
charge/discharge operation that is desirable in an electro-
chemical capacitor [41]. In addition, graphitic carbons are
more amenable to the co-intercalation of solvent molecules
between the graphene layers, which results in an increased
decomposition of the electrolyte [10,42]. On the other hand,
amorphous carbons possess much higher surface areas, due
to its open porous structure, which allows for the Li ions to
198 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
Fig. 4 – Charge and discharge mechanisms for the operation of a lithium ion capacitor that employs a pre-lithiated carbon
negative electrode. The Li salt concentration in the electrolyte is not diminished during SEI layer formation when a pre-
lithiated negative electrode is used. Adapted from Ref. [20]. (A color version of this figure can be viewed online.)
more rapidly access the outer surface layers. In addition, the
amorphous structure’s high resistance to diffusion greatly
diminishes the electrochemical access of co-intercalating sol-
vent molecules. Lastly, amorphous carbons have shown to be
more resistant to structural changes that arise during ion
intercalation [43]. The restrictions on the rate operation may
also limit the use of lithiated transition metal oxides as the
anode in developing a high-power hybrid capacitor device.
Therefore, the use of a more amorphous carbon that pos-
sesses some graphitic character, or that has been partially
graphitized [44–47], is one approach to addressing these lim-
itations. The larger, more defined and oriented crystallite
domains of a slightly graphitic amorphous carbon would
allow for increased lithium insertion capability while the rela-
tively higher surface area and porous structure would provide
for a more rapid access to the accessible surface area, as com-
pared to graphite or lithiated metal oxides [48]. Under this
mode of operation, the lithium insertion process shares simi-
lar traits to the energy storage processes in other pseu-
docapacitive materials. The number of sites in the
amorphous carbon that can accommodate the lithium atom
is fixed. As the availability of these sites decreases (increase
in stored charge), the work required for the insertion of more
Li ions increases. This sets up a direct functional relationship
between the amount of stored charge and the electrode
potential that is exhibited in symmetric double-layer or pseu-
docapacitive capacitors. In this regard, ion insertion into an
amorphous carbon material demonstrates a behavior that
appears pseudocapacitive in nature.
With the use of any carbon material as the negative elec-
trode in an LIC, the increase in the operating potential that
comes as a result of the much lower insertion–deinsertion
potential also results in an increase of the irreversible capac-
ity due to the formation of the SEI layer. The lower insertion–
deinsertion potential (0.2 V) is well below the decomposition
potential of the organic electrolytes that are typically used in
LIBs. While SEI layer formation is unavoidable, the decrease in
capacity due to the loss of Li ions from out of the electrolyte
can be minimized by pre-lithiating the negative electrode. In
that process, a sacrificial piece of lithium or lithium particles
coated on the material are used to lithiate the negative elec-
trode and form the SEI layer prior to the normal operation
of the device. The operation of an LIC that employs a pre-lithi-
ated negative electrode is illustrated in Fig. 4.
In the operation of an LIC, the Li atoms are stored in the
carbon matrix of the anode (negative) electrode while in the
charged state. At this stage there is no double-layer estab-
lished on the cathode (positive) electrode. During discharge,
the inserted Li atoms lose electrons and become Li ions,
which subsequently establish a double layer at the positive
electrode. Since the negative electrode loses both Li cations
and electrons, it maintains electrical neutrality during this
process and the anions of the electrolyte do not form a double
layer at the electrodes surface. During charging of the device,
the process is reversed. The lithium ions break from the dou-
ble layer and re-insert into the carbon matrix of the anode
(positive) electrode. In addition, the capacitor can be further
charged, up to the oxidative potential limit of the electrolyte,
by establishing double layers at the surface of both electrodes.
In this state, the Li cations are contained in a double layer at
the lithiated carbon electrode (anode) and the anions (e.g.
hexafluorophosphate) are contained in a double layer at the
cathode. Under this scenario, the LIC functions as both a dou-
ble layer capacitor and hybrid pseudocapacitor at different
stages of its operation.
2.3. Sodium ion batteries (NaIB)
Being as part of the same group, sodium shares some of the
same advantageous qualities (negative redox potential, low
density) that lithium does in terms of its properties and its
potential for applications in electrochemical energy storage
devices. In addition, sodium resources are not limited in their
geographical location and sodium is one of the most
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
abundant elements in the Earth’s crust. These advantages
make the development of sodium ion batteries attractive
alternatives to LIBs for both mobile and grid-scale applica-
tions [49]. However, it should be noted that the substantially
higher mass of sodium ions could significantly impact the
specific energy, depending upon the intercalation material
employed. Just as with lithium ion batteries, charge storage
is accomplished through the intercalation or insertion of Na
ions into host materials that can accommodate the ion. Due
to the slightly larger size of a Na ion relative to a Li ion, the
choice of intercalation materials that are applicable for a
sodium ion battery (NaIB) are somewhat more limited.
While graphite is the standard material for the negative elec-
trode in LIBs, it is less electrochemically active in Na cells.
Even under high temperature conditions, the amount of
sodium atoms that have been reported to be inserted into gra-
phite is much smaller than that for Li and K insertion, only
resulting in the formation of NaC64 [49].
Given the limitations posed by graphite or graphitic car-
bons, attention turned to the use of amorphous carbons.
Amorphous carbons can be further separated into hard and
soft carbons, in which soft carbons are graphitizable at high
temperature whereas hard carbons are not. In 1993, Doeff
et al. reported on the first use of a soft carbon as the inter-
calation material for the negative electrode in a Na ion cell
[50]. A maximum composition of NaC15 was achieved,
although the cells were cycled at 86 C. In 2000, the first report
on the electrochemically-reversible Na insertion into and
deinsertion out of a hard carbon at room temperature was
made by Stevens and Dahn [51]. Their results showed that
the hard-carbon electrodes could deliver 300 mAh g1 of
reversible capacity in Na cells. Compared to graphite, a much
higher amount of Na ions can reversibly, electrochemically
insert into hard carbons. Therefore, it may be inferred that
the carbon-based intercalation materials of choice for the
negative electrode are hard and soft carbons [48]. Although
soft, or hard, carbon electrodes exhibited higher capacity
than graphite and good rate performance, a large irreversible
capacity was observed during the initial cycle due to reductive
decomposition of the electrolyte on the surface of carbon.
Similar to what is seen on graphite in Li cells. Therefore, a
major challenge to the development of viable Na ion batteries,
as well as Li ion batteries and capacitors, is the surface
passivation of the negative electrode.
3. SEI layer formation and composition
3.1. Layer composition
The majority of the electrolytes used in ion (Li or Na) inter-
calation devices, batteries or capacitors, typically contain
acyclic carbonates [52–54]. These include more commonly
used carbonates, diethyl or dimethyl carbonate, plus more
recently evaluated carbonates such as asymmetric and/or
butyl-substituted carbonates [55–57]. Examples of the acyclic
carbonates are shown in Fig. 5.
In addition, cyclic carbonates, especially ethylene carbon-
ate, have been shown to be necessary for the development of
a stable solid electrolyte interphase (SEI) layer to obtain a
199
Fig. 5 – Common electrolyte components. Acyclic solvent
molecules that are components of common electrolytes for
lithium ion intercalation devices.
prolonged cycling life [52–54,58,59]. As with the acyclic car-
bonates, new cyclic carbonates have also been synthesized
to provide stability at higher potential limits. Although devel-
oped for electrochemical double-layer capacitors, the results
obtained from Chiba et al. indicate that these components
could be applicable for lithium intercalation electrode materi-
als [57,60]. Examples of cyclic carbonate electrolyte compo-
nents are shown in Fig. 6.
The development of the SEI layer is important for the cycle
life of electrochemical ion insertion devices because the layer
passivates those active sites that facilitate electrolyte
decomposition, thereby halting decomposition by inhibiting
electron tunneling. Depending upon the nature of the carbon
material, the type and distribution of surface functional
groups can either enhance the chemical bonding of the SEI
layer, thus stabilizing the layer [61], or enhance the
decomposition of the electrolyte thereby increasing the irre-
versible capacity [61–63]. The irreversible capacity refers to
the energy storage capacity that is irretrievably lost in the for-
mation of the SEI layer. Once a stable layer has been deposited
on the electrode surface, the inorganic and organic, insoluble
Li salts that comprise the layer prevents further solvent
reduction reactions, while still allowing for the intercalation
of Li ions into the carbon matrix. Therefore, the formation
of a stable SEI layer is a key factor that is important to all
ion intercalation energy storage systems.
It was the Aurbach group that performed much of the
experimental work that was used to establish the fundamen-
tal concepts that underpins the development and composi-
tion of the SEI layer. They examined the decomposition of
lithium salt electrolytes on the surface of metallic lithium
and other metals. The analytical techniques employed to
evaluate the formation of the film typically included Fourier
Transform Infrared spectroscopy (FTIR) [53,54,64–68] and
Electrochemical Impedance Spectroscopy (EIS) [54,69,70];
techniques that are still widely used today. Infrared spec-
troscopy is typically used to elicit information about the
structure of a molecule since they will absorb specific fre-
quencies of the infrared portion of the electromagnetic
Fig. 6 – Common electrolyte components. Cyclic solvent
molecules that are components of common electrolytes for
lithium ion intercalation devices.
200 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
spectrum that match the transition energy of a bond or group
that vibrates within the molecule. The wavelengths and
intensities of these absorption bands can be used to deter-
mine the presence and density of certain functional groups.
Since carbon-based electrodes are typically used in Li ion bat-
teries and capacitors, the DRIFTS (Diffuse Reflectance
Infrared Fourier Transform Spectroscopy) technique has been
routinely employed in determining the composition of the SEI
layer since it is applicable to examining the surfaces of pow-
dered materials [13,71–75]. Other surface techniques, most
notably X-ray Photoelectron Spectroscopy (XPS), have also
been employed to examine the surface composition during
SEI layer development [11,76–78].
EIS has frequently been used not only for elucidating how
the development of an SEI layer affects the physical and elec-
tronic properties of a carbon electrode [79–82], but also to
probe the electronic properties of the layer itself and, from
that analysis, elicit some information about the physical
structure of the layer. EIS is an analytical technique that mea-
sures the impedance of a system by minutely varying the cell
potential in a sinusoidal pattern over a range of frequencies
and then measuring the current response. An electrode mate-
rial can then be modeled as a passive complex electrical sys-
tem that is comprised of both resistive and capacitive
elements and, with an EIS analysis, both the energy dissipa-
tive and storage properties of the material can be determined.
Those properties are also influenced by the composition of
the electrode material. The type, distribution, and quantity
of attached functional groups will have an effect on the dis-
tribution of p electrons in the ring system that comprises a
graphene crystallite, which will impact the overall electronic
properties of a particular carbon material. As can be expected,
the development of the SEI layer on the surface of the carbon
material will then also have an effect on those physical and
electronic properties [81–85].
What has been determined from these analyses and other
analyses can be summarized in four observations. First, both
the solvent components and the lithium salt anions of the
electrolyte undergo reductive decomposition. The products
of reduction of salt anions are typically inorganic compounds
like LiF, LiCl, flurophosphates, and Li2O, while solvent reduc-
tion products are typically lithium carbonates and lithium
alkyl carbonates, other partially soluble semicarbonates and
oligomers [86]. Second, which reduction reaction takes place
and which species are reduced is dependent upon the cell
potential. Due to this cell potential dependency, the composi-
tion of the deposited SEI layer will change as the cell potential
is decreased from open circuit potential, or OCP, (3.0 V vs. Li)
to the lithium insertion potential (0.1 V). Third, already
deposited components will typically continue to undergo
reduction reactions with continued cycling of the electro-
chemical cell. Therefore, the SEI layer will, over time, develop
a multiphasic composition [57,87]. EIS analyses and other
studies have shown that the innermost phase, nearest to
the carbon interface, will possess a more compact, inorganic
composition, whereas the outermost phase, at the layer/elec-
trolyte interface, will possess a more porous, organic
composition [88]. Lastly, the presence or absence of elec-
trolyte contaminants, most notably water, has a significant
effect on what reactions take place and how the composition
of the SEI layer changes.
The issue of the SEI layer development during Na ion inter-
calation was addressed in a recent paper by Komaba et al.,
who examined the solid electrolyte interphase that had
developed on hard carbon electrodes as a result of sodiation
and compared it to one that developed during lithiation [89].
Using TOF-SIMS, the author’s analysis of the formed SEI lay-
ers indicated that the SEI layer formed during Na inter-
calation was more inorganic in nature, containing oxides,
hydroxides, halides, and carbonates, relative to the layer that
formed during Li intercalation which is composed alkyl car-
bonates in addition to halides. While the XPS results did indi-
cate the presence of alkyl and alkylene groups, and polymer
species, the surface film formed during Li intercalation con-
tained a larger amount of hydrocarbon compounds. The
results of SEM and TEM analyses also indicated differences
in the structure of the layers where the layer deposited during
Na intercalation was rough and non-uniform, which was in
contrast with the uniform layer formed during Li
intercalation.
3.2. Formation of layer
Although much research has been focused on determining the
exact reaction pathways that the electrolyte undergoes during
reductive decomposition, the precise mechanisms still have
not been firmly established. However, it has been proposed
that decomposition of the cyclic carbonates that gives rise to
common components of the SEI layer and results in the
generation of gasses can be attributed to either a 2-electron
reduction of a single molecule or two 1-electron reductions
of two molecules [11,71,90,91]. In addition, computational
studies conducted by the Balbuena group have predicted that
the energy barrier associated with the initial reduction of a
cyclic carbonate would essentially be eliminated if the solvent
molecule were coordinated with a lithium ion [92–95]. Those
results indicate that it is the Li-coordinated molecules that
are preferentially reduced at the electrode surface. The sub-
stantial efforts of Aurbach and others have led to a detailed
representation of the probable reduction pathways for EC,
which is shown in Fig. 7 [74,88,93,96,97]. The ‘low-population’
and ‘high-population’ conditions generally refer to the
concentration of the cyclic carbonate (EC) in the electrolyte
relative to the other solvent components. However, it can
Li
Li O
Li
+ H2C CH2
Li Li (g)
+ Li+
O
O O
O O
+ e– + e–
O O
O O O O
+ EC--Li+
(CH2OCO2Li)2(s) + H2C CH2
(g)
Fig. 7 – 2-Electron EC reduction pathways. The scheme
shows the two 1-electron reductions that an EC molecule
goes through under either (upper) ‘low-population’
conditions or (lower) ‘high-population’ conditions.
 CARBON
Li Li
O O
+ e– + e–
O O O O
Fig. 8 – 2-Electron PC reduction pathways. The scheme shows the two 1-electron reductions that a PC molecule goes through
under either (upper) ‘low-population’ conditions or (lower) ‘high-population’ conditions.
O
EC + e–+ Li+ O O
O
PC + e- + Li+ O O
Fig. 9 – 1-Electron reduction pathway. The scheme shows the 1-electron reduction pathway for either (upper) an EC or (lower)
a PC molecule.
Fig. 10 – Common electrolyte additives. Additives that have
been used in electrolytes to aid in the formation of the SEI
layer.
also refer to a lower or higher concentration of other Li-coordi-
nated solvent molecules within the immediate environment
relative to the reacting solvent molecule.
As would be expected in an electrolyte, the Li ion is sol-
vated by one or more solvent molecules. As predicted by the
Balbuena group [93], coordination of a solvent molecule with
a Li ion facilitates its reduction because this results in a nega-
tive free energy change for the first reduction reaction. As
noted by Wang et al. [93], there is an energy barrier associated
with the ring-opening step that has to be overcome. When a
Li-coordinated cyclic carbonate adsorbs onto the carbon sur-
face, that additional coordination introduces strain to the ring
structure. This facilitates the reduction of the cyclic molecule
by lowering the activation energy barrier for the reaction
[11,98,99]. Li-coordination helps to stabilize the radical anion
that is then formed, which can then undergo a second 1-elec-
tron reduction. The electron affinity for the anion is predicted
to be much lower than the uncharged molecule, so it is rea-
sonable to expect that the second reduction may not immedi-
ately follow the first reduction and, since these reactions take
place at the carbon interface, the radical anion can be stabi-
lized by the active surface [11]. Once the second reduction
occurs, the molecule can either react with a Li ion under
‘low-population’ conditions (upper pathway in Fig. 7) or with
9 2 (2 0 1 5) 1 9 3–24 4 201
Li
Li O
Li + H3C C CH2
H (g)
O + Li+ O O
(s)
O O
+ PC--Li+ O
O OLi + H3C C CH2
LiO O (s) H (g)
Li
(CH2OCO2Li)2(s) + H2C CH2(g)
(2 x)
O
Li
O OLi + H3C C CH2
(2 x) LiO O (s) H (g)
another Li-coordinated molecule under ‘high-population’
conditions (lower pathway in Fig. 7). Both pathways result in
the generation of ethene and either lithium carbonate or
the alkyl carbonate. These two pathways are, of course,
applicable to the reduction of PC [77,88,93,96], which is shown
in Fig. 8.
Extending from the mechanisms presented in Figs. 7 and
8, it has been shown that a single EC molecule is first reduced
and, rather than undergoing a second reduction, it can form
the alkyl carbonate and ethene gas through a disproportiona-
tion reaction with another EC radical anion, which is shown
in Fig. 9 [77,88,93,96]. This latter pathway is referred to as
the ‘1-electron’ reduction pathway, while the mechanisms
illustrated in Figs. 7 and 8 are referred to as the ‘2-electron’
pathway.
There is evidence that the ‘1-electron’ and ‘2-electron’
reduction pathways are both important contributors to the
development of the SEI layer. This can be further understood
in the context of the variability in the activity of the carbon
surfaces and the effect that changing the electrode potentials
has on the activation energy barrier associated with charge-
transfer reactions [100]. What determines which reaction
pathway may dominate during the lithiation process depends
on the environmental conditions, the composition of the elec-
trolyte, the potential of the electrochemical cell, and the state
of the lithium intercalation process, as discussed by Naji et al.
[74]. More in depth discussions of these reactions have also
been provided in the literature by others [74,75,78,86,101].
In order to facilitate the development of a stable SEI layer,
additives have also been employed, most of which are func-
tional derivatives of the cyclic carbonates [102–105].
Examples of these additives are shown in Fig. 10.
Vinylene carbonate (VC) has proven to be one of the more
successful additives employed for the purpose of developing a
stable SEI layer [57,106–110]. The advantages of employing VC
202 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Fig. 11 – Typical cycle life curves (capacity vs. cycle number) of graphite electrodes obtained in coin-type cells. Li metal counter
electrodes, EC:D–EC:DMC, 1 M (a) LiFAP, (b) LiFAP + 5% VC and (c) LiFAP + 1% AD25 solutions, as indicated in the figure. (A,
upper chart) 30 C, (B, lower chart) 60 C. The current rates for the charge and the discharge processes are C/10 for the first 5
cycles and the rest at C/4 testing at (A) 30 C and (B) 60 C. Reproduced from Ref. [111].

(vinylene carbonate) as an additive is clearly illustrated in the
work published by Aurbach et al., who investigated the bene-
fits of the additives VC, for stabilizing the anode, and Li sali-
cylatoborate, for stabilizing the cathode, in LiPF3(CF2CF3)3
electrolyte solutions [111]. The electrolyte to which the VC
was added consisted of a solvent system of EC/DEC/DMC
(2:1:2 by volume). The addition of VC to the electrolyte
enhanced the long-term stability of the anode so that the
charge/discharge capacity was maintained for over 80 cycles
at elevated (60 C) temperatures, as reproduced here in Fig. 11.
In their conclusion, the authors noted that VC was the pre-
dominant reactant with the Li-carbon electrode surface
despite the high reactivity of the other alkyl carbonate in
the electrolyte. The authors speculated that, based on the
analyses of the surface, VC was reduced to species such as
poly-Li alkyl carbonate, ROCO2Li species, and polycarbonates.
Reports have indicated that unsaturated functionalities
(double or triple bonds) in cyclic structures provide a site for
polymerization under reductive conditions. In their com-
putational analysis, Wang et al. showed that, once the carbon
anode is polarized to low potentials, VC is initially reduced to
a more stable intermediate than one from EC reduction [94].
The reduced VC undergoes decomposition to form a radical
anion, which then may follow several termination reactions
to produce alkyl dicarbonates, alkoxides, Li-carbides, and oli-
gomers. These reduction products, which contain double
bonds, may further polymerize on the electrode’s surface
and therefore have the potential to build up an effective SEI
film. This hypothesis was supported by the work of Ouatani
et al. who, in their recent investigation into the mechanism
of VC reactions on the surfaces of electrode materials, estab-
lished that the radical polymer product from VC is the main
product on graphitic anode using ab initio calculations and
experimental spectroscopy [112]. In addition, Aurbach et al.
concluded in their work that the presence of VC improved
the performance of Li-graphite anodes because the polymeric
species formed by VC reduction improved both passivation
and Li-ion transport through the SEI layer [111]. These results
indicate that VC makes an effective additive in non EC-based
electrolytes.
The presence of contaminants is another important con-
sideration in any electrolyte; especially water, which is
unavoidable in nonaqueous systems. In general, trace water
either in the electrolyte or adsorbed onto the surface of the
carbon material will react with the products of the other
decomposition reactions and produce inorganic products,
such as lithium carbonate. These compounds can react at
the charged electrode interface, with the solvent components,
 CARBON
and with the products that arise from electrolyte decomposi-
tion. This has the effect of altering the composition of the
electrolyte itself and the SEI layer. The reactions of electrolyte
contaminants with the components of the developing SEI
layer have been generally considered to occur at the SEI
layer/electrode interface, which results in the inner phase of
the SEI layer becoming more ionic and more compact in char-
acter, as was discussed earlier and described in the literature
[12,42,91,113,114]. The evidence for these proposed
decomposition reaction pathways arise from the character-
ization of the SEI layer using FTIR, XPS, and EIS analyses
[73,76,87,115].
In addition to semicarbonates, other salt and non-salt spe-
cies have also been detected as components of the SEI layer.
In an investigation of the decomposition of EC/PC or EC/
DMC electrolytes on graphitic anode surfaces using selective
excitation X-ray emission spectra, Augustsson et al. found
species that included oxalate, succinate, and alkoxide [116].
The presence of these carboxylate species indicates alterna-
tive reduction pathways that differ from what was shown in
Figs. 7–9. The first step in these mechanisms involves the
generation of acyl-radicals through a cleavage of the ethereal
bond, from which follows a radical-recombination step to
form the new CAC bonds, a reduction step that has been pre-
dicted for both acyclic [77,78,117,118] and cyclic carbonates
[97,99,119]. Although no detailed mechanisms were offered
by the authors [116], possible reaction pathways were pro-
vided by Xu in his review and are shown in Fig. 12 [57].
Furthermore, the work of the Zhuang group showed that
reduction of DMC produced similar species in addition to
the expected semicarbonates [120] and Zhao et al. indicated
that these oxalates result from additional reductions of the
semicarbonates by the lithiated carbon material [121]. Their
work demonstrated that graphite cycled in typical elec-
trolytes resulted in the production of oxalate.
In a more recent effort to directly observe the reaction
intermediates involved in the formation of the SEI layer,
Shkrob et al. employed electron paramagnetic resonance
spectra to monitor the typical carbonate molecules under
irradiation via either radiolysis or photoionization [122].
While their work indicated that the ring-opening reactions
O O
+ Fig. 13 – Mechanism that illustrates generation of carbonate
O O
O O
Li Li Li
Li
O O
O O
O
+ e– O
O O O O
O
Li Li
O R1
O O
O O
+ e–
O O O O Li O
O O
Fig. 12 – Possible reaction pathways for the formation of
oxalate (upper) and succinate (lower). Reproduced from Ref.
[57].
9 2 (2 0 1 5) 1 9 3–24 4 203
occurred, the predicted cyclic radicals were not observed.
Their observations led them to suggest an alternative path-
way that might involve the carbonate radical anion (CO–3*),
which is shown in Fig. 13. Note that the gaseous decomposi-
tion products (e.g. ethene or propene) are still formed.
One conclusions that arose out of their work was that the
proposed reaction mechanism (Fig. 13) would seem to be
more reasonable from an energetics standpoint, considering
that the recombination of two cyclic radical anions should
be rather short-lived [57,122].
The formation of polymeric or oligomeric products from
electrolyte reduction has been proposed by many researchers
as components of the SEI layer [1,107,123–125]. A limitation of
the spectroscopic tools (FTIR, XPS, etc.) that are typically used
for characterizing the components of the SEI layer is that
those tools cannot clearly distinguish these macromolecular
structures from their monomeric forms. Therefore, only the
presence of possible oligoether compounds that come as a
result of the polymerization of the cyclic carbonates after
the ring-opening step has been established. However, the
work by the Zhao and Watanabe groups using thermogravi-
metric-mass spectra (TG-MS) of graphite anodes after cycling
has provided indirect evidence of polymeric moieties
[121,126].
Tavassol et al. employed the MALDI (matrix-assisted laser
deposition ionization) mass spectrometry technique opti-
mized for the detection of macromolecules to study the for-
mation of the SEI layer as it developed on the surfaces of Au
and Sn electrodes when cycled down to 0.1 V vs. Li [127,128].
That work provided the clearest identification of polymeric
components in the SEI layer with long chain oligomers with
m/z ratio as high as 3000 from PC or 1500 from EC/DMC being
identified. The detected compounds contained repeating
units that varied with solvent composition and electrode
materials. Using results from DFT calculations, mechanisms
that involved radical initiation/propagation that could
Li Li
Li Li
O O Li O
O
+ e– O O O
O O O O + O O
O O
O O O R
R Li
R R
R
radical anion in the formation of lithium alkylene
dicarbonate.
Li Li
O Li
O O R2
+ e– O O
O O O O O O
O Li
O
R1 R1 O O Li
Li
R2
Fig. 14 – Mechanism involving carbonate solvent that results
in formation of radical alkyl-lithium initiator that was
predicted to be involved with the formation of oligomers in
Ref. [127,128].
204 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
account for the formation of the oligomeric compounds were
proposed by the authors. A mechanism that illustrates the
reductive decomposition of the corresponding carbonate sol-
vents that results in the formation of the initiator is shown in
Fig. 14 [57].
As it is expected that the products that arise from reduc-
tive decomposition of the electrolyte may possess a certain
degree of solubility in the electrolyte, analyses of the
composition of the electrolyte during cycling provides further
insight into these processes. The work performed by the
Laruelle group has produced one of the more interesting stud-
ies conducted on electrolyte decomposition. Their work
examined the changes in the composition of the electrolyte
over a period of hundreds of cycles [117]. What was concluded
was that, in addition to the cyclic carbonates, the linear car-
bonates are also reduced to form radical and alkoxide anions,
an observation that was also indicated by Aurbach
[12,77,88,129]. This mechanism is shown in Fig. 15.
From those analyses, the Laruelle group proposed mecha-
nisms that would result in the formation of oligomeric com-
pounds [117,118]. The alkoxide anions generated from the
reduction of DEC can react with the cyclic carbonates to form
longer chain carbonates, that may or may not be substituted
depending upon the cyclic carbonates involved in the reac-
tions. Their work showed that this process could continue
to form oligomeric compounds that contain between 3 and
6 repeating units. It should be noted, though, that the electro-
chemical Li half-cells used in this work did not employ a car-
bon-based working electrode and so extending those results
to the decomposition of the electrolyte during development
of SEI layer on a carbon surface must be considered with
some caution. That work was extended by the Gourdin et al.
Fig. 15 – Linear carbonate decomposition reaction. Reaction
mechanism for the two-step, 2-electron reduction of a single
molecule of a linear carbonate.
Fig. 16 – Example mechanism that illustrates the generation of an electrolyte-soluble decomposition product.
who used electrochemical Li half-cells containing carbon-
based working electrodes [130]. During cycling, the electrolyte
was directly sampled and analyzed using LC–MS. Their work
showed the development of oligomeric compounds in the
electrolyte that arise from the reductive decomposition and
recombination of the electrolyte components. An example
of this reaction is presented in Fig. 16, where the ethoxide
anion can be produced from the reaction illustrated in Fig. 15.
Furthermore, smaller compounds that arise from the acyl-
oxygen cleavage of the cyclic carbonates, as indicated in
Fig. 12 [57,116], were also identified and were considered as
possible precursors involved in the reactions that form the
higher molecular weight compounds. It is important to note
that reductive decomposition of the electrolyte that results
in the formation of electrolyte-soluble compounds will result
in consumption of charge (increased initial discharge capac-
ity), but will not result in passivation of the carbon surface,
since these compounds are not involved in the formation of
the SEI layer.
The majority of the studies of the SEI layer have focused
on the solid state: the SEI layer itself. However, analysis of
the gasses that are generated during electrolyte decomposi-
tion [113] and examining how the composition of the elec-
trolyte changes during SEI layer formation have also yielded
important information. Although not directly related to elec-
trolyte decomposition on carbon-based electrodes, Hahn
et al. reported on the decomposition of a carbonate-based
electrolyte that was used in a supercapacitor [42]. When taken
to oxidative potentials (>4.0 V) during slow scan voltammetry,
CO2, propene, and H2 were detected as gaseous decomposi-
tion products from a propylene carbonate (PC) electrolyte. It
was proposed that the propene and H2 were the result of sol-
vent reduction at the negative electrode, while the CO2 is
formed by solvent oxidation at the positive electrode [42]. In
addition, Yoshida et al. in 1997 reported on their investigation
into the degradation mechanism of LiPF6-based electrolytes
in a lithium ion battery cell [131]. For the EC-containing elec-
trolytes, carbon monoxide and ethene were concluded to be
the major components of the generated gasses, which fits
well with the proposed decomposition mechanisms dis-
cussed above [131].

Li Li
O O
+ e– + e– Li Li O O Li
O O O O
Fig. 17 – Mechanism illustrating acyl-oxygen bond cleavage
of propylene carbonate that results in formation of CO.
2ROCO 2Li(s) + H2O Li2CO3(s) + 2ROH + CO2(g)
Fig. 18 – Reaction of trace water with lithium alkyl
carbonates that generates CO2 and Li2CO3.
Analyses of the gasses that are generated during reductive
decomposition of the electrolyte components has provided
important information for correlating proposed mechanisms
for the decomposition of the electrolyte to the experimental
results [75,114,131]. Gourdin et al. examined the generation
of decomposition gasses during the primary lithiation of a
carbon-based anode for a lithium ion capacitor [100]. The car-
bon used was a non-graphitic carbon with a more amorphous
character, and so it would be expected that the overall activity
of the surface would be higher as compared to graphite
resulting in increased solvent decomposition. Nevertheless,
the detected gasses (ethene, propene, and carbon dioxide)
were in line with the previously discussed decomposition
mechanisms (Figs. 7–9).
In work that supports the advantages of the use of VC in
mixed solvent electrolytes, Ota et al. investigated the forma-
tion of the SEI layer on graphitic substrates using EC/DMC
electrolytes that contained VC as an additive [123]. The gasses
that evolved during cycling were analyzed by gas chro-
matography (GC) and it was concluded that the addition of
VC to the ethylene carbonate (EC)-based electrolyte caused a
decrease in the reductive gases such as C2H4, CH4, and CO.
In addition, the VC-derived SEI layer formed at a potential
more positive than 1.0 V vs. Li/Li+, which incurs an advantage
of passivating the electrode surface well outside the potential
range for Li deposition.
In the work by Onuki et al., the EC and DEC components
were labeled with the 13C-isotope and then gas chro-
matography with an atomic emission detector (GC-AED) was
used to differentiate the source of gaseous products generated
during the initial cycling of full cells containing graphite
anodes [119]. In addition to the expected alkanes/alkenes, they
detected CO, which was traced to EC as the source. This
LiPF6 + H2O LiF (s) + 2HF + PF3O
Li2CO3(s), ROCO 2Li(s)
HF
CO2(g),ROCO2H + H2O + LiF(s) (5)
Fig. 19 – Reactions of LiPF6 salt. (4) Chemical equation
showing the LiPF6 salt in equilibrium with lithium fluoride
and phosphorus pentafluoride (PF5), which can react with
trace water to generate PF3O and HF. (5) Chemical equation
showing reaction of HF with precipitated lithium carbonate
or alkyl carbonates to form CO2 gas or the corresponding
alcohol, respectively.
CARBON 9 2 (2 0 1 5) 1 9 3–24 4 205
provides additional support for the alternative EC-reduction
pathway in which the ring structure is cleaved at the acyl-oxy-
gen bond rather than alkyl-oxygen as was shown in Figs. 7–9.
+ CO
This mechanism is illustrated in Fig. 17 [57,119].
During those processes, there are various reactions that
occur at the interface with the carbon surface as the SEI layer
builds up. The deposited materials from the initial reduction
further undergo secondary reduction reactions that ulti-
mately change the composition of the inner phase (nearest
to the electrode surface) of the SEI layer to one of a more ionic
character. Most electrolytes contain trace amounts of water,
(3)
in addition to other contaminants, that can react with the sol-
vent reduction products. The formation of alkyl carbonates at
the electrode surface as shown in Figs. 7–9 allows for the reac-
tion with surface-adsorbed water or trace water that has
migrated through the developing SEI layer, which results in
the formation of Li2CO3 at the surface and the generation of
the CO2 gas, as shown in Fig. 18 [132].
In addition, there is another possible source of CO2 that
arises from electrolytes that use LiPF6 as the salt. The LiPF6
salt exists in equilibrium with phosphorus pentafluoride
(PF5) and lithium fluoride. The PF5 molecule can then react
with any trace water to generate PF3O and HF, which, in turn,
reacts with the precipitated lithium carbonates or alkyl car-
bonates to form CO2 gas or the corresponding alcohol, respec-
tively. It is these processes that can also account for the
generation of CO2, as detected by the gas analyzer during
gas analysis experiments [75,100,114,131]. This mechanism
is shown in Fig. 19.
The conditions used during the preparation of the carbon
materials will affect not only the final physical structure of
the material, but also its chemical composition. Exposure to
the atmosphere, or more specifically the oxygen, nitrogen
and water in the atmosphere, leads to the formation of oxy-
gen- and nitrogen-containing functionalities on the surface
of the carbons and as heteroatom dopants. As indicated in
Section 1.2, the type and distribution of these surface func-
tionalities will have an impact on the electronic and physical
properties of the material—through the alteration of the elec-
tron density distribution—and consequently affect electro-
chemical performance properties of the materials, including
the formation of the SEI layer.
4. Carbon surface functionalization
The wide range of electrochemical applications for carbon
substrates can be attributed to their amphoteric, highly polar-
izable properties [15,20,133–144]. Among the most influential
factors controlling the electrochemical properties of carbon
(4)
substrates, such as the resistance of electron pathways and
highly active surface sites, are carbon surface heteromaterial
(non-carbon functionality; e.g. oxygen and nitrogen groups.
The majority of heteromaterial implemented from industrial
and synthetic properties are composed of surface oxygen
group (SOG) and surface nitrogen group (SNG) species.
These heteromaterial groups dominantly influence the elec-
tron donor/acceptor properties of carbon substrates (e.g.
adsorption properties, electron delocalization extent), along
with the substrate’s overall conductivity, pore distribution
206 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
Fig. 20 – Decomposition products of specific surface oxygen
groups as specified by temperature and evolved species.
Adapted from Refs. [158,166,169,174,184,185].
and even control of the graphitic network’s overall
microstructure [47,139,140,145–148]. The general catalytic
and adsorptive properties attributed to the presence of SOG
and SNG species are commonly categorized into Lewis acidic
and Lewis basic-type functionality [47,139,147,149–156].
Overwhelmingly, common methods of SOG and SNG imple-
mentation create heterogeneous mixtures of both basic and
acidic functional groups—with the general understanding
that increased oxygen concentration induces electron with-
drawing, Lewis acidic character while increased nitrogen con-
centration induces electron donating, Lewis Basic character
[139,145,153,157–167]. Consistently creating carbon surfaces
of predominantly Lewis basic character is particularly chal-
lenging, as oxygen species are always present on carbon sur-
faces and therefore greatly influence surface acidity. Lewis
basicity is a highly favored property of carbon materials for
a multitude of reasons such as their ability to maintain stable
catalytic active sites, buffered charge incorporation and
transfer, p-bond delocalization character and hydrophobic
properties. What is especially key for the future of carbon
materials in electrochemically advanced and sustainable
energy storage systems is the correlation of specific SOG
and SNG species, their inherent sp2 and sp3 hybridization
character, and relative surface concentrations to electro-
chemical performance.
4.1. Surface oxygen group (SOG) functionalization of
carbon surface
4.1.1. Basic and acidic SOG functionalities
Oxygen surface functionality has been extensively quantified
and characterized on various thermally and chemically modi-
fied carbon materials [139,149,151–153,158,166,168–182]. One
difficulty when using chemical oxidation treatments is that
they all create a mixture of both basic and acidic SOGs on car-
bonaceous substrates. Carboxylic acids, lactones, phenols
and carboxyl-carbonate species are responsible for acidic
properties [47,139,149], where pyrone, chromene, quinone in
combination with ether groups are responsible for basic prop-
erties [150,151,181].
A well-known method to quantify and thermally remove
particular SOGs is temperature programmable desorption-
mass spectrometry (TPD-MS) [158,168,169,174,175,183–187].
At characteristic temperatures, specific SOGs decompose into
CO2, H2O and CO upon heating and are measured by the mass
spectrometer, (Fig. 20). CO2 evolves at low temperatures as a
consequence of acidic group decomposition (e.g. carboxylic
groups, phenols, carboxylic anhydrides and lactones). H2O
evolves from carboxylic and anhydride functionality also at
relatively low temperatures, with CO2 evolving at low to rela-
tively moderate temperature and CO evolving at higher tem-
peratures, originating from the decomposition of acidic,
basic and neutral groups (carboxylic acids, quinones, ethers,
carbonyls, and pyrones). The resulting peaks can be deconvo-
luted using multi-Gaussian/Lorentz functions [158,166,169].
For example, Li et al. [166] illustrate the deconvolution of both
the CO and CO2 species from the same sample and have iden-
tified each peak corresponding SOG (e.g. carboxylic acids, phe-
nols, pyrones, strong acids, weak acids, lactones, lactols, and
carbonyls/quinones).
The considerable overlapping of SOG desorption tempera-
tures and therefore broad CO and CO2 peaks can make decon-
volution quite difficult. Intermittent temperature
programmable desorption (ITPD) can be utilized to assist in
the more precise quantification of SOG species, desorbing
temperature ranges and activation energy of oxygen group
decomposition [168,184,185]. This technique is a differential
form of TPD where a saw-tooth heating program is used to
generate a sequence of interrupted desorption steps. Such
small temperature ramps allow for very small concentrations
of SOGs to desorb. Once a target temperature is reached and
held for a period of time, the substrate is cooled back to ambi-
ent temperatures and the process is repeated for the next tar-
get temperature. With this method, the desorption patterns
result in linear, partial desorption plots, implying quasi-con-
stant surface coverage of a particular SOG or SOGs. This pro-
cess yields different rates of MS signals detected for the CO2
and CO species detected. The Arrhenius equation can then
be utilized to calculate the precise number of desorption steps
through experimentally determining the activation energy of
desorption for each species evolved. Groupings of similar par-
tial desorption slopes yield a more precise target temperature
for all SOGs, as significant slope changes indicate new species
desorption. Hence, the precise number of oxygen groups,
their precise desorption temperature ranges and activation
energy of decomposition can be determined thus allowing
for a more clear picture of SOG quantification and their
respective strength of adsorption.
X-ray photoelectron spectroscopy (XPS) is a valuable tool
for examining surface functional group concentrations
[159,169,174–176,188–196]. Literature values reveal the follow-
ing approximate binding energies for the C1s bond of
activated carbon under oxidative conditions: CAC at
284.6 eV, CAO at 286.0–286.3 eV (phenol, alcohol, or ether),
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
Sample Manipulating Arm
Carbon
Bulk SOGs
Heating
Source H2O, CO, CO2
& T
Thermo-
couple
Extended Sample
Manipulating Arm
Ultra-high Vacuum
10-9 – 10-12 Torr
T
Electron
Collection
Lens
Fig. 21 – Schematic of TPD-MS and XPS instrument for in situ, inert-phase SOG-manipulation and characterization.
C@O at 287.3–287.6 eV (carbonyl/quinone) and OAC@O at
288.8–289.2 eV (carboxyl/ester) [197]. Oxygen based bonding
yields the following approximate O1s binding energies: C@O
at 531–531.9 eV (quinone), C@O at 532.3–532.8 eV (esters,
anhydrides and hydroxyl), CAO 533.1–532.8 eV (ethers, esters
and anhydrides), C@O at 543.3–535.4 eV (carboxyl), and
536.0–536.5 eV (adsorbed water and/or oxygen) [175]. XPS pro-
vides the surface concentration of SOGs for any given tem-
perature, while TPD-MS yields the quantification of the
desorbed SOG species. Coupled together, and with an inert
environment vacuum setup, these two methods can yield a
full, in situ characterization of SOGs at any time/temperature
[169,174]. Upon reaching each target TPD temperature in a low-
vacuum atmosphere, the sample is allowed to cool, and then
transferred into the high vacuum XPS chamber for surface
characterization while in the same inert, vacuumed environ-
ment, as illustrated through Fig. 21. Although a few groups
207
Medium Vacuum
10-3 – 10-5 Torr
Mass Spectrometer
Medium Vacuum
10-3 – 10-5 Torr
Detector
Inner
Hemisphere
Outer
Hemisphere
are using this combined technique currently, wide adoption
of such a setup would be useful in advancing understanding
of carbon functionalization and functional group manipulation
through thermal desorption post functionalization.
Diffuse Reflectance FTIR (DRIFTS) can further confirm the
qualitative identification and pseudo-quantitative character-
ization of functionality [47,139,145,170–172,177,182,195,198–
200]. By calculating differential SOG peak frequencies (i.e. blue
and red shifts) upon varying the type and concentration of
SOGs, the effect of specific SOGs on surface-to-bulk con-
jugation, and therefore chemical graphitization effects, can
be determined [47,139]. The understanding of surface con-
jugation and polarizing effects from the given acidic/basic
carbon surface makeup has direct implications for the elec-
tron conduction channels and therefore adsorption capability
of carbons as electrode materials—deeming FTIR, as well as
monitoring the polarizability with the surface layer through
208 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

O OHO O O O
O O O
C C C OH O O H H H OH O O
O O

O O

O O

O O

O O
H H H H H H H H H H H H H H
O H

O H

O O

O O

H H H H H H H H H
H

Fig. 22 – Initial SOG doped carbon surface (with diverse acidic and basic SOGs) and examples of its temperature-dependent
derivatives. Temperatures shown illustrate groupings of specific SOG removal. Low-to-moderate temperature ramps enable
the custom formation of selective, strongly adsorbed acidic SOGs along with basic SOGs. Higher temperature treatments
enable exclusively basic SOG doped carbon surfaces. Moderate to low temperature (<25–650 C) H-passivation of active
surface area sites, for extensive time periods, occurs upon selective SOG desorption.

Specifically, the control of hydrogenation temperature [201]

Fig. 23 – Carboxylate and carboxylic acid formation from
oxidation of aliphatic sites. Reproduced from Ref. [139].
Raman spectroscopy, analysis critical in coming full circle in
regards to understanding surface functionalization effects
on the carbon lattice. Coupled with atmospheric controlled
in situ TPD/XPS analysis, washed and thoroughly dried func-
tionalized carbon powders in environmentally controlled
DRIFTS apparatus allows for complete molecular identifica-
tion of a given doped carbon surface.
4.1.2. Control of SOG distribution and passivation of active
surface area
TPD may be used to remove specific SOGs as determined by
their temperature of desorption. In order to passivate the
active surface area (ASA) left behind by desorbed SOGs,
molecular hydrogen can be introduced at specific tempera-
tures and concentrations in order to neutralize ASA from fur-
ther airborne-oxidants, helping to maintain the customized
SOG carbon materials. Past studies have displayed the reac-
tion of molecular hydrogen with ASA and SOGs as character-
ized with regard to temperature [48,181,197,201–203].
can determine the uptake of covalently bonded hydrogen.
The relative concentration of C-H bonds notably influ-
ences the relative sp2/sp3 carbon bond hybridization at the
time of lithium CAH site adsorption during Li insertion
[203]. The pioneer work by Zheng and Dahn et al. [48] has
shown hydrogenation significantly influences Li-ion irreversi-
ble adsorption for both hard and soft carbon materials treated
at a variety of temperatures. As shown with the extensive
work by Béguin and Frackowiak et al. [140,204–206], control
of irreversible capacity is a primary component in avoiding
detrimental cycling efficiency. Thus, passivation of ASA with
hydrogen is important to increase Li-insertion cycle-ability,
electron-conductive/adsorption properties, and overall
mechanical stability [207,208] of Li-charge storage.
The particularly powerful technique introduced above,
when combined with the effective chemical treatments in
the same controlled-atmosphere vessel, even more advance-
ment can be achieved in method development of consistent
carbon functionalization and passivation. Utilizing a similar
carbonization/analytical instrument as shown in Fig. 21,
selective functional group desorption and passivation (with
e.g. molecular hydrogen) processes can be easily formulated.
Fig. 22 displays a potential selective desorption scheme of
SOG-concentrated carbonaceous material based upon the
temperatures of desorption shown in Fig. 20. Temperatures
of selective SOG desorption, and subsequent hydrogen
passivation of ASA sites are illustrated up to 980 C. The
hydrogen-based ASA neutralization enables preservation of
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4 209

C. Acid (mmol/g) Acidity (mmol/g)

3.0
Δ
2.0
Δ 1.40 Δ

I(D):I(G)
1.8

R-value
1.33
1.5 1.7 1.26
1.5 1.19
1.4 1.12
0.0
Δ 50 Δ 20
1.2
0.9 18 Δ

La (A0)

Lc (A0)
45 16
0.6
40 14
0.3
12
0.0 35 10
0 1 2 3 4 5 0 1 2 3 4 5 0 1 2 3 4 5
Oxidation Stage Oxidation Stage Oxidation Stage

Fig. 24 – Total surface acidity as determined with NaOH titrations (1-E), carboxylic acid surface concentration determined by
NaHCO3 titrations (2-E), R-value (3-E), La crystallite dimension (4-E), Raman I(D):I(G) (5-E) and Lc crystallite dimension (6-E)
results for E-series. D represents the difference of the 5th oxidation stage magnitude and unoxidized substrate magnitude.
Titration data error bars represent error propagation and crystallite dimension error bars represent standard error of
Gaussian fits. Reproduced from Ref. [47]. Note that the total surface acidity (in this case, predominantly carboxylic acids)
shows parallel trends with the total concentration of single graphene layer (R-value) and the crystallite length (La).
Accordingly, the graphitic order (I(D):I(G)) and the crystallite height (Lc) reveal an inversely proportional trend as the graphitic
crystallite height increases (higher Lc), the graphitic order also increases (lower I(D):I(G)).

Fig. 25 – Proposed potential energy pathway for unoxidized (A), oxidized (B), elongated (C) and stacked (D) forms of single
graphene layers under investigation. Blue bonds represent relatively strong olefin and aromatic bonds due to SOG
conjugation. Red bonds represent weaker aromatic bonds due to the formation of partial positive charge as p-density is
pulled towards attached SOGs. Reproduced from Ref. [47]. (A color version of this figure can be viewed online.)

the desired SOG acidic/basic character or exclusively basic
SOGs on a particular substrate, locking in precise surface
functionalization ratios and their inherent electronic, con-
ductive and adsorptive impact on the carbon surface charac-
ter. The tunable SOG selection and passivation technique
reviewed herein provides an avenue for customized SOGs,
revealing an engineering template for advancement of appli-
cations in Faradaic, fast-Faradaic and electrostatic forms of
Li-ion charge storage.
4.1.3. Acidic SOGs
Electron-withdrawing, acidic SOGs (carboxylic acids, lactones,
etc.) provide higher, short-range graphitic order of the carbon
surface through conjugation of SOGs with the basal lattice.
This effect has been attributed to an aromatic-to-olefin bond
transformation induced by attached SOGs [139]. Such a pro-
posed mechanism for carboxylic-type groups is presented in
Fig. 23 based on DRIFTS and Raman trend correlations from
a sequentially oxidized activated carbon.
The SOG/p-bonding structure relationship was further elu-
cidated by Collins et al. [47] in a subsequent study utilizing
the same sequential oxidation treatments on 3 different acti-
vated carbons. Due to the polarization effects of primarily
acidic SOGs, p-bond density was displayed to be controlled
by a dominant SOG that directly influenced the control of
crystallite structure/dimensions, single graphene layer con-
centration and overall graphite-like order, as shown by the
(I(D):I(G)) ratio via Raman spectroscopy. Fig. 24 shows one
example where the authors demonstrated carboxylic acids
as being the dominant SOG that controlled the substrate’s
microstructure, and therefore potential electrochemical
applications.
Such SOG/structure trends were shown to be similar for all
carbons so long as they displayed a low overall density of total
acidity (DTA), where DTA = total surface acidity/total surface
area. When the DTA was too great for a particular carbon,
the trends correlated in such a way where added surface acid-
ity increased the overall graphitic disorder (higher I(D):I(G))
210 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
with larger crystallites (larger Lc). The contrast with regard to
the different DTA samples helped to prove the short-range
graphitic-ordering limitations of adding acidic SOGs to a car-
bon’s surface.
Fig. 25 displays the mechanism associated with the single
graphene layer (A), being raised in potential energy (B) due to
the addition of SOGs—thereby creating a pseudo-charge sep-
aration and inducing electron holes from the acidic group’s
electron-withdrawing effect. In response to this raise in
potential energy, and electron hole concentration increase, a
nearby single graphene layer fuses (C) with the energetically
elevated single graphene layer making a lower concentration
of single graphene layers (increasing R-value), and thereby
neutralizing the charge separation/electron hole and leading
to a longer single graphene layer (increasing La). The longer,
more aromatic and energetically stable single graphene layer
(C) can now readily stack with another elongated single gra-
phene layer in the standard p–p stacking fashion, creating a
more heightened (increasing Lc), and more graphitic (decreas-
ing I(D):I(G)) crystallite. The proposed mechanism was only
found to work with carbons displaying a low DTA. High
DTAs were reasoned to inherently contain too many electron
holes due to the very high electron-withdrawing character of
the densely populated acidic SOG carbon surface—thereby
destroying the overall graphitic ordering effect.
Consequently, high DTA carbons illustrated single graphene
layers that still bonded together, as illustrated by increasing
R-values and La magnitudes. However, increased surface acid-
ity illustrated proportional graphitic disorder, due to steric
repulsion between the high DTA elongated single graphene
layers, when stacked in a p–p fashion. One additional note-
worthy observation was that when basic SOGs (pyrones) were
present on a carbon surface, they dominated control of the
microstructure; even with acidic SOGs simultaneously pre-
sent in concentrations an order of magnitude higher. This
study methodically illustrated the limitations of acidic
SOGs. Namely, that the short-range conjugation effects of
acidic SOGs and the resulting low conductivity and structural
stability influence on carbon substrates are dominated by the
controlling conjugation, conductivity-promoting, electron–
hole suppressing and structural stability enhancing proper-
ties of basic SOGs, even when they are present at very low
+ HCl + H2O
Cl OH
H H
Fig. 26 – Chemical identification of an oxygen-free,
positively charged basic site on the carbon surface.
Reproduced from Ref. [217].
concentrations among densely concentrated acidic SOGs.
Hence, the manufacture of strictly basic SOG hosting car-
bonaceous electrodes would be highly beneficial for Li-inser-
tion materials for both battery and capacitor forms of
charge storage—where both forms of charge storage can be
readily enhanced. In this respect, an outline of chemical/ther-
mal procedures for implementing sustainable conjugated
functional group system, along with control of the relative
hybridization of the surface active sites, is necessary for the
sustainable advancement of Li charge storage.
4.1.4. Basic SOGs
Basic SOGs are known to adsorb more acidic (e.g. phenols)
type compounds while adsorbing less moisture than acidic
SOGs, allowing for longer lasting (better aging), unadulterated
pore and surface molecular structure [179,209,210]. The gen-
erally lower oxygen content of basic SOG doped carbonaceous
materials enables a less outwardly polar and edge-reactive
nanostructure compared to carbons with primarily acidic
SOG character. In contrast, carbons with a very high oxygen
content display higher surface acidity with proportional
decreases in surface basicity [139,149,153,154]. Basic SOGs
are often characterized as creating a more hydrophobic-pro-
moting substrate with positively charged sites making them
favorable for adsorption of anions [209]. Additionally, both
quinone and pyrone groups have been shown to be primarily
responsible for the protonation/reduction processes
[147,150,152,209,211,212] of the carbon surface, which makes
them excellent candidates for Li-ion adsorption/desorption
processes. As with the formulations put forth long ago by
Garten and Weiss [155,156,213], Boehm [150,151,214], and
Donnet [215] and much later reviewed and advanced by
Radovic [147], quinone and pyrone functionalities with their
olefin-associated bonds have long been attributed as the stan-
dard Lewis-basic (electron-donating) sites. These sites are
thought to be responsible for catalyzing the oxygen reduction
reaction on activated carbon and certain carbon blacks, while
H
O O
ΔG
+ H+
O O
B B-H +
Fig. 27 – Quinonoid-type and chromene type groups
separated by multiple aromatic rings—forming a long-range
pyrone group (B). Upon protonation (BH+) the pyrone
species maintains its cumulative sp3/sp2 oxygen group
hybridization through the migration of charge through the
aromatic lattice conjugating the two oxygen groups.
Reproduced from Ref. [211].
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
also being able to retain their original active molecular struc-
ture. Basic SOGs allow for clustering of sixfold aromatic rings
through a cooperative, charge-stable sharing of p-electron
density between both carbonyl (sp2) and ether (sp3) hybri-
dized SOGs. The long range delocalization character allows
for higher catalytic retention of the carbon/heteromaterial
network [47,147,211].
In addition to the electron-donating character of quinone
and pyrone groups, positively charged, oxygen-free basic sites
on edge sites of aromatic rings have been elucidated by the
work of Rivin [216] and the computational work of Radovic
[147,217]. Fig. 26 displays a zigzag carbene site that has been
proposed (theoretically) as a potential active site for the
incorporation of positive charge in the carbon aromatic lattice
with the addition of HCl or H2O. Understandably, the conse-
quence of a highly electron-donating site such as the carbene
active site bonding with a proton atom allows for increased
electrostatic adsorption character of negatively charged
ions—in this case the Cl– and OH– ions. However, the theoreti-
cal, thermodynamically short-lived edge sites put forth by
Radovic et al. are not the only Lewis-basic, SOG sites capable
of positive charge generation within the carbon lattice.
Pyrone-type groups are combinations of separated car-
bonyl and ether groups on edge sites of the carbon lattice
and have been shown to play an integral part in the basicity
of carbonaceous materials [150,151,211]. The sustainable
redox activity as well as the charge-separation capability of
pyrones have been proposed and thoroughly investigated
for their sustainable catalytic properties. Fuente et al. have
produced computational calculations which contribute
towards the understanding of specific pyrone formations
[211]. Using calculated isodesmic (hypothetical) energies,
Fuente et al. provided clear evidence that the position of the
etheric moiety relative to the carbonyl group does not solely
determine the stability of the pyrone group, nor its relative
basicity. Rather, just as important is the fact that pyrone
groups contain both a mixture of sp3 (etheric) and sp2 (car-
bonyl) hybridized oxygen groups. Compared with other
SOGs that display all sp2 or all sp3 hybridized oxygen groups,
pyrones are more thermodynamically stable basic SOGs due
to the combination of the said hybridizations. Furthermore,
O
O
O
O
I II
Fig. 28 – The resonant structures of a di-quinone system.
Resonant structure II contains a positive charge that is
delocalized throughout the p system, which is redshifted
(1572 cm1) relative to the characteristic CAC frequency
(1590–1600 cm1) of aromatic compounds. Reproduced from
Ref. [219].
211
it was determined that bicyclic pyrones and multi-cyclic pyr-
ones, which contain multiple aromatic rings separating both
oxygen moieties, create particularly stable structures.
Hence, the sharing of electron p-density between both sp3
and sp2 hybridized oxygen groups is at the heart of pyrone’s
superior stability, and no doubt the conjugation of the aro-
matic rings between the oxygen groups, a general require-
ment of their Lewis-basic properties. It is not a stretch of
the imagination to understand that the stability of multi-cyc-
lic pyrones comes from the ability for charge compensation
from the conjugated aromatic rings between both sp2 and
sp3 hybridized oxygen groups. Similar charge compensating
procedures have been explored using Si/F co-doping that
has produced a novel method of the same donor–acceptor
charge compensating mechanism currently under discussion
[218]. Once an individual oxygen group is polarized, oxidized,
reduced, and/or holds a formal charge, the entire functional
group’s stability is maintained through charge compensation
by the other, complimentary oxygen group. Fig. 27 shows this
process occurring for the protonation of pyrone-type species.
Once the sp2 hybridized carbonyl group becomes protonated
and transforms to sp3 hybridization, the positive charge
within the system migrates to the ether type group, altering
its hybridization to sp2 and thus maintaining the dual sp2/
sp3 hybridization of the oxygen groups from the original pyr-
one species.
In fact, in a separate study by Fuente et al. [219], the pres-
ence of sp3 hybridized O groups in the AC@CAOAC@CA moi-
ety of pyrones has been shown to promote the conjugation
effect of pyrones, relative to diketone (di-quinone) analogs.
Hence, the active C@C normal vibration modes of pyrone spe-
cies have been shown, computationally, to reveal stretching
peaks at higher wavenumbers compared with di-quinone
analogs—effectively proving that the dual sp2/sp3 mixture of
oxygen groups enables charge to be localized on one of the
conjugated sp2 or sp3 oxygen sites, rather than in the aro-
matic lattice itself. This C@C weakening effect is displayed
in Fig. 28 for the di-quinone species—revealing the loss of
Fig. 29 – Potential Faradaic reactions of Li cation with (a)
carboxlic, (b) pyrone and (c) quinone surface oxygen groups.
(d) The electrostatic adsorption depiction of di-quinone, di-
ketone and pyrone species for both the Li+ cation and PF 6
anion at high and low electrode potentials, respectively.
Adapted from [141,208,210,211,219].
212 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
conjugation between the di-quinone system, as an electron
hole is created within the basal lattice itself instead of on
one of the oxygen groups thereby diminishing the conductiv-
ity and stability of quinone groups relative to pyrones.
Therefore, the ability to preserve both the original C/O
structure combined with the maintenance of sp2/sp3 oxidized
oxygen groups promotes good aromatic character throughout
the surface and basal conjugation system. It is, therefore,
understandable that both polarization (Figs. 23, 25 and 26)
and Faradaic (Fig. 27) processes occurring at Lewis basic sites
are relatively stable, catalytic active sites. These properties of
basic SOGs can be directly applied to hybrid Li-charge storage
processes for both battery and capacitor type systems. In this
respect, polarization of the electrode at high potentials can
favor anion-electrostatic binding and low potential polariza-
tion would facilitate Li-ion Faradaic processes. Basic SOGs
are far more suitable for both Faradaic and electrostatic forms
of charge storage when compared to acidic SOGs, which lose
their original molecular structure due to the hydrogen atoms
attached to oxygen groups (e.g. carboxylic/phenolic groups).
Additionally, acidic SOGs do not maintain conjugation
between sp2 and sp3 hybridized oxygen groups. The mecha-
nism of charge transfer at SOGs involves transferring elec-
trons between valence-electron states of the surface redox
species and adsorbing ions [140,141,217]. Fig. 29a displays a
typical charge transfer reaction of Li at an acidic (carboxylic)
SOG site. A Li ion replaces an H atom at the acidic site, and
the proton is lost to solution. Fig. 29b and c illustrates charge
transfer reactions with basic SOGs (pyrone and diketone (di-
quinone)). Note that the positive charge is incorporated into
the SOG/carbon lattice for basic SOGs, whereas the positive
charge is lost to solution with the acidic species (Fig. 29a).
Fig. 29d illustrates the possible sites of electrostatic adsorp-
tion of both Li+ cation and PF 6 anion on di-quinone, di-ketone
and pyrone basic SOG sites for the LiPF6 electrolyte at low and
high potentials, respectively. Again, basic SOGs stabilize the
positive charge of Li-ions at oxygen sites, allowing for the
Fig. 30 – Capacitance vs. CO content. Anhydride-containing
data points display corrected values that take into account
the two-electron transfer contribution of anhydrides.
Electrolyte used was 1 M H2SO4 at a current density of 2 mA
and a potential range of 0–1 V vs. RHE. Reproduced from Ref.
[197].
maintenance of both sp3 as well as sp2 hybridized oxygen
sites and continued strong aromatic and conductive character
[211,220]. Hence, basic SOGs offer both stable and reversible
Faradaic and electrostatic adsorption character to the carbon
surface whereas acidic SOGs degrade their original structure
upon adsorption of Li-ions.
4.1.5. Capacitance-promoting basic SOGs
The primary factors that enable an increase in capacitance of
carbonaceous materials are electrochemically accessible sur-
face area and surface functional groups. Surface area
improvements for carbonaceous materials are approaching
physical limitations. Additionally, the relationship between
specific surface area and specific capacity [204] or capacitance
[138,140,221,222] can be non-linear due to contributions from
surface functionalization. However, when accurately
accounting for the factors that promote pseudocapacitance
from voltage-dependent Faradaic-type reactions of carbon
surface functional groups, far better correlations of the total
capacitance with specific functionality and cycling conditions
can and have been established.
One thoroughly supported conclusion regarding capaci-
tance performance and surface functionality lies in the cor-
relation of high capacitance performance with CO-evolving
SOGs. CO-evolving groups are primarily attributed to Lewis
basic SOG species (Fig. 20). Not long ago, Bleda-Martinez
et al. [197,221], Fuente et al. [211,219], Montes-Moran et al.
[220], Radovic et al. [147], Menendez et al. [181], Boehm et al.
[150,151], and Centeno et al. [223] were each able to contribute
significantly to the understanding of Lewis-basic type surface
oxygen groups (SOGs) on carbonaceous surfaces and their
direct responsibility for the increase in capacitance activity
of carbons in ambient and variable temperatures.
Bleda-Martinez et al. [197] illustrated the relationship
between capacitance and the CO desorbing SOGs for an
anthracite activated carbon, with the additional considera-
tion of carboxylic anhydride groups. Fig. 30 displays the
relationship between capacitance and concentration of des-
orbed CO species for a number of KOH (AKN) and NaOH
(ANaN) activated carbons, followed by chemical oxidation
with concentrated HNO3. A number of the carbons were then
heat treated to specific temperatures in an N2 environment
(indicated with each data point), thus allowing specific sur-
face functionality to desorb from the surface. All carbons
investigated were microporous, containing approximately
the same average pore-sizes. The plot displayed reveals a sig-
nificantly improved line of best fit due to the incorporation of
a carboxylic anhydride adjustment factor (where anhydride
groups were considered to contribute two electrons in their
redox process with other SOGs contributing only one elec-
tron). The redox activities of anhydrides were shown to occur
at relatively higher potentials (>0.60 V vs. RHE) whereas the
redox activities of basic SOGs were described occurring at
lower potentials (<0.60 V vs. RHE). As displayed in other stud-
ies examined in the current review, the more structurally
integrous, CO evolving basic SOGs are shown to be most
active at high applied currents, and in various electrolyte
mediums. Bleda-Martinez et al., however, did not examine
the respective treated carbons at different applied currents
nor electrolytes. The conditions for the respective study
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
appear to facilitate the redox/pseudocapacitive activity of car-
boxylic anhydrides and their two electron transferring redox
processes—allowing for dramatically higher observed capaci-
tances. Additionally the authors did not display capacitance
measurements for extensive cycling conditions and therefore
the sustainability of the respective anhydride-doped elec-
trodes cannot be presently elucidated.
Anhydride groups evolve both CO2 and CO species when
heated under TPD conditions (Fig. 20). Even though anhydride
groups are formally classified as acidic SOGs, anhydride
groups can also be included as a dominant contributor to
capacitance since they also evolve CO—a trait shared by every
basic SOG (Fig. 20). Additionally, anhydride groups are the
only acidic SOGs which contain both sp2 and sp3 hybridized
oxygen groups—thereby facilitating charge storage/transfer
processes, just as discussed above for pyrones. Hence, even
though basic SOGs (or CO evolving SOGs) traditionally display
the best overall redox/structural cycle-ability, CO desorbing
ability in combination with sp2/sp3 oxygen groups presents
the greatest overall electrochemical performance.
4.2. Surface nitrogen group (SNG) functionalization of
carbon surface
4.2.1. SNGs
N-doped graphene-based substrates have displayed unique,
tunable properties compared with standard heteromaterial
containing carbon materials. Integration of nitrogen into the
graphene edge and lattice sites has been shown to directly
influence the spin density [224] as well as charge distribution
and therefore activation of adsorption/donor properties of
neighboring carbon sites [165,225]. Along with the controlled
implementation oxygen content of carbon substrates, nitro-
gen doping of the carbon surface creates a powerful electron
Donor–p–Acceptor system through rearranging the electronic
symmetry of the conjugated system. Nitrogen chemically
bound to carbon edge sites increase the static charge on the
carbon atoms to which N is bound, due to the additional labile
p-electron density from covalently bonded nitrogen species.
Fig. 31 – Illustration of common nitrogen functionalities,
with XPS abbreviations, commonly present in carbon-based
Li-charge storage materials.
213
This facilitates self-assembly, as has been illustrated and
characterized in a multitude of carbonaceous substrates,
including both amorphous and fullerene-type carbon materi-
als [146,226–229]. These examples are excellent models for
nitrogen induced changes to the electronic and donor proper-
ties of carbon based systems due to both the contrast of
highly reactive, amorphous carbon materials compared with
the more ordered-structure of onion and fullerene type car-
bon structures.
Ferrari et al. [146] illustrate that increased Raman intensity
changes in carbon-nitride species are not due to a structure/
symmetry-breaking mechanism from nitrogen incorporation,
but is rather, purely an electronic effect, where changes in
intensity are due to the added electron density from nitrogen
species on both olefin and aromatic sp2 bonding. As the
authors point out, such a mechanism polarizes the sp2 skele-
ton, thereby increasing the bond dipole moments of both six-
fold aromatic and olefin type bonding. Consequently this
increases the conjugated olefin system as well as sixfold aro-
matic ring clustering throughout the carbon basal lattice,
thus being responsible for a larger dipole/peak intensity effect
as was observed through Raman spectroscopy. Such observa-
tions are supported by the electronegativity of nitrogen (3.5)
being higher than carbon (3.0) and nitrogen’s smaller diame-
ter [230]. Hence, N-doping of carbonaceous systems is a stan-
dard method of creating n-type semiconductor properties,
allowing for electron-donating properties which result near
the substrate’s Fermi level [162,163,231–233]. As shown above
for SOGs, the electronic transition of such a semiconducting
system can be affirmed and altered by monitoring the relative
bonding hybridization for the carbon–nitrogen based system.
The hybridization can be controlled through tuning the %N in
the system at specific reaction conditions. For example,
between 0.4% and 10% N can generally induce sp2 clustering
effects, thereby reducing the band gap and increasing con-
ductivity, whereas greater than 10% N induces a shift from
primarily sp3 hybridization to sp2 C–N hybridization—creat-
ing more of a hard, graphitic-type carbon–nitride system
[233]. Such an effect allows for the possibility of a more favor-
able and stronger nitrogen–lithium interaction as well as
nitrogen-SEI layer development compared with non-altered
carbon–lithium, as observed with lithium insertion and
lithium battery type N-doped systems [230,234–238].
Along with the %N present in a carbon based system, the
specific SNG species present are responsible for the relative
hybridization of a given C–N bonded system. Knowing the
various concentrations of SNG functionality present on a car-
bon substrate is necessary in understanding the acidic/basic
and withdrawing/donating properties of N-doped carbon-
based electrochemical charge storage materials. As seen in
previous sections with SOGs, XPS has proven an effective
method by which to determine the functionality and relative
surface concentrations of SNGs [188,239–246]. Fig. 31 illus-
trates the major nitrogen groups found in electrochemically
utilized carbon materials [246]. The primary nitrogen 1s
groups observed in XPS are sp2 hybridized pyridinic nitrogen
(N-6: 398.7 eV), sp3 hybridized pyrrolic/pyridone nitrogen
(N-5: 400.3 eV), sp2 hybridized quaternary nitrogen (N-Q:
401.4 eV) and to a less common-extent, sp2 hybridized pyri-
donic-nitrogen oxide/nitrate structures (N-X: 402–405 eV)
214 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

[165,246]. Pyridine nitrogen is located at the edges of gra-
phene layers, contributing one p-electron to the aromatic p-
bond lattice, with a lone electron pair in the plane of the
ring—thereby often associated with electron donor proper-
ties. Pyrrollic nitrogen contributes two electrons to the aro-
matic p-lattice with a hydrogen atom in the plane of the 5-
membered ring, whereas pyridone nitrogen is similar to 6-
membered pyridinic rings that are in close proximity to oxy-
gen functionality. Quaternary, or graphitic nitrogen, inside
the graphitic bonds with three sp2 bonded carbons is often
associated with positive charge generation and therefore elec-
tron acceptor sites [230].
The specific methods to create nitrogen-doped carbon
based materials involve either direct synthesis of graphene-
type materials or chemical substitution of carbon/graphitic
based materials. Common methods employed have utilized
ammonia treatments [239,247], liquid treatments (melamine
[241,248], urea [241,248], pyrroles [237,249], etc.), chemical
vapor deposition [250–252], plasma processes [253], and
deposition/carbonization of nitrogen containing precursors
[234,236,242,254]. Due to the fact that each nitrogen specie’s
incorporation to the graphene lattice, as well as decomposi-
tion, is highly dependent on the surrounding oxygen and
nitrogen functionality [230,246,255–257], standard
decomposition profiles are not as readily available for nitro-
gen functionality as seen in previous sections for SOGs.
Therefore, temperature-programmable desorption (TPD) and
temperature-programmable reaction (TPR) profiles are often
analyzed and constructed on a case by case basis for each par-
ticular N-doped carbon substrate. This leaves significant
opportunity for the development of standardized chemical
implementation/thermal-desorption schemes for consis-
tently produced SNG-carbons.
The primary challenge of effective SNG carbon substrates
for electrochemical charge storage lies first and foremost with
consistent substrate production. Every study reviewed in this
section that displays N-doped charge storage enhancement,
therefore, will also be analyzed for their specific synthesis
and characterization procedures. Hybrid battery-capacitor
type Li-charge storage is arguably one of the major products
that can sustain future energy demands with alternative
energy use, especially in regards to the transportation sector.
Optimization of sustainable hybrid Li-technology is most
achievable through control of the carbon materials present
in the cell setup. Among the most important carbon proper-
ties controlled by the specific functionality present are the
electrode/electrolyte wettability, nanoparticle distribution,
electrode conductivity, and as previously described func-
tional-group enabled electronic properties. SNG controlled
carbons representing a means to more advanced Li-ion
charge storage mechanisms has been climbing steadily in
the past decade [230,239,244,254]. The following review

Fig. 32 – Li storage in the interwall space of NCNTs. TEM images of an individual NCNT at the same spot (a) before and (b) after
the full lithiation. The scale bars are 20 nm. (Middle inset) Enlarged TEM images with lattice distances. (b, right inset) An FT
pattern of the selected areas. (b, bottom inset) A low-magnification TEM image of lithiated NCNT. The scale bar is 50 nm. (c)
The gravimetric capacities and cycling performance of as-grown NCNTs and commercial multiwall CNTs. The current
densities of both cells were 80 mA g–1 using 1 M LiPF6 in 1:1 EC:DEC electrolyte. (d) A schematic illustration showing that
lithium ions insert into the interwall space of NCNTs through wall defects originating from defected nitrogen configurations.
Reproduced from Ref. [234]. (A color version of this figure can be viewed online.)
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
sections are a few areas of recent SNG, along with SNG/SOG
development.
4.2.2. Nitrogen and nitrogen/oxide doped nanotubes
The superior structural stability and electron-conductive
properties of carbon nanotubes are consistently utilized for
the advancement of effective, reversible lithium charge stor-
age, with the pending advent of economic methods of sub-
strate production. Nonetheless, the spectacular potential
applications for nitrogen and oxygen doped carbon nanotube
(CNT) must be exploited and advanced for the sake of sustain-
able, reversible Li-charge storage.
Shin et al. [234] uniquely describe a method via nitrogen
doped multiwall nanotubes which allows for Li-ions to diffuse
through defective nanotube basal lattices—significantly
increasing electrochemical access of Li-ions to nanotube car-
bon surfaces. The functional groups, such as quaternary
nitrogen groups, are argued to create access into the multi-
walled molecular space by creating openings in the basal lat-
tice of outer and inner and outer nanotubes. Fig. 32a and b
displays evidence that the MWCNT’s interwall space is used
for Li storage. The high resolution transmission electron
micrographs displayed are taken at the same spot and show
an increase in MWCNT’s interwall spacing, from 0.34 nm to
0.37 nm, before and after lithiation, respectively.
Fig. 32a and b additionally displays Fourier transformed pat-
ters of the white boxed regions (top right of figures)—display-
ing spots assigned to the (0 0 2) planes of the interwall
structure—indicating both decreasing distances in the spots
and an increase in the wall thickness from 15.7 nm to
17.8 nm, thereby further supporting the interwall spacing
increase. Fig. 32b also displays the SEI formation upon lithia-
tion (bottom right of figure). Hence, lithiation of the interwalls
of MWCNTs is confirmed, and Fig. 32c displays the gravimet-
ric capacity differences of commercial multiwall carbon nan-
otubes (CNT) and the nitrogen doped multiwall carbon
nanotubes (NCNT)—due to the proposed Li-insertion diffu-
sion phenomenon enabled by the increased interwall access
Fig. 33 – The cycling performance of the NiO3nm – NCNT, the
NiO10nm – NCNT, NCNT, and NiO alone. The current densities
of those samples were 200, 200, 80, 200 mA g–1, respectively.
1 M LiPF6 in 1:1 EC:DEC electrolyte. Reproduced from Ref.
[234]. (A color version of this figure can be viewed online.)
215
of nitrogen-doped MWCNTs illustrated by Fig. 32d. At the
current density applied (80 mA g–1), typical Li-insertion pat-
terns are observed for non-doped multiwall CNTs, with
charge and discharge capacities plateauing around
300 mAh g–1. At the same applied current density, extended
cycling displays a very significant, exponential type increase
in the reversible charge/discharge capacity—eventually
plateauing at 1920 mAh g–1 by the 200th cycle. When evalu-
ated as a capacitor, the final capacity is 2300 F g–1. These
results indicate that the SNG-doping treatments utilized cre-
ate effective defects in the graphene-lattice—allowing for pro-
gressive diffusion access into interwall active sites with each
cycle. However, one cannot ignore the p-bond dependent,
electronic properties of the graphene basal lattice that are sig-
nificantly altered by SNG-doping—thus greatly altering the
physiochemical reactive properties of the CNT sidewalls
[162,258].
Shin et al. [234] suggest it is also very likely that the nitro-
gen groups introduced into the lattice provide higher electro-
statically attractive sites for Li-ion adsorption in combination
with higher reactivity of nitrogen neighboring carbon sites,
which contribute to the dramatic increases in capacity
observed. One major difference of the non-nitrogen doped
(CNT) MWCNT control vs. nitrogen doped (NCNT) MWCNT
used in Fig. 32c is that the NCNT is a bamboo type structure,
which contain lattice distortions often associated with
heteromaterial doping. However, the control CNT was not a
bamboo structure due to lack of doping. This simple discrep-
ancy in the lattice structure could also contribute to the
charge storage differences observed. As recently described
by Gogotsi [259] 5- and 7-membered ring structures which
directly create lattice distortions are probable active sites
responsible for large increases in capacitance. Such signifi-
cant differences in the ion-hosting active sites of the distorted
lattice materials are directly rooted in the inherent electronic
properties of nitrogen containing materials, as elucidated by
Cervantes-Sodi and Ferrari et al. [231], discussed in
Section 4.2.1 and contribute to effects seen here with bamboo
type structure.
After exploring the direct impacts of nitrogen doping on
Li-insertion, Shin et al. [234] proceeded to study the disper-
sion effects of Nickel nanoparticles (NPs) on the electro-
chemical properties of Li-ion capacitor (LIC) electrodes.
Fig. 33 displays the capacity retentions of 3 nm nickel oxide
doped NCNT, 10 nm nickel oxide doped NCNT, the NCNT elec-
trode shown from Fig. 32c, and pure Nickel oxide. No con-
ducting agent was used for the NCNT-based electrodes and
were cycled between 0.001 and 3 V (vs. Li/Li+) over the course
of a 2-month period.
NP agglomeration is assumed to be the reason for the dra-
matic capacity drop observed in the pure NiO, where electri-
cal contact loss from carbon material diminishes the
conductivity of the system. Similar to the trend observed with
the NCNT electrode, both the NiO3nm – NCNT and NiO10nm –
NCNT electrodes exhibit exponential type increases in capac-
ity with cycle number. Both NiO-doped NCNTs display far
higher reversible capacity plateaus, especially the smallest
NP size tested, NiO3nm – NCNT, which produced a continuous
capacity increase of up to 3500 mAh g–1. Additionally, the
authors show via power capability tests that when the
216 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Fig. 34 – XPS characterization of the NiO3nm – NCNT and NCNT. (a) N 1s data for the NiO3nm – NCNT taken at different stages of
electrochemical and other processes. (b) A graphical illustration of Ni diffusion between N-doped sites during Lithiation.
Reproduced from Ref. [234]. (A color version of this figure can be viewed online.)

NiO3nm – NCNTs were cycled at 15 A g–1, a charging/discharg-
ing time of 1.5 min was observed and a max specific capacity
of 350 mAh g–1. The cycle life and retention properties also
displayed exceptional performance under various current
densities and cycling intermissions after 10,000 charge/dis-
charge cycles. At 100 times (20 A g–1) the original current den-
sity (0.2 A g–1), NiO3nm – NCNTs retained 45% of the original
capacity after 70 charge/discharge cycles—indicating the
nickel grown nanoparticles on NCNTs as a viable opportunity
for tremendously higher charge storage values in LIC systems
in the 0–3 V range.
The authors went on to describe the chemical properties of
NiO doped NCNTs using XPS. One significant observation was
that pure NiO, with an average diameter of >10 nm, displayed
N2p binding energy patterns consistent with a transition
from the N0 to N2+ oxidation states for lithiation and delithia-
tion, respectively. However, the NiO3nm – NCNT material
maintained a Ni oxidation state of N0, on average for both
lithiation and delithiation, respectively. Hence, the abnormal
capacity rises observed are assumed to be due to the extre-
mely small size of Ni particles and its ability to maintain an
elemental oxidation state throughout its electrochemical
reaction with lithium. The authors show that the initial pro-
cess of Ni–O binding to NCNTs is preferentially at pyridine-
type sites (N-6) rather than graphite-like, quaternary sites
(N-Q). This process is displayed by Fig. 34a with the decreas-
ing N-6 peak shown after NiO growth on NCNTs and illus-
trated in the top of Fig. 34b. Upon lithiation, the pyridine
sp3 hybridized peak significantly increases, which is attribu-
ted to the introduction of Ni0 oxidation state particles to pyr-
idine-type sites, especially those with nearby carbon
vacancies—further illustrated by the bottom of Fig. 34b. The
proposed mechanism was attributed to lithiation allowing
for the diffusion and settlement of Ni nanoparticles at the
less-favorable electron accepting, quaternary sites.
Shin et al. however do not detail further the specifics of
NiO/Li-ions, however their work implies the enhanced diffu-
sion of the charge-storage promoting Ni0 particles to less
energetically favorable graphite-like (quaternary) N-sites.
The top of Fig. 34a displays the return to the original pre-
lithiated surface state—helping to validate the weaker bind-
ing ability of the graphite-like N-sites compared with pyri-
dine-type groups.
The adsorption capability of Ni nanoparticles is signifi-
cantly increased due to the pyridine-type structures found
in the NCNT treatments. The adsorption increases for Ni
nanoparticles at nitrogen (pyridine) mediated nanotube
treatment have been analyzed in great detail by Yang et al.
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4 217

Fig. 35 – Optimized structures of Ni bound to tubes containing (a) no nitrogen, [(b)–(d)] graphite-like nitrogen, (e) pyridine-like
nitrogen, and (f) a vacancy–nitrogen complex. The calculated Ni binding energies are (a) 0.47 eV, (b) 0.34 eV, (c) 0.68 eV, (d)
0.66 eV, (e) 1.62 eV, and (f) 4.59 eV. The graphite-like nitrogen contributes to the enhancement of the N- binding energy
by activating surrounding carbon atoms whereas pyridine-like nitrogen strongly binds to the Ni atom as shown in (e) and (f).
Reproduced from Ref. [258]. (A color version of this figure can be viewed online.)

[258] using first principle calculations, as displayed in Fig. 35.
The primary conclusions surrounding pyridine-dependent
nanoparticle binding enhancements were discussed by ana-
lyzing the hybridization capabilities of graphite-like nitrogen
vs. pyridine-like nitrogen groups in sp2 carbon networks.
Graphite-like nitrogen is described as using three valence
electrons in sigma bonds, one in p bond, and one in a p*
orbit—allowing for activation of neighboring carbon sites
and some degree of enhanced binding with nanoparticles.
However, pyridine-like nitrogen uses only two valence elec-
trons for sigma bonds, one for p-bond, and two for a filled,
non-bonding p-orbital—allowing for effective hybridization
states with d orbitals of Ni atoms. Pyridine-like carbon
atoms that neighbor a carbon vacancy site were understand-
ably the most effective binding sites of Ni nanoparticles
(4.59 eV) as there are three possible overlap sites for
hybridization bonding to occur.
Questions concerning both the diffusion mechanisms of
extremely small Ni nanoparticles onto nitrogen-based
materials, before, during and after lithiation are still in need
of being addressed. In particular, clearer comprehension of
carbon/nitrogen lattice polarization mechanisms monitored
during Ni (or any nanoparticle) diffusion/deposition and
lithiation processes below 1 V vs. Li (monitored via in situ
Raman and FT-IR) will be highly beneficial. Such work will
allow us to better pinpoint the complex, cooperative elec-
tronic properties of various nitrogen/carbon active groups in
adsorption/desorption and charge storage processes of Li-
charge storing substrates.
4.2.3. Nitrogen and nitrogen/oxide doped graphene oxide
The functionalization of graphene oxide can provide very
high Li-ion charge storage for both Faradaic [236] and capaci-
tive [240,260] modes of charge storage [261,262]. Urea treated
GO is one such method of functionalization that has dis-
played beneficial results for enhancing both the elec-
trocapacitive [263] and energy–density enhancing properties
[240] of LIC electrodes.
218 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Fig. 36 – SEM (a), TEM (b) and HRTEM (c) and (d) images of APGs and (e) dark-field TEM image of APGs and corresponding EDS
elemental mapping of (f) carbon and (g) nitrogen. Reproduced from Ref. [236]. (A color version of this figure can be viewed
online.)

Fig. 37 – APG charge/discharge rate performance at various applied current densities displayed for every 10 cycles.
Reproduced from Ref. [236]. (A color version of this figure can be viewed online.)

Fig. 38 – Schematic illustration for the fabrication processes of nitrogen-doped CNFs. Reproduced from Ref. [242].
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
Crumpled nitrogen doped porous carbon sheets [264] cre-
ated by KOH activation of polypyrrole functionalized GO were
effectively fabricated by Wang et al. [236]. The application of
pyrrole monomer coating on GO allowed for a nitrogen doped,
crumpled, N-doped carbon microstructure when activated
with KOH and then carbonized at 800 C. The crumpling pro-
cess is observed with SEM and TEM figures displayed in
Fig. 36(a–c). The 2D structure is obviously preserved with
the combined polymerization, activation and carbonization
process. The increased average lattice spacing between the
graphene layers (0.37 nm), compared to graphite (0.335 nm),
as shown in Fig. 36d, is expected to help in facilitating more
effective Li-ion diffusion/insertion processes. Fig. 36(e–g)
shows the scanning TEM and energy dispersive X-ray spectro-
scopic analysis of the same sample, which indicates the
highly concentrated and more uniform N-doping present on
both sides of the disfigured graphene sheets.
The authors additionally support the disordered and
micro/mesoporous crumpled carbon material via broad
(0 0 2) peaks (XRD) and differential pore volumes. The authors
correctly indicate that the Raman G-band redshift of APGs
relative to GO is the result of the electron-donating character
of SNG-species [250,265], where GO shows primarily electron-
withdrawing character and therefore G-band blue-shifting
properties [47,139]. However, the authors do not further inves-
tigate the relative D-band properties, which can be utilized to
explain the increased aromatic, decreased olefin bonding
consequences of electron-donating N-doping. XPS is utilized
to identify pyridonic-N (N-6), pyrrolic-N (N-5) and graphitic
(N-Q) nitrogen groups at a doping level of 2.05% N—indicating
the transformation of pyrrole pentagon rings into the com-
mon SNG-doped species due to the carbonization process.
The resulting N-doped, crumpled graphene sheets (APGs)
allowed for a more electrochemically-accessible, conductive
substrate and provided good reversible cycle ability for Li-in-
sertion. The APGs displayed long-term stability at various cur-
rent densities (302 mAh g–1 at 2 A g–1 current density after
1600 cycles and 159.1 mAh g–1 at 10 A g–1 current density after
Fig. 39 – XRD patterns of the samples CNFs@Ppy, N-CNFs-
500, N-CNFs-700, N-CNFs-900, and N-CNFs-1100,
respectively. Reproduced from Ref. [242].
219
10,000 cycles). The good cycling stability was attributed to the
unique, open pore structure of the APGs with large inter-lat-
tice dimensions that allow for the large volumetric change
during Li-insertion without structure degradation, combined
with the large number of donor-type surface defects created
by the uniform N-doping.
The quality rate performance of the APG electrode is dis-
played in Fig. 37 for increasing applied current densities every
tenth cycle. Reversible capacities span from 726 mAh g–1 at
0.5 A g–1 to 133 mAh g–1 at 40 A g–1. After 90 cycles, a discharge
capacity of 1286 mAh g–1 is recovered (comparable to the ini-
tial discharge capacity) when the current density is greatly
decreased back to 0.1 A g–1. Hence, with the extremely stable
microstructure and the highly enhanced electronic conduc-
tivity and donating-character of the SNG-doped crumpled
carbon substrates, the rate performance is maintained. Such
rate performance exemplifies the utility of SNG-induced
structural integrity for partially graphitic, even crumpled car-
bon substrates under Li-insertion conditions.
4.2.4. Nitrogen doping by pyrrole deposition/carbonization
One recent study by Chen et al. [242] describes a simple, scal-
able method to create nitrogen doped carbonaceous nanofi-
bers (CNFs) also by utilizing pyrrole deposited groups.
Previous work by these same authors revealed a hydrother-
mal carbonization (HTC) template method [266] for creating
the starting material (Fig. 38) [267]. The low content of nitro-
gen incorporation resulting from traditional ammonia/air
[268,269] and tedious hydrothermal carbon oxidation [270–
272] treatments was overcome by employing polypyrrole as
a precursor species to the final nitrogen doped CNFs. Lately,
the control of mesoporosity coupled with SNG-doped materi-
als has been a forefront of ion-kinetics and active surface
enhancement due to the ion/pore size similarity and elec-
tronic alterations, respectively, of SNG-mediated surface
microstructure [271,273]. Such modern methods utilize car-
bonization temperature control for tuning the mesoporosity
of the substrate. The polymerization of the material with
the (NH4)2S2O8 creates polypyrrole coated CNFs (CNFs@Ppy).
Once coated, the diameter of the CNFs increased [267] by
roughly 15 nm.
Using various carbonization temperatures, Chen et al. were
able show that there was a correlation of N–CNF diameter with
carbonization temperature. The CNF@Ppy carbonized at
900 C was shown to display a large amount of interstitial
porosity combined with increases in the X-ray diffraction
intensity of (0 0 2) and (1 0 0) planes (Fig. 39). Compared with
the non-carbonized (CNFs@Ppy) sample, both the 900C (N-
CNFs-900) and 1100C (N-CNFs-1100) carbonized samples dis-
play intensity increases in both the (0 0 2)—21.99 and (1 0 0)—
43.56 planes, combined with decreases in their full-width at
half maximums (FWHMs). As expected with thermal-induced
carbonization and SNG incorporation, the graphitization of
the substrate increases [47,138,244,274]. Hence the electrical
conductivity of the material can be expected to increase as
the turbostratic character of the CNFs@Ppy is decreased.
However, for a more complete understanding of the role of
SNG functionality in the electronic/structure alterations, the
SNGs that evolve with each carbonization temperature need
220 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Fig. 40 – (a) XPS survey spectra of CNFs@Ppy and N-CNFs. (b-f) High-resolution XPS spectra of the deconvoluted N1s peak: (b)
CNFs@Ppy, (c) N-CNFs-500, (d) N-CNFs-700, (e) N-CNFs-900, and (f) N-CNFs-1100. Reproduced from Ref. [242]. (A color version
of this figure can be viewed online.)

to be precisely contrasted with the morphology and structure
properties discussed thus far.
XPS employed with the above described carbons displayed
%’s of nitrogen in the surface layers that decreased propor-
tionally with carbonization temperature—12.14%, 12.04%,
9.57%, 7.22% and 4.02% as calculated from CNFs@Ppy, N-
CNFs-500, N-CNFs-700, N-CNFs-900, and N-CNFs-1100 XPS
spectra, respectively. Fig. 40a displays detected XPS survey
spectra revealing O, N and C peaks. The deconvolution of
the N1s region displayed between 1–3 different SNGs from
the non-carbonized CNFs@Ppy substrate (Fig. 40b) up to the
CNFs@Ppy substrate carbonized at 1100 C (Fig. 40f). The
nitrogen functionalities identified were pyrrolic/pyridone
(N-5), pyridinic (N-6) and quaternary (graphitic) nitrogen (N-
Q). Non-carbonized, polypyrrole coated CNFs (Fig. 40b) show
exclusively pyrrolic/pyridone groups, as expected from the
nitrogen species in the 5-membered ring of polypyrrole.
As the carbonization temperature increases, it is apparent
that the polypyrrole coating is converted into both quaternary
(N-Q) and pyridine (N-6) groups. Fig. 40c (N-CNFs-500) and
Fig. 40d (N-CNFs-700) illustrate the decomposition of the
original polypyrrole coating as illustrated by the N-5 peak sig-
nificantly decreasing in intensity and widening. In response,
the quaternary and pyridine groups get integrated at inner
and outer carbon lattice sites, respectively. By 900 C, the
original polypyrrole is completely decomposed, producing a
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
Fig. 41 – (c) Specific capacitances of CNFs-900, CNFs@Ppy, N-CNFs-500, N-CNFs-700, and N-CNFs-1100 at different current
densities. Voltage range was 1.0 V to 0.0 V vs. Hg/HgO in 6M KOH (d) Electrochemical impedance spectra (inset: magnified 0–
4 X region) under the influence of an ac voltage of 5 mV. Reproduced from Ref. [242]. (A color version of this figure can be
viewed online.)
quaternary and pyridine exclusive N-doped surface. The per-
centage of pyridine, relative to quaternary groups (n(N-6)/n(N-
Q)) decreases from 31% to 14% over the course of the entire
carbonization process up to 1100 C, revealing that the in-lat-
tice quaternary groups are much more stable than pyridine
groups at higher carbonization temperatures [244]. The N-
CNFs-900 is indicated as the best candidate for electrochemi-
cal charge storage—displaying a 10x BET surface area
increase relative to the non-carbonized, CNFs@Ppy sample,
as well as the coexistence of micro-, meso- and macropores,
and an average pore diameter size of 3.64 nm. The high con-
centration of inter-crossed nanofiber stacks were additionally
reasoned to contribute to the higher concentration of meso-
pore observed with the N-CNFs-900 sample, and no doubt
influence higher conductivity properties of the carbonized
CNFs [267]. The method outlined thus far illustrates how to
effectively engineer nitrogen into both the graphene basal
plane and edge, utilizing a simple coating, decomposition
and carbon target-carbonization techniques.
Electrochemical testing was conducted with the N-CFNs
materials for the various carbonization temperatures in aque-
ous 6 M KOH using three-electrode cells at room temperature.
The N-CNFs-900 electrode material presents a far larger, more
rectangular CV curve with a few humps in the curve at all
scan rates applied (5–200 mV s–1). Unfortunately, the authors
do not further discuss the combined double layer capacitive
and pseudocapacitive behavior beyond saying ‘‘high specific
capacitance may be attributed to the combined effect of a
high nitrogen doping level changing the electron donor/ac-
ceptor characteristics of carbon and large BET surface area
increasing the surface area accessibility for electrolyte ion
transport.’’ The enhanced capacitive behavior of the N-
CNFs-900 electrode was significantly apparent, as seen in
Fig. 41.
The capacitance retention is shown to be 82% upon a 30-
fold increase in current density (1–30 A g–1) as shown in
Fig. 41c—indicating quality performance for versatile operat-
ing conditions and applications. The enhanced kinetic and
diffusion character supporting N-CNFs-900’s capacitive
behavior is further reinforced with the electrochemical
221
impedance spectroscopy (EIS), as shown with Fig. 41d. The
extremely small semicircle displayed in the inset of Fig. 41d
indicates very low charge transfer resistance in the high fre-
quency surface region of the substrate. Accordingly, N-
CNFs-900 solution resistance (0.14 X) was far below the non-
carbonized sample, CNFs@Ppy (1.25 X), and non-coated sam-
ple, CNFs-900 (0.92 X)—further illustrating the enhanced
power capability of the combined quaternary and pydrine
co-doped system. Even though the exceptional electrochemi-
cal performance is not shown via Li-ions, the SNG-doping
processes valuable in advancing carbon-based storage medi-
ums of Li-storage systems.
The contributions of nitrogen species in regard to Lewis
basicity, in combination with other Lewis acidic and basic sur-
face oxygen groups, have yet to be precisely determined and
therefore warrant such a study. Kelemen et al. [189] have
shown there to be a correlation between the oxygen content
of carbons and quaternary nitrogen present. More specifically,
an inverse relationship between quaternary nitrogen and
pyridic groups is observed—where quaternary nitrogen spe-
cies are decomposed with the loss of oxygen species during
pyrolysis—thereby creating pyridine-type groups in the pro-
cess. As reviewed previously for the polypyrrole decomposi-
tion on CNFs, both quaternary and pyridine groups also
displayed an inversely proportional relationship as carboniza-
tion temperature was increased above 700 C [242]. Hence, for
both thermal/chemical pyrolysis as well as the carbonization
treatments, in-lattice, graphene-like quaternary groups are
inversely proportional to pyridine-type nitrogen groups.
Furthermore, Kelemen et al. understood quaternary nitrogen
to be ‘‘basic nitrogen associated with nearby hydroxyl groups’’
[189]. Such understanding is parallel with the modern con-
ventions behind Lewis-basicity in regards to surface oxygen
groups (SOGs). Where Lewis basicity from SOGs is understood
to arise from the short-to-long range sharing of electron den-
sity between sp3 hybridized oxygen groups (ether-like groups)
and sp2 hybridized oxygen groups (carbonyl/quinone-groups)
[211]. Hence, quaternary (graphene-type) nitrogen groups
seem to facilitate similar electron sharing, sixfold aromatic
ring promoting and charge-distributing/charge-buffering
222 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Table 1 – Results of Boehm titration (numbers of surface groups in mmol g–1) and surface pH values. S = untreated carbon; S-
O = oxidized 4hrs with 50% HNO3; S-U = urea treated carbon; S-UO = oxidized 4hrs with 50% HNO3 then treated with urea; S-
M = melamine treated carbon, S-MO = oxidized 4hrs with 50% HNO3 then treated with melamine. Reproduced from Ref. [241].
Ratio column added.
Sample pH Basic groups Acidic groups All groups Ratio of Basic to Acidic groups

S 10.15 0.464 0.328 0.792 1.4

S-O 3.43 – 1.134 1.134 –
S-U 10.20 1.181 0.022 1.203 53.7
S-UO 9.15 0.836 0.284 1.120 2.94
S-M 9.98 1.037 0.110 1.147 9.4
S-MO 9.30 0.858 0.274 1.132 3.1

stabilization properties so closely associated with ether-type 10· increase in basicity over acidity. The authors attribute
Lewis basic groups [47,139,147,151,181,211,217,220,221,275]. the relatively lower basicity of the pre-oxidized, S-UO and S-
The sp2 hybridized graphite-like quaternary nitrogen allows MO samples, to the lower amount of oxygen and nitrogen
for facilitation of p-bond electron sharing between lattice functional groups present in the carbon bulk of these sam-
and sp3 hybridized edge functionality (pyridine/pyrone)— ples, as revealed by elemental analysis. However, as men-
thereby keeping the edge-to-basal lattice mechanically strong tioned, the relative surface basicity is a function of the
and electronically active for pseudocapacitive and low resis- specific SOG [47,139] and SNG species comprising the initial
tance charge-transfer processes. As reviewed with the work layers of the carbon surface.
presented above from Chen et al. [242], the specific capaci- XPS is used with deconvolution techniques to illustrate the
tance of the N-doped CNFs displayed outstanding perfor- specific nitrogen (N-5: pyrrolic/pyridonic, N-6: pyridinic, N-Q:
mance when exclusively pyridine and quaternary groups Quaternary, N-X: N-oxide) and oxygen (O-I: Quinone, O-II:
were present in concentrated amounts on the carbon surface ether and phenol, O-III: carb. acid/water) functionality pre-
(N-CNFs-900). Such an observation supports the theory that sent in the surface layers from each non-treated and treated
both quaternary and pyridine groups act together in order carbon samples. Table 2 illustrates the relative surface con-
to create an increased capacitive effect where studies centrations from fitting the N1s and O1s core level XPS spec-
addressed in the previous sections also illustrate the need tra. Urea treatments are displayed to favor pyridine group
for combinations of sp2 and sp3 Basic type SOGs and/or formation and the unoxidized S-U sample displays the high-
SNGs for more Faradaic type charge transfer. est concentration of pyrrolic/pyridine groups. One of the most
interesting features in contrasting Tables 1 and 2 lies in look-
4.2.5. Combined nitrogen and oxygen co-doping ing at the proportionalities or parallel increasing and decreas-
In a much needed focus area [241,248], Hulicova-Jurcakova ing trends of total basicity and the relative concentrations of
et al. [241] examined the combined effect of both nitrogen specific surface groups. For the S-U samples, both N-5 and N-
and oxygen containing functional groups on a microporous- Q are relatively higher in concentration than the pre-oxidized
only activated carbon. Hulicova-Jurcakova et al. expands sample, S-UO, whereas the opposite, increasing trend occurs
upon the quaternary/pyridine bi-functional-group relation- with the N-6 and N-X functionality. This contrast in concen-
ship by examining both the overall capacitance and pseudo- tration min/max tends, between the oxidized and unoxidized
capacitive performance of the sp2/sp3 electron for both oxy- nitrogen treated carbons, is precisely the same as the trend of
gen and nitrogen Lewis basic functionality. The microp- their overall surface basicity (Table 1). This observation was
orous-only activated carbon was subjected to combinations not implied by Hulicova-Jurcakova et al. to be correlated, as
of HNO3 oxidation, urea and/or melamine treatments. they did not directly utilize XPS analysis in surface acid/base
Table 1 displays total acidic vs. basic groups and surface pH characterization. Further validation of the surface basicity
values for the untreated and treated microporous activated trend is seen with the relative S-U vs. S-UO quinone surface
carbon.
As expected, concentrated nitric acid treatments create a
dramatic increase of surface oxygen concentration
Table 2 – Relative surface concentrations of nitrogen and
[47,139,149–151,153], resulting in the oxidized sample (S-O)
oxygen species obtained by fitting the N1s and O1s core
showing the complete elimination of basic groups and the level XPS spectra. Reproduced from Ref. [241].
highest concentration of surface acidity. Upon treatment with
Sample N-5 N-6 N-Q N-X O-I O-II O-III
urea (S-UO), this surface basicity is restored with almost 3x
surface basicity compared with acidity—indicating the inher- S – – – – 37.0 59.5 3.5
ent Lewis-basic SOG-promoting nature of nitrogen incorpora- S-O – – – – 42.0 54.8 3.2
tion. The unoxidized, urea-treated carbon (S-U) displays even S-U 27.0 48.2 20.5 4.30 44.6 47.9 7.5
more basicity compared with acidity (53·). The same trend is S-UO 19.9 53.5 16.4 10.10 37.8 54.1 8.1
S-M 22.2 44.7 26.1 7.04 51.6 51.6 6.1
observed with the melamine treatments, however the non-
S-MO 24.5 46.1 22.3 7.09 30.8 57.9 11.5
oxidized, melamine treatment (S-M) displayed less than a
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4 223

Fig. 42 – Specific capacitance per surface area of pores less than 10 Å (CsaCO2 in F/m2) as a function of average pore size (L in Å)
at the current loads of 0.05 A g–1, 0.1 A g–1, 0.5 A g–1, and 1 A g–1. Surface areas and mean pore diameters were calculated from
CO2 adsorption. The correlations on the left side include all samples whereas the right hand sided graphs include all but the
S-O sample. Conducted in 1 M H2SO4 with a potential window of 1 V. Reproduced from Ref. [241].

concentration (O-I), which is also in parallel with the N-5 and [47,139,147,151,180,220]. The S-U vs. S-UO acidic SOGs, O-II
N-Q groups, and a well-known basic-type SOG and O-III, also display parallel trends and follow an opposite
224 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
pattern than the N-5, N-Q and O-I (basic) groups—further vali-
dating the inverse surface acid/base relationship observed in
carbon oxidation processes [139,153].
The acidic (O-II and O-III), along with the basic (O-I) SOG
groups for the melamine treated carbons, S-M and S-MO, dis-
play the same concentration trends as was observed for the S-
U and S-UO groups. Such an observation implies that the
same general SOGs contribute to overall SOG-related surface
acidity/basicity in both oxidized and non-oxidized urea and
melamine treated carbons. Hence with the given trend paral-
lels, it is fair to assume that the SOG’s present in both urea
and melamine samples are of the same origin, yet vary in
concentration due to specific interaction with the nitrogen-
containing chemical treatments. Melamine has showed
specific dipole and reversible charge–transfer interactions
with quinone species [276]. Indeed such strong interactions
could likely be the reason as to why melamine treated (S-M)
carbons display relatively higher quinone concentration com-
pared with the urea treated (S-U) carbons. Such strong inter-
action with quinone sites would not only preserve
quinones, but also promote the ‘‘bulky polymers formed from
melamine’’ and open an additional pathway for the formation
of a higher quinone concentration—as seen for the signifi-
cantly higher O-I concentration (51.6) compared with the urea
treated sample (44.6). Urea treated carbons are likely to lead
to chemical reduction/interaction with quinone sites [277].
Such oxygen-reducing properties of urea have been well
established [278], similarly with hydrazine [279], as expan-
sion–reduction agents used in the production of graphene.
The urea treatments administered in the present study by
Hulicova-Jurcakova et al., thereby reveal lower O-I concentra-
tions for urea treatments (S-U) due to surface decomposition
reactions compared with the bulky polymer-promoting mela-
mine treatments (S-M). Interestingly, melamine treatment (S-
M) displays relatively low pyrrolic/pyridone groups (Table 2)
compared with the urea treated carbon (S-U), yet S-M also dis-
plays high pyridine (N-6) and quaternary groups (N-Q). Hence
the deviation in trends observed for the melamine (S-M and
S-MO) treated samples compared with the counterpart urea-
treated carbons must be due to the poor pore access due to
melamine polymerization around SOG-doped pore-sites. In
fact, increases in pyridine and quaternary nitrogen concen-
trations have previously [242] been correlated with a decrease
in pyrrolic/pyridone groups. Additionally this correlation has
been shown to occur with the formation of a hierarchical
(micro, meso, macro) pore structure—as observed with the
carbons present study. Due to melamine size, clustering/poly-
merization and low access to inner porosity, the primary
Lewis basic SNGs are pyridine and quaternary groups,
whereas the inner-pore access of urea-treated carbon allows
for pyrrole/pyridone and quaternary groups to act as the pri-
mary Lewis-basic SNGs.
In order to illustrate the capacitance differences of the
treated / non-treated materials with respect to pore diameter,
Fig. 42 displays the specific capacitances per unit surface area
(specific gravimetric capacitance (F g–1) per specific CO2-deter-
mined surface area (m2 g–1)) vs. average pore size in ang-
stroms. The plots on the left include all samples studied in
Tables 1 and 2. Poor correlations of decreasing capacitance
with increasing surface area were observed (left side of
Fig. 42). However, when removing the most outlying data
point (S-O) from the plots, the regression correlations improve
significantly, as seen in the right side of Fig. 42. Hence, for all
of the carbons that did not show significant pseudocapaci-
tance contribution due to highly acidic SOG concentration
(S-O), a good linear correlation was observed between average
pore-size and specific capacitance per unit area. The primary
pore sizes responsible for capacitance, ultramicropores < 10 Å
were shown to display an inverse linear response to increas-
ing pore size. Additionally, for all the highly basic carbons,
and the most Lewis-basic carbons also displayed the smallest
average pore sizes: S-U (5.4 Å) and S-M (5.2 Å), the electric
double layer was shown to be maximized. Understandably,
the pore sizes of the adsorbing ions (5.33 Å and 4.2 Å)
matched well with average pore sizes of the high capacitance
electrodes—as would be expected as the most effective ion
adsorption occurs where pore and ion sizes are highly similar
[280–282]. Hence, Hulicova-Jurcakova et al. [241] effectively
displayed the increase in capacitance for ultramicropores
with regard to both pore-size and specific Lewis basic SOG
and SNGs—clarifying their major contributions to capaci-
tance. The authors further discuss combined effects of het-
eroatoms to analyze the pseudocapacitive effects
concerning pores > 10 Å.
4.2.6. Combining acidic/basic surface character with sp2/sp3
hybridized SOGs and SNGs
One new avenue for Li-ion based pseudo-capacitance
enhancement utilizing effective surface acidic/basic and
hybridization techniques of SOG and SNG groups has been
seen with functionalized multiwalled carbon nanotubes
(MWNT) utilizing Decher’s [283] layer-by-layer technique
(LBL) [207,208]. LBL techniques can utilize complimentary
acidic and basic functional groups for self-assembly and
thickness control. Lee et al. [207] immersed an indium tin
oxide (ITO) coated glass slide into alternating solutions con-
taining either acidic or basic functionalized MWNTs, creating
bilayers of oppositely charged MWNT and thereby developing
a simple aggregation method for the development struc-
turally strong MWNT conductive materials for charge storage
based on opposite carbon-surface donor/acceptor properties.
In the case of Lee et al. [208], carboxylic acid MWNTs and
amine-doped MWNTs were utilized for the negative (acidic)
and positively (basic) charged complimentary components,
respectively. The films were then hydrogenated at elevated
temperatures producing significantly high density, layer-by-
layer MWNT (LBL-MWNT) electrodes with a pore distribution
centering around 20 nm. The atomic composition of the LBL
electrodes used for electrochemical testing in the study under
review was 85.7% C, 10.6% O and 3.7% N—displaying a pre-
dominantly oxygen functionalized substrate. It is interesting
to note that for this particular treatment, a mixture of both
sp2 and sp3 hybridized nitrogen (pyridine, amide) and oxygen
(carboxylic acid, ether) groups were observed via XPS for LBL-
MWNTs. Accordingly, Lee et al. displayed the positive effect of
Faradaic reactions as shown with the additional gravimetric
capacitance increase outside of the 3.0–4.25 V vs. Li range,
as shown with Fig. 43a. The authors report that the typical
3.0–4.25 V vs. Li is comparable to standard functionalized
MWNTs and porous materials in aqueous solutions—shown
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4 225

Fig. 43 – Potential-dependent electrochemical behavior of LBL-MWNT and functionalized MWNT composite electrodes
measured in two-electrode lithium cells. a, Cyclic voltammogram data for an LBL-MWNTelectrode obtained with different
upper- and lower-potential limits. Reducing the lower-potential limit from 3 to 1.5 V vs. Li resulted in increased current and
gravimetric capacitance. b, Cyclic voltammogram data for an LBL-MWNT electrode before and after 500C-treatment in 4% H2
and 96% Ar by volume for 10 h. c, XPS C1s spectra of an LBL-MWNT electrode before and after this additional heat treatment,
which is seen to remove a considerable amount of surface oxygen and nitrogen functional groups from the MWNT surface. d,
Cyclic voltammogram data for an LBL-MWNT electrode and composite electrodes of pristine MWNT, MWNT–COOH and
MWNT–NH2, with the LBLMWNT electrode having higher current and capacitance normalized to the MWNT weight than the
composite electrodes. The composite electrodes consisted of 20 wt% PVdF and 80 wt% MWNT. Composite MWNT electrodes
were prepared from slurry casting and dried at 100 C for 12 h under vacuum. The thickness of the LBL-MWNT electrode was
0.3 lm, and the thicknesses of the pristine MWNT, MWNT–COOH and MWNT–NH2 composite electrodes were 40, 50 and
30 lm, respectively. The density of the composite electrodes was 0.45 g cm3. Reproduced from Ref. [208]. (A color version of
this figure can be viewed online.)

in Lee’s respective study and their cited studies to yield a
capacitance of 125 F g–1. Reducing the lower limit to 1.5 V
(green CV) displayed approximately a double increase
(250 F g–1) in gravimetric capacitance—further validating
that stable, Faradaic type reactions enabled the additional
capacitance. This lower range Faradaic activity was attributed
to quinone-type groups allowing for the reversible reduction
of Li+ in the 3.5–1.5 V vs. Li potential range [284,285], in par-
allel with the earlier review of Bleda-Martinez et al. [197,221].
Gravimetric current and capacitance values were shown to
decrease dramatically (Fig. 43b) after the LBL-MWNTs were
exposed to 4% H2 and 96% Ar v/v at 500 C for 10 h. Fig. 43c
illustrates the decrease in both sp2 and sp3 hybridized C and
N functionalities after the heat/H2 treatment. The high tem-
perature, hydrogenation treatments confirm that the added
capacitance (40%) is due to Faradaic-type reactions occurring
from oxygen and nitrogen functional groups present on LBL-
MWNTs. Fig. 43d displays the differences in gravimetric
capacitances due to Faradaic-type reactions from both amide
and carboxylic acid MWNT functionalization (2· increase),
and their significantly large capacitance increase (5·) when
assembled in the LBL-MWNT fashion. Hence, the high density
and lack of binder allows for much greater electrochemical
access to the Faradaic-promoting C and N sites.
The high rate capable LBL-MWNT electrodes were also
shown to display a gravimetric capacity of 200 mAh g–1 at
low rates of 0.4 A g–1, yet retained up to half (100 mAh g–1)
at the very high discharge rate of 180 A g–1. Fig. 44b illus-
trates that the LBL-MWNT electrodes do not display any
capacity loss after 1000 cycles at moderate applied current
densities and voltage maximum of 4.5 V vs. Li. TEM and XPS
analysis of the cycled electrodes further reveal there to be
no significant degradation of atomic structure and functional
groups—further validating the lasting integrity of the LBL-
MWNT electrode construction method. The functional group
stability is extremely remarkable considering that primarily
carbonyl-type functional groups on MWNTs are known to
degrade within 100 cycles [284–286]. The authors attribute
226 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
Fig. 44 – Gravimetric energy and power densities, and cycle
life of LBL-MWNT electrodes obtained from measurements
of two-electrode cells. b, Gravimetric capacities of Li/
LBLMWNTcells as a function of cycle number, measured at a
current density of 0.25 A g1 once every 100 cycles, after
voltage holds at the end of charging and discharging for
30 min. Within each 100 cycles, these cells were cycled at an
accelerated rate of _2.5 A g1 d, Ragone plot for Li/LBL-
MWNT (black squares), LTO/LBL-MWNT (green circles), LTO/
LiNi0.5Mn1.5O4 (gray circles) and LBL-MWNT/LBL-MWNT
(orange triangles) cells with 4.5 V vs. Li as the upper-
potential limit. The thickness of the LBL-MWNT electrode
was 0.3 lm for asymmetric Li/LBL-MWNT and LTO/LBL-
MWNT, and 0.4 lm for symmetric LBL-MWNT/LBL-MWNT.
Gravimetric energy and maximum power densities were
reduced for the LTO/LBL-MWNT cells subjected to the same
testing conditions due to a lower cell voltage. Reproduced
from Ref. [208]. (A color version of this figure can be viewed
online.)
such strong functional group stability to the strong chemical
covalent bonding between the surface functional groups
and the MWNTs, but do not elaborate on the possible elec-
tronic, hybridization nor functional group species mixture
that may enable the stated performance.
The LBL-MWNT electrodes displayed a high gravimetric
energy (200 Wh kg–1) corresponding with a very high power
of 100 kW kg–1 when normalized to a single electrode weight.
100000 296
Specific Applied Current (mA/g)
235
238
10000
235 290
298 294 290 293
299 291 292
1000 297
300 294 295
296
290 291
292 233 233
298 293
100
297 299 235
300 238 234
10
64 128 256 512 1024 2048 4096 8192
Specific Capacity (mAh/g)
Fig. 45 – Plot of N-doped functionalized carbonaceous
substrates and their corresponding specific capacity at
various applied currents. Open circles represent substrates
which displayed favorable sp2/sp3 hybridized N-group
combinations (e.g. primarily pyridine/pyrrolic or pyridine/
quaternary) that display enhanced Li-ion capacity. Closed
circles represent substrates that did not display favorable
sp2/sp3 hybridized N-group combinations (e.g.
approximately equal concentrations of pyrrolic, pyridine
and quaternary groups), which display relatively poor
capacity/applied current relationships. Many of the
substrates are shown at multiple applied currents.
References are shown for each data point.
This relatively high gravimetric energy and high power
lithium storage electrode makes it an excellent candidate
for asymmetric capacitor applications. To provide insightful
application of this technology in moving past the problematic
Li-metal anode systems, Fig. 44d displays the use of symmet-
ric LBL/LBL and asymmetric Li4Ti5O12 (LTO)/LBL systems in
comparison to the Li-metal/LBL and conventional LTO/
LiNi0.5Mn1.5O4 systems. The LTO/LBL systems display much
greater gravimetric energy density at powers greater than
10 kW kg–1 compared with the LTO/LiNi0.5Mn1.5O4 system.
The LTO/LBL asymmetric system has lower gravimetric
energy and power compared with the Li-metal/LBL system
due to reduced cell voltage. However the authors provide evi-
dence for comparable rate capability, gravimetric capacity
and capacity retention relative to the Li-metal/LBL system.
Hence, the significantly high gravimetric capacity and
capacitance values obtained with LBL-MWNT reflect the
state-of-the art for maintaining highly stable electron-con-
duction channels and, therefore, preserving the integrity of
both nitrogen and oxygen functional groups and their asso-
ciated redox and charge storage capabilities. This novel devel-
opment of metal-free highly efficient, Li-charge storage
materials is an excellent candidate for hybrid Li-ion capaci-
tors, with the optimization/modification of surface func-
tionality in the sp2 and sp3 carbon/functional group matrix
potentially allowing for further increases in redox potentials,
voltage tuning and therefore charge storage efficiency.
The present review section on SOG and SNG functionality,
hybridization and surface acidity/basicity has thus far
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
illustrated that primarily metal-free carbon substrates can
have their effective Li-ion charge storage enhanced from tun-
ing respective surface properties of purely carbon substrates.
However, the effective combinations of SOG and SNG func-
tionality, hybridization and overall surface acidity/basicity
can display the same enhanced Li-storage effects additionally
in SOG and/or SNG-doped carbon/metal composites. Fig. 45
displays the Li-ion capacity results for primarily SNG-doped
(as reviewed, oxygen groups are always present to some
degree on carbon) substrates of all species/hybridizations
and some composites reviewed herein. The effects of effec-
tive SNG-doping are apparent as observed with the increased
capacities displayed for all substrates that contain effective
charge-buffering and sustainable donor properties through
specific nitrogen group combinations (open circles). These
include favorable charge storage substrates resulting from
combinations of primarily both sp2 and sp3 hybridized pyri-
dine/pyrrolic N-groups (N-doped graphene [239,287], coaxial
MnO/N-doped carbon nanorods [288], Sn nanoparticle
embedded in N-doped carbon [289], N-doped graphene and
few layer tungsten composites [290]) and quaternary/pyrrolic
N-groups (CNT/CNF hybrids [291]). As discussed in this
review, these combinations allow for charge buffering, open
electron conductive pathways and molecular integrity of
charge-storage active sites—thereby enabling such high per-
formance characteristics. However, due to specific structural
and molecular properties, the sp2/sp3 hybridization combina-
tion is not the only effective manner by which to promote N-
doped Li-ion charge storage capacity. As also seen in Fig. 45,
structural modifications of SNG-doped MWCNTs and NiO/N-
doped MWCNTs [234] that display primarily sp2 hybridized
quaternary and quaternary/pyridine groups can produce very
enhanced Li-ion capacity results. The same quaternary/pyri-
dine group combination is also effective on SNG-doped gra-
phene shells that are deposited on the highly integrous
silicon nanowires [292] via CVD—where the already highly
conductive electron pathways on silicon nanowires yield
improved electron-donor character and therefore Li-charge
storage character from the nitrogen doping. Additionally,
the quaternary/pyridine combination is shown effective for
N-doped graphene which also contains hierarchically porous
structures [293], allowing both higher power and energy den-
sities due to the enhanced diffusion pathways of the
hierarchical system in concert with the electron-donating
abilities of the sp2-hybridized nitrogen groups. The carbon
systems that do not contain either the innate structural prop-
erties that allow for enhanced electron conduction or ion-dif-
fusion, as well as the substrates that lack the appropriate sp2/
sp3 nitrogen group hybridization, fail at achieving sustainably
high Li-ion capacity. In Fig. 45, these include substrates which
simultaneously display all 3 groups—pyrrolic, pyridine and
quaternary nitrogen groups (crumpled N-doped graphene
nanosheets [236], highly concentrated doped CNTs [294],
nitrogen doped carbon fiber nanowebs [295], N-doped MnO
nanoparticles anchored on N-doped graphene nanosheets
[296], and N-doped graphene sheets [235]. Additionally, sub-
strates displaying predominantly pyrrolic groups, without
any quaternary nor pyridine groups, also lacked the effective
charge-buffering stabilization necessary for high sustainable,
227
reversible Li-ion charge storage—even when integrating
nickel sulfide with N-doped graphene composites [297].
Conclusively, the promotion of a substrates electron donor
character through increasing Lewis basicity is not adequate
for sustainable charge storage enhancements due to the
required structurally integrous, open electron conductive
pathways necessary for charge transfer and mobility. On the
other hand, a highly conductive and uniform substrate will
also perform poorly without the presence of stable, active
donor sites. Yet, as shown through the discussion of Fig. 45,
having a less conductive or stable carbon substrate can be
compensated for by integrating both sp2 and sp3 hybridized
nitrogen and/or oxygen groups that allow for preservation
of conductive pathways and structural stability—thereby
enabling high Li-ion charge storage performance.
Concurrently, an extremely structurally integrous and elec-
tron-conducting substrate does not appear to require the
sp2/sp3 hybridization nitrogen mixture that enables the
charge-buffering/structure—preserving mechanism, yet still
demands either or both sp2 hybridized pyridine or quaternary
groups—as exclusively sp3 hybridized pyrrolic groups does
not facilitate sustainable electron-donor character.
5. Impact of surface functionality on SEI layer
development
The discussion in the preceding section was focused on the
effect that surface functionalities, whether natural or syn-
thetically introduced, have on the physical and electronic
properties of the carbon material itself, including how those
effects have been exploited in the research on advanced elec-
trochemical energy storage. In addition, reports in the litera-
ture have shown that surface functional groups can undergo
and induce redox reactions. Under the best conditions, this
behavior could result in an increase in the charge storage
capacity of the material through reversible, pseudocapacitive
means [211,220,221,298–300]. However, one question that is
important to address is: how does the presence and density
of surface functional groups, specifically oxygen or nitrogen
Fig. 46 – Initial discharge/charge plots of the graphite
electrodes, scan rate: 0.2 mV s–1. Reproduced from Ref. [308].
228 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Fig. 47 – Initial discharge/charge plots of the modified (a) and original (b) graphite electrodes; insets are the specific capacity
as a function of cycling numbers. Reproduced from Ref. [309].

functionalities, affect the development of SEI layer?

Unfortunately, the current literature that directly addresses
this question is somewhat sparse, yet three common aspects
can be garnered from these resources that provide an illustra-
tion of the effects that surface functionality has on ion inter-
calation materials and the development of the SEI layer.
These three aspects are: (1) possible reactive sites for the
functionalization of the carbon surface, (2) reversible redox
reactions with the functionality itself, and (3) irreversible
reactions with Li, or other, ions.

5.1. Reactive sites for functionalization

What is perhaps one of the oldest applications of porous, acti-

vated carbon materials lies in the area of purification.
Activated carbon has been proven to be an effective adsorbent
for the removal of a wide variety of organic and inorganic pol-
lutants dissolved in aqueous media. These adsorbent proper-
ties can be tailored through the functionalization of carbon
surface [209,301–304]. The capacity for chemical adsorption
at the site of surface functionality has been exploited in the
development of materials tailored for specific applications
(e.g. catalysts) via the functionalization of the carbon surface
[301,305–307]. Pan et al. used this approach of functionalizing
carbon materials to create new anode materials for lithium
ion batteries [308,309].
In the first example, 4-nitrobenzyl multilayer films were Fig. 48 – Galvanostatic insertion/extraction of lithium into
established on natural graphite [308]. Natural graphite was (a) as-received nanotubes and (b) P/Al800 nanotubes at a
treated with 4-nitroaniline and isoamyl nitrite for one hour current load of 20 mA g–1. Reproduced from Ref. [310].
at room temperature. The authors speculated that multilayer
formation could come as result of azo coupling of the diazo-
nium cation with a functionalized carbon ring. Hydroxyl cathodic peak during the first intercalation indicated that
groups that are likely present on the carbon surface were pre- the nitrophenyl multilayers could effectively suppress solvent
dicted to undergo a coupling reaction with the diazonium decomposition, as reproduced here in Fig. 46. As a result, the
cations leading to the establishment of the initial organic initial de-intercalation capacity was calculated to be larger
layer of azo derivatives on the surface of the materials. than 330 mAh g–1 with a coulombic efficiency over 89% [308].
After the initial layer was formed, it was predicted that the In a subsequent publication, the same authors were suc-
subsequently generated radicals attacked the attached phe- cessful in creating lithium benzoate multilayers on graphite
nyl rings to form the multilayers. When the authors evaluated [309]. The modified graphite was prepared using a similar
the materials as possible anodes, the presence of a small technique, but with 4-aminobenzoic acid as the derivatizing
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
Fig. 49 – Dependence of irreversible capacity Cirr vs. mesopore volume for different types of nanotubes. The inset shows the
absence of proportionality between Cirr and the specific surface area in the case of a mesoporous material. Reproduced from
Ref. [310]. (A color version of this figure can be viewed online.)
agent. The evaluation of those materials produced an initial
deintercalation capacity larger than 345 mAh g–1 with a
coulombic efficiency of over 91.5%. For unmodified graphite,
the authors obtained an initial deintercalation capacity and
coulombic efficiency of only 311 mAh g–1 and 76%, respec-
tively. In addition, the reversible capacity of the unmodified
graphite decreases dramatically with cycling, only holding
88.3% of its initial capacity for the 20th cycle. These results
are evident in the plots reproduced here as Fig. 47.
Both sets of results indicated that added functionality
increased the overall capacity while decreasing the irreversi-
ble capacity. However, what was not clearly explained in their
discussion is whether or not the new functionality played any
direct role in the increased capacity via a redox process dur-
ing cycling or by reacting with the lithium ions directly in a
reversible manner. In the case of the former possibility, the
irreversible capacity would not have necessarily decreased
unless Li intercalation access had been blocked by the func-
tionality that also results in limiting electrolyte decomposi-
tion. In the latter case, the portion of the Li ions that
reacted with the added functionality would be in addition to
the Li ions that intercalate and so it could be expected that
there would be a much larger increase in the initial capacity.
5.2. Reversible redox reactions – increase in storage
capacity
The capacity for the surface functional groups themselves to
undergo reversible redox reactions follows naturally from the
previous discussion. Under this behavior, the functional
groups may react with the Li (or other) ions in a reversible
manner. Possible reversible reactions that lithium can have
with oxygen surface groups were presented in Fig. 29 in
Section 4.1. These reversible reactions would have the net
effect of increasing the overall Li loading capacity and, if a
reversible reduction of the functionality occurs in
229
combination with the interaction with a Li ion, then this will
also result in an increase in the reversible capacity.
In an article that examined electrochemical energy storage
in carbon nanotube and nanostructured carbons, Frackowiak
et al. noted that there was a significant hysteresis in the Li
deintercalation curve after the electrode material composed
of multi-walled nanotubes (MWNTs) was lithiated [310].
During preparation, two of the samples were treated in dilute
nitric acid to eliminate free Co particles and as a result of that
treatment, they contained a significantly higher oxygen con-
tent (5–10%) relative to the untreated samples. It was found
that those samples exhibited a larger hysteresis between the
1st extraction and 2nd insertion, as reproduced here in
Fig. 48a.
It was suggested that the convexity of the curves during
deinsertion might be partly attributable to quasi-reversible
interactions between oxygenated surface groups and lithium.
For example, the reaction: COOH + Li+ ! COO–Li+. The
authors also postulated that the surface functionality might
also contribute to the higher capacity through pseudocapaci-
tance, or redox reactions. Shown in Fig. 48b is the first inser-
tion/extraction cycle for the same material after a heat
treatment at 2400 C for 1 h under argon. This treatment
resulted in a decrease in the mesopore volume (from 381 to
242 cm3 STP g–1) and the removal of oxygen functionality.
The as-received materials showed an oxygen content of
4.6 wt%. The authors noted that there was a correlation
between the mesopore volume of the carbon nanotubes and
the irreversible capacity, as reproduced here in Fig. 49. This
differs from powdered porous carbons, which can normally
correlate the BET surface area to the irreversible capacity.
However for the heat-treated sample, there does not seem
to be a clear correlation. The as-received sample and the
heat-treated sample are marked in Fig. 49. On the basis of
their discussion concerning the possible cause of the hystere-
sis in the insertion/extraction curves, the larger than
230 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4

Table 3 – Chemical, Structural and Charge–Discharge Properties of RGOs. Adapted from Ref. [311].
C/OXPS C/OEA H/CEA BET (m2 g–1) Charge/discharge capacities (50 mAh g–1)

H-RGO1 15.85 10.89 0.28 397.3 2052/871

S-RGO1 17.73 11.15 0.72 100.7 733/337
H-RGO2 10.67 5.66 0.82 527.2 2121/1078
S-RGO2 12.33 9.40 2.27 147.2 3350/1521

predicted decrease in the irreversible capacity could likely be are compared for the H-RGO1, S-RGO1, H-RGO2 and S-RGO2
attributed to irreversible reactions involving the oxygen sur- materials as shown here in Table 3, there is a good correlation
face functionality. between the amount of oxygen (C/OXPS ratios of 15.85, 17.83,
Yoon et al. examined the electrochemical performance of 10.67, and 12.33, respectively) and the coulombic efficiency
hydrogen-enriched reduced graphene oxide as potential inter- of the first intercalation/deintercalation cycle (42%, 46%,
calation anode materials for lithium ion batteries [311]. Two 51%, and 45%, respectively), which is in an indication that, at
graphene-oxide (GO) materials were prepared that differed least in these materials, the reactions with the surface oxygen
only in the number of oxidation steps used to prepare the functionality are somewhat reversible.
materials, from which reduced graphene-oxide (RGO) materi- To account for the superior reversible capacity of the S-
als were produced through reduction using either supercritical RGO2 electrode as compared to other RGOs electrodes, the
IPA (S-RGO) or through calcination at 400 C (H-RGO). In the authors postulated that the key factor is the larger amount
first charge curves, a pseudo-plateau was evident at around
0.7 V vs. Li that was associated with SEI layer formation.
While the concentration of surface defects has normally been
considered to be responsible for SEI layer formation during Li
ion intercalation, the authors suggested that reactions
between lithium ions and the surface oxygenated functional
groups also contribute. The authors compared the amount
of oxygenated groups (C/OXPS ratios of 15.85 and 17.83) to the
lithium uptake (2052 and 753 mAh g–1) in the singly oxidized
materials (H-RGO1 and S-RGO1, respectively), which showed
that the oxygenated groups seemed to have a positive effect
on the capacity. However, this correlation was not evident
for the twice-oxidized materials (RGO2) materials. Electrodes
prepared from the RGO2 materials exhibited a larger fraction
of their capacity above 0.5 V than that of the RGO1 electrodes.
The authors suggested that Faradaic capacitance might have
been more important in the mechanism for Li ion storage in
the RGO2 electrodes and that this could be attributed to the
larger amount of defects and residual oxygen functionalities
in that material. However, when the materials C/OXPS ratios

Fig. 51 – Voltage profiles of each of Samples 1–7. The voltage

Fig. 50 – Charge–discharge characteristics of lithium
insertion into MWNT 900 C at a current of 17 mA g1.
Reproduced Ref. [314].
ranges from 0 to 2 V for each panel. A: irreversible capacity;
B: hysteresis; C: 1st charge (deintercalation) curve; D1: 1st
discharge (intercalation) curve; D2: 2nd discharge curve; E:
1st discharge capacity; F: reversible capacity. Reproduced
from Ref. [315].
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
of hydrogen-terminated sites that resulted from the reduction
treatment with the supercritical isopropanol. They further
concluded that the incorporation of hydrogen-terminated
groups in S-RGO2 was enhanced by the use of doubly oxidized
graphite oxides that contained a larger amount of oxygen
functionalities and larger surface areas [311].
5.3. Irreversible redox reactions – increase in irreversible
capacity
Lastly, the surface functional groups could react with the Li
ions in an irreversible manner (refer to Fig. 29) that could pro-
vide anchoring points for the development of the SEI layer,
thus contributing to the overall lithium loading capacity and
also increasing the irreversible capacity. In their work pub-
lished in 1997, Xing and Dahn showed that with a decrease
in the surface functionality there was a corresponding
decrease in the irreversible capacity [312]. During the prepara-
tion of carbon materials from the pyrolysis of sugar, the
researchers exposed the materials to different gasses (Ar,
N2, CO2, and O2) and different combinations with steam and
air. The authors predicted that the materials exposed to air,
steam or O2 would develop oxygen functionalities based off
of the work of Peled et al. [313]. Electrochemical testing of
the materials showed that those materials with oxygen sur-
face functional groups exhibited increased irreversible capac-
ity, by forming COOLi from COOH and OLi from OH, and that
reactions with the functional groups accounted for about
70% of the irreversible capacity. Furthermore, exposure to
air had an even more pronounced effect on irreversible capac-
ity than exposure to oxygen. This implied that the combina-
tion of water and oxygen is more reactive with the surface
than oxygen alone [312].
The work by Frackowiak et al. examined the lithium inser-
tion properties of carbon nanotubes [314] and, during the
evaluation of their materials, they noted that their sample
exhibited a significant hysteresis between the
Fig. 52 – First galvanostatic lithium insertion/deinsertion in
Timrex SLX50 and heat-treated (HT) Timrex SLX50 at a
specific current of 10 mA g–1 using 1 M LiPF6 in EC/DMC 1:1
(w/w) as electrolyte. Reproduced from Ref. [317].
231
electrochemical insertion and deinsertion of lithium, which
is reproduced here as Fig. 50.
The authors reported that their samples exhibited notice-
able capacity above 2 V vs. Li, which is above the typical elec-
trolyte decomposition potential of 1.5 V. The authors noted
that the purification treatment to remove silica and cobalt
with oxidizing nitric acid could partially functionalize the car-
bon nanotubes with oxygen functionality. Therefore it was
quite likely that surface functional groups of mostly oxygen
moieties were formed since, during the preparation of the
samples, they were either exposed to air or held in dilute
HNO3 for 4 h. The authors attributed the increased capacity
to the surface functional groups and that it was surface
ACAOAH groups that played a significant role in lithium
adsorption through the formation of ACAOALi+. Therefore it
was this reaction that resulted in the large the hysteresis
between the insertion and deinsertion curves. It is also evi-
dent that, with continued cycling, the magnitude of that hys-
teresis decreases and so it can also be concluded that process
is not completely reversible.
In their work studying vapor-derived carbon filaments as
anode materials, Lu and Chung compared the performance
of the activated materials that possessed oxygen or nitrogen
functional groups [315]. The same material was prepared
using four conditions: as-received (Sample 1), acetone washed
(Sample 2), activated following the method of Buiel and Dahn
[316] for 30 min (Sample 3) and 20 min (Sample 4), and activa-
tion followed by reduction in H2 (Sample 5). A last sample was
prepared from Sample 4 by a second activation and then
functionalizing the material with nitrogen functional groups
(Sample 6). Their results indicated that a carbon with the
same specific surface area and the same porous structure,
but a lower amount of oxygen containing functional groups,
showed higher capacities and decreased irreversible capacity.
This is evident in a comparison of the results for Samples 4
and 6 as shown in the figure reproduced here as Fig. 51.
After activation of the sample (Samples 3 and 4), the
charge and discharge capacities increased resulting in a
decrease in the irreversible capacity and this was attributed
to the increase in the oxygen-containing surface functional
groups relative to the un-activated materials. A comparison
Table 4 – Amount of desorbed H2, H2O, CO, and CO2 gas
obtained in temperature-programmed desorption mea-
surements of TIMREX SLX50 and SLX50 (HT) up to 950 C as
well as the active site surface area, the active site surface
area normalized to the total specific BET surface area (dASA),
and the amount ratio of CO and CO2 desorbed up to 950 C,
which was determined for TIMREX SLX50 and SLX50 (HT)
in the same experimental set-up after oxygen chemisorp-
tion at 300 C. Reproduced from Ref. [318].
TPD results SLX50 SLX50 (HT)
TSA (m2 g1) 4.0 2.6
H2 (lmol m2) 0.55 0.4
H2O (lmol m2) 3.25 5
CO (lmol m2) 3.75 1
CO2 (lmol m2) 1.48 0.33
ASA (m2 g1) 0.3 0.008
dASA = ASA/TSA 0.08 0.003
232 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
of the results showed that nitridation was slightly more effec-
tive than reduction in H2 (Samples 6 and 5, respectively) in
this regard as it gave slightly higher capacities and slightly
lower irreversible capacity. The authors speculated that the
mesoporous surface structure and the decreased amount of
oxygen-containing surface functional groups in the reduced
carbons may be responsible for the lower irreversible capacity
since the CAO and C@O functional groups may not be stable
in the electrolyte. They concluded that oxygen-containing
surface functional groups results in high irreversible capacity
and that decreasing the surface oxygen content by nitridation
or reduction in H2 decreases the irreversible capacity [315].
Spahr et al. examined the differences that the type of sur-
face oxygen functionality has on the propensity for graphite
to exfoliate during lithium intercalation [317]. Synthetic gra-
phite was heat treated at 3000 C in an inert helium atmo-
sphere for two weeks, cooled to room temperature and then
exposed to air. The authors stated that the oxygen surface
groups on the untreated graphite seem to exhibit mainly
acidic properties, whereas high temperature treatment of gra-
phite followed by exposure to air at room temperature results
in the oxygen surface groups mainly showing basic proper-
ties. This was confirmed by measuring the pH of a suspension
of the graphite samples, which showed that the untreated
graphite in water exhibited pH values of about 6–7, whereas
suspensions of the treated graphite in water showed pH val-
ues of 9. The authors evaluated the materials as Li inter-
calation anodes using electrolyte systems composed of
different combinations of EC, PC, dimethyl carbonate, diethyl
carbonate, methyl propyl carbonate, and ethyl methyl car-
bonate, as well as the conducting salts, LiPF6 and LiClO4. In
their electrochemical evaluation, the authors noted a shift
in the potential associated with electrolyte decomposition to
lower potentials in the heat-treated graphite. This phe-
nomenon is evident in their figure reproduced here as Fig. 52.
It was noted that the heat-treatment apparently decreased
the reactivity of the surface graphite surface toward EC,
Fig. 53 – Cyclic voltammogram (first cycle) of TIMREX SLX50 and SLX50 (HT) using 1 M LiPF6 in EC:1-fluoroethylene carbonate
1:1 (w/w) as electrolyte system at a scan rate of 10 lV s1. Reproduced from Ref. [318].
causing the shift of the SEI formation process to less positive
potentials. A lower decomposition potential increases the
probability for graphite to exfoliate during lithium inter-
calation. The authors concluded that this lower decomposi-
tion potential lead to a hindered graphite passivation and
SEI film formation in the EC electrolyte systems and that
the exfoliation process could not be suppressed by the forma-
tion of an effective SEI layer [317]. What is unfortunate is that
the authors did not provide an analysis of the type and dis-
tribution of the oxygen surface functionality on the treated
and untreated samples as that information could be ben-
eficial to guiding the development of tailored materials.
In another work published in 2006, the same researchers
stated that the defects in the basal planes could be considered
as ‘active sites’ of the carbon surface and that the surface of
the carbon solid can be characterized in terms of graphitic
surface sites [318]. Using that approach, Spahr et al. devel-
oped the concept of the ‘active surface area’ (ASA) of graphite
material and that the degree of electrolyte decomposition can
be correlated to the proportion of active surface area.
Furthermore, the concentration of surface oxygen groups
could be correlated with ASA. Their assertion was supported
by an electrochemical and chemical analyses of the TIMREX
SLX50 graphite before and after heat treatment. As stated in
Section, 4.1, temperature-programmed desorption is a useful
tool to characterize the amount and nature of the surface
groups on the carbon surface. The amount and nature of gas-
eous species desorbed from the graphite surface between 100
and 1000 C at reduced pressure of 104 Pa was continuously
analyzed by mass spectroscopy and the results are presented
in Table 4.
Furthermore, the oxygen content of the heat-treated sam-
ple was shown to have decreased from 1.2% to 0.6% on the
basis of an XPS analysis. Among the various electrochemical
analyses, the materials were also evaluated using cyclic vol-
tammetry in a 1 M LiPF6 in EC:1-fluoroethylene carbonate
electrolyte and those results are reproduced here in Fig. 53.
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4 233

Fig. 54 – Charge derivative vs. potential plots (dQ/dE vs. E plots) obtained from the first galvanostatic intercalation at a current
of 100 mA g1 for as-received carbon cloth, as-received carbon cloth after treatment in H2 at 800 C in 1:1 EC:DMC, and as-
received carbon cloth after treatment in H2 at 800 C in 1:1 PC:DMC solution. Reproduced from Ref. [319]. (A color version of
this figure can be viewed online.)

Fig. 55 – Charge derivative vs. potential plots (dQ/dE vs. E plots) obtained from the first galvanostatic intercalation at
100 mA g1 for carbon cloth samples oxidized in HNO3 vapor at 200 C for 24 h (O-24 h), 72 h (O-72 h) and 144 h (O-144 h).
Reproduced from Ref. [319]. (A color version of this figure can be viewed online.)

There are clear differences in the curves of the untreated
and heat-treated samples. The expansion of the specific cur-
rent axis reveals a significant cathodic current observed at
1.75 V vs. Li for the as-received graphite sample that the
authors concluded is an indication of the start of develop-
ment of the SEI layer. These potentials are significantly more
positive than the potentials at which the electrochemical
exfoliation process is expected to occur. A similar increase
in the cathodic current associated with the heat-treated sam-
ple is not evident until much lower cell potentials, a differ-
ence that can be correlated with the extent of ASA and
oxygen functionality. The authors concluded that graphite
electrode materials with high crystallinity, low superficial
defect concentration, low amount of edge surfaces, and low
surface impurity concentration represent low ASA values,
which indicates that the that surface would therefore have
low reactivity towards the electrolyte [318].
Ventosa et al. approached this topic directly in their report
on the how surface functional groups influence lithium ion
intercalation of carbon cloth [319]. In that work, the authors
investigated the influence of oxygen-containing functional
groups on the Li-ion intercalation performance. The carbon
cloth materials were either reduced under H2 at high tem-
peratures to remove existing functionality or oxidized using
HNO3 vapor at 200 C for increasing time periods of 24, 72,
144 h. Portions of the oxidized materials were then also
reduced. Reproduced in Fig. 54 is the plot of the charge deriva-
tive dQ/dE normalized by mass against the potential E during
the first cathodic scan for the as-received and reduced
samples.
Visible in the potential range between 0.75 and 1.0 V vs. Li
is a shallow peak that the authors have correlated to the
development of the SEI layer, since the peak was not evident
in the second discharge cycle. The reduction treatment of the
234 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
Fig. 56 – XPS spectra of the FN-CNF: (a) C1s, (b) O1s and (c) N1s. (d) Schematic model of N- and O-containing surface functional
groups on FN-CNF. Reproduced from Ref. [320]. (A color version of this figure can be viewed online.)
original sample resulted in a slight decrease in the surface
oxygen concentration (from 2.6 to 1.9%) as determined by
XPS, which could account for the slight shift in that reduction
peak. The charge derivative plot for the heat-treated, oxidized
samples is reproduced in Fig. 55.
Their results showed a shift in the peak potentials upon
thermal treatment, which revealed that electrolyte
decomposition is strongly dependent on the surface func-
tional groups. However, they also noted that there is a slight
impact due the chemical nature of the surface groups and
that it is supposedly related to their ability to reduce the sol-
vent. In addition, there was a progressive increase in the
reversible charge that correlated to an increasing amount of
oxygen groups producing values of 142 mAh g1,
1 1 1
155 mAh g , 158 mAh g , and 162 mAh g obtained for the
as-received, 24, 72, and 144 h samples, respectively. Based
upon the evaluation of their materials, the authors concluded
that the surface functional groups contributed substantially
to the irreversible capacity during the first cycle, and that
the increase in the irreversible capacity could be attributed
to the reduction of surface functional groups [319].
In their paper, Wang et al. demonstrated the viability of N-
functionalized carbon nanofibers (CNFs) as ion intercalation
anode material for a Na ion battery [320]. The Polypyrrole
(PPy) starting material was functionalized using ammonium
persulfate from which the nanofibers were prepared by
heat-treating at 600 C under a nitrogen atmosphere. The
XPS analysis of the nanofibers indicated a composition of C,
O, N and H at 73.82%, 9.25%, 13.93% and 1.96%, respectively.
As is reproduced here in Fig. 56, the reduction current
between 1.10 and 1.88 V and the oxidation current between
0 and 0.48 V in subsequent cycles are both obviously larger
than what was exhibited in the first cycle. The authors attrib-
uted these behaviors to the adsorption of Na ions with charge
transfer on both sides of single graphene layers and to reac-
tions of the Na ions with nitro or carbonyl groups [321].
In addition, there was a broad redox peak in the potential
range of 0.6–2 V that the authors also attributed to reactions
between sodium and the functional groups at the carbon sur-
face. During the initial charge/discharge cycle, the func-
tionalized-CNF electrode delivered specific discharge and
charge capacities of 411 and 172 mAh g–1, respectively, at a
constant current density of 50 mA g–1, corresponding to an
initial coulombic efficiency of 41.8%. The large irreversible
capacity was attributed to the formation of SEI layer and to
the irreversible sodium absorption onto the surface func-
tionality as was described above. The authors concluded that
the SNG-doped sites and functionalized surface of the CNFs
are capable of rapidly and reversibly capturing sodium ions
through surface adsorption and redox reactions [320].
6. Conclusion
There were four objectives to this review: (1) briefly summar-
ize how intercalation materials have been employed in elec-
trochemical energy storage and provide a concise discussion
on the currently accepted ideas concerning the development
of the solid electrolyte interphase (SEI) layer, (2) discuss how
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
the physical and electronic properties of carbon materials are
modified by existing and increased concentrations of surface
functional groups and how those changes affect the perfor-
mance of electrochemical energy storage devices, (3) analyze
the specific contributions that the most abundant oxygen and
nitrogen carbon-surface functionality, in particularly
hybridization and their influence on Lewis basicity/acidity,
have towards promoting Li-ion charge storage and (4) exam-
ine the impact that those heteroatom functionalities have
on the formation of the SEI layer.
What has been shown is that surface functional groups are
inherent to carbon substrates. Whether they come as result of
activating the materials for specific applications or they are
induced to create tailored materials, they critically impact
the performance of these materials in electrochemical energy
storage devices. One key step for determining the future of car-
bon as an ion intercalation material is to correlate specific SOG
and SNG species to the carbon substrate’s performance in elec-
trochemical energy storage applications. The present review
discussed numerous examples of how to consistently engineer
specific SOG and/or SNGs into the edge or basal lattice of car-
bon substrates. The utility of Lewis acidic vs. Lewis basic sur-
face functional groups was clarified for both SOGs and SNGs,
revealing that the simultaneous presence of both sp2 and sp3
hybridized SOGs and/or SNGs are a requirement for effective,
long lasting capacitive, pseudocapacitive and Faradaic forms
of charge storage. Hence, primarily oxygen and nitrogen
Lewis basic groups, containing inherently sp2/sp3 hybridized
combinations, enable advanced, long-lived electrochemical
performance character in carbon substrates. Most Lewis acidic
groups, where either sp2 or sp3 hybridization is dominant, do
not contain the necessary conjugated hybridization variations
that facilitate charge transfer, storage, buffering and catalytic
retention—thereby resulting in poor electrochemical perfor-
mance. In addition, separating out the different contributions
of SOGs and SNGs to the irreversible capacity (electrolyte
decomposition vs. redox behavior of surface functionality) is
essential for minimizing the loss of storage capacity. Given suf-
ficient knowledge on the effects of specific surface functional
groups, this could be accomplished through the tailoring of car-
bon substrates via the introduction of specific functionalities.
Unfortunately, designing carbon materials with specifically
tailored performance characteristics still remains a significant
challenge. However, studies such as those reviewed herein
incrementally improve carbon surface functionalization
through the most common, natural and synthetic, imple-
mented heteromaterial—thereby providing integral con-
tributions towards the development of sustainable charge
storage.
The importance of ion intercalation materials in electro-
chemical energy storage application cannot be understated.
It was only through the utilization of graphite—a model
intercalation material—as the anode that allowed for the
potential of lithium to be effectively utilized for its applica-
tion in, what could arguably be considered, the foremost
electrical energy storage device in use today: the Li ion bat-
tery. However, as was shown in this review and other recent
reviews [17,38,49,322], improving our understanding on how
the surface properties (i.e. surface functionality, ASA, etc.)
of carbon intercalation materials and the formation of the
235
SEI layer are the keys to exploiting the potential limits of
lithium and other ions in energy storage devices. Early work
in this field has been accomplished, yet further development
is necessary for the future advancement of sustainably rever-
sible, ion intercalation charge storage devices for the con-
sumer world.
R E F E R E N C E S
[1] Xu K. Nonaqueous liquid electrolytes for lithium-based
rechargeable batteries. Chem Rev 2004;104(10):4303–417.
Available from: http://pubs.acs.org/doi/abs/10.1021/
cr030203g?journalCode=chreay.
[2] Haynes WM, editor. CRC handbook of chemistry and
physics. CRC Press; 2012.
[3] Whittingham MS. Electrical energy storage and intercalation
chemistry. Science 1976;192(4244):1126–7.
[4] Murphy DW, Christian PA. Solid state electrodes for high
energy batteries. Science 1979;205(4407):651–6.
[5] Auborn JJ, Barberio YL. Lithium intercalation cells without
metallic lithium: MoO2/LiCoO2 and WO2/LiCoO2. J
Electrochem Soc 1987;134(3):638–41.
[6] Scrosati B. Lithium rocking chair batteries: an old concept? J
Electrochem Soc 1992;139(10):2776–81.
[7] Nagaura T, Tozawa K. Lithium ion rechargeable battery. Prog
Batteries Sol Cells 1990;9:209–17.
[8] Winter M, Besenhard JO, Spahr ME, Novák P. Insertion
electrode materials for rechargeable lithium batteries. Adv
Mater 1998;10(10):725–63.
[9] Peled E. The electrochemical behavior of alkali and alkaline
earth metals in nonaqueous battery systems—the solid
electrolyte interphase model. J Electrochem Soc
1979;126(12):2047.
[10] Besenhard JO, Winter M, Yang J, Biberacher W. Filming
mechanism of lithium–carbon anodes in organic and
inorganic electrolytes. J Power Sources 1995;54(2):228–31.
Available from: http://linkinghub.elsevier.com/retrieve/pii/
037877539402073C.
[11] Aurbach D, Markovskya B, Weissmana I, Levia E, Ein-Eli Y.
On the correlation between surface chemistry and
performance of graphite negative electrodes for Li ion
batteries. Electrochim Acta 1999;45(1–2):67–86.
[12] Aurbach D, Zaban A, Ein-Eli Y, Weissman I, Chusid O,
Markovsky B, et al. Recent studies on the correlation
between surface chemistry, morphology, three-dimensional
structures and performance of Li and Li-C intercalation
anodes in several important electrolyte systems. J Power
Sources 1997;68(1):91–8.
[13] Gnanaraj JS, Levi MD, Levi E, Salitra G, Aurbach D, Fischer JE,
et al. Comparison between the electrochemical behavior of
disordered carbons and graphite electrodes in connection
with their structure. J Electrochem Soc 2001;148(6):A525.
[14] Jiang M, Key B, Meng YS, Grey CP. Electrochemical and
structural study of the layered, ‘‘Li-Excess’’ lithium-ion
battery electrode material Li[Li1/9Ni1/3Mn5/9]O2. Chem Mater
2009;21(13):2733–45.
[15] Amatucci GG, Badway F, Pasquier Du A, Zheng T. An
asymmetric hybrid nonaqueous energy storage cell. J
Electrochem Soc 2001;148(8):A930–9.
[16] Pasquier AD, Plitz I, Gural J, Badway F, Amatucci GG. Power-
ion battery: bridging the gap between Li-ion and
supercapacitor chemistries. J Power Sources
2004;136(1):160–70.
[17] Choi N-S, Chen Z, Freunberger SA, Ji X, Sun Y-K, Amine K,
et al. Challenges facing lithium batteries and electrical
236 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
double-layer capacitors. Angew Chem Int Edit
2012;51(40):9994–10024.
[18] Naoi K, Ishimoto S, Miyamoto J-I, Naoi W. Second generation
‘‘nanohybrid supercapacitor’’: evolution of capacitive energy
storage devices. Energy Environ Sci 2012;5(11):9363–73.
[19] Yoo HD, Salitra G, Sharon D, Aurbach D. On the challenge of
developing advanced technologies for electrochemical
energy storage and conversion. Mater Today
2014;17(3):110–21.
[20] Gourdin G, Smith PH, Jiang T, Tran TN, Qu D. Lithiation of
amorphous carbon negative electrode for li ion capacitor. J
Electroanal Chem 2013;688:103–12. Available from: http://
www.sciencedirect.com/science/article/pii/
S1572665712003384.
[21] Cheng L, Li H-Q, Xia Y-Y. A hybrid nonaqueous
electrochemical supercapacitor using nano-sized iron
oxyhydroxide and activated carbon. J Solid State
Electrochem 2005;10(6):405–10.
[22] Cai Y, Zhao B, Wang J, Shao Z. Non-aqueous hybrid
supercapacitors fabricated with mesoporous TiO2
microspheres and activated carbon electrodes with superior
performance. J Power Sources 2014;253:80–9.
[23] Naoi K, Ishimoto S, Isobe Y, Aoyagi S. High-rate nano-
crystalline Li4Ti5O12 attached on carbon nano-fibers for
hybrid supercapacitors. J Power Sources 2010;195(18):6250–4.
[24] Chen F, Li R, Hou M, Liu L, Wang R, Deng Z. Preparation and
characterization of ramsdellite Li2Ti3O7 as an anode
material for asymmetric supercapacitors. Electrochim Acta
2005;51(1):61–5.
[25] Aravindan V, Shubha N, Ling WC, Madhavi S. Constructing
high energy density non-aqueous Li-ion capacitors using
monoclinic TiO2-B nanorods as insertion host. J Mater Chem
A 2013;1(20):6145–51. Available from: http://pubs.rsc.org/en/
Content/ArticleLanding/2013/TA/c3ta11103b#!divAbstract.
[26] Wang G-X, Wang G-X, Zhang B-L, Zhang B-L, Yu Z-L, Yu Z-L,
et al. Manganese oxide/MWNTs composite electrodes for
supercapacitors. Solid State Ionics 2005 Mar 31;176(11–
12):1169–74.
[27] Aravindan V, Reddy MV, Madhavi S, Mhaisalkar SG, Subba
Rao GV, Chowdari BVR. Hybrid supercapacitor with nano-
TiP2O7 as intercalation electrode. J Power Sources
2011;196(20):8850–4.
[28] Aravindan V, Chuiling W, Reddy MV, Rao GVS, Chowdari
BVR, Madhavi S. Carbon coated nano-LiTi2(PO4)3 electrodes
for non-aqueous hybrid supercapacitors. Phys Chem Chem
Phys 2012;14(16):5808–14. Available from: http://pubs.rsc.
org/en/content/articlehtml/2012/cp/c2cp40603a.
[29] Kim J-H, Kim J-S, Lim Y-G, Lee J-G, Kim Y-J. Effect of carbon
types on the electrochemical properties of negative
electrodes for Li-ion capacitors. J Power Sources
2011;196(23):10490–5.
[30] Aida T, Yamada K, Morita M. An advanced hybrid
electrochemical capacitor that uses a wide potential range
at the positive electrode. Electrochem Solid State Lett
2006;9(12):A534–6.
[31] Park M-S, Lim Y-G, Park J-W, Kim J-S, Lee J-W, Kim JH, et al.
Li2RuO3 as an Additive for high-energy lithium-ion
capacitors. J Phys Chem C 2013;117(22):11471–8.
[32] Yoon JH, Bang HJ, Prakash J, Sun YK. Comparative study of
Li[Ni1/3Co1/3Mn1/3]O2 cathode material synthesized via
different synthetic routes for asymmetric electrochemical
capacitor applications. Mater Chem Phys 2008;110(2–
3):222–7.
[33] Li H, Cheng L, Xia Y. A hybrid electrochemical
supercapacitor based on a 5 V Li-ion battery cathode and
active carbon. Electrochem Solid States 2005;8(9):A433–6.
[34] Ma S-B, Nam K-W, Yoon W-S, Yang X-Q, Ahn K-Y, Oh K-H,
et al. A novel concept of hybrid capacitor based on
manganese oxide materials. Electrochem Commun
2007;9(12):2807–11.
[35] Wu XL, Jiang LY, Cao FF, Guo Y-G, Wan L-J. LiFePO4
nanoparticles embedded in a nanoporous carbon matrix:
superior cathode material for electrochemical energy-
storage devices. Adv Mater 2009;21(25–26):2710–4.
[36] Karthikeyan K, Amaresh S, Kim KJ, Kim SH, Chung KY, Cho
BW, et al. A high performance hybrid capacitor with
Li2CoPO4F cathode and activated carbon anode. Nanoscale
2013;5(13):5958–64. Available from: http://pubs.rsc.org/en/
Content/ArticleLanding/2013/NR/c3nr00760j#!divAbstract.
[37] Karthikeyan K, Aravindan V, Lee SB, Jang IC, Lim HH, Park GJ,
et al. Electrochemical performance of carbon-coated
lithium manganese silicate for asymmetric hybrid
supercapacitors. J Power Sources 2010;195(11):3761–4.
[38] Aravindan V, Gnanaraj J, Lee Y-S, Madhavi S. Insertion-type
electrodes for nonaqueous Li-ion capacitors. Chem Rev
2014. 141118084758002.
[39] Hao YJ, Lai QY, Wang L, Xu X-Y, Chu HY. Electrochemical
performance of a high cation-deficiency Li2Mn4O9/active
carbon supercapacitor in LiNO3 electrolyte. Synthetic Met
2010;160:669–74.
[40] Khomenko V, Raymundo-Pinero E, Béguin F. High-energy
density graphite/AC capacitor in organic electrolyte. J Power
Sources 2008;177(2):643–51.
[41] Sivakkumar SR, Sivakkumar SR, Nerkar JY, Pandolfo AG.
Rate capability of graphite materials as negative electrodes
in lithium-ion capacitors. Electrochim Acta
2010;55(9):3330–5.
[42] Hahn M, Würsig A, Gallay R, Novak P, Kötz R. Gas evolution
in activated carbon/propylene carbonate based double-layer
capacitors. Electrochem Commun. 2005;7(9):925–30.
[43] Hardwick L, Ruch PW, Hahn M, Scheifele W, Koetz R, Novák
P. In situ Raman spectroscopy of insertion electrodes for
lithium-ion batteries and supercapacitors: first cycle effects.
J Phys Chem Solids 2008;69(5–6):1232–7.
[44] Yang S, Kim I-J, Jeon M-J, Kim K, Moon S-I, Kim H-S, et al.
Preparation of graphite oxide and its electrochemical
performance for electric double layer capacitor. J Ind Eng
Chem 2008;14(3):365–70.
[45] Zhao JG, Li FY, Jin CQ. Graphitization of activated carbon
under high pressures and high temperatures. Solid State
Commun 2009;149:818–21.
[46] Aida T, Murayama I, Yamada K, Morita M. Improvement in
cycle performance of a high-voltage hybrid electrochemical
capacitor. Electrochem Solid States 2007;10(4):A93–6.
[47] Collins J, Zheng D, Ngo T, Qu D, Foster M. Partial
graphitization of activated carbon by surface acidification.
Carbon 2014;79:500–17.
[48] Dahn JR, Zheng T, Liu Y, Xue JS. Mechanisms for lithium
insertion in carbonaceous materials. Science
1995;270(5236):590–3.
[49] Yabuuchi N, Kubota K, Dahbi M, Komaba S. Research
development on sodium-ion batteries. Chem Rev 2014.
141201142552002.
[50] Doeff MM, Ma Y, Visco SJ, De Jonghe LC. Electrochemical
insertion of sodium into carbon. J Electrochem Soc
1993;140(12):L169–70.
[51] Stevens DA, Dahn JR. High capacity anode materials for
rechargeable sodium-ion batteries. J Electrochem Soc
2000;147(4):1271–3.
[52] Plichta EJ, Hendrickson M, Thompson R, Au G, Behl WK,
Smart MC, et al. Development of low temperature Li-ion
electrolytes for NASA and DoD applications. J Power Sources
2001;94(2):160–2.
[53] Aurbach D, Zaban A, Schechter A, Ein-Eli Y, Zinigrad E,
Markovsky B. The study of electrolyte-solutions based on
ethylene and diethyl carbonates for rechargeable Li
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
batteries. J Electrochem Soc 1995;142(9):2873–82. Available
from: http://jes.ecsdl.org/content/142/9/2873.abstract.
[54] Aurbach D, Ein-Eli Y, Markovsky B, Zaban A, Luski S, Carmeli
Y, et al. The study of electrolyte solutions based on ethylene
and diethyl carbonates for rechargeable Li batteries. J
Electrochem Soc 1995;142(9):2882–90.
[55] Vetter J, Novak P. Novel alkyl methyl carbonate solvents for
lithium-ion batteries. J Power Sources 2003;119–121:338–42.
[56] Vetter J, Buqa H, Holzapfel M, Novák P. Impact of co-solvent
chain branching on lithium-ion battery performance. J
Power Sources 2005;146(1–2):355–9.
[57] Xu K. Electrolytes and interphases in Li-ion batteries and
beyond. Chem Rev 2014. 141117082135006.
[58] Abraham DP, Furczon MM, Kang SH, Dees DW, Jansen AN.
Effect of electrolyte composition on initial cycling and
impedance characteristics of lithium-ion cells. J Power
Sources 2008;180(1):612–20. Available from: http://
www.sciencedirect.com/science/article/pii/
S0378775308003157.
[59] Wang F-M, Shieh D-T, Cheng J-H, Yang C-R. An investigation
of the salt dissociation effects on solid electrolyte interface
(SEI) formation using linear carbonate-based electrolytes in
lithium ion batteries. Solid State Ionics 2010;180(40):1660–6.
[60] Chiba K, Ueda T, Yamaguchi Y, Oki Y, Saiki F, Naoi K.
Electrolyte systems for high withstand voltage and
durability II. Alkylated cyclic carbonates for electric double-
layer capacitors. J Electrochem Soc 2011;158(12):A1320–7.
[61] Novak P, Goers D, Spahr ME. Ch 7: Carbon materials in lithium-
ion batteries p288. In: Frackowiak F, Elzbieta B, editors.
Carbons for electrochemical energy storage and conversion
systems. Boca Raton, FL: CRC Press; 2010. p. 288–9.
[62] Buiel E, Dahn JR. Li-insertion in hard carbon anode materials
for Li-ion batteries. Electrochim Acta 1999;45:121–30.
[63] Banks CE, Davies TJ, Wildgoose GG, Compton RG.
Electrocatalysis at graphite and carbon nanotube modified
electrodes: edge-plane sites and tube ends are the reactive
sites. Roy Soc Chem 2005;0(7):829–41. Available from: http://
pubs.rsc.org/en/Content/ArticleLanding/2005/CC/b413177k.
[64] Aurbach D. Identification of surface films formed on lithium
surfaces in-butyrolactone solutions: II. Contaminated
solutions. J Electrochem Soc 1989;136(6):1611–4.
[65] Aurbach D. Identification of surface films formed on lithium
surfaces in-butyrolactone solutions: I. Uncontaminated
solutions. J Electrochem Soc 1989;136(6):1606–10.
[66] Aurbach D, Gottlieb H. The electrochemical behavior of
selected polar aprotic systems. Electrochim Acta
1989;34(2):141–56.
[67] Aurbach D, Gofer Y, Ben-Zion M, Aped P. The behaviour of
lithium electrodes in propylene and ethylene carbonate: the
major factors that influence Li cycling efficiency. J
Electroanal Chem 1992;339(1–2):451–71.
[68] Aurbach D, Youngman OC. The study of surface films
formed on lithium and noble metal electrodes in polar
aprotic systems by the use of in situ fourier transform
infrared spectroscopy. J Electrochem Soc 1993;140(1):L1–4.
[69] Aurbach D. Impedance spectroscopy of nonactive metal
electrodes at low potentials in propylene carbonate
solutions. J Electrochem Soc 1994;141(7):1808.
[70] Zaban A, Aurbach D. Impedance spectroscopy of lithium
and nickel electrodes in propylene carbonate solutions of
different lithium salts: A comparative study. J Power Sources
1995;54(2):289–95.
[71] Ostrovskii D, Ronci F, Scrosati B, Jacobsson P. Reactivity of
lithium battery electrode materials toward non-aqueous
electrolytes: spontaneous reactions at the electrode–
electrolyte interface investigated by FTIR. J Power Sources
2001;103(1):10–7.
237
[72] Zhuang GV, Xu K, Jow TR, Ross PN. Study of SEI layer formed
on graphite anodes in PC/LiBOB electrolyte using IR
spectroscopy. Electrochem Solid States 2004;7(8):A224–7.
Available from: http://esl.ecsdl.org/content/7/8/A224.
abstract.
[73] Lee S-B, Pyun S-I. Critical assessment of a new in situ
spectroelectrochemical cell designed for the study of
interfacial reactions between a porous graphite anode and
alkyl carbonate solution. J Solid State Electrochem
2003;7(4):201–7. Available from: http://www.
springerlink.com/content/qg7vapb5945tjc75/.
[74] Naji A, Ghanbaja J, Humbert B, Willmann P, Billaud D.
Electroreduction of graphite in LiClO4-ethylene carbonate
electrolyte. Characterization of the passivating layer by
transmission electron microscopy and Fourier-transform
infrared spectroscopy. J Power Sources 1996;63(1):33–9.
[75] Imhof R, Novák P. In situ investigation of the
electrochemical reduction of carbonate electrolyte solutions
at graphite electrodes. J Electrochem Soc 1998;145(4):1081–7.
[76] Eshkenazi V, Peled E, Burstein L, Golodnitsky D. XPS analysis
of the SEI formed on carbonaceous materials. Solid State
Ionics 2004;170(1–2):83–91.
[77] Aurbach D, Weissman I, Schechter A, Cohen H. X-ray
photoelectron spectroscopy studies of lithium surfaces
prepared in several important electrolyte solutions. A
comparison with previous studies by Fourier Transform
Infrared Spectroscopy. Langmuir 1996;12(16):3991–4007.
[78] Schechter A, Aurbach D, Cohen H. X-ray photoelectron
spectroscopy study of surface films formed on Li electrodes
freshly prepared in alkyl carbonate solutions. Langmuir
1999;15(9):3334–42.
[79] Takami N, Satoh A, Hara M, Ohsaki T. Structural and kinetic
characterization of lithium intercalation into carbon anodes
for secondary lithium batteries. J Electrochem Soc
1995;142(2):371.
[80] Barsoukov E. Effect of low-temperature conditions on
passive layer growth on Li intercalation materials. J
Electrochem Soc 1998;145(8):2711–7.
[81] Piao T, Park SM, Doh CH. Intercalation of lithium ions into
graphite electrodes studied by AC impedance
measurements. J Electrochem Soc 1999;146(8):2794–8.
Available from: http://jes.ecsdl.org/content/146/8/2794.
abstract.
[82] Wang C, Appleby AJ, Little FE. Electrochemical impedance
study of initial lithium ion intercalation into graphite
powders. Electrochim Acta 2001;46(12):1793–813.
[83] Zhang S, Ding MS, Xu K, Allen J, Jow TR. Understanding solid
electrolyte interface film formation on graphite electrodes.
Electrochem Solid States 2001;4(12):A206–8.
[84] Itagaki M, Kobari N, Yotsuda S, Watanabe K. In situ
electrochemical impedance spectroscopy to investigate
negative electrode of lithium-ion rechargeable batteries. J
Power Sources 2004;135(1–2):255–61.
[85] Zhang S, Xu K, Jow TR. EIS study on the formation of solid
electrolyte. Electrochim Acta 2006;51(8–9):1636–40.
[86] Peled E, Golodnitsky D. SEI on lithium, graphite, disordered
carbons and tin-based alloys. In: Balbuena PB, Wang Y,
editors. Lithium-ion batteries: solid-electrolyte
interphase. London: Imperial College Press; 2004. p. 1–69.
[87] Lu P, Li C, Schneider EW, Harris SJ. Chemistry, impedance,
and morphology evolution in solid electrolyte interphase
films during formation in lithium ion batteries. J Phys Chem
C 2014;118(2):896–903.
[88] Aurbach D, Cohen YS. Identification of surface films on
electrodes in non-aqueous electrolyte solutions:
spectroscopic, electronic and morphological studies. In:
Balbuena PB, Wang Y, editors. Lithium-ion batteries: solid-
238 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
electrolyte interphase. London: Imperial College Press;
2004. p. 70–139.
[89] Komaba S, Murata W, Ishikawa T, Yabuuchi N, Ozeki T,
Nakayama T, et al. Electrochemical Na insertion and solid
electrolyte interphase for hard-carbon electrodes and
application to Na-ion batteries. Adv Funct Mater
2011;21(20):3859–67.
[90] Moshkovich M, Gofer Y, Aurbach D. Investigation of the
electrochemical windows of aprotic alkali metal (Li, Na, K)
salt solutions. J Electrochem Soc 2001;148(4):E155.
[91] Aurbach D, Markovsky B, Levi MD, Levi E, Schechter A,
Moshkovich M, et al. New insights into the interactions
between electrode materials and electrolyte solutions for
advanced nonaqueous batteries. J Power Sources 1999;81–
82:95–111.
[92] Li T, Balbuena PB. Theoretical studies of the reduction of
ethylene carbonate. Chem Phys Lett 2000;317(3–5):421–9.
[93] Wang Y, Nakamura S, Ue M, Balbuena PB. Theoretical
studies to understand surface chemistry on carbon anodes
for lithium-ion batteries: reduction mechanisms of ethylene
carbonate. J Am Chem Soc 2001;123(47):11708–18. Available
from: http://pubs.acs.org/doi/full/10.1021/ja0164529.
[94] Wang Y, Nakamura S, Tasaki K, Balbuena PB. Theoretical
studies to understand surface chemistry on carbon anodes
for lithium-ion batteries: how does vinylene carbonate play
its role as an electrolyte additive? J Am Chem Soc
2002;124(16):4408–21.
[95] Wang Y, Balbuena PB. Theoretical insights into the reductive
decompositions of propylene carbonate and vinylene
carbonate: density functional theory studies. J Phys Chem B
2002;106(17):4486–95. Available from: http://pubs.acs.
org/doi/full/10.1021/jp014371t.
[96] Wang Y, Balbuena PB. Theoretical insights into the SEI
composition and formation mechanism: density functional
theory studies. In: Balbuena PB, Wang Y, editors. Lithium-
ion batteries: solid-electrolyte
interphase. London: Imperial College Press; 2004. p. 227–75.
[97] Marom R, Haik O, Aurbach D, Halalay IC. Revisiting LiClO4 as
an electrolyte for rechargeable lithium-ion batteries. J
Electrochem Soc 2010;157(8):A972–83.
[98] Wang Z, Huang X, Chen L. Performance improvement of
surface-modified LiCoO[sub 2] cathode materials: an
infrared absorption and X-Ray photoelectron spectroscopic
investigation. J Electrochem Soc 2003;150(2):A199–208.
[99] Marom R, Amalraj SF, Leifer N, Jacob D, Aurbach D. A review
of advanced and practical lithium battery materials. J Mater
Chem 2011;21(27):9938–54.
[100] Gourdin G, Zheng D, Smith PH, Qu D. In-situ electrochemical
– mass spectroscopic investigation of solid electrolyte
interphase formation on the surface of a carbon electrode.
Electrochim Acta 2013;112:735–46.
[101] Arora P, White RE, Doyle M. Capacity fade mechanisms and
side reactions in lithium-ion batteries. J Electrochem Soc
1998;145(10):3647–67.
[102] Sun X-G, Dai S. Electrochemical investigations of ionic
liquids with vinylene carbonate for applications in
rechargeable lithium ion batteries. Electrochim Acta
2010;55(15):4618–26.
[103] Ein-Eli Y, McDevitt SF, Aurbach D, Markovsky B, Schechter A.
Methyl propyl carbonate: a promising single solvent for li-
ion battery electrolytes. J Electrochem Soc 1997;144(7):L180.
[104] Xing LD, Wang CY, Xu MQ, Li WS, Cai ZP. Theoretical study
on reduction mechanism of 1,3-benzodioxol-2-one for the
formation of solid electrolyte interface on anode of lithium
ion battery. J Power Sources 2009;189(1):689–92.
[105] Yao W, Zhang Z, Gao J, Li J, Xu J, Wang Z, et al. Vinyl ethylene
sulfite as a new additive in propylene carbonate-based
electrolyte for lithium ion batteries. Energy Environ Sci
2009;2(10):1102–8.
[106] Yun YS, Kim JH, Lee S-Y, Shim E-G, Kim D-W. Cycling
performance and thermal stability of lithium polymer cells
assembled with ionic liquid-containing gel polymer
electrolytes. J Power Sources 2011;196(16):6750–5.
[107] Tsubouchi S, Domi Y, Doi T, Ochida M, Nakagawa H,
Yamanaka T, et al. Spectroscopic characterization of
surface films formed on edge plane graphite in ethylene
carbonate-based electrolytes containing film-forming
additives. J Electrochem Soc 2012;159(11):A1786–90.
[108] Hongyou K, Hattori T, Nagai Y, Tanaka T, Nii H, Shoda K.
Dynamic in situ Fourier transform infrared measurements
of chemical bonds of electrolyte solvents during the initial
charging process in a Li ion battery. J Power Sources
2013;243:72–7.
[109] Kim H, Grugeon S, Gachot G, Armand M, Sannier L, Laruelle
S. Ethylene bis-carbonates as telltales of SEI and electrolyte
health, role of carbonate type and new additives.
Electrochim Acta 2014;136:157–65.
[110] Bodenes L, Darwiche A, Monconduit L, Martinez H. The solid
electrolyte interphase a key parameter of the high
performance of Sb in sodium-ion batteries: comparative X-
ray photoelectron spectroscopy study of Sb/Na-ion and Sb/
Li-ion batteries. J Power Sources 2015;273:14–24.
[111] Aurbach D, Gnanaraj JS, Geissler W, Schmidt M. Vinylene
carbonate and Li salicylatoborate as additives in
LiPF3(CF2CF3)3 solutions for rechargeable li-ion batteries. J
Electrochem Soc 2004;151(1):A23.
[112] Ouatani El L, Dedryvère R, Siret C, Biensan P, Reynaud S,
Iratçabal P, et al. The effect of vinylene carbonate additive
on surface film formation on both electrodes in li-ion
batteries. J Electrochem Soc 2009;156(2):A103–13. Available
from: http://jes.ecsdl.org/content/156/2/A103.abstract.
[113] Aurbach D, Zinigrad E, Cohen Y, Teller H. A short review of
failure mechanisms of lithium metal and lithiated graphite
anodes in liquid electrolyte solutions. Solid State Ionics
2002;148:405–16.
[114] Broussely M, Biensan P, Bonhomme F, Blanchard P, Herreyre
S, Nechev K, et al. Main aging mechanisms in Li ion
batteries. J Power Sources 2005;146(1–2):90–6.
[115] Wang Z, Huang X, Chen L. Spectroscopy studies of solid-
electrolyte interphase on positive and negative electrodes
for lithium ion batteries. In: Balbuena PB, Wang Y, editors.
Lithium-ion batteries: solid-electrolyte
interphase. London: Imperial College Press; 2004. p. 140–97.
[116] Augustsson A, Herstedt M, Guo JH, Edström K, Zhuang GV, P
N Ross J, et al. Solid electrolyte interphase on graphite Li-
ion battery anodes studied by soft X-ray spectroscopy. Phys
Chem Chem Phys 2004;6(16):4185–9. Available from: http://
pubs.rsc.org.ezproxy.lib.umb.edu/en/content/articlehtml/
2004/cp/b313434b.
[117] Laruelle S, Pilard S, Guenot P, Grugeon S, Tarascon JM.
Identification of Li-based electrolyte degradation products
through DEI and ESI high-resolution mass spectrometry. J
Electrochem Soc 2004;151(8):A1202.
[118] Gachot G, Grugeon S, Armand M, Pilard S, Guenot P,
Tarascon J-M, et al. Deciphering the multi-step degradation
mechanisms of carbonate-based electrolyte in Li batteries. J
Power Sources 2008;178(1):409–21.
[119] Onuki M, Kinoshita S, Sakata Y, Yanagidate M, Otake Y, Ue
M, et al. Identification of the source of evolved gas in Li-Ion
Batteries Using 13C-labeled Solvents. J Electrochem Soc
2008;155(11):A794–7.
[120] Zhuang GV, Yang H, Philip N Ross J, Xu K, Jow TR. Lithium
methyl carbonate as a reaction product of metallic lithium
and dimethyl carbonate. Electrochem Solid States
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
2006;9(2):A64–8. Available from: http://esl.ecsdl.org/content/
9/2/A64.abstract.
[121] Zhao L, Watanabe I, Doi T, Okada S, Yamaki J-I. TG-MS
analysis of solid electrolyte interphase (SEI) on graphite
negative-electrode in lithium-ion batteries. J Power Sources
2006;161(2):1275–80.
[122] Shkrob IA, Zhu Y, Marin TW, Abraham D. Reduction of
carbonate electrolytes and the formation of solid–
electrolyte interface (SEI) in lithium-ion batteries. 1.
Spectroscopic observations of radical intermediates
generated in one-electron reduction of carbonates. J Phys
Chem C 2013. 130913123008003.
[123] Ota H, Sakata Y, Inoue A, Yamaguchi S. Analysis of vinylene
carbonate derived SEI layers on graphite anode. J
Electrochem Soc 2004;151(10):A1659–69. Available from:
http://jes.ecsdl.org/content/151/10/A1659.abstract.
[124] Xiao A, Yang L, Lucht BL, Kang S-H, Abraham DP. Examining
the Solid Electrolyte Interphase on Binder-Free Graphite
Electrodes. J Electrochem Soc 2009;156(4):A318–27.
[125] Shu J. Study of the interface between li4ti5o12 electrodes and
standard electrolyte solutions in 0.0–5.0 V. Electrochem
Solid States 2008;11(12):A238–40.
[126] Watanabe I, Yamaki J-I. Thermalgravimetry–mass
spectrometry studies on the thermal stability of graphite
anodes with electrolyte in lithium-ion battery. J Power
Sources 2006;153(2):402–4.
[127] Tavassol H, Chan MKY, Catarello MG, Greeley J, Cahill DG,
Gewirth AA. Surface coverage and SEI induced
electrochemical surface stress changes during Li deposition
in a model system for Li-ion battery anodes. J Electrochem
Soc 2013;160(6):A888–96.
[128] Tavassol H, Buthker JW, Ferguson GA, Curtiss LA, Gewirth
AA. Solvent oligomerization during SEI formation on model
systems for Li-ion battery anodes. J Electrochem Soc
2012;159(6):A730–8.
[129] Aurbach D, Markovsky B, Shechter A, Ein-Eli Y, Cohen H. A
comparative study of synthetic graphite and Li electrodes in
electrolyte solutions based on ethylene carbonate-dimethyl
carbonate mixtures. J Electrochem Soc 1996;143(12):3809–20.
[130] Gourdin G, Collins J, Zheng D, Foster M, Qu D. Spectroscopic
compositional analysis of electrolyte during initial SEI layer
formation. J Phys Chem C 2014;118(31):17383–94.
[131] Yoshida H, Fukunaga T, Hazama T, Terasaki M, Mizutani M,
Yamachi M. Degradation mechanism of alkyl carbonate
solvents used in lithium-ion cells during initial charging. J
Power Sources 1997;68(2):311–5.
[132] Bar-Tow D, Peled E, Burstein L. A study of highly oriented
pyrolytic graphite as a model for the graphite anode in Li-
ion batteries. J Electrochem Soc 1999;146(3):824–32.
[133] Anjos DM, McDonough JK, Perre E, Brown GM, Overbury SH,
Gogotsi Y, et al. Pseudocapacitance and performance
stability of quinone-coated carbon onions. Nano Energy
2013;2(5):702–12.
[134] Qu D. Investigation of oxygen reduction on activated carbon
electrodes in alkaline solution. Carbon 2007.
[135] Tran C, Kafle J, Yang X-Q, Qu D. Increased discharge capacity
of a Li–air activated carbon cathode produced by preventing
carbon surface passivation. Carbon 2011;49(4):1266–71.
[136] Kafle J, Qu D. Enhancement of hydrogen insertion into
carbon interlayers by surface catalytic poisoning. J Phys
Chem C 2010;114(44):19108–15.
[137] Qu D, Smith P, Gourdin G, Jiang T, Tran T. A hydrogen-
insertion asymmetric supercapacitor. Chem Eur J
2012;18(11):3141–3.
[138] Qu D. Studies of the activated carbons used in double-layer
supercapacitors. J Power Sources 2002;109(2):403–11.
[139] Collins J, Ngo T, Qu D, Foster M. Spectroscopic investigations
of sequential nitric acid treatments on granulated activated
239
carbon: effects of surface oxygen groups on p density.
Carbon 2013;57:174–83.
[140] Béguin F, Frackowiak E. Electrochemical energy storage. In:
Bottani EJ, Tascón JMD, editors. Adsorption by
carbons. Elsevier Ltd; 2008.
[141] Frackowiak F, Elzbieta B, editors. Carbons for
electrochemical energy storage and conversion
systems. Boca Raton, FL: CRC Press; 2010.
[142] Zheng D, Lee H-S, Yang X-Q, Qu D. Electrochemical
oxidation of solid Li2O2 in non-aqueous electrolyte using
peroxide complexing additives for lithium–air batteries.
Electrochem Commun 2013;28:17–9.
[143] Wang Y, Zheng D, Yang X-Q, Qu D. High rate oxygen
reduction in non-aqueous electrolytes with the addition of
perfluorinated additives. Energy Environ Sci
2011;4(9):3697–702.
[144] Wang Q, Zheng D, McKinnon ME, Yang X-Q, Qu D. Kinetic
investigation of catalytic disproportionation of superoxide
ions in the non-aqueous electrolyte used in Li–air batteries. J
Power Sources 2015;274:1005–8.
[145] Mangun CL, Benak KR, Daley MA, Economy J. Oxidation of
activated carbon fibers: effect on pore size, surface
chemistry, and adsorption properties. Chem Mater
1999;11(12):3476–83.
[146] Ferrari A, Rodil S, Robertson J. Interpretation of infrared and
Raman spectra of amorphous carbon nitrides. Phys Rev B
2003;67(15):155306.
[147] Radovic LR. Ch 5: Surface chemical and electrochemical
properties of carbons. In: Frackowiak F, Elzbieta B, editors.
Carbons for electrochemical energy storage and conversion
systems. Boca Raton, FL: CRC Press; 2010. p. 163–220.
[148] Radovic LR, Silva IF, Ume JI, Menéndez JA, Leon CALY,
Scaroni AW. An experimental and theoretical study of the
adsorption of aromatics possessing electron-withdrawing
and electron-donating functional groups by chemically
modified activated carbons. Carbon 1997;35(9):1339–48.
[149] Moreno-Castilla C. Adsorption of organic molecules from
aqueous solutions on carbon materials. Carbon
2004;42(1):83–94.
[150] Boehm HP. Carbon surface chemistry. In: Delhaes P, editor.
Graphite and precursors. CRC Press; 2000. p. 141–78.
[151] Boehm HP. Surface oxides on carbon and their analysis: a
critical assessment. Carbon 2002;40(2):145–9.
[152] Boehm HP. Some aspects of the surface chemistry of carbon
blacks and other carbons. Carbon 1994;32(5):759–69.
[153] Lopez-Ramon MV, Stoeckli F, Moreno-Castilla C, Carrasco-
Marin F. On the characterization of acidic and basic surface
sites on carbons by various techniques. Carbon
1999;37(8):1215–21.
[154] Barton SS, Evans MJB, Halliop E, MacDonald JAF. Acidic and
basic sites on the surface of porous carbon. Carbon
1997;35(9):1361–6.
[155] Garten VA, Weiss DE, Willis JB. A new interpretation of the
acidic and basic structures in carbons. I. Lactone groups of
the ordinary and fluorescein types in carbons. Aust J Chem
1957;10(3):295.
[156] Garten VA, Weiss DE, Willis JB. A new interpretation of the
acidic and basic structures in carbons. II. The chromene–
carbonium ion couple in carbon. Aust J Chem 1957;10(3):309.
[157] Jaramillo J, Álvarez PM, Gómez-Serrano V. Oxidation of
activated carbon by dry and wet methods. Fuel Process
Technol 2010;91(11):1768–75.
[158] Perrard A, Retailleau L, Berjoan R, Joly J-P. Liquid phase
oxidation kinetics of an ex-cellulose activated carbon cloth
by NaOCl. Carbon 2012;50(6):2226–34.
[159] Burg P, Cagniant D. Characterization of carbon surface
chemistry. In: Radovic LR, editor. Chemistry and physics of
carbon. New York: CRC Press; 2007. p. 130–77.
240 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
[160] Shen W, Fan W. Nitrogen-containing porous carbons:
synthesis and application. J Mater Chem A 2012;1(4):999.
[161] Wei J, Hu H, Zeng H, Zhou Z, Yang W, Peng P. Effects of
nitrogen substitutional doping on the electronic transport of
carbon nanotube. Phys E 2008;40(3):462–6.
[162] Nevidomskyy A, Csányi G, Payne M. Chemically active
substitutional nitrogen impurity in carbon nanotubes. Phys
Rev Lett 2003;91(10):105502.
[163] Yang SH, Shin WH, Kang JK. The nature of graphite- and
pyridine like nitrogen configurations in carbon nitride
nanotubes: dependence on diameter and helicity. Small
2008;4(4):437–41.
[164] Kawaguchi M, Yagi S, Enomoto H. Chemical preparation and
characterization of nitrogen-rich carbon nitride powders.
Carbon 2004;42(2):345–50.
[165] Wang H, Maiyalagan T, Wang X. Review on recent progress
in nitrogen-doped graphene: synthesis, characterization,
and its potential applications. ACS Catal 2012;2(5):781–94.
[166] Li N, Ma X, Zha Q, Kim K, Chen Y, Song C. Maximizing the
number of oxygen-containing functional groups on
activated carbon by using ammonium persulfate and
improving the temperature-programmed desorption
characterization of carbon surface chemistry. Carbon
2011;49(15):5002–13.
[167] Burg P, Fydrych P, Cagniant D, Nanse G, Bimer J, Jankowska
A. The characterization of nitrogen-enriched activated
carbons by IR, XPS and LSER methods. Carbon
2002;40(9):1521–31.
[168] Alvarez-Merino MA, Joly JP, Carrasco-Marin F, Moreno-
Castilla C. Application of ammonia intermittent
temperature-programmed desorption to evaluate surface
acidity of tungsten oxide supported on activated carbon. J
Colloid Interf Sci 2003;260(2):449–53.
[169] Brender P, Gadiou R, Rietsch J-C, Fioux P, Dentzer J, Ponche
A, et al. Characterization of carbon surface chemistry by
combined temperature programmed desorption with in situ
X-ray photoelectron spectrometry and temperature
programmed desorption with mass spectrometry analysis
2012;84(5):2147–53.
[170] Chingombe P, Saha B, Wakeman RJ. Surface modification
and characterisation of a coal-based activated carbon.
Carbon 2005;43(15):3132–43.
[171] Fanning PE, Vannice MA. A DRIFTS study of the formation of
surface groups on carbon by oxidation. Carbon
1993;31(5):721–30.
[172] Dandekar A, Baker RTK, Vannice MA. Characterization of
activated carbon, graphitized carbon fibers and synthetic
diamond powder using TPD and DRIFTS. J Mater Chem
1998;36(12):1821–31.
[173] Sellitti C, Koenig JL, Ishida H. Surface characterization of
graphitized carbon fibers by attenuated total reflection
Fourier transform infrared spectroscopy. Carbon
1990;28(1):221–8.
[174] Rosenthal D, Ruta M, Schlögl R, Kiwi-Minsker L. Combined
XPS and TPD study of oxygen-functionalized carbon
nanofibers grown on sintered metal fibers. Carbon
2010;48(6):1835–43.
[175] Zhou J-H, Sui Z-J, Zhu J, Li P, Chen D, Dai Y-C, et al.
Characterization of surface oxygen complexes on carbon
nanofibers by TPD, XPS and FT-IR. Carbon 2007;45(4):785–96.
[176] Yue ZR, Jiang W, Wang L, Gardner SD, Pittman Jr CU. Surface
characterization of electrochemically oxidized carbon
fibers. Carbon 1999;37(11):1785–96.
[177] Moreno-Castilla C, Ferro-Garcia MA, Joly JP, Bautista-Toledo
I, Carrasco-Marin F, Rivera-Utrilla J. Activated carbon
surface modifications by nitric acid, hydrogen peroxide, and
ammonium peroxydisulfate treatments. Langmuir
1995;11(11):4386–92.
[178] Moreno-Castilla C, Carrasco-Marin F, Mueden A. The
creation of acid carbon surfaces by treatment with
(NH4)2S2O8. Carbon 1997;35(10–11):1619–26.
[179] Beck NV, Meech SE, Norman PR, Pears LA. Characterisation
of surface oxides on carbon and their influence on dynamic
adsorption. Carbon 2002;40(4):531–40.
[180] Otake Y, Jenkins RG. Characterization of oxygen-containing
surface complexes created on a microporous carbon by air
and nitric acid treatment. Carbon 1993;31(1):109–21.
[181] Menéndez JA, Phillips J, Xia B, Radovic LR. On the
modification and characterization of chemical surface
properties of activated carbon: in the search of carbons with
stable basic properties. Langmuir 1996;12(18):4404–10.
[182] Kohl S, Drochner A, Vogel H. Quantification of oxygen
surface groups on carbon materials via diffuse reflectance
FT-IR spectroscopy and temperature programmed
desorption. Catal Today 2010;150(1–2):67–70.
[183] Ota H, Sato T, Suzuki H, Usami T. TPD–GC/MS analysis of the
solid electrolyte interface (SEI) on a graphite anode in the
propylene carbonate/ethylene sulfite electrolyte system for
lithium batteries. J Power Sources 2001;97–98:107–13.
[184] Gaillard F, Abdat M, Joly JP, Perrard A. An intermittent
temperature-programmed desorption method for studying
kinetics of desorption from heterogeneous surfaces. Appl
Surf Sci 2004;238(1–4):91–6.
[185] Gaillard F, Hachimi AE, Descorme C, Besson M, Joly J-P,
Polyanskaya EM, et al. Study of oxygen groups at a porous
carbon surface by a new fast intermittent thermodesorption
technique. Carbon 2011;49(6):2062–73.
[186] Figueiredo JL, Pereira MFR, Freitas MMA, Órfão JJM.
Characterization of active sites on carbon catalysts. Ind Eng
Chem Res 2007;46(12):4110–5.
[187] Hordy N, Meunier JL, Coulombe S. Thermal stability of
plasma generated oxygenated functionalities on carbon
nanotubes. Plasma Processes Polym 2014. n/a–n/a.
[188] Jansen RJJ, van Bekkum H. XPS of nitrogen-containing
functional groups on activated carbon. Carbon
1995;33(8):1021–7.
[189] Kelemen SR, Freund H. XPS characterization of glassy-
carbon surfaces oxidized by O2, CO2, and HNO3. Energy Fuel
1988;2(2):111–8.
[190] Biniak S, Szymański G, Siedlewski J, Światkowski A. The
characterization of activated carbons with oxygen and
nitrogen surface groups. Carbon 1997;35(12):1799–810.
Available from: http://www.sciencedirect.com/science/
article/pii/S0008622397000961.
[191] Rey A, Zazo JA, Casas JA, Bahamonde A, Rodriguez JJ.
Influence of the structural and surface characteristics of
activated carbon on the catalytic decomposition of
hydrogen peroxide. Appl Catal A 2011;402(1–2):146–55.
[192] Lakshminarayanan PV, Toghiani H, Pittman Jr CU. Nitric acid
oxidation of vapor grown carbon nanofibers. Carbon
2004;42(12–13):2433–42.
[193] la Puente de G, Pis JJ, Menéndez JA, Grange P. Thermal
stability of oxygenated functions in activated carbons. J
Anal Appl Pyrol 1997;43(2):125–38.
[194] Vass EM, Hävecker M, Zafeiratos S, Teschner D, Knop-
Gericke A, Schlögl R. The role of carbon species in
heterogeneous catalytic processes: an in situ soft X-ray
photoelectron spectroscopy study. J Phys Condens Matter
2008;20(18):184016.
[195] Figueiredo JL, Pereira MFR, Freitas MMA, Órfão JJM.
Modification of the surface chemistry of activated carbons.
Carbon 1999;37(9):1379–89.
[196] Hontoria-Lucas C, López-Peinado AJ, López-González J de D,
Rojas-Cervantes ML, Martı́n-Aranda RM. Study of oxygen-
containing groups in a series of graphite oxides: physical
and chemical characterization. Carbon 1995;33(11):1585–92.
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
[197] Bleda-Martinez MJ, Lozano-Castelló D, Morallon E, Cazorla-
Amorós D, Linares-Solano A. Chemical and electrochemical
characterization of porous carbon materials. Carbon
2006;44(13):2642–51.
[198] Ros TG, van Dillen AJ, Geus JW, Koningsberger DC. Surface
oxidation of carbon nanofibres. Chem Eur J
2002;8(5):1151–62.
[199] Zhuang Q-L, Kyotani T, Tomita A. DRIFT and TK/TPD
analyses of surface oxygen complexes formed during
carbon gasification. Energy Fuel 1994;8(3):714–8.
[200] Milosevic M, Berets SL. A review of FT-IR diffuse reflection
sampling considerations. Appl Spectrosc Rev
2002;37(4):347–64.
[201] Bansal RC, Vastola FJ, Walker Jr PL. Studies on ultra-clean
carbon surfaces—III. Kinetics of chemisorption of hydrogen
on graphon. Carbon 1971;9(2):185–92.
[202] Verma SK, Walker Jr PL. Carbon molecular sieves with stable
hydrophobic surfaces. Carbon 1992;30(6):837–44.
[203] Zheng T, McKinnon WR, Dahn JR. Hysteresis during lithium
insertion in hydrogen-containing carbons. J Electrochem
Soc 1996;143(7):2137–45.
[204] Béguin F, Chevallier F, Vix-Guterl C, Saadallah S, Bertagna V,
Rouzaud JN, et al. Correlation of the irreversible lithium
capacity with the active surface area of modified carbons.
Carbon 2005;43(10):2160–7.
[205] Béguin F, Chevallier F, Letellier M, Vix C, Clinard C, Rouzaud
J-N, et al. Mechanisms of reversible and irreversible
insertion in nanostructured carbons used for Li-ion
batteries. In: Barsukov IV, Johnson CS, Doninger JE, Barsukov
VZ, editors. New carbon based materials for electrochemical
energy storage systems: batteries, supercapacitors and fuel
cells. Dordrecht: Springer; 2003.
[206] Béguin F, Chevallier F, Vix C, Saadallah S, Rouzaud JN,
Frackowiak E. A better understanding of the irreversible
lithium insertion mechanisms in disordered carbons. J Phys
Chem Solids 2004;65(2–3):211–7.
[207] Lee SW, Kim B-S, Chen S, Shao-Horn Y, Hammond PT. Layer-
by-layer assembly of all carbon nanotube ultrathin films for
electrochemical applications. J Am Chem Soc
2009;131(2):671–9.
[208] Lee SW, Yabuuchi N, Gallant BM, Chen S, Shao-Horn Y. High-
power lithium batteries from functionalized carbon-
nanotube electrodes. Nat Nanotechnol 2010;5(7):531–7.
Available from: http://www.nature.com/doifinder/10.1038/
nnano.2010.116.
[209] Tascón JMD, editor. Novel Carbon
Adsorbents. Oxford: Elsevier; 2012.
[210] Béguin F, Raymundo-Pinero E. Nanocarbons for
supercapacitors. In: Brodd RJ, editor. Batteries for
sustainability. New York, NY: Springer New York; 2012. p.
393–421.
[211] Fuente E, Menéndez JA, Suárez D, Montes-Morán MA. Basic
surface oxides on carbon materials: a global view. Langmuir
2003;19(8):3505–11.
[212] Abdelwahab AA, Jung O-S, Shim Y-B. Enhanced
electrocatalytic reduction of oxygen with a molecule having
multi-quinone moieties adsorbed in the nanofiber film. J
Electroanal Chem 2009;632(1–2):102–8.
[213] Garten VA, Weiss DE. The Quinone–Hydroquinone character
of activated carbon and carbon black. Aust J Chem
1955;8(1):68.
[214] Boehm HP, Diehl E, Heck W, Sappok R. Surface oxides of
carbon. Angew Chem Int Edit 1964;3(10):669–77.
[215] Donnet JB. The chemical reactivity of carbons. Carbon
1968;6(2):161–76.
[216] Rivin D. Surface properties of carbon. Rubber Chem Technol
1971;44(2):307–43.
241
[217] Radovic LR, Bockrath B. On the chemical nature of graphene
edges: origin of stability and potential for magnetism in
carbon materials. J Am Chem Soc 2005;127(16):5917–27.
[218] Ban C, Yin W-J, Tang H, Wei S-H, Yan Y, Dillon AC. A novel
codoping approach for enhancing the performance of
LiFePO4 cathodes. Adv Energy Mater 2012;2(8):1028–32.
[219] Fuente E, Menéndez JA, Dı́ez MA, Suárez D, Montes-Morán
MA. Infrared spectroscopy of carbon materials: a quantum
chemical study of model compounds. J Phys Chem B
2003;107(26):6350–9.
[220] Montes-Morán MA, Suárez D, Menéndez JA, Fuente E. On the
nature of basic sites on carbon surfaces: an overview.
Carbon 2004;42(7):1219–25.
[221] Bleda-Martinez MJ, Maciá-Agulló JA, Lozano-Castelló D,
Morallon E, Cazorla-Amorós D, Linares-Solano A. Role of
surface chemistry on electric double layer capacitance of
carbon materials. Carbon 2005;43(13):2677–84.
[222] Shi H. Activated carbons and double layer capacitance.
Electrochim Acta 1996;41(10):1633–9.
[223] Centeno TA, Stoeckli F. The role of textural characteristics
and oxygen-containing surface groups in the
supercapacitor performances of activated carbons.
Electrochim Acta 2006;52(2):560–6.
[224] Zhang L, Xia Z. Mechanisms of oxygen reduction reaction
on nitrogen-doped graphene for fuel cells. J Phys Chem C
2011;115(22):11170–6.
[225] Groves MN, Chan ASW, Malardier-Jugroot C, Jugroot M.
Improving platinum catalyst binding energy to graphene
through nitrogen doping. Chem Phys Lett 2009;481(4–
6):214–9.
[226] Gueorguiev GK, Neidhardt J, Stafström S, Hultman L. First-
principles calculations on the role of CN precursors for the
formation of fullerene-like carbon nitride. Chem Phys Lett
2005;401(1–3):288–95.
[227] Gueorguiev GK, Neidhardt J, Stafström S, Hultman L. First-
principles calculations on the curvature evolution and
cross-linkage in carbon nitride. Chem Phys Lett 2005;410(4–
6):228–34.
[228] Zhang E-Y, Wang C-R. Fullerene self-assembly and
supramolecular nanostructures. Curr Opin Colloid Interface
Sci 2009;14(2):148–56.
[229] Rodil SE, Muhl S. Bonding in amorphous carbon nitride.
Diamond Relat Mater 2004;13(4–8):1521–31.
[230] Mao Y, Duan H, Xu B, Zhang L, Hu Y, Zhao C, et al. Lithium
storage in nitrogen-rich mesoporous carbon materials.
Energy Environ Sci 2012;5(7):7950.
[231] Cervantes-Sodi F, Csányi G, Piscanec S, Ferrari A. Edge-
functionalized and substitutionally doped graphene
nanoribbons: electronic and spin properties. Phys Rev B
2008;77(16):165427.
[232] Ferrari A, Robertson J. Interpretation of Raman spectra of
disordered and amorphous carbon. Phys Rev B
2000;61(20):14095–107. Available from: http://prb.aps.org/
abstract/PRB/v61/i20/p14095_1.
[233] Kleinsorge B, Ferrari AC, Robertson J, Milne WI, Waidmann
S, Hearne S. Bonding regimes of nitrogen in amorphous
carbon. Diamond Relat Mater 2000;9(3–6):643–8.
[234] Shin WH, Jeong HM, Kim BG, Kang JK, Choi JW. Nitrogen-
doped multiwall carbon nanotubes for lithium storage with
extremely high capacity. Nano Lett 2012;12(5):2283–8.
[235] Cai D, Wang S, Lian P, Zhu X, Li D, Yang W, et al. Superhigh
capacity and rate capability of high-level nitrogen-doped
graphene sheets as anode materials for lithium-ion
batteries. Electrochim Acta 2013;90:492–7.
[236] Wang H-G, Wang Y, Li Y, Wan Y, Duan Q. Exceptional
electrochemical performance of nitrogen-doped porous
carbon for lithium storage. Carbon 2015;82:116–23.
242 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
[237] Wang H, Zhang C, Liu Z, Wang L, Han P, Xu H, et al.
Nitrogen-doped graphene nanosheets with excellent
lithium storage properties. J Mater Chem 2011;21(14):5430.
[238] Bulusheva LG, Okotrub AV, Kurenya AG, Zhang H, Zhang H,
Chen X, et al. Electrochemical properties of nitrogen-doped
carbon nanotube anode in Li-ion batteries. Carbon
2011;49(12):4013–23.
[239] Wu Z-S, Ren W, Xu L, Li F, Cheng H-M. Doped graphene
sheets as anode materials with superhigh rate and large
capacity for lithium ion batteries. ACS Nano
2011;5(7):5463–71.
[240] Lee JH, Shin WH, Ryou M-H, Jin JK, Kim J, Choi JW.
Functionalized graphene for high performance lithium ion
capacitors. ChemSusChem 2012;5(12):2328–33.
[241] Hulicova-Jurcakova D, Seredych M, Lu GQ, Bandosz TJ.
Combined effect of nitrogen- and oxygen-containing
functional groups of microporous activated carbon on its
electrochemical performance in supercapacitors. Adv Funct
Mater 2009;19(3):438–47.
[242] Chen L-F, Zhang X-D, Liang H-W, Kong M, Guan Q-F, Chen P,
et al. Synthesis of nitrogen-doped porous carbon
nanofibers as an efficient electrode material for
supercapacitors. ACS Nano 2012;6(8):7092–102.
[243] Kundu S, Xia W, Busser W, Becker M, Schmidt DA, Havenith
M, et al. The formation of nitrogen-containing functional
groups on carbon nanotube surfaces: a quantitative XPS and
TPD study. Phys Chem Chem Phys 2010;12(17):4351.
[244] Su F, Poh CK, Chen JS, Xu G, Wang D, Li Q, et al. Nitrogen-
containing microporous carbon nanospheres with improved
capacitive properties. Energy Environ Sci 2011;4(3):717.
[245] Kelemen SR, Gorbaty ML, Kwiatek PJ. Quantification of
nitrogen forms in argonne premium coals. Energy Fuel
1994;8(4):896–906.
[246] Pels JR, Kapteijn F, Moulijn JA, Zhu Q, Thomas KM. Evolution
of nitrogen functionalities in carbonaceous materials
during pyrolysis. Carbon 1995;33(11):1641–53.
[247] Wang X, Li X, Zhang L, Yoon Y, Weber PK, Wang H, et al. N-
doping of graphene through electrothermal reactions with
ammonia. Science 2009;324(5928):768–71.
[248] Seredych M, Hulicova-Jurcakova D, Lu GQ, Bandosz TJ.
Surface functional groups of carbons and the effects of their
chemical character, density and accessibility to ions on
electrochemical performance. Carbon 2008;46(11):1475–88.
[249] Chandra V, Yu SU, Kim SH, Yoon YS, Kim DY, Kwon AH,
et al. Highly selective CO2 capture on N-doped carbon
produced by chemical activation of polypyrrole
functionalized graphene sheets. Chem Commun
2012;48(5):735–7.
[250] Wei D, Liu Y, Wang Y, Zhang H, Huang L, Yu G. Synthesis of
N-doped graphene by chemical vapor deposition and its
electrical properties. Nano Lett 2009;9(5):1752–8.
[251] Reddy ALM, Srivastava A, Gowda SR, Gullapalli H, Dubey M,
Ajayan PM. Synthesis of nitrogen-doped graphene films for
lithium battery application. ACS Nano 2010;4(11):6337–42.
[252] Qu L, Liu Y, Baek J-B, Dai L. Nitrogen-doped graphene as
efficient metal-free electrocatalyst for oxygen reduction in
fuel cells. ACS Nano 2010;4(3):1321–6.
[253] Jeong HM, Lee JW, Shin WH, Choi YJ, Shin HJ, Kang JK, et al.
Nitrogen-doped graphene for high-performance
ultracapacitors and the importance of nitrogen-doped sites
at basal planes. Nano Lett 2011;11(6):2472–7.
[254] Qie L, Chen WM, Wang ZH, Shao QG, Li X, Yuan LX, et al.
Nitrogen-doped porous carbon nanofiber webs as anodes
for lithium ion batteries with a superhigh capacity and rate
capability. Adv Mater 2012;24(15):2047–50. Available from:
http://onlinelibrary.wiley.com/doi/10.1002/adma.
201104634/full.
[255] Kapteijn F, Moulijn JA, Matzner S, Boehm HP. The
development of nitrogen functionality in model chars
during gasification in CO2 and O2. Carbon
1999;37(7):1143–50.
[256] Kumar A, Ganguly A, Papakonstantinou P. Thermal stability
study of nitrogen functionalities in a graphene network. J
Phys Condens Matter 2012;24(23):235503.
[257] Arrigo R, Hävecker M, Wrabetz S, Blume R, Lerch M,
McGregor J, et al. Tuning the acid/base properties of
nanocarbons by functionalization via amination. J Am
Chem Soc 2010;132(28):9616–30.
[258] Yang SH, Shin WH, Lee JW, Kim HS, Kang JK, Kim YK.
Nitrogen-mediated fabrication of transition metal-carbon
nanotube hybrid materials. Appl Phys Lett
2007;90(1):013103.
[259] Gogotsi Y, Guldi D, McCreery R, Hu C-C, Merlet C, Béguin F,
et al. Carbon electrodes for energy storage: general
discussion. Faraday Discuss Roy Soc Chem 2014;172:239–60.
[260] Lin Z, Liu Y, Yao Y, Hildreth OJ, Li Z, Moon K, et al. Superior
capacitance of functionalized graphene. J Phys Chem C
2011;115(14):7120–5.
[261] Huang X, Qi X, Boey F, Zhang H. Graphene-based
composites. Chem Soc Rev 2012;41(2):666.
[262] Sun Y, Wu Q, Shi G. Graphene based new energy materials.
Energy Environ Sci 2011;4(4):1113–32.
[263] Lei Z, Lu L, Zhao XS. The electrocapacitive properties of
graphene oxide reduced by urea. Energy Environ Sci
2012;5(4):6391–9. Available from: http://pubs.rsc.org.
ezproxy.lib.umb.edu/en/Content/ArticleLanding/2012/EE/
c1ee02478g#!divAbstract.
[264] Wen Z, Wang X, Mao S, Bo Z, Kim H, Cui S, et al. Crumpled
nitrogen-doped graphene nanosheets with ultrahigh pore
volume for high-performance supercapacitor. Adv Mater
2012;24(41):5610–6.
[265] Li X, Wang H, Robinson JT, Sanchez H, Diankov G, Dai H.
Simultaneous nitrogen doping and reduction of graphene
oxide. J Am Chem Soc 2009;131(43):15939–44.
[266] Qian H-S, Yu S-H, Luo L-B, Gong J-Y, Fei L-F, Liu X-M.
Synthesis of uniform Te@Carbon-rich composite
nanocables with photoluminescence properties and
carbonaceous nanofibers by the hydrothermal
carbonization of glucose. Chem Mater 2006;18(8):2102–8.
[267] Liang H-W, Guan Q-F, Chen L-F, Zhu Z, Zhang W-J, Yu S-H.
Macroscopic-scale template synthesis of robust
carbonaceous nanofiber hydrogels and aerogels and their
applications 2012;51(21):5101–5.
[268] Kim ND, Kim W, Joo JB, Oh S, Kim P, Kim Y, et al.
Electrochemical capacitor performance of N-doped
mesoporous carbons prepared by ammoxidation. J Power
Sources 2008;180(1):671–5.
[269] Cao B, Zhang B, Jiang X, Zhang Y, Pan C. Direct synthesis of
high concentration N-doped coiled carbon nanofibers from
amine flames and its electrochemical properties. J Power
Sources 2011;196(18):7868–73.
[270] Zhao L, Fan L-Z, Zhou M-Q, Guan H, Qiao S, Antonietti M,
et al. Nitrogen-containing hydrothermal carbons with
superior performance in supercapacitors. Adv Mater
2010;22(45):5202–6.
[271] Yang X, Wu D, Chen X, Fu R. Nitrogen-enriched
nanocarbons with a 3-D continuous mesopore structure
from polyacrylonitrile for supercapacitor application. J Phys
Chem C 2010;114(18):8581–6.
[272] Titirici M-M, Antonietti M. Chemistry and materials options
of sustainable carbon materials made by hydrothermal
carbonization. Chem Soc Rev 2009;39(1):103.
[273] Liu D, Zheng D, Wang L, Qu D, Xie Z, Lei J, et al.
Enhancement of electrochemical hydrogen insertion in N-
 CARBON 9 2 (2 0 1 5) 1 9 3–24 4
doped highly ordered mesoporous carbon. J Phys Chem C
2014;118(5):2370–4.
[274] Li ZQ, Lu CJ, Xia ZP, Zhou Y, Luo Z. X-ray diffraction patterns
of graphite and turbostratic carbon. Carbon
2007;45(8):1686–95.
[275] Stein SE. Thermal reactions and properties of polycyclic
aromatic hydrocarbons. Acc Chem Res 1991;24(11):350–6.
[276] Zhang L, Li T, Yu P, Ohsaka T, Mao L. Charge–transfer
interaction between melamine and quinones: towards
voltammetric determination of melamine. Electrochem
Commun 2013;26:89–92.
[277] Schaber PM, Colson J, Higgins S, Thielen D, Anspach B,
Brauer J. Thermal decomposition (pyrolysis) of urea in an
open reaction vessel. Thermochim Acta 2004;424(1–
2):131–42.
[278] Wakeland S, Martinez R, Grey JK, Luhrs CC. Production of
graphene from graphite oxide using urea as expansion–
reduction agent. Carbon 2010;48(12):3463–70.
[279] Ju H-M, Huh SH, Choi S-H, Lee H-L. Structures of thermally
and chemically reduced graphene. Mater Lett
2010;64(3):357–60.
[280] Largeot C, Portet C, Chmiola J, Taberna P-L, Gogotsi Y, Simon
P. Relation between the ion size and pore size for an electric
double-layer capacitor. J Am Chem Soc 2008;130(9):2730.
[281] Chmiola J, Largeot C, Taberna P-L, Simon P, Gogotsi Y.
Desolvation of ions in subnanometer pores and its effect on
capacitance and double-layer theory. Angew Chem Int Edit
2008;120(18):3440–3. Available from: http://onlinelibrary.
wiley.com/doi/10.1002/anie.200704894/abstract.
[282] Chmiola J, Yushin G, Gogotsi Y, Portet C, Simon P.
Anomalous increase in carbon capacitance at pore sizes less
than 1 nanometer. Science 2006;313:1760–3.
[283] Decher G. Fuzzy nanoassemblies: toward layered polymeric
multicomposites. Science 1997;277(5330):1232–7.
[284] Le Gall T, Reiman KH, Grossel MC, Owen JR. Poly(2,5-
dihydroxy-1,4-benzoquinone-3,6-methylene): a new organic
polymer as positive electrode material for rechargeable
lithium batteries. J Power Sources 2003;119–121:316–20.
[285] Chen H, Armand M, Demailly G, Dolhem F, Poizot P,
Tarascon J-M. From biomass to a renewable LiXC6O6 organic
electrode for sustainable Li-ion batteries. ChemSusChem
2008;1(4):348–55.
[286] Chen H, Armand M, Courty M, Jiang M, Grey CP, Dolhem F,
et al. Lithium salt of tetrahydroxybenzoquinone: toward
the development of a sustainable Li-ion battery. J Am Chem
Soc 2009;131(25):8984–8.
[287] Hu T, Sun X, Sun H, Xin G, Shao D, Liu C, et al. Rapid
synthesis of nitrogen-doped graphene for a lithium ion
battery anode with excellent rate performance and super-
long cyclic stability. Phys Chem Chem Phys 2013;16(3):
1060.
[288] Gu X, Yue J, Chen L, Liu S, Xu H, Yang J, et al. Coaxial MnO/
N-doped carbon nanorods for advanced lithium-ion battery
anodes. J Mater Chem A 2014;3(3):1037–41.
[289] Zhu Z, Wang S, Du J, Jin Q, Zhang T, Cheng F, et al.
Ultrasmall Sn nanoparticles embedded in nitrogen-doped
porous carbon as high-performance anode for lithium-ion
batteries. Nano Lett 2014;14(1):153–7.
[290] Chen D, Ji G, Ding B, Ma Y, Qu B, Chen W, et al. In situ
nitrogenated graphene—few-layer WS2 composites for fast
and reversible Li+ storage. Nanoscale 2013;5(17):7890.
[291] Chen Y, Li X, Park K, Song J, Hong J, Zhou L, et al. Hollow
carbon-nanotube/carbon-nanofiber hybrid anodes for Li-ion
batteries. J Am Chem Soc 2013;135(44):16280–3.
[292] Cho YJ, Kim HS, Im H, Myung Y, Jung GB, Lee CW, et al.
Nitrogen-doped graphitic layers deposited on silicon
nanowires for efficient lithium-ion battery anodes. J Phys
Chem C 2011;115(19):9451–7.
243
[293] Wang Z-L, Xu D, Wang H-G, Wu Z, Zhang X-B. In situ
fabrication of porous graphene electrodes for high-
performance energy storage. ACS Nano 2013;7(3):2422–30.
[294] Li X, Liu J, Zhang Y, Li Y, Liu H, Meng X, et al. High
concentration nitrogen doped carbon nanotube anodes with
superior Li+ storage performance for lithium rechargeable
battery application. J Power Sources 2012;197:238–45.
[295] Wang Z, Xiong X, Qie L, Huang Y. High-performance lithium
storage in nitrogen-enriched carbon nanofiber webs derived
from polypyrrole. Electrochim Acta 2013;106:320–6.
[296] Zhang K, Han P, Gu L, Zhang L, Liu Z, Kong Q, et al.
Synthesis of nitrogen-doped MnO/graphene nanosheets
hybrid material for lithium ion batteries. ACS Appl Mater Int
2012;4(2):658–64.
[297] Tao H-C, Yang X-L, Zhang L-L, Ni S-B. One-step synthesis of
nickel sulfide/N-doped graphene composite as anode
materials for lithium ion batteries. J Electroanal Chem
2015;739:36–42.
[298] Nakamura M, Nakanishi M, Yamamoto K. Influence of
physical properties of activated carbons on characteristics
of electric double-layer capacitors. J Power Sources
1996;60(2):225–31.
[299] Kim C-H, Pyun S-I. Activated carbons as electrode materials
in electric double-layer capacitors. J Korean Ceram Soc
2003;40(9):819–26.
[300] Frackowiak E, Béguin F. Carbon materials for the
electrochemical storage of energy in capacitors. Carbon
2001;39(6):937–50.
[301] Yin C, Aroua MK, Daud W. Review of modifications of
activated carbon for enhancing contaminant uptakes from
aqueous solutions. Sep Purif Technol 2007;52(3):403–15.
[302] Li L, Quinlivan PA, Knappe DR. Effects of activated carbon
surface chemistry and pore structure on the adsorption of
organic contaminants from aqueous solution. Carbon
2002;40(12):2085–100.
[303] Goyal RCBAM. Activated carbon adsorption. CRC Press;
2007. 487p.
[304] Marsh H, Rodriguez-Reinoso F. Ch 8: Applicability of
activated carbon. Activated carbon. 1st ed. Elsevier Science
& Technology Books; 2006. p. 383–453.
[305] Stein A, Wang Z, Fierke MA. Functionalization of porous
carbon materials with designed pore architecture. Adv
Mater 2009;21(3):265–93.
[306] Balasubramanian K, Burghard M. Chemically functionalized
carbon nanotubes. Small 2005;1(2):180–92.
[307] Shen W, Li Z, Liu Y. Surface chemical functional groups
modification of porous carbon. Recent Patents on Chem Eng
Int. 2008;1(1):27–40.
[308] Pan Q, Wang H, Jiang Y. Natural graphite modified with
nitrophenyl multilayers as anode materials for lithium ion
batteries. J Mater Chem 2007;17(4):329.
[309] Pan Q, Wang H, Jiang Y. Covalent modification of natural
graphite with lithium benzoate multilayers via diazonium
chemistry and their application in lithium ion batteries.
Electrochem Commun 2007;9(4):754–60.
[310] Frackowiak E, Béguin F. Electrochemical storage of energy in
carbon nanotubes and nanostructured carbons. Carbon
2002;40(10):1775–87.
[311] Yoon D, Chung KY, Chang W, Kim SM, Lee MJ, Lee Z, et al.
Hydrogen-enriched reduced graphene oxide with enhanced
electrochemical performance in lithium ion batteries. Chem
Mater 2014. 141215145811007.
[312] Xing W, Dahn JR. Study of irreversible capacities for li
insertion in hard and graphitic carbons. J Electrochem Soc
1997;144(4):1195–201. Available from: http://jes.ecsdl.org/
cgi/doi/10.1149/1.1837572.
[313] Peled E, Menachem C, Tow DB, Melman A. Improved
graphite anode for lithium-ion batteries chemically bonded
244 CARBON 9 2 ( 2 0 1 5 ) 1 9 3 –2 4 4
solid electrolyte interface and nanochannel formation. J
Electrochem Soc 1996;143(1):L4–7.
[314] Frackowiak E, Gautier S, Gaucher H, Bonnamy S, Béguin F.
Electrochemical storage of lithium in multiwalled carbon
nanotubes. Carbon 1999;37(1):61–9.
[315] Lu W, Chung DDL. Anodic performance of vapor-derived
carbon filaments in lithium-ion secondary battery. Carbon
2001;39(4):493–6.
[316] Buiel E, Dahn JR. Reduction of the irreversible capacity in
hard-carbon anode materials prepared from sucrose for
Li-ion batteries. J Electrochem Soc 1998;145(6):
1977–81.
[317] Spahr ME, Palladino T, Wilhelm H, Würsig A, Goers D, Buqa
H, et al. Exfoliation of graphite during electrochemical
lithium insertion in ethylene carbonate-containing
electrolytes. J Electrochem Soc 2004;151(9):A1383–95.
Available from: http://jes.ecsdl.org/content/151/9/A1383.
abstract.
[318] Spahr ME, Buqa H, Würsig A, Goers D, Hardwick L, Novák P,
et al. Surface reactivity of graphite materials and their
surface passivation during the first electrochemical lithium
insertion. J Power Sources 2006;153(2):300–11.
[319] Ventosa E, Xia W, Klink S, La Mantia F, Muhler M,
Schuhmann W. Influence of surface functional groups on
lithium ion intercalation of carbon cloth. Electrochim Acta
2012;65:22–9.
[320] Wang Z, Qie L, Yuan L, Zhang W, Hu X, Huang Y.
Functionalized N-doped interconnected carbon nanofibers
as an anode material for sodium-ion storage with excellent
performance. Carbon 2013;55:328–34.
[321] Lota G, Fic K, Frackowiak E. Carbon nanotubes and their
composites in electrochemical applications. Energy Environ
Sci 2011;4(5):1592–605. Available from: http://pubs.rsc.org/
en/Content/ArticleLanding/2011/EE/
c0ee00470g#!divAbstract.
[322] Palomares V, Casas-Cabanas M, Castillo-Martı́nez E, Han
MH, Rojo T. Update on Na-based battery materials. A
growing research path. Energy Environ Sci 2013;6(8):2312–37.
Available from: http://pubs.rsc.org/en/content/
articlelanding/2013/ee/c3ee41031e#!divAbstract.