Advanced Energy Devices: Lithium Ion

Battery and High Energy Capacitor

59

M. K. Devaraju, M. Sathish, and I. Honma

Abstract

The development of modern technology toward energy production and storage

is essential to support human life with wide impact on the environment,
human health, and worlds economy. Through the development of the advanced
energy systems, human life can be ensure in a networked society even more
conveniently. In the electric and energy field, secondary batteries will play a
critical factor in reducing the environmental hazard and enable the effective
construction of the green energy society. At present, high power density and high
energy density are required as a power sources for the hybrid electric vehicle
(HEV) and electric vehicle (EV). As we know, Li-ion battery has high energy
density but low power density. The energy density of Li-ion battery decreases
with the increase in rate capability, but electric double-layer capacitor has high
power density but low energy density. So, this chapter focuses on the advanced
energy devices such as lithium-ion battery and high energy capacitors beginning
with brief introduction.
The importance of the solution process mainly including the hydrothermal
and solvothermal method as sustainable chemistry toward the processing of
the positive electrode materials for lithium-ion batteries has been discussed.
The requirement and different techniques of the carbon coating using different
carbon sources to improve the electrochemical property of the positive electrode
materials have been focused. The electrochemical property of the olivinestructured cathode materials affected by different particles size and morphology
has been addressed. The concept of using graphene-based compounds for
the electric double-layer capacitor applications and electrochemical capacitor

M.K. Devaraju ()  M. Sathish  I. Honma

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Aoba-ku,
Sendai, Japan
e-mail: devarajumk@rediffmail.com; marappan.sathish@gmail.com;
i.honma@tagen.tohoku.ac.jp;
J. Kauffman, K.-M. Lee (eds.), Handbook of Sustainable Engineering,
DOI 10.1007/978-1-4020-8939-8 105,
Springer Science+Business Media Dordrecht 2013

1149

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M.K. Devaraju et al.

based on pseudocapacitance has been discussed. The hybrid capacitors such

as metal oxide-doped graphene and PANI/graphene nanocomposites with their
electrochemical performances have also been discussed.

Introduction

The rapid growth of science and technology during the last several decades in the
world is keep changing the human life by contributing to their needs to enjoy
their living. Recently, the development of the advanced energy devices becomes
critical to global human development including the ecosystems, economic growth,
employment, and prosperity of the present and future generation. In addition, the
slow diminishing of available energy resources is an alarm to change the present
energy system to the sustainable and renewable one for a long-term energy supply
for the mankind. Moreover, realization of the low carbon society based on
the advanced technologies for the sustainable development is one of the greatest
challenges at present.
The key technology for this challenge is to develop the next generation of clean
energy storage devices with high power density, high energy density, and high safety
for the hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), and
pure electric vehicles (PEV) (Aric-o et al. 2005). The practical realization of these
applications involves the development of the advanced energy functional materials
for the high energy storage and for a long-term performance. Lithium-ion battery
and capacitors are considered as the future advanced energy storage systems for
various next generation electronic and electrical applications.
Lithium-Ion Battery: Lithium-ion (Li-ion) batteries are comprised of cells that
employ lithium intercalation compounds as the positive and negative materials. As
a battery is cycled, lithium ions (LiC ) exchange between the positive and negative
electrodes. They are also referred to as rockingchair batteries as the lithium ions
rock back and forth between the positive and negative electrodes as the cell is
charged and discharged. The positive electrode material is typically a metal oxide
with a layered structure, such as lithium cobalt oxide (LiCoO2 ), or a material with
a tunneled structure, such as lithium manganese oxide (LiMn2 O4 ), on a current
collector of aluminum foil. The negative electrode material is typically a graphitic
carbon, also a layered material, on a copper current collector. In the charge/discharge
process, lithium ions are inserted or extracted from the interstitial space between
atomic layers within the active materials (Ehrlich 2001).
The mechanism involved in Li-ion battery is shown in Fig. 59.1. Where the
lithium metal was substituted with other insertion compounds, such as graphite
or non-graphitic carbon, LiCoO2 was used as the cathode material. The entire
electrochemical process would involve the reversible transfer of lithium ions
between the two electrodes. During the charge process, lithium ion is de-intercalated
from the cathode layers, then transported and intercalated into the carbonaceous
anode. While the discharge process occurred, the lithium ions are deintercalated
from the carbonaceous anode and intercalated again to empty site between layers of
the cathode materials (Park 2010).

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1151

e
A

Li1xCO2

LixC6
Li+

charge

Li+
e

discharge
e

Fig. 59.1 Schematic representation of Li ion battery showing discharge intercalation mechanism
(Ehrlich 2001)

Among the batteries, especially secondary batteries have been essential part of
the power source for the advanced energy devices. In the future, they will become
a key factor to pursue comfortable human life. The electric power source will
be produced by the environmentally friendly wind generation and solar cell, and
the produced electric power can charge the batteries which are not harmful and
friendly to the environment. In the electric and energy field, secondary batteries
will play a critical factor in reducing the environmental hazard and enable the
effective construction of the green energy society (Park 2010). After three decades
of development in battery technology, the Li-ion battery technology has emerged
as one of the most popular battery technologies (Tarascon and Armand 2001).
They are widely used in various electronic devices because of their good cycle
life, high energy density, and high capacity over any other battery technologies.
The Li-ion battery technology that now dominates much of the portable battery
business has matured enough over the last 5 years to be considered for the shortterm implementation in the hybrid electric vehicles (HEV) and electric vehicles
(EV) applications (Tarascon and Armand 2001).
High Energy Capacitors: The discovery of a so-called condenser, now referred
to as a capacitor that electric charges could be stored on the plate, was made in
the mid-eighteenth century during the period when the phenomena associated with
static electricity were being revealed. The embodiment known as a condenser is
attributed to Musschenbroek (Encyclopedia Britannica 1926) in 1746 at Leyden in
the Netherlands, hence the name Leyden jar. The electrochemical capacitor was
supposed to boost the hybrid electric vehicle to provide the high or strong power
for acceleration and additionally allow the recovery of braking energy. The electric
double-layer capacitor consisting of a single cell with a high surface area electrode
material is loaded with electrolyte (Kotz and Carlen 2000). The schematic diagram

1152

M.K. Devaraju et al.

collector
+
+
+
+
+
+

polarizing
electrodes

collector

electrolyte

separator +
+
+

+
+
+
+

electric double layer

Fig. 59.2 Schematic representation showing basic structure of electric double layer (Kotz and
Carlen 2000)

of the double-layer electric capacitor is shown in Fig. 59.2. Electric double-layer

capacitors store the electric energy in an electrochemical double layer (Helmholtz
layer) formed at the solid/electrolyte interface. Positive and negative ionic charges
within the electrolyte accumulate at the surface of the solid electrode. The quantity
of ion removed from the electrolyte equals the charge developed on the electrode
surface. Therefore, the maximum energy stored in a capacitor is limited by the
capacitance of the capacitor, C, and the maximum operating voltage, V.
Recently, high-performance electrochemical energy storage systems are being
investigated as they are very important for the electric vehicles and hybrid electric
vehicles (Liu et al. 2010). Great efforts have been made to develop high-power
(10 kW kg1 ) electrochemical capacitors (ECs) due to their faster charge and
discharge processes, in seconds, than those of batteries. In addition, electrochemical
capacitors have a longer cycle life as compared to batteries because no or negligibly
small chemical charge transfer reactions are involved.
When compared with those of other secondary batteries and Li-ion battery, it has
the following advantages: long cycle life, >100,000 cycles; some system up to 106 ;
good power density (under certain conditions, limited by IR or equivalent series
resistance (esr) complexity of equivalent circuit); simple principle and mode of
construction; cheap material (for aqueous embodiment); combines state-of-charge
indication, Q D CV; and can be combined for the rechargeable battery for the hybrid
application (electric vehicles). However, ECs suffer from a lower energy density
than batteries (Liu et al. 2010). The energy density can be improved by adopting
asymmetric (hybrid) systems; at present they have been extensively explored by
combining a battery like Faradic electrode (as energy source) and a capacitive
electrode (as power source) to increase the operation voltage, which leads to a
notable improvement of the energy density of high-power ECs nearly to that of
batteries (Yoshino 2004).

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1153

In this chapter, solution-based synthesis and characterization of the olivinestructured lithium metal phosphates (LiFePO4 , LiMnPO4 , and LiCoPO4 ) nanomaterials used as the positive electrode materials will be focused. The sustainable
chemistry process such as supercritical solvothermal method and solution process
that has been used for the materials synthesis is discussed. These methods can
be considered as environmentally friendly, rapid, and easy process for largescale synthesis or preparation of the advanced functional materials. High-energy
capacitors such as metal oxidedoped graphene, PANI/graphene nanocomposites,
and electrochemical capacitors based on pseudocapacitance have been discussed
along with their electrochemical property for the advanced energy systems.

Positive Electrode Materials for Li-Ion Battery

Among the battery components, the cathode materials are the one which are crucial
in determining the high power, safety, longer life, and cost of the battery that satisfies
the requirements of the larger battery system. These can be applicable to the electric
vehicles, power tools, energy storage equipment, and so on (Padhi et al. 1997).
There are various types of materials being used as the positive electrode materials
for the lithium-ion batteries as shown in Fig. 59.3 (Tarascon and Armand 2001).
The structural, chemical stability, availability of redox couples at a suitable energy,
specific capacity, operating voltage, and safety issues are the primary considerations,
and these properties are different among the positive electrode materials shown
in Fig. 59.3. Lithium-based electrodes have four types of structure which have
lithium insertion voltage of above 3 V. They include layers of lithium metal oxides
such as LiCoO2 , LiNiO2 , LiCoNiO2 , and LiMnNiO2 ; the zigzag layers structure
of LiMnO2 ; the three-dimensional spinel type, LiMn2 O4 and Li1=2 Mn3=2 O4 ; and
the olivine structure of LiMPO4 (M=Fe, Mn, Co, and Ni). Recently, Li2 MSiO4
(M=Fe, Mn, and Co) based cathodes have been investigated, which are envisaged
as the potential cathode candidate for the high-power batteries (Dominko 2010).
This is because of their overwhelming advantages such as high theoretical capacity
(>330 mAh g1 which is possible while extracting more than one LiC ion per
formula unit), high thermal stability through strong SiO bonding, safety, costeffectiveness, eco-friendliness, and ease to synthesize. This chapter discusses the
olivine-structured LiMPO4 cathode materials.

LiMPO4 (M=Fe, Mn, Co, and Ni) as Positive Electrodes for

Li-Ion Battery

In 1990s, LiCoO2 was commercialized by Sony. Since then, a series of excellent

candidates has appeared because of high cost and oxidative instability of LiCoO2 for
use as the cathode material. In this regard, the layered rock salt systems, LixNiO2
(0<x<1)-, and the manganese spinel framework systems, Lix Mn2 O4 , are now used
commercially as the 4-V cathode materials because they have met above needs

1154

M.K. Devaraju et al.

Li1xMn2yMyO4
of Li ion

Li1xNi1yzCoyMzO4[M=Mg,AI,...]

limited RT cycling

Polyanionic compound [Li1xVOPO4,LixFePO4]

Potential versus Li/Li+ (v)

of Li metal
LixMn1yMyO2 [M=Cr, Co,...]

Positive materials

Positive material:

Li1xCo1yMyO2

3
MnO2

Vanadium oxides
[V2O5, LiV3O8]

Li-metal
potential

Li-ion
potential

2
3d-Metal oxidea

Negative material:

Negative materials

of Li ion
Composite alloys
[Sn(M)-based]

[Sn(O)-based]

limited cycling)
of Li metal

Nitrides LiMyN2

Carbons
Graphite

Li metal

0
0

200

400

600

800

1000

3,800

4,000

Capacity (A h kg1)

Fig. 59.3 Voltage vs. capacity of some cathode materials (Tarascon and Armand 2001)

to some degree. However, they are still problematic due to their compositions.
To overcome these disadvantages and problems, the olivine-structured lithium metal
phosphate cathode materials are considered as the attractive cathode materials
because they are in low cost, abundant in nature, exhibit high theoretical capacity
(170 mAh g1 ) (Padhi et al. 1997), high thermal stability owing to the presence of
a strong PO covalent bond, and easy to synthesize.
LiMPO4 (M=Fe, Mn, Co, and Ni) belongs to the orthorhombic structure, which
consists of the hexagonal closed packing (HCP) of the oxygen atoms with LiC and
M2C cations located in half of the octahedral sites and P5C cations in one eighth of
the tetrahedral sites (Fig. 59.4). This structure may be described as chains (along the
c direction) of edge sharing MO6 octahedra that are cross-linked by the PO4 groups
forming a three-dimensional network. Tunnels perpendicular to the [010] and [001]
directions contain octahedrally coordinated LiC cations (along the b-axis), which
are mobile in these cavities (Jin and Jiang 2009). Among the phosphates, LiFePO4
is considered most stable, low cost, and high compatibility with the environments.

3.1

Synthesis of LiMPO4 (M=Fe, Mn and, Co) Cathodes by the

Solution Process

Since the demand for the cathode materials for lithium-ion battery is increasing
continuously, various methods have been developed to prepare lithium metal
phosphate nanoparticles, such as the solgel method (Choi and Kumta 2007),

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1155

Fig. 59.4 The schematic representation of the crystal structure of LiMPO4 (M=Fe, Mn, Co, and
Ni) compounds showing the HCP oxygen array with MO6 and PO4 groups (Jin and Jiang 2009)

coprecipitation (Arnold et al. 2003), mechanochemical activation (Kim et al. 2007),

spray technology (Konarova and Taniguchi 2009), and solid-state reaction (Padhi
et al. 1997). However, all these methods have limitations in practice. Commercial
success of new cathode materials is mainly dependent on the preparation method,
which controls morphology, particle size, and cation order among other critical
experimental parameters. Although traditionally high-temperature methods have
been used, they are both energy intensive and cannot readily produce many
potentially metastable structures that might result in high lithium-ion diffusivity.
However, they do have the advantage of being hydroxyl/water-free. There are
many possible approaches for the synthesis of active materials, but in the end, a
commercially viable approach must be used (Whittingham et al. 2004). Therefore,
simple solution process could be required to overcome practical problems.
Recently, soft chemical approaches such as hydrothermal and solvothermal or
ion exchange offer several advantages and are being used on the tonnage quantities,
as such, the chemical industry considers them viable. Hydrothermal synthesis has
been extensively studied for the synthesis of simple oxides such as those of tungsten,
molybdenum, and vanadium, and today many of the key parameters are understood
(Chirayil et al. 1997). Different kinds of phosphates have also been successfully
prepared by the hydrothermal method (Byrappa et al. 2008). The advantages of

1156

M.K. Devaraju et al.

Hydrothermal and solvothermal process

Precursors

FURNACE/OVEN

Teflon
liner

Autoclave

Hydrothermal and solvothermal products

Precursors

Spheres

Plates

Cubes

Rods

Fig. 59.5 Showing experimental scheme of hydrothermal and solvothermal process for the design
of nanoparticles with various shapes (Author unpublished work)

using the hydrothermal and solvothermal methods are shown in Fig. 59.5, where
morphology, size, and other experimental parameters can be easily controlled.
Moreover, low-temperature solution process is environmentally friendly, low energy
consuming, and easy to perform for the large-scale production.
The concept of the hydrothermal process for the preparation of LiFePO4 was
first realized by Yang et al. in (2001). However, preparation of the nanocrystalline
particles ranging from 500 to 1,500 nm was reported by Tajimi et al. (2004) under
the hydrothermal reaction condition at the reaction temperature of 150220C for
several hours using various amounts of polyethylene glycol (PEG).
Recently, monodispersed particles of LiFePO4 were prepared using a mixture of
isopropanol and aqueous solution by controlling the RH factor (Zhang et al. 2009).
The monodispersed LiFePO4 particles were controlled from 1 to 4 m in length
and 12 m in diameter. Small particles of LiFePO4 measuring 4001 m with
the shape of discrete short rods were obtained at the RH factor of 1 (Fig. 59.6a).
However, several attempts have been made to obtain cathode materials with different
size and morphology. In this regard, the rodlike LiFePO4 particles with 100 nm
of uniform diameter and 510 nm of the aspect ratio were synthesized by the
hydrothermal reaction at 220C (Huang et al. 2010), and the rodlike morphology
can be seen in Fig. 59.6b.
In order to reduce the reaction time and to obtain homogeneous monodispersed
particles, a few attempts have been made to synthesize the cathode materials at a
shorter reaction period. Hence, a rapid production of the cathode materials by the

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1157

Fig. 59.6 LiFePO4 cathode materials with different morphology synthesized by hydrothermal
method (Reproduced with permission from Zhang et al. (2009), Huang et al. (2010) and Xu et al.
(2008))

continuous hydrothermal method has been adopted to synthesize LiFePO4 nanoparticles (Xu et al. 2008) ranging from 20 to 40 nm in diameter as shown in Fig. 59.6c.
This process is promising for the large-scale synthesis of high purity monodispersed
nanocrystalline electrode materials for the application in the Li-ion battery.
Recently, surface modified LiFePO4 /C nanocrystals were synthesized from the
supercritical batch reactors at 400 C for 30 min using inexpensive environmentally
friendly solvent such as ethanol and water (Rangappa et al. 2009). The assynthesized particles exhibited less than 15 nm in diameter. Morphology can also be
easily controlled by this process such as the nanoarchitectured structure of LiFePO4
as shown in Fig. 59.7a (Rangappa et al. 2010), and nanoplate/nanorods of LiMnPO4
(Fig. 59.7b, c) were synthesized in the presence of surfactants such as oleic acid and
oleylamine at 400 C for 410 min (Rangappa et al. 2010a). In addition, LiCoPO4
nanoparticles were also synthesized by this method. The as-synthesized LiCoPO4
particles showed 50100 nm in diameter (Fig. 59.7d). The experimental results
confirmed that using selective surfactants and solvents, morphology and size of
the cathode materials could be easily modified. Furthermore, the reaction time and
temperature can be shortened in the light of the energy savings.
The microwave-hydrothermal and microwave solvothermal methods have been
used to synthesize the positive electrode materials within a short period of reaction
time as these methods have advantage of changing the reaction kinetics while
irradiating microwave. The platelets like LiMnPO4 nanoparticles (Ji et al. 2011)
were synthesized using the microwave hydrothermal method at 120180C for
a short period of reaction time, and the as-synthesized particles are shown in
Fig. 59.8a. The size of the platelets was controlled to 150 nm thickness and 5 m
basal dimensions. The nanorods of LiFePO4 were prepared by the rapid microwave
solvothermal method (Murugan et al. 2008) at 300 C for 5 min. The large nanorods
of LiFePO4 with a width of 40 6 nm and a length of up to 1 m were successfully
synthesized in presence of tetraethylene glycol (TEG) as shown in Fig. 59.8b.
This result showed the effect of selective solvents on the morphology of the final
products.

1158

M.K. Devaraju et al.

Fig. 59.7 (a) Nanoarchitectured of LiFePO4 (b) and (c) nanoplate and nanorods of LiMnPO4
and (d) sphere-like particles of LiCoPO4 synthesized by supercritical method (Reproduced with
permission from Rangappa et al. (2010a) and Rangappa et al. (2010b) and LiCoPO4 from authors
unpublished work)

Polyol-mediated solvothermal synthesis (Lim 2010) of LiMPO4 (M=Fe and

Mn) particles with dimensions of length and width in the range of 200350 and
200400 nm, respectively, are shown in Fig. 59.8c. The use of the polyol solvents
acts not only as a solvent but also as a reducing environmental agent and stabilizer,
thereby limiting particle growth and preventing agglomeration. Thickness of the
plate-like LiFePO4 down to 30 nm, width of 100 nm, and length of 200 nm were
synthesized by the solvothermal method at 180C for 18 h (Nan et al. 2011).
Morphology and well-resolved lattice fringes of LiFePO4 can be seen in Fig. 59.8d.
Morphology and size have their own effects on the property of the cathode materials.
Therefore, the solution-based green synthesis methods are much beneficial in
designing the nanocrystalline electrode materials since the nanocrystalline materials

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1159

Fig. 59.8 (a) Platelet like of LiMnPO4 nanoparticles synthesized by microwave hydrothermal
method (b) large nanorods of LiFePO4 synthesized by microwave solvothermal method (c)
platelike LiFePO4 synthesized by polyol method (d) thin plate like LiFePO4 synthesized by
solvothermal method (Reproduced with permission from Ji et al. (2011), Murugan et al. (2008),
Lim et al. (2011) and Nan et al. (2011))

possessing different shape are promising to behave much differently than the
bulk materials. Hence, from the nanocrystalline materials, improved and surprising
physicochemical reaction can be expected, which could play a vital role in various
technological and chemical applications.

3.2

Conductive Coating of Cathode Materials

The practical capacity and high rate performance of the olivine-structured lithium
metal phosphates are not impressive due to its low electronic conductivity

1160

M.K. Devaraju et al.

(1  109 scm1 at room temperature). To improve the electronic conductivity

of these materials, the following approaches have been considered:
(a) Decreasing the particle size for shortening the ionic and electronic transport
(b) Surface modification by the conductive carbon coating
(c) Doping the supervalent cations to enhance the intrinsic conductivity
(d) Designing different morphology and changing the texture and pore size
However, the expected electronic conductivity cannot be reached simply by
producing the cathode materials with different morphology, size, or doping supervalent cations. Therefore, surface modification of these materials is necessary
by conductive carbon coating because carbon coating offers better electronic
conductivity. The conductive carbon coating can be done either by the in situ or
ex situ coating technique. The in situ coating involves mixing of the carbon source
during the synthesis of the cathode materials at various reaction temperatures. This
method is useful to achieve homogeneous coating around the individual particles.
However, sometimes coating may not be uniform due to inhomogeneous mixing or
improper design of the experimental conditions. The ex situ coating involves mixing
of the carbon source either by the physical mixing or by high-energy ball milling
method.
Recently, various conductive carbon sources were successfully coated on to the
cathode materials, and this chapter discusses several carbon coating techniques.
Sugar was used as the carbon source by Jeon et al. (2007), and the in situ mixing
was carried out during the synthesis of the LiFePO4 particles, and carbon was
successfully mixed with the cathode materials as shown in Fig. 59.9a. Under the
supercritical water conditions, ascorbic acid was used as the carbon source, and the
in situ coating was carried out to synthesize the LiFePO4 /C particles (Rangappa
et al. 2009). Formation of the carbon layer can be seen in Fig. 59.9b for the heat
treated LiFePO4 particles at 500 C. This result shows that ascorbic acid can act as
the reducing agent to prevent the oxidation of metal ion from divalent to trivalent
and also as effective carbon source for the conductive coating.
Saravanan et al. (2009) have used D-gluconic acid lactone (C6 H10 O6 ) as the
carbon source, and the in situ coating was carried out using the solvothermal
method. Figure 59.9c shows 5-nm carbon layer formation around the particles.
This result shows that at low temperature (250C), the carbon coating can be
achieved using the selective carbon sources. The conductive polymer such as
PEDOT was used to coat LiFePO4 by Murugan et al. (2008) via the rapid microwave
solvothermal method. The homogeneous conductive polymer coating can be seen
around the LiFePO4 nanorod as shown in Fig. 59.9d.
Hence, better carbon coating can be made through the solution process as all of
the solution routes start from a precursor in a liquid solution which provides intimate
mixing of the carbon source with the ingredients on the atomic level, leading to
the rapid homogeneous nucleation and uniform particle formation. Moreover, when
compared with the other methods such as the carbonothermal and high-temperature
heating process used for the carbon coating and materials preparation, the solutionbased synthesis methods have advantages on the materials preparation and the
carbon coating at the low temperature with the selection of suitable organic solvents

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1161

Fig. 59.9 Carbon-coated LiFePO4 materials using (a) sugar, (b) ascorbic acid, (c) D-gluconic acid
lactone, and (d) PEDOT polymer (Reproduced with permission from Jeon et al. (2007), Rangappa
et al. (2009), Saravanan et al. (2009) and Murugan et al. (2008))

which can contribute as carbon source during the synthesis of the cathode materials.
High-boiling point solvents like glycols can be beneficial as the carbon source and
to achieve better in situ coating at the time of synthesis.

3.3

Charge/Discharge Process of Cathode Materials

Specific capacitance of the potential Lithium-ion battery cathode material is usually determined by the electrochemical galvanostatic charge/discharge technique.
Specific amount of the cathode materials was mixed with the carbon additives

1162

M.K. Devaraju et al.

Voltage versus Li/Li+ (V)

3.5
Discharge
Voltage gap resulting from hysteresis

3.0

2.5
Charge
2.0
1.2

1.3

1.4

1.5 1.6 1.7

x in LixFeSiO4

1.8

1.9

2.0

Fig. 59.10 Typical galvanostatic chargedischarge curve of LiFeSiO4 at a C/20 rate (Reproduced
with permission from Dreyer et al. (2010))

and then with the binder to make electrode paste. The electrode paste will be
pressed on Ni mesh and then cell assembled in the argon glove box. For the
charge/discharge measurement, the current rates of the cathode materials will be
calculated based on its theoretically calculated specific capacity in various time
spans and considering the amount of the cathode material present in the electrode
paste. The cut-off voltages used for the measurements are adapted according to the
type of the measured cathode material. It is important to note that materials that can
be cycled at high C-rates and operating in the voltage window of commercially used
electrolytes are desirable. During the galvanostatic cycling, structural change occurs
inside the electrode material as a result of the LiC insertion/extraction (lithium metal
is used as a counter electrode anode). The results from the measurements can be
plotted in the galvanostatic charge/discharge curves (voltage vs. capacity, voltage
vs. composition as shown in Fig. 59.10 (Dreyer et al. 2010), and capacity vs. cycle
number). Important parameters that can be determined from these curves are specific
capacity, voltage, and reversibility (e.g., polarization, voltage gap between charge
and discharge).
The LiMPO4 (M=Fe and Mn) cathode materials with similar crystal structure
synthesized by various solution routes show different electrochemical property.
The discharge capacity is not only dependent on the structure of the cathode
materials, but other facts also influence the electrochemical property of the cathode
materials, for example, crystal size, morphology, and method of carbon coating. For
example, the charge/discharge profile of the LiFePO4 nanorods shown in Fig. 59.10a
shows the discharge capacity of 140 mAhg1 (Fig. 59.11a) for the first cycle and
decreases to 130 mAhg1 after 20 cycles (Huang et al. 2010). The potential voltage
gap between the charge and discharge profile is wide. This might be due to low
conductivity, and it can be overcome by proper conductive carbon coating to

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

5.0
4.5

1163

4.5
4.0

0.5C
3.5
First cycle
3.0
2.5

Voltage (V)

Voltage (V)

4.0
3.5
3.0
2.5
2.0
2.0

1.5
1.0
20

1.5
0

20

40

60

80 100 120 140 160 180

20

40

60

80

100 120 140 160

Capacity (mAh/g)

4.5

4.0

3.5

1
25
50

3.0

Voltage (V vs. Li/Li+)

Cell Voltage (V vs. Li/Li+)

4.5
1
50
25

4.0

3.5

3.0

Charge-discharge at 0.1C

2.5

2.5
0

60

120

Capacity (mAhg1)

180

10

20

30

40

50

60

70

Capacity (mAh/g)

Fig. 59.11 Chargedischarge curves of (a) LiFePO4 nanorods, (b) sphere-like LiFePO4 /C,
(c) thin plate like LiFePO4 /C, and (d) colloidal nanocrystal of LiMnPO4 (Reproduced with
permission from Huang et al. (2012), Rangappa et al. (2009), Saravanan et al. (2009) and Rangappa
et al. (2010a))

improve the electrochemical property. Discharge capacity of about 165 mAhg1

(Fig. 59.11b) for a sphere-like LiFePO4 /C particle is synthesized by supercritical
water in the presence of ascorbic acid as the carbon source and reducing agent
(Rangappa et al. 2009). The discharge capacity of these materials is close to the
theoretical capacity of LiFePO4 (170 mAhg1 ). The cyclic performance of these
material was quiet satisfactory. However, further study is necessary to reduce the
wide potential observed in the chargedischarge profile and to increase the high rate
performance.
The thin platelike LiFePO4 /C (Saravanan et al. 2009) showed the discharge
capacity of around 150160 mAhg1 up to 50th cycle as shown in Fig. 59.11c. The
chargedischarge profile of this material shows relatively low potential gap between
the charge and discharge profile. This is due to the platelike morphology, which
can provide short distance for the Li-ion insertion and exertion and also due to the
homogeneous coating of carbon around the platelike LiFePO4 /C particles. The colloidal nanocrystal of LiMnPO4 with rodlike morphology (Rangappa et al. (2010a))

1164

M.K. Devaraju et al.

shows the discharge capacity of around 70 mAhg1 (Fig. 59.11d). The development
of new strategy of conductive carbon coating can enhance the discharge capacity
of LiMnPO4 materials. The intrinsic electronic conductivity of LiMnPO4 is very
low due to the JahnTeller distortion, and it is not possible to achieve full
theoretical capacity of LiMnPO4 . However, further study is necessary to improve
the electrochemical property of the LiMnPO4 cathode materials.

Electrochemical Capacitors

Electrochemical capacitors, also called supercapacitors, store energy using either

ion adsorption (electrochemical double-layer capacitors) or fast surface redox
reactions (pseudocapacitance). It is well known that the electrochemical doublelayer capacitors (EDLC) store the opposite charge electrostatically using reversible
adsorption of ions of the electrolyte on active materials surface that is electrochemically stable and has high accessible surface area (Conway 1999). As
there is no chemical reaction involved in the storage mechanism, the process is
highly reversible for millions of cycles and results long life for the capacitors.
And the specific capacitance depends on the available active specific surface
area of the active materials. Whereas, in the pseudocapacitance, surface or near
surface redox reactions occur during the charge storage mechanism, resulting high
specific capacitance with relatively short cycle life compared to EDLCs. Thus, the
development of high capacitive energy storage systems with optimum cycle life, low
cost, and environmentally friendly materials is essential to meet the energy demands
of modern society and emerging environmental concerns.

4.1

Graphene-Based Electrochemical Double-Layer Capacitors

Carbons and carbon-based composites materials are the most widely used owing
to their high surface area, moderate cost, and ecofriendly nature. A variety of
carbon morphologies with different surface area and chemical nature such as carbon
nanotubes, carbon nanofibers, carbon fibres, onions, and nanohorns have been
investigated (Simon and Gogotsi 2008; Zhang et al. 2009). Similarly, activated
carbons, mesoporous carbon, template carbon, and chemically derived carbon have
been examined. The carbons used in EDLC are generally pretreated to remove
moisture, and most of the surface functional groups are present on the carbon surface
to improve stability during cycling.
The presence of functional groups will result in increased serious resistance and
capacitance fading during aging. The double-layer capacitance of activated carbon
reaches 100120 F/g in organic electrolytes; this value can exceed 150300 F/g in
aqueous electrolytes, but at a lower cell voltage because the electrolyte voltage
window is limited by the water decomposition. The research on carbon materials
was directed toward increasing the pore volume by developing high surface area

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1165

carbon and refining the activation process. However, the capacitance increase was
limited even for the most porous samples (Simon and Gogotsi 2008). From a series
of activated carbons with different pore sizes in various electrolytes, it was shown
that there was no linear relationship between the surface area and the capacitance
owing to the inability of electrolyte access to the entire surface through smaller
pores. Also, the poor conductivity of the porous carbon materials limits the high
capacitance. Thus, high surface area carbon material with optimum pore size and
conductivity is essential to realize the high capacitance.
The key to reaching high capacitance by charging the double layer is using high
surface area carbon materials with electronically conducting electrodes. Graphitic
carbon satisfies all the requirements for this application, including high conductivity,
electrochemical stability, and open porosity that offer huge surface area (Simon
and Gogotsi 2008). Thus, graphene-based supercapacitors are under intensive
investigation as potential alternative to the activated carbon that is used in the
current supercapacitor electrodes. The effective surface area of graphene materials
should depend highly on the number of layers, that is, single- or few-layered
graphene sheets with less agglomeration might be expected to exhibit higher
effective surface area. The recent research reports on clean graphene materials
with specific capacitance ranging from 120 to 250 F/g. The chemical nature of the
graphene nanosheets and its purity greatly depend on the method of preparation and
subsequent processing of the resulting graphene sheets.
As mentioned earlier, the presence of functional groups on the graphene surface
greatly influences on its capacitance. In general, the presence of oxygen containing
functional groups result diminishes the capacitance and cycle life (Pandolfo and
Hollenkamp 2006). Wang et al. (2009) reported a maximum specific capacitance
of 205 F/g with an excellent long cycle life along with 90% specific capacitance
retained after 1,200 cycle tests. Also, it is confirmed that the interfacial capacitance
of the multilayer graphene sheets is found to depend on the number of layers. In
addition to the graphene quality, the fabrication of electrodes and its structure also
influences the performance of the resulting supercapacitors. Recently, P.M. Ajyan
group reported an in-plane fabrication approach for ultrathin supercapacitors
based on electrodes comprised of pristine graphene and multilayer reduced graphene
oxide (Yoo et al. 2011). And this approach allows for the formation of an efficient
electrical double layer by utilization of the maximum electrochemical surface area
and results a maximum specificapacitance of 247 F/g. The research on supercapacitors using graphene nanosheets is under tremendous progress. Combining highquality graphene sheets with suitable electrode fabrication technique will lead to the
commercial production of EDLC capacitors with high capacitance in the near future.
In the row of various chemical modification processes, doping of hetero-atoms,
such as nitrogen, sulfur, and boron, into the graphene backbone is another possible
route. Also, the heteroatom doping in the carbon materials (CNTs, graphene)
and metal oxides has always created excitement in the material chemistry as the
materials property can be tuned significantly. Recently, studies have focused on
direction, and several possible routes have been identified for the effective N- or
B-doping in the graphene sheets (Hulicova et al. 2006; Kwon et al. 2009).

1166

M.K. Devaraju et al.

Significant enhancement in capacitance has been reported for the heteroatomdoped graphene sheets, and the following possible mechanisms have been proposed
for the enhancement: (1) the improvement of the electrode wet-ability, due to the
increase in the number of hydrophilic polar sites; (2) the decrease of equivalent
series resistance (ESR) of a capacitor cell by the increase of the carbon electric
conductivity; (3) the occurrence of space-charge-layer capacitance in carbon by the
increase of its electron density; and (4) the occurrence of that pseudocapacitance
through the Faradic charge transfer, because the nature of carbon becomes electron
donor. Though, it is difficult to point out one particular effect for the capacitance
enhancement, it is believed that the pseudocapacitance through Faradic charge
transfer is the most important factor in enhancing the capacitance of the N- or
B-doped graphene sheets. Since the research on this direction is still in infancy stage,
additional experiments and theoretical understating are necessary. Understanding of
the mechanism and further development in the preparation method is expected to
play an important role in the improvement of the supercapacitor performance in the
coming years.

4.2

Electrochemical Capacitors Based on Pseudocapacitance

The large specific pseudocapacitance of Faradaic electrodes (typically 3001,000

F/g) exceeds that of the carbon-based materials using double-layer charge storage,
resulting in great interest in these systems. Specific capacitance of more than 600 F/g
has been reported for the RuO2 -based system owing to its good conductivity,
fast and reversible electron transfer together with the electroadsorption of protons
on the surface. However, the Ru-based aqueous electrochemical capacitors are
expensive, and the 1-V voltage window limits their applications to small electronic
devices (Simon and Gogotsi 2008). Thus, pseudocapacitive transition-metal oxides
such as MnO2 , NiO, and redox polymers such as polyanilines, polypyrroles, and
polythiophenes could be used to make electrodes, because they are predicted to
have a high capacitance for storing electrical charge, inexpensive, and not harmful
to the environment. Poor conductivity and lack of stability during cycling are
major drawbacks associated with these materials for their usage in supercapacitors.
Thus, numerous efforts have been made to use these metal oxides successfully
in supercapacitors by making composite with conductive support such as carbon
and gold.
Recently, Lang et al. (2011) developed a nanoporous gold/MnO2 electrode by
combining chemical de-lloying Ag65 Au35 (at %) with the electroless plating of
MnO2 (Fig. 59.12), in which nanoporous gold acts as a double-layer capacitor and
also provides good electronic/ionic conductivity to enhance the pseudocapacitive
behavior of the nanocrystalline MnO2 . And the MnO2 loading can be controlled by
adjusting the platting time. The gold/MnO2 hybrid material has very high specific
capacitance of 1,145 F/g at a scan rate of 50 mV/s. The obtained high specific
capacitance at a scan rate of 50 mV/s is higher (one order of magnitude) than
the reported MnO2 film electrodes at 5 mV/s (Toupin et al. 2004). This could be

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1167

MnO2
nanocrystals
Growth
N2H4

NPG

Mn7+

N2H4

Fig. 59.12 Schematic showing the fabrication process for nanoporous gold/MnO2 hybrid materials by directly growing MnO2 onto nanoporous gold (Reproduced with permission from Lang
(2011))

attributed to the porous metal/oxide structure, in which the nanocrystalline MnO2

grows epitaxially into the internal surface of the highly conductive nanoporous gold,
allowing easy and efficient access of both electrons and ions so as to afford a fast
redox reaction at high scan rates as well as good cyclic stability. The power and
energy densities of the hybrid structure increase with the loading rate of MnO2 and
reach maximum of 57 Wh/kg and 16 kW/kg, respectively, with the MnO2 plating
time of 20 min. The high specific capacitances, charge/discharge rates, and good
cyclic stability offered by this hybrid structure make them promising electrodes
materials in supercapacitors.

4.2.1 GrapheneMetal Oxide Nanocomposites

As the graphene nanosheets have vast surface area with excellent conductivity, it
will be an appropriate candidate to accommodate a large amount of metal oxides.
In addition, the EDLC behavior of the graphene nanosheets can also be enhanced,
which contributes to the total capacitance of the resulting composite. Recently,
graphenemetal oxide nanocomposite systems have been developed by various researchers, and high specific capacitances with good cycling performance have been
reported (Zhang et al. 2009, 2010; Huang et al. 2012; Simon and Gogotsi 2008).
Also, layered double hydroxides (LDH) materials containing transition metals have
been reported to be promising electrode materials for supercapacitors because of
their relatively low cost, high redox activity, and environmentally friendly nature.
Gao et al. reported the preparation of graphene Ni/Al layered double hydroxide
(LDH) nanocomposite and a maximum specific capacitance of 781.5 F/g with an
excellent cycle life (Gao et al. 2011). The observed capacitance is almost 1.5 times
higher than that of the pure LDH electrodes. The larger capacitance for GNS/LDH
may be caused by the combination of electric double-layer capacitance and Faradic
pseudocapacitance. At the same time, the open structure system of GNS/LDH
improves the contact between the electrode materials and the electrolyte and thus
makes full use of the electrochemical active material contribution to the overall

1168

M.K. Devaraju et al.

capacitance. Development of suitable GNSmetal oxide or LDH nanocomposites

with appropriate ratio will lead to high capacitance owing to the combination of
EDLC and pseudocapacitance from GNS and metal oxide or LDH, respectively.

4.2.2 GraphenePolymer Nanocomposites

To exploit the potential of the graphene-based materials for the supercapacitor
applications, graphene-conducting polymer nanocomposite was prepared by several
preparation route, and electrochemical capacitance was reported in the range of
233  500 F/g (Zhang et al. 2009). However, the capacitance was mainly dominated
by the pseudocapacitance from the polymer films coated on the graphene paper
surface, and the EDLC from the graphene sheet was less utilized due to the agglomerated layer-like structure in the graphene paper. Among the conductive polymers,
carbon (or) graphenePANI composites have been extensively studied and well
documented in the literature for supercapacitor applications (Zhang et al. 2010;
Huang et al. 2012). And flexible nanoelectrodes also have been developed using
carbon nanotube/PANI or graphene/PANI nanocomposites for the supercapacitors
applications (Meng et al. 2010).
Typically, in all these studies, the aniline polymerization on the graphene surface
was carried out using oxidants such as ammonium persulfate ((NH4 /2 S2 O8 ) or
ferric chloride (FeCl3 ), and the experimental strategy plays a vital role on the
morphology of the graphene/PANI composite and their electrochemical response.
Recently, preparation of graphenepolyaniline nanocomposite electrodes via oxidative polymerization of aniline by MnO2 was shown. And a superior supercapacitive
performance (641 F/g, 1540 % enhancement than the reported capacitance for
graphenepolyaniline) has been observed (Sathish et al. 2011). As mentioned
earlier, the method of polymerization plays a vital role on the materials property.
GO/MnO2 composite was prepared (Sathish et al.) by mixing appropriate amount
of MnO2 nanosheets and GO nanosheets. Then, appropriate amount of aniline
was added to the above composite, and the chemical oxidation polymerization of
aniline was initiated by the reduction of Mn4C ion, and the resulting Mn2C ions
will go to the solution. This process enables the formation of slow and uniform
polyaniline nanofibers on the graphene surface with significant porosity, which
enables the impulsive peculation of electrolyte to access large surface area (authors
unpublished work). Thus, the graphene surface also has been used for EDLC
in addition to the pseudocapacitance from polyaniline. Figure 59.13 shows the
schematic representation of the polyaniline formation on the graphene sheets.
Similarly, Xu et al. (2010) introduced a facile method to construct the hierarchical
nanocomposites by combining the one-dimensional (1D) conducting polyaniline
(PANI) nanowires with the 2D graphene oxide (GO) nanosheets. It is shown
that the aniline concentration plays a key role on the PANI morphology, at
lower concentration (0.05 M); vertically aligned PANI nanowire arrays on GO
surface are observed owing to the heterogeneous nucleation on the GO nanosheets
(Fig. 59.14a). When aniline concentration was increased to 0.06M, homogeneous nucleation will take place after the initial nucleation on the solid surface.

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1169

MnO2 nanosheets

Mn4+
Graphene oxide

GO-MnO2

Mn2+
(i) Aniline

GO-PANI

Fig. 59.13 Schematic representation of polyaniline formation on graphene surface via oxidative
polymerization of aniline by MnO2 (Reproduced with permission from (From authors work))

Consequently, random connected PANI nanowires were produced (Fig. 59.14b).

The hierarchical nanocomposite structures of PANI/GO were further proved by the
UV-vis, FTIR, and XRD measurements. The hierarchical nanocomposite possessed
higher electrochemical capacitance of 555 F/g at a discharge current density of
0.2 A/g and better stability than each individual component as the supercapacitor
electrode materials, showing a synergistic effect of PANI and GO. Also, the
observed specific capacitance of the nanocomposite is much higher than that of the
random connected PANI nanowires (298 F/g) obtained under the same condition.
This study will further guide the preparation of functional nanocomposites by
combining different dimensional nanomaterials.

4.3

Asymmetric (or) Hybrid Capacitors

Asymmetric or hybrid systems offer an attractive alternative to the

conventional pseudocapacitance or EDLCs by combining a battery-like electrode
(energy source) with a capacitor-like electrode (power source) in the same cell
(Simon and Gogotsi 2008). The high specific capacitances, cell voltage, and
charge/discharge rates offered by such hybrid structures make them promising
candidates as the electrodes in supercapacitors. MnO2 graphene composite electrodes have been developed for the high-voltage hybrid electrochemical capacitor
based on graphene as the negative electrode and MnO2 graphene composite
as the positive electrode in the neutral aqueous Na2 SO4 solution as electrolyte

1170

M.K. Devaraju et al.

Aniline
Aniline anion
GO sheet

b
Nucleation

Growth

Growth further

Fig. 59.14 Schematic illustration of nucleation and growth mechanism of PANI nanowires:
(a) heterogeneous nucleation on GO nanosheets; (b) homogeneous nucleation in bulk solution
(Reproduced with permission from Xu (2010))

0.5

0.3

Current Density (A g1)

Current Density (A g1)

0.4
0.2
0.1
0.0
0.1
0.2
0.3
0.4
0.5

0.5

1.0
Voltage (V)

1.5

2.0

1
0
1
2
3

0.0

1.0 0.8 0.6 0.4 0.2 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V vs. SCE)

Fig. 59.15 Schematic representation of polyaniline formation on graphene surface via oxidative
polymerization of aniline by MnO2 (Reproduced with permission from Wu et al. (2010))

59 Advanced Energy Devices: Lithium Ion Battery and High Energy Capacitor

1171

Fig. 59.16 Schematic illustration of two key steps for preparing hybrid graphene/MnO2 nanostructured textiles as high-performance EC electrodes. (i) Conformal coating of solutionexfoliated graphene nanosheets (gray color) onto textile fibers. (ii) Controlled electrodeposition
of MnO2 nanoparticles (yellow dots) on graphene-wrapped textile fibers (Reproduced with
permission from Yu et al. 2011)

(Wu et al. 2010). These ECs can be cycled reversibly in the high voltage region of
02.0 V (Fig. 59.15a). The resulting energy density of 30.4 Wh/kg is much higher
than those of the symmetric ECs based on graphene//graphene (2.8 Wh/kg)
(Fig. 59.15b) and MnO2 graphene//MnO2graphene (5.2 Wh/kg) (Fig. 59.15c) and
higher than those of other MnO2 -based asymmetric ECs. These findings open
up the possibility of the graphene-based composites for applications in safe
aqueous electrolyte-based high-voltage hybrids systems with high energy and power
densities.
Yu et al. (2011) demonstrated the solution-processed graphene/MnO2 nanostructured textiles for the high-performance electrochemical capacitors applications.
In their study, solution-exfoliated graphene nanosheets (5 nm thickness) were
conformably coated on the three-dimensional, porous textiles support structures,
and pseudocapacitive MnO2 nanomaterials was deposited by the controlled electrodeposition (Fig. 59.16). This technique offers high loading of active electrode
materials and facilitates the easy access of electrolytes to those materials. The hybrid
graphene/MnO2-based textile yields high-capacitance performance with specific
capacitance up to 315 F/g. Also, they have fabricated asymmetric electrochemical
capacitors with the graphene/MnO2-textile as the positive electrode and singlewalled carbon nanotubes (SWNTs)-textile as the negative electrode in an aqueous
Na2 SO4 electrolyte solution. These devices exhibit promising characteristics with
a maximum power density of 110 kW/kg, an energy density of 12.5 Wh/kg, and
excellent cycling performance of 95 % capacitance retention over 5,000 cycles.
These kinds of low-cost, high-performance energy textiles-based nanostructures
offer great promise to realize the future large-scale energy storage devices.

1172

M.K. Devaraju et al.

Conclusions

In conclusion, this chapter began with the brief introduction of the advanced energy
devices such as lithium-ion batteries and high energy capacitors. The importance of
the positive electrode materials and their synthesis by the solution process including
the hydrothermal and solvothermal method were discussed. These methods are
popularly used for the preparation of various inorganic materials owing to their
advantages such as size-controlled synthesis, morphology-controlled synthesis,
safety, easy synthesis, environmentally benign, and cost-effectiveness.
Among the lithium-ion batteries, cathodes are essential parts of the batteries.
The olivine-structured lithium metal phosphates are very much attractive due to
their cheap, environmentally friendly, and high theoretical capacity. The carbon
coating of lithium metal phosphates using different carbon sources via in situ or
ex-situ coating techniques has been discussed. The electrochemical property depended on the morphology of LiFePO4 and LiMnPO4 cathodes has been discussed.
Most of the LiFePO4 nanomaterials less than 100250 nm in diameter exhibited
the discharge capacity close to the theoretical capacity (170 mAhg1 ). Thin plate
and rod morphology provides short diffusion length for the LiC -ion insertion and
exertion process. The discharge capacity of LiMnPO4 is not very impressive due
to its low intrinsic conductivity. New strategy development could improve the
electrochemical property of LiMnPO4 for commercial purpose.
In the electrochemical capacitors, graphene-based compounds such as metal
oxide-doped graphene and PANI/graphene showed excellent capacitance when
compared to the other capacitors. In addition, asymmetric hybrid capacitors are
promising with higher capacitance for various powder density electric and electronic
devices. Further, continuous study of graphene could enable to understand its
physicochemical property for the electrochemical applications. New breakthrough
in these fields can change the performance of the energy devices and thus can make
human life more comfortable.

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