Review
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Structure Design and Composition Engineering
of Carbon-Based Nanomaterials for Lithium Energy
Storage
Hongya Geng, Yan Peng, Liangti Qu,* Haijiao Zhang,* and Minghong Wu*
Carbon-based nanomaterials have significantly pushed the boundary
of electrochemical performance of lithium-based batteries (LBs) thanks
to their excellent conductivity, high specific surface area, controllable
morphology, and intrinsic stability. Complementary to these inherent
properties, various synthetic techniques have been adopted to prepare
carbon-based nanomaterials with diverse structures and different
dimensionalities including 1D nanotubes and nanorods, 2D nanosheets
and films, and 3D hierarchical architectures, which have been extensively
applied as high-performance electrode materials for energy storage
and conversion. The present review aims to outline the structural
design and composition engineering of carbon-based nanomaterials
as high-performance electrodes of LBs including lithium-ion batteries,
lithium–sulfur batteries, and lithium–oxygen batteries. This review
mainly focuses on the boosting of electrochemical performance of
LBs by rational dimensional design and porous tailoring of advanced
carbon-based nanomaterials. Particular attention is also paid to
integrating active materials into the carbon-based nanomaterials, and
the structure–performance relationship is also systematically discussed.
The developmental trends and critical challenges in related fields are
summarized, which may inspire more ideas for the design of advanced
carbon-based nanostructures with superior properties.
Dr. H. Y. Geng, Prof. H. J. Zhang
Institute of Nanochemistry and Nanobiology
Shanghai University
Shanghai 200444, P. R. China
E-mail: hjzhang128@shu.edu.cn
Dr. H. Y. Geng, Prof. L. T. Qu
Department of Chemistry
Tsinghua University
Beijing 100084, P. R. China
E-mail: lqu@mail.tsinghua.edu.cn
Prof. Y. Peng
Institute of USV Engineering
Shanghai University
Shanghai 200444, P. R. China
Prof. M. H. Wu
School of Environmental and Chemical Engineering
Shanghai University
Shanghai 200444, P. R. China
E-mail: mhwu@shu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201903030.
DOI: 10.1002/aenm.201903030
Adv. Energy Mater. 2020, 1903030 1903030  (1 of 34)
1. Introduction
Currently, lithium-based batteries (LBs)
represent one of the most promising
energy storage devices due to their high
theoretical capacity (3860 mAh g−1 with a
lithium metal electrode,) and low negative
electrochemical of rechargeable potential
(−3.04 V vs the standard hydrogen
electrode).[1,2] LBs including lithium-ion
batteries (LIBs), lithium–sulfur batteries
(Li–S batteries), and lithium–oxygen
batteries (Li–O2 batteries) are truly revo-
lutionizing our daily life. However, there
are at least three major obstacles before
LBs continue this revolution: 1) Poor
durability caused by the uneven and den-
dritic lithium deposition, decomposition
of unstable solid electrolyte, and uncon-
trollable expansion of electrodes during
charge/discharge processes;[3] 2) Slow
interface charge-transfer kinetics arise
from the uncontrollable reaction of Li+
conductors with electrode materials. Thus,
the enhancement of Li+ conductivity by
substitution within a given structure is
highly desired;[4] 3) LBs are gradually
approaching their theoretical limitations
in terms of energy density, but the gravimetric and volumetric
energy density of commercial LBs are still very low, espe-
cially in some portable devices. Therefore, the exploitation of
alternative electrode materials with a higher lithium storage
capacity, faster interface charge-transfer kinetics, and better
cycling stability are still great challenges for achieving the high-
performance next generation LBs.
The rapid development of electric devices causes the ever-
increasing demands of LBs. Carbon-based nanomaterials have
been considered as the versatile platform for building superior
LBs due to their high electronic/ionic conductivity, diversity,
excellent structural and chemical stability, easy surface/struc-
ture engineering, and tunable mechanical properties. Generally
speaking, the main functions of carbon-based electrode mate-
rials are as follows: 1) Diversified carbon nanostructure can
serve as anodes or cathodes for immobilizing different active
materials like lithium, sulfur, and oxygen; 2) Highly conductive
network can directly determine the electrochemical properties
of LBs by transferring electrons and ions for fast reaction
kinetics, which make sure the connection between internal
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circuitry and external circuit (current collector); 3) Excellent

structural stability can effectively buffer large volume changes Liangti Qu received his Ph.D.
during the insertion/extraction processes of Li-ions, thus in chemistry from Tsinghua
improving the cycling life of electrodes. Furthermore, homoge- University (Beijing, China) in
neously distributed active sites on carbon matrix can also guide 2004. He is now a professor
uniform lithium nucleation/deposition and regulate the growth of chemistry at Tsinghua
of lithium dendrites. University and leads the
It is widely accepted that multidimensionality and multi­ nanocarbon research group.
phase assisted structural design is an accessible way to His research interests in
improve the electrochemical performances for LBs.[5] In the materials chemistry mainly
last decades, 1D, 2D, and 3D carbon-based nanomaterials (i.e., focus on the synthesis,
carbon nanotubes, graphene, and mesoporous carbon, etc.) functionalization, and
have been extensively investigated owing to their excellent application of nanomaterials
electronic, mechanical and chemical properties. Previous work with carbon–carbon conjugated structures, including
has demonstrated that selected dimensionality and precise carbon nanotubes, graphene, and conducting polymers.
assembly can enable high performance in specific applica-
tions. Moreover, the performance of an electrode material not
only depends on the building units but also largely on how Haijiao Zhang received
they are assembled.[6,7] As a result, the integration of elec- her Ph.D. in chemistry
trode materials with one, two, and three dimensionalities have from East China Normal
become a research hotspot for a long time.[8–11] These desired University supervised by
structures show great potential to overcome the shortcomings Professor Mingyuan He.
under various conditions, offering an intelligent way to expand From 2015 to 2016, she was
the boundaries of LBs. Issues surrounding rational structural engaged as a senior visiting
design and composition engineering have promoted robust scholar in The University
and reliable implementation of carbon-based nanomaterials in of Queensland, Australia.
widespread technologies. She is now a professor at
Rationally designed carbon-based nanomaterials can provide Shanghai University in China.
a wide range of possibilities to meet the growing requirements Currently, her main research
of energy storage by improving surface area, adjusting pore interests include the design of nano/mesomaterials and
size, enhancing ionic and electric conductivity, and promoting their applications in new energy and catalysis.
cycling stability.[12] The structural engineering of carbon-based
nanomaterials is also an efficient way to inhibit the growth of
lithium dendrites and facilitate their interface charge-transfer Minghong Wu obtained
kinetics, thus enhancing the electrochemical performances.[13] her Ph.D. from the Chinese
Additionally, engineering of carbon-based materials into a Academy of Science in
given structure or effective combination of several active mate- 1999. After several years
rials can further explore the potential of single material.[14,15] of postdoctoral research
On the other hand, the demand for substantial improvement of in Japan, she became a
energy density motivates a lot of approaches to develop the new professor in 2002 at the
type of batteries such as Li–S batteries and Li–O2 batteries.[16] School of Environmental
Alternatively, in practical applications, Li–S batteries and Li–O2 and Chemical Engineering
batteries have considered as the main next generation energy of Shanghai University
storage systems because of their higher theoretical capacity than in China. Her research
that of LIBs. Li–S batteries and Li–O2 batteries share the same interests mainly focus on
anode, while the different active cathode components (S and O) the preparation of functional nanomaterials and their
necessitate a conducting additive to ensure the electronic and related applications.
ionic conductivity. In this case, carbon-based nanomaterials
have become the mainstream to address the nonconductive and
low reactive nature of sulfur or oxygen.[17,18]
In the operation of Li–S batteries and Li–O2 batteries, peroxide composition (Li2O2).[20] Practical speaking, carbon-
sulfur or oxygen is reduced to form the discharge product based matrixes are widely utilized to accommodate the large
lithium polysulfides (LiPSs) and Li2O2 on the cathode surface volume changes and promote sulfur utilization to ensure the
upon discharge. Subsequently, the reduced products chemi- safety and durability.[21] The carbon-based matrixes can not only
cally decomposed to release Li upon charge. Li–S batteries act as the reservoir for the discharge products and effective
can deliver a significantly higher theoretical energy density polysulfide immobilization, but also provide an interconnected
(2567 Wh kg−1) in comparison to LIBs.[19] On the other hand, conductive framework for facilitating the electron transfer. The
a Li–O2 battery system provides much higher theoretical chemical inertness and easy engineering of carbon is neces-
specific energy of 3623 Wh kg−1 when discharged to the lithium sary for the deposition of a plenty of reachable active sites to

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Scheme 1. An overview of carbon-based nanomaterials with different
dimensionalities and compositions as the LBs electrode materials.
promote the oxygen reduction and oxygen evolution reactions
in case of a Li–O2 battery system.[22]
Herein, we give a comprehensive overview of carbon-based
nanomaterials with engineered structures based on the design
of different dimensionalities and compositions, and further
summarize these newly emerged sophisticated architectures for
recent development of LBs including LIBs, Li–S batteries, and
Li–O2 batteries. This review summarizes current significant
works on carbon-based materials and highlights breakthrough
following the advanced synthesis techniques. Meanwhile,
the general synthetic strategies of carbon-based materials are
systematically outlined such as dimensionality design, porous
tailoring, composite of functional materials, and heteroatom
doping (Scheme  1). The relationship between engineering
structures and improvement of electrochemical performances
are also discussed. Finally, this article provides the outlook and
trends on the further development of carbon-based nanomate-
rials in this research fields.
2. Preparation of Carbon-Based Nanomaterials
In view of structural features and chemical compositions,
carbon-based nanomaterials can be constructed in sev-
eral dimensionalities with nanoparticles, carbon nanotubes
(CNTs), graphene, film, and hierarchical nanostructures as
building units. The flexibility and controllable mechanical
properties of the components make it easy to prepare fiber,
film, sheets, cloth, and monolith, together with their corre-
sponding composites. Notably, previous works have shown
that carbon-based materials exhibit relatively high gravimetric
capacities of 300–1100 mAh g−1 for LBs, which could be fur-
ther improved to 1043–1594 mAh g−1 via chemical modification
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and dimensionally structural design.[23,24] Furthermore, the
facile assembly of individual carbon-based nanomaterial into a
macroscopic and functional integration endows them the high
specific capacity and long durability. Herein, this work will
mainly deal with the unique geometry and various dimensional
assemblies of carbon nanomaterials and their applications in
lithium storage fields.
2.1. Structures Consist of 1D Carbon Nanostructures
The superior mechanical and electrochemical properties make
1D nanostructures attractive for LBs in the form of coaxial and
twisted structures.[25] 1D carbon-based nanomaterials have
large specific surface areas and lathy structures, which can
promote the transmission of Li-ions and accelerate the charge
transfer between electrode and electrolyte.[26] Significantly, 1D
carbon-based materials are suitable for flexible energy storage
devices. A wide range of 1D carbon nanostructures with precise
structure design and ingenious hybridization, including CNTs,
carbon fibers (CFs), graphene fibers, has shown great advan-
tages as electrode materials.[27] Benefiting from the conducting
and flexible networks of 1D carbon nanostructure, high areal
capacity and effective suppression of electrode volume variation
have been successfully realized.
2.1.1. Carbon Nanotubes
CNTs with high aspect ratio and superior conductivity have
great potential as the conductive matrix for energy storage
devices.[28,29] CNTs are a type of quantum wire, showing
ballistic electron transport without scattering.[30,31] It can be
mainly divided into two categories including metallic nanotube
and semiconducting nanotube. The former conducts electricity
in the same way as gold or aluminum, while the conductivity
of semiconducting nanotube is tunable similar to silicon.
Slight change of diameter and wrapping angle can shift the
conductivity from metallic state to semiconducting state. The
sp2 hybridized CC bond accelerates the electron transfer.[32]
The resistivity in the individual single-walled CNTs (SWNTs)
can be as low as 10−6  Ω cm−1, which far exceeds conventional
conductive metal.[33] The maximum current density measured
experimentally in individual SWNTs at room temperature
amounts to 109–1010 A cm−2, which is much higher than
the critical current density of superconductors. Apart from
the unique electrical properties, CNTs have an excellent
mechanical performance. The measured tensile moduli reach
about 0.3–0.95 TPa, while the value of tensile strengths is
≈10–100 GPa. At a constant piezo bias of 2.3 V, SWNTs show a
tensile elongation of 280%.[34] Embedding CNTs in the polymer
or epoxy matrix, the modulus and strength under uniform
compression are even higher because of the increased particle–
particle and particle–fluid interaction, resulting from the orien-
tation effect of CNTs.[35]
CNTs are generally used as regulator rather than active
lithium storage materials owing to the large change in
voltage during discharge. Consequently, CNTs serve to
modify the lithium storage behavior and increase the range of
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Figure 1.  A) Two-step control of the chirality of SWNTs in ethanol CVD. Reproduced with permission.[36] Copyright 2014, Nature Publishing Group.
B) Preparation of the W-Co nanocrystal catalyst and the templated growth of a SWNT with specified (n,m). C,D) Atomic force microscopy (AFM) and
transmission electron microscopy (TEM) images of CNTs corresponds to (A). E) SEM image of CNTs. Reproduced with permission[38] Copyright 2017,
Nature Publishing Group.
applications owing to their outstanding mechanical properties.
The assembling CNTs with continuous structure and perco-
lating electron-/ion-transport are helpful to achieve optimized
reaction kinetics and high active materials utilization. In this
regard, integrating the active materials with CNTs tends to
form a robust network for fast charge transport with a relative
shorter lithium diffusion length and moderate the large volume
expansion upon cycles.
However, the large-scale preparation of CNTs under a mild
condition is a long-standing issue. Some methods have been
developed such as laser ablation, arc discharge, and chemical
vapor deposition (CVD). The growth mechanism involves
the selective dissociation of the hydrocarbon precursors and
the sequential rearrangement of carbon atoms into a desired
nanotube structure. The preparation of CNTs can be thermo­
dynamically controlled by employing different catalysts.
External factors including temperature and gas environment
can also affect the growth rate of CNTs. Taking symmetry effect
into account, SWNTs with low formation energy and high
symmetry (Figure  1A) can be yielded based on the symmetry
match between CNTs and catalysts.[36] The symmetry matching
has been confirmed by the appearance of a tungsten carbide
catalyst at the end of each tube (Figure 1C). Similarly, due to
the compatibility with CNTs, graphene can also be an ideal
substrate for the growth of CNTs.[37] The length of CNTs can
be determined by controlling the kinetic growth rates, where
a slower growth rate shortens the lifetime of catalysts, thus
forming the nanotubes with shorter length. On the other hand,
for kinetics favored growth, when enough carbon fragments are
presented, CNTs can grow at the fastest rate for a given dia­
meter and chirality assignment (Figure 1D). For solid catalyst,
crystal symmetry should be taken into account instead of struc-
ture matching when considering the stable existence of CNTs.
Perfect symmetry matching leads to low formation energy and
then high populations of CNTs. Yang et al. used tungsten-based
alloys (W6Co7) with specific structure to direct the growth of
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SWNTs via CVD (Figure 1B).[38] Tungsten-based clusters form
under moderate conditions with specific structural features
directed the structure-specific growth of SWNTs (Figure 1E).
Despite great advancements have been achieved in the syn-
thesis of CNTs through CVD, the harsh synthetic conditions,
high cost, and large energy dissipation seriously hamper
the large-scale production.[39] Furthermore, the purification
steps are necessary for the separation of around 5–50 species
in many preparation methods.[40] Fortunately, metal-organic
frameworks (MOFs) have been conducted to prepare CNTs by
varying the metal ions/clusters and organic likers without sepa-
ration procedure. Meng et al. developed a high yield strategy
for oriented formation of CNTs from MOFs at relatively low
temperature (430 °C) (Figure  2A).[41] The broken coordination
bonds between metal ions and organic ligands resulted in the
formation of metal ions and gas (NH3 and H2). After pyrolysis,
nanocatalysts emerged on the surface of zeolitic imidazolate
frameworks-67 (ZIF-67) dodecahedra, promoting the formation
of CNTs from inside to outside similar to the aforementioned
CVD method. The as-prepared CNTs possessed a high surface
area, controlled nitrogen dopants, hierarchical pores and
stable frameworks, which has outer diameters ranging from
10 to 20 nm and inner diameters of ≈5 nm with a multiwalled
feature (Figure 2B–D).
CNTs follow a line-to-point conducting mode, which can
pick up long-distance transport of electrons. The classic 1D
structure endows exclusive superiority in construction of an
effective conducting network with active materials.[42] As a
host material, the capillary filling of active materials in CNTs
leaves CNT–CNT electrical pathways unimpeded.[43] The self-
weaving behavior of CNTs to construct an interwoven conduc-
tive network allows fast transfer of electrons.[44] A good example
is a low-density CNTs foam with high areal loading and areal
capacity sulfur cathodes prepared via freeze-drying.[45] Vapor-
phase capillary infiltration of sulfur into this CNTs foam leads
to a mass loading of 79%, showing a high sulfur areal loading
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www.advancedsciencenews.com
Figure 2.  A) Synthesis of N-doped CNT-assembled hollow dodecahedra from zeolitic imidazolate frameworks (ZIF-67). B) SEM image of fresh ZIF-67.
C,D) TEM and HRTEM images of N-CNT-assembled hollow dodecahedra. Reproduced with permission.[41] Copyright 2017, American Chemical Society.
of 19.1 mg cm−2, and high areal capacity of 19.3 mAh cm−2. In
this case, CNTs can promote the electrons transfer, accommo-
date the volume expansion of electrodes and trap polysulfide
species, and sulfur species precipitated on the outer and inside
surface of CNTs can rapidly diffuse into the electrolyte, leading
to a superior electrochemical performance. Another example
is a 3D graphene nanosheet–CNT matrix prepared through
one-pot pyrolysis process.[46] The rapid charge transfer and
favorable electrolyte infiltration endowed this novel structure
an initial discharge capacity of 1164.5 mAh g−1 and remained a
large capacity of 891.5 mAh g−1 after 200 cycles at 1 C.
Achieving close to theoretical performance of LBs is an
ongoing challenge. Apart from the abovementioned electrons/
ions transport in electrodes, electrochemical performances are
largely dominated by the electron resistance. However, severe
volume changes upon charge/discharge processes usually
lead to the pulverization of the electrodes, thus exacerbating
electrode resistance.[47] Whereas typical electrode comprises
metal foil substrate and polymeric binder have been developed,
discontinuities in electron pathways and blockage of ion trans-
port passages can impede electrons/ions movement. CNTs with
highly electrical conductive functionalities have been suggested
to address these problems.[48,49] A CNT network has demon-
strated high-rate capability without sacrificing performance.
CNTs web electrodes comprising magnetite spheres offer a
proper proof for this perspective.[45] This freestanding CNTs
web displayed high mechanical strength and long-range con-
ducting networks (25 S cm−1). When the voltage was below
1.0 V, the intercalation/deintercalation of Li ions may arise.[47]
CNTs tend to undergo non-Faradaic reaction at their interface
and behave as electrochemically active materials, boosting
the battery capacity. This attribute was directly reflected in
increased electrode capacity (1031 vs 944 mAh g−1 of Cu foil
electrode). In addition, CNTs web electrode with improved elec-
trochemistry exhibited polarization values that are noticeably
lower. Thus, the effect of Ohmic polarization of CNTs becomes
negligible, resulting in a lower Tafel slope, suggesting an
improved kinetics.
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2.1.2. Carbon Nanofibers
The definition of CFs is fibers of at least 92% of carbon
made from polymeric precursor or carbon allotrope building
blocks.[50] CFs have high tensile strengths of up to 7 GPa with
superior creep resistance, low density (ρ  = 1.75–2.00 g cm−3),
and high moduli up to 900 GPa. Attribute to the intrinsic cova-
lent connection of sp2 carbon atoms, CFs using graphene as the
building blocks have extremely high mechanical strength, up to
130 GPa tensile strength and 1.1 TPa elastic modulus.[51] Since
the first report on graphene fiber in 2011,[52] the development
of carbon-based fibers has attracted more and more attention
in constructing high-strength, low-weight structural materials
in a wide range of fields. The loose conducting network of CFs
promises high utilization and sufficient loading of active mate-
rials. These substrates serve as linear backbones and current
collectors for deposition of active materials. The porous struc-
ture provides short pathways to facilitate rapid electrons/ions
transport, reducing the local current density. CFs are chemically
stable resistant to most of chemical species. The flexible and
sturdier network of CFs can effectively buffer the large volume
expansion during deep cycles. CFs with large surface area can
depress the volume variation of LBs anodes with free-dendrite
morphology. Moreover, the high conductivity allows metallic
lithium to deposit onto the surface of the network and lowers
the impedance of the electrode. Thus, the favorable resistance
to chemicals and harsh environments renders CFs a desirable
component for LBs.
Recently, it has been demonstrated that a variety of precur-
sors, such as poly(acrylonitrile),[53] pitch,[54] natural cellulose,[55]
lignin,[56] poly(ethylene oxide),[57] poly(ethylene glycol)-block-
poly(propylene glyco)-block-poly(ethylene glycol) (F127)[58] and
poly (styrene)-block-poly (butadiene)-block-poly (methylmeth-
acrylate) triblock copolymer[59] can be used for fabricating long
and continuous CFs by electrospinning, melt-spinning, and
wet-spinning techniques. The diameters of the formed CFs
can be adjusted from tens of nanometers to several micro­
meters with tunable surface area and porosity.[60] Generally, the
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preparation of CFs undergoes several steps including the cycli-
zation reaction of precursors, and subsequent heat treatment.
In this regard, the precursor is first oxidized at the temperature
range of 200–300 °C. After that, the fibers are further carbon-
ized at higher temperature about 1200—1600 °C in an inert
atmosphere. Finally, the fibers are graphitized at up to 3000 °C
to improve the ordering and orientation of the basal planes in
the direction of the fiber axis.
New fibers with enhanced conductivity and higher active
materials loading efficiency have been untiringly pursued by
material scientists. In recent years, the fabrication of fibers
constructed by CNTs has appealed tremendous attention
by integrating their unique properties of CNTs into a useful,
macro­scopic ensemble for LBs electrodes.[63,64] Compared with
other fibers (e.g., metal wire and polymer wire), the aligned
structure of CNTs fibers exhibits high conductivity, good flexi­
bility, and stability. For instance, Peng et al. prepared aligned
CNTs fibers containing MWCNTs with diameter of ≈10 nm
through CVD, followed a twisting treatment.[61] The fiber was
≈30 µm in diameter (Figure 3A,B) with a high conductivity level
of 102–103 S cm−1. The stretchable and flexible LIBs exhibit
boosted electrochemical properties (Figure 3C–E).[62] The
spring-like CFs consist of twisted aligned multiwalled CNTs,
exhibiting high stretchability and elongation of over 300%
(Figure 3F–H).
Along with CNTs, graphene as the most representative
2D materials with long-range order up to millimeter scale is
possibly perfect building blocks for formation of new type of
CFs. In contrast to conventional CFs, graphene fibers (GFs)
show extreme asymmetry in both its structure and property.
Graphene oxides (GO) with good dispersibility and rich liquid
crystalline behaviors are attractive for generation of CFs. The
most applied method for producing fibers from GO is wet-
spinning process. GO liquid crystal is uniaxially extruded into
a coagulation bath to first form fibers,[65] and phase transition
Figure 3.  A,B) SEM images of a bare aligned MWCNT fiber. Reproduced with permission.[61] Copyright 2014, Wiley-VCH. C–E) SEM images of a
spring-like fiber at different magnifications. F–H) SEM images of a fiber at different strains F: 0%, G: 50%, H: 100%. Reproduced with permission.[62]
Copyright 2014, Wiley-VCH.
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emerge as solvents exchange and evaporating.[66] Finally,
graphene-based GFs are obtained after thermal treatment or
chemical reduction procedure. Wet-spinning method is also
employed to reduce defects and increase interfacial interac-
tion among graphene sheets using phenolic resin as coagu-
lation bath to form phenolic carbon.[67] The phenolic carbon
modified graphene fibers have a tensile strength of 1.45 GPa
after annealing at 1000 °C. The phenolic carbon helps to
enhance the densification of graphene fibers as well as form
new CC bonds, providing longer slipping distance of gra-
phene sheets. By using ionic liquid with organic solvent as
coagulation and functional diamines (phenylenediamine) as
cross-linkers, the tensile strength of graphene fibers can be
further increased to ≈729 MPa.[68] Incorporating graphene into
GF realizes the macroscopic assembly of 2D nanostructure,
which is achievable for large-scale production of graphene.
The integrated macroscopic materials possess remarkable
endurance attributes to 2D graphene nanosheets remedying
the defects of single units.[69] Noteworthy, extrusion with uni-
axial flow forces, GO liquid crystal dopes unifies the random
alignments of GO in 3D space and orient GO nanosheets
along the fiber axis. Proper coagulation baths are necessary
for maintaining the structural integrity by hydrogen bonds
between GO nanosheets or ions crosslinking. For example,
high-performance graphene fibers was made from GO by
wet-drawing liquid crystalline gel in coagulation bath consist
of ethanol/water (1:3 v/v), 5 wt% KOH, 1 wt% CaCl2, 5 wt%
CuSO4.[70] Hoshide et al. integrated TiO2 and rGO into a
macro­scopic fiber via the wet-spinning process.[71] The titania
sheets could be conformally and regularly stacked with rGO.
This novel fiber current collector showed excellent mechanical
properties and superior electrochemical performance due to
the uniform alignment and flexibility of the graphene sheets,
where the capacity retention was 70% after 200 cycles, giving a
high capacity of 100 mAh g1.
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2.1.3. Carbon Composites Consist of 1D Nanostructures
The conventional design of pure carbon materials has a draw-
back of limited capacity owing to the low activity of carbon. In
this case, to improve the overall performance of carbon-based
electrodes, some active components are always added. The
preparation of 1D carbon nanocomposites, such as heteroatom
doping and surface modification, offers a much higher lithium
capacity without pulverization.[72] In practical terms, 1D carbon
structures have always been used as efficient matrix to host
many guests ranging from polymers, nanoparticles, nanowires,
and many other various dimensional materials. Many studies
have demonstrated that 1D carbon composites composed of
metal sulfides/oxides[73] are vital candidates to improve the
energy density and specific capacity of LBs. Nevertheless, three
major constrains remain in hindering these carbon-based 1D
composites. First, the diffusion of electrolyte from carbon
matrix to active materials is relatively slow, which limits the rate
capability of electrodes. Second, significantly low mass loading
of active overconfines the electrode and causes mechanical
problems.[74] Third, the direct nucleation of Li on the top
surface of the network is inevitable on pure carbon-based
materials due to high conductivity. An electrically insulating
surface is usually coated to prevent direct lithium deposition on
the insulating electrolyte-facing surface and to accommodate
lithium deposition inside the spacious voids.[75]
1D carbon-based materials combined with active materials
have been demonstrated to suppress the pulverization of the
electrodes during cycles.[76] However, the reported approaches
undergo disconnectivity between supporters and the loaded
active materials during repeated charge/discharge processes
because of poor interactions, thereby leading to the poor cycling
stability. Additionally, the introduced binding component can be
expected to eventually increase the electrode resistance. Structure
engineering is also an effective route to prevent the electrical
breakdown to some extent. For instance, Lou et al.[77] wired a hier-
archical MoS2 tubular structures with aligned CNTs to enhance
the lithium storage capability. CNTs were first carbonized and
embedded into PAN nanofibers by electrospinning method,
forming a CNT/PAN tube-in-fiber structure. A protective layer of
CoSx was grown to prevent the damage of this structure. Then,
tubular MoS2 structure was formed while simultaneously remove
CoSx and PAN through hydrothermal approach. By virtue of the
tubular structure, the 1D CNT/MoS2 composite exhibits excep-
tional electrochemical performance due to a short diffusion
distance for Li+ and stable 1D tubular structure. Recently, 1D
CNTs were planted on the surface of a N-doped carbon nanosheet
developed from biomass to prevent the stacking of carbon nano-
materials.[78] This system provided sufficient surface area for
holding Li metal, addressing the dendritic Li growth. Benefitting
from the porosity for Li plating, a stable Coulombic efficiency of
average 98.8% was realized after 2000 h.
According to the state of guests in 1D nanostructures, two
strategies have been developed toward versatile guest–host 1D
carbon-based composites: 1) homogenous mixture of 1D carbon
materials with other active materials. This approach increases
contact areas between the electrolyte and electrode buffer the
mechanical stress during Li+ insertion/deintercalation process,
thus improving lithium storage capability. Various active
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materials with high theoretical specific capacities including
transition metal oxides, polymers, semiconductors, and mineral
substance[79–82] have been studied as potential next-generation
electrode materials for LBs; 2) building-block approach, where
1D carbon-based materials are attached with active materials
or doped heteroatoms to form hybridized building blocks.
For instance, posthybridization of CFs with heteroatoms can
significantly enhance the electrochemical performances due
to the intercalation of electron donors and acceptors.[83] Chen
et al. prepared B,O-codoped CNTs derived from covalent
organic framework by in situ organic condensation reaction.[84]
As a result, the doped carbon promoted the chemical absorp-
tion of polysulfides with 68.5% of sulfur absorptivity, giving a
large reversible capacity of 1077 mAh g1 after 200 cycles. As a
typical wet-chemistry method, heterogeneous nucleation and
growth are widely used for preparing 1D carbon composites.
It has been reported that a simple template-directed hydro-
thermal carbonization process can obtain a high nitrogen
doped CNTs.[85] In comparison to heterogeneous nucleation,
common deposition method, such as physical vapor deposition
and atomic layer deposition, is also a useful technique to realize
the uniformity of structures.[86]
Specifically, spinning method and solvent-assisted approach
are usually utilized to prepare homogenous 1D carbon
composites. Various guests including linear and branched
polymers, graphene, metal oxides and nanoparticles have
been introduced into 1D carbon materials through covalent
bonds, Van der Waals’ force and hydrogen bonds, respectively.
For example, Jiang and co-workers reported a Ag-modi­ fied
mesoporous CNTs with Ag-V2O5/polydopamine core–shell nano-
wires as the precursor under inert atmosphere (Figure  4A).[87]
The product demonstrated the tubular nanostructure with a
diameter of 10–20 nm and a length of several micrometers
(Figure 4B,C). The mesopores can allow the diffusion of Li+, and
the in situ decorated Ag nanoparticles cannot only accelerate
electrons transport by improving the electrical conductivity, but
also greatly improve the first Coulombic efficiency.
Figure 4. A) Schematic illustration of the formation of Ag-MCNTs via
self-volatilization methods. B,C) SEM and TEM images of Ag-MCNTs.
Reproduced with permission.[87] Copyright 2016, American Chemical Society.
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
2.2. Carbon-Based Nanomaterials Assembled
with 2D Nanostructures
2.2.1. Graphene
Graphene has garnered extensive attention because of unique
2D structure and superior properties.[88–90] The flexibility, large
surface area, chemical stability, and remarkable conductivity
together endow it the potential to reform the landscape of
LBs.[91] Graphene has been used as both anode and cathode
materials for LBs. A widely accepted way to improve the
performance of LBs is to hybrid graphene with another
component such as metal and metal oxides to enhance electron
transport, reduce the volume change and shorten the transpor-
tation length of Li+.[92] Meanwhile, graphene is also essential
component of advanced LBs, such as ultrasmall, transparent
batteries with complete flexibility and fast charge rate. In
particular, graphene can improve the gravimetric capacity and
energy density when utilized as both cathodes and anodes com-
pared with current graphite owing to its large number of active
sites for Li+ storage, and short Li+ diffusion distance. Assuming
that Li+ adsorbed on both sides of graphene nanosheets to form
Li2C6, the theoretical specific capacity of graphene amount to
744 mAh g−1.[93] Compared with graphite, graphene shows
faster Li-ions diffusion and lower resistance at the interface of
electrode/electrolyte especially at high rates. For instance, Fu
et al. reported all-component 3D printed graphene-based LIBs,
exhibiting stable cycling performance with specific capacities
of 160 mAh g−1.[94] Another remarkable finding is given by a
3D graphene foam and rGO hybrid nest hierarchical foam
network. It served as the current collector to anchor sulfur, real-
izing a high sulfur loading of 14.4 mg cm−2 and sulfur content
of 89.4%. The resulted cathode delivered a reversible capacity as
high as 846 mAh g−1 at 0.05 C after 90 cycles.[95]
Graphene can also be used as a substrate for the growth of
anode/cathode nanomaterials to achieve high-performance
electrodes with respect to insulating materials.[96] For
instance, by entrapping sulfur into hierarchical graphene, the
resulting electrode exhibits high discharging capacitance of
1068 mAh g−1 and 543 mAh g−1 at current density of 0.5 and
10 C, respectively.[17] The mainly decorated epoxy and hydroxyl
Figure 5.  A) Schematic illustration for the synthesis of double-layer template graphene. Mesoporous MgAl nanoflakes were employed as the hard
template to cast graphene. Subsequently, double-layered graphene was produced by etching the nanoflakes. B,C) HRTEM images of graphene nanosheets
cast onto the MgAl-layered double oxide flakes. Scale bars are 10 nm. Reproduced with permission.[97] Copyright 2016, Nature Publishing Group.
Adv. Energy Mater. 2020, 1903030 1903030  (8 of 34)
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groups enhance the binding of S through CC bonds via
the formed ripples. Such entrapment presents an electronic
conduit for sulfur and a minielectrochemical reaction chamber,
thus improving the utilization of sulfur.
The easy engineering and fabrication of graphene further
expand their applications in LBs. A lot of methods have been
explored to meet different requirements including bottom-up
and top-down strategies. The former is similar to that of CNTs,
including epitaxial growth, CVD, and thermopolymerization of
small molecules. To date, CVD on transition metals, especially
on copper, becomes one of the most useful methods for
synthesis of graphene with large size and good uniformity.[98]
Zhao et al. employed MgAl-layered double oxide flakes as the
hard template to form hydrotalcite-like graphene flakes via
CVD technique (Figure  5). Plenty of mesosized protuberances
in the flakes prevent the π–π stacking of graphene layers. A
high sulfur loading of ≈64 wt% was incorporated into the pro-
tuberances, giving a high reversible capacity of ≈1200 mAh g−1.
However, graphene nanosheets prepared by CVD always
possess a high density of grain boundaries, which can degrade
its electrochemical/mechanical properties. Large-area single-
crystal graphene with low defects are significantly desired. Liu’s
group developed a new growth system using ethane as carbon
source to achieve the large single-crystalline graphene.[99] The
utilization of ethane instead of a conventional methane could
continuously accelerate the growth of graphene via supplying
a large number of methyl radicals. The reduced energy barrier
for the decomposition of ethane deduces the growth tempera-
ture to 750 °C, much lower than previous work. Additionally,
they controlled the interfacial force during a polymer-free clean
transfer procedure to produce large-area and high quality sus-
pended graphene.
Despite the rapid growth of bottom-up method, industrial
level production of graphene is still challenging. Mass pro-
duction of highly conductive graphene sheets represents an
essential step toward the extensive applications of graphene
for LBs.[100] Chemical reduction of GO is the most popular
technique to prepare graphene with high yields. Chemically
reduced GO (rGO) is a low-cost alternative material for lithium
storage.[101] The initial capacity value of rGO reaches as high as
2000 mAh g−1, which is much higher than that of single layer
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graphene owing to the abundant defects.[102] The top-down
route offers a simple and effective strategy to develop reliable,
cost-effective, and facile process for fabrication of aqueous
dispersions of high-quality GO nanosheets. The top-down
procedure includes the mechanical exfoliation of graphite,
oxidation, delamination into GO nanosheets, and subsequent
reduction. The first preparation of exfoliation of graphite is
reported by Brodie in 1859, followed by Staudenmaier method,
using KClO3 and HNO3 to oxidize graphite, respectively.[103]
The most applied Hummers’ method employs concentrated
H2SO4 and KMnO4 to realize sufficient oxidation. The oxida-
tive wet-chemical delamination of graphene from graphite is
widely accepted as the scalable production method. The per-
formance of the as-prepared graphene varies between 100 and
1000 mAh g−1 when used as electrodes for LIBs, depending
especially on the structural design, electrode processing, mass
loading, and the way to assemble graphene sheets. Seiler et al.
found that only well-ordered, highly crystalline graphite delami-
nates into oxo-functionalized graphene, whereas other graphite
grade reverts back to graphite during hydrolysis.[104] The
electronic oxidation significantly lowered the friction of sul-
furic acid confined between layers, initiating the intercalation
process.
The assembly of 2D graphene derived from top–down
method into hierarchical architectures precisely controlling
porosity, orientation and interaction has been recognized as
promising hosts for active materials. For example, sulfur could
be deposited inside porous rGO architecture to improve the
rate and cycling capacities of Li–S batteries, as reported by Yeon
et al.[105] Benefiting from the open-porous structure, strong
bonding of sulfur and rGO can be reached, enabling the opti-
mization of redox kinetics for high sulfur utilization. Only 0.8%
of capacity decay per cycle was found over 500 cycles.
All the three conventional wet-chemical exfoliation methods
suffer from explosion risk, time-consuming and the release
of hazardous gases. Alternatively, electrochemical process has
Figure 6. A) Schematic illustration of the fabrication of crumpled graphene microflower by thermal annealing at 3000 °C (GmF3000) and the
corresponding local structure. B) SEM image of ultralarge GO. C) SEM image of rGF. D) SEM image of GmF3000-S. E) Corresponding Raman spectra.
Cartoon of a folded edge and channel of three graphene layers. Scale bars: B) 100 µm and C) 3 nm. Reproduced with permission.[109] Copyright 2017,
Wiley-VCH.
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emerged as a green protocol for synthesis of graphene. The
C/O ratio could be simply tuned by controlling electrochem-
ical parameters.[106] For example, Pei et al. developed a water
electrolytic oxidation method, which is over 100 times faster
than the present method.[107] They found that the key point for
efficient synthesis and controlling the chemical properties of
the produced GO nanosheets is the preintercalation of graphite,
which inhibits the anodic electrocatalytic oxygen evolution.
The electrochemical oxidation could be finished within a
few seconds. Tuning the concentration of H2SO4 from 40 to
60 wt%, highly oxidized GO could be obtained (C/O < 2). Below
and above this concentration range, C/O could also be tuned to
achieve higher and lower oxidation degree. After suitable sheet
assembly, graphene could be used in both the positive and
negative electrodes, making the fabrication of an all-graphene
battery realizable.
The performance of graphene-based electrodes can be
optimized when graphene is fabricated into flexible and/or
stretchable battery devices. This engineered structure helps to
accommodate volume changes and retain their function. Zhao
group presented a solution deposition method towards flexible
mesoporous graphene nanosheets by using anodic aluminum
oxide (AAO) as a substrate.[108] A thin layer of graphene
nanosheets formed aligned open macropores of 200–300 nm
along the inner sizes of the AAO pore channels. The ordered
mesopores perpendicular to the graphene layer provided high
surface area for Li+ adsorption and intercalation. The flex-
ible graphene layers with mesopores efficiently inhibited the
volume expansion. As a result, the reversible capacity amounted
to 1040 mAh g−1 and retained at 833 mAh g−1 after 70 cycles.
Actually, the superior electrochemical properties of graphene
can only be achieved in the high quality graphene with defect-
free sheets and high content of single layer.[110] A crumpled
flower-like structure made from high quality graphene is con-
sistent with this concept (Figure 6A). Taking advantages of the
shrinkage and compression of ultralarge GO nanosheets, rapid
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evaporation of droplets during the spray-drying process affords
the flower-like morphology with diameters of 1–6 µm. The
resultant morphology prevents sheet stack. Thermal annealing
at relative high temperature (3000 °C) gains defect-few high
quality graphene. The high annealing temperature and
numerous nanosized channels enhance the mechanical sta-
bility of the flower-like structure (Figure 6B–D). Visual sites of
polygons and atomic vacancy holes restore into the sp2 carbon
hexagonal 2D lattice, resulting in the formation of long-range
crystalline order (Figure 6C,E). Due to the absence of defects
and a low stacking degree, more graphene surfaces could be
fully utilized. Therefore, higher capacity (1020 mAh g−1 at
constant current rates of 0.2 C) and less decay (0.047% decay
cecle−1 at 0.5 C) can be remained.
The specifically fabricated graphene film can also tackle the
infinite relative electrode dimension changes caused by the
formation of dendrite Li, which is one of the biggest hurdle
impeding the practical application of LBs.[74] Graphene-based
materials with high surface areas and proper mechanical
strength are the ideal host candidates for Li storage.[111] The
formed graphene flexible nanostructure predefines the space to
prestore Li+ into the electrode and supplies the Li source.[112]
For most of the carbon-based materials, rGO exhibits the
highest Li affinity, which is critical for realizing uniform molten
Li infusion and a low Li nucleation barrier in battery cycling.[113]
The energy density of rGO-based LBs is much higher than that
of the commercial rechargeable graphite based ones. Lin et al.
fabricated a layered Li–graphene composite film.[114] Metallic
lithium was thermally infused in between graphene sheets.
Significantly enlarged interlayer space could be found after
the spark reaction. Layered graphene offered a stable scaf-
fold for Li stripping/plating based on its affinity with Li. The
rGO layer also provided an electrochemically and mechani-
cally stable artificial interface to stabilize the as-formed SEI.[115]
The Li–graphene layered electrode cells showed stable voltage
profiles over 100 cycles at 1 mA cm−2. When charged to 1 V,
this electrode material archived a capacity of ≈3390 mAh g−1,
which is very close to the theoretical capacity of Li.
2.2.2. Graphene Composites
Although the preparation of pure graphene has made some
progress, commercialization of pure graphene electrodes is
still a long way to go. A large fraction of lithium are irrevers-
ibly consumed during the first lithiation step when graphene
as an anode, leading to a quite low Coulombic efficiency.[116]
After several cycles, graphene layer restacking occurs, lowering
the storage capacity. In most practical applications, issues with
the high cost and poor Coulombic efficiency of graphene-based
anodes are still pendent. All these drawbacks inhibit the substi-
tution of commercially available graphite by graphene.
Complementary to the inherent properties of pure gra-
phene, functionalization or hybridization can substantially
improve the performance of these graphene-based mate-
rials.[119] Graphene-based composites inherit the flexibility
and high conductivity of graphene, which can offer good
tolerance to the volume expansions and enhance electrical
preservation. Currently, many efforts have been made to
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Figure 7.  A) Schematic illustration and digital picture of proposed hybrid
structure of the freestanding paper along with the atomic structure of pyro-
lyzed SiOC particles. Reproduced with permission.[117] Copyright 2016,
Nature Publishing Group. B) Illustration of the graphene-based electrode.
Reproduced with permission.[118] Copyright 2016, Wiley-VCH.
develop graphene-based composites electrodes including
the addition of electroactive materials to provide reversible
alloying, insertion and conversion reactions with Li+.[116,120]
The additive active materials effectively inhibit the restacking
of graphene layers. On the other hand, the large surface area,
high intrinsic conductivity, and favorable mechanical flexibility
of graphene also promote the electrons transmission and
alleviate volume expansions of active materials, generating a
high reversible capacity. David et al. prepared the self-standing
macroscopic silicon oxycarbide (SiOC) glass graphene com-
posite (15 cm × 2.5 cm, Figure  7A).[117] The SiOC particles
were embedded in rGO matrix, generating an open polymer-
like network structure. The unique structure of SiOC and
low weight density (≈2.1 g cm−3) enabled two times higher of
charge/discharge rate than commercial graphite electrode. As
a result, the electrode showed a high first cycle charge capacity
of 702 mAh g−1 at 100 mA g−1, and high efficiency even after
more than 1000 cycles. Additionally, coating some cathode
materials (e.g., Li2S) onto graphene can lower the initial charge
voltage barrier, yielding extended cycling life and high specific
capacity.[121,122] Zhou et al. fabricated B/N-doped rGO hydro-
gels via hydrothermal reaction to adsorb Li2S into anhydrous
ethanol solution (Figure 7B).[118] The absorption ability of the
pores, boron and nitrogen site in graphene was thought to
enhance the interaction with lithium polysulfides. The good
dispersion and strong coupling of Li2S in the interconnected
graphene network improved cycling and rate performances.
Density functional theory calculations demonstrated that the
energy of bidentate adsorption of Li2S on the basal plane of
doped graphene decreased from about 1.11 eV to about 0.4 eV
for charge transfer from Li2S to graphene. The B/N codoping
contributed to higher conductivity and more heteroatom active
sites, showing the boosted electrochemical performance.
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Figure 8.  Mechanism for improving the stability of SiO based on vertical growth of graphene. A) The fast fading of capacity in Si-based anodes is
due to the loss of electrical contact and formation of electrical isolation during cycles because of the pulverization of particles. B) Vertical graphene
encapsulation not only enhances the conductivity but also provides the preserved connections between SiO particles during cycles. C) TEM image of
connected particles of d-SiO@vG. D) Magnified TEM image of the selected area in white box of panel (C). E) HRTEM image of a vertical graphene
sheet with a triangle shape. Insets are the line profiles from the marked boxes, respectively. Reproduced with permission.[128] Copyright 2017, American
Chemical Society.

Graphene nanosheets can provide a stable conducting net-
work for some active materials including Co3O4, Fe2O3, MnO2,
and SnO2, etc.[123–125] Meanwhile, the pulverization and delami-
nation of the decorated active materials can be significantly
suppressed. As a result of the synergy effect, these graphene-
based composites are prone to show a high rate capability, fast
reaction kinetics, and long cycling stability. One example was
an atomic layer-by-layer Co3O4/graphene composite, which
possessed an increased density of states near the Fermi level,
resulting in an accelerated reaction kinetics.[126] Furthermore,
the combination of Co3O4 and graphene greatly improved the
structural integrality and cycling stability. When used as the
anode for LIBs, the electrode delivered a high discharge capacity
of 2014.7 and 1134.4 mAh g−1 at 0.11 and 2.25 C, respectively,
achieving a high capacity retention rate of 92.1% for 2000 cycles
at 2.25 C.
It is the ability of graphene to be interfaced with Li active
redox components including Si, Ti, and transition metal
sulfides/oxides, leading to a faster and more stable diffusion
of Li+.[127] Nonetheless, the practical utilization of this kind
of graphene composites is largely limited considering insuf-
ficient active mass loading and poor capacity retention at
high current densities. Shi et al. reported a graphene-based
SiO particles by vertically growing graphene on the surface
of particles (Figure  8).[128] The vertical graphene encapsulated
SiO (d-SiO@vG) anode provided a stable conducting network
via interconnected vertical graphene, which greatly improved
the cycling stability of SiO, and exhibited a high capacity of
1600 mAh g−1 and a retention up to 93% after 100 cycles at a
high areal mass loading of 1.5 mg cm−2. In our previous work,
the constructed ternary Fe2O3–SnO2/graphene hybrids showed
a high reversible capacity of 1530 mA g−1 at 100 mA g−1 after
200 cycles.[129]
2.2.3. Carbon Films
Carbon films contain graphitization films, amorphous carbon
films, as well as films prepared by modified 1D/2D carbon
nanostructures such as chemically modified graphene, GO,
rGO, arrayed CNTs, and flexible CFs. Carbon films are sug-
gested as an ideal separator with nonpolar nature that facilitates
electron transfer and restrict the diffusion of active materials
like polysulfides.[130] They can be viable option to cater for the

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Figure 9.  A) Injection of CNTs ethanol dispersions spreading onto the surface of water. B) The well-dispersed CNTs film in a loosely compacted state
floats on the surface of water. C) A sponge assisted capillary force driven compression process for a closely packed CNTs film. D) A closely compacted
state of the free-standing 2D CNTs film could be transferred to any other various target substrates. Reproduced with permission.[132] Copyright 2016,
American Chemical Society. E) Schematic representation of the fabrication procedure toward porous CFs, and the corresponding photographs of the
flexible carbon films. Reproduced with permission.[133] Copyright 2016, Wiley-VCH.

bendable and wearable modern gadgets. They can also be readily
fabricated from their dispersions by vacuum-assisted filtration,
evaporation induced self-assembly, electrospray coating, or
wet spinning.[131] Xiao et al. employed a Lamgmuir–Blodgett
technique to fabricate freestanding 2D CNTs network on air/
water interface (Figure 9A–D).[132] CNTs in ethanol dispersions
were rapidly pushed outward as being injected on an air–water
interface due to strong Marangoni forces. A closely compacted
CNTs film was formed when using a porous sponge to siphon
water from one side. The formed CNTs networks could be fur-
ther transferred to specific substrates. Liu et al. developed a
new porous CFs film by a high-temperature pyrolysis of elec-
trospun polyimide (Figure 9E).[133] The synthesis could be easily
scaled up to acquire large-area homogenous carbon films with
outstanding thermal stability and mechanical properties.
In virtue of unique 2D structure and partial restoration of
their conjugated structures, carbon films are of high electrical
and thermal conductivities. The alignment of some active
carbon materials into carbon films is also found to boost their
mechanical and electrical properties.[61,134] Huang et al. fabri-
cated a semitubular carbon film via electrospinning technique,
followed by coating a layer of amorphous carbon. The carbon
coating enabled a fast ions transportation.[135] As can be seen
from Figure 10A–C, the carbon-coated polymer nanofiber film
with less pores offered a good physical protection to Li metals,
demonstrating significantly improved cycling stability. Pan
et al. controlled the coaxial growth of N-doped graphene on the
surface of aligned CNTs by a CVD method (Figure 10D). The
CNT films were stable and lightweight with densities of 0.25
and 0.796 mg cm−2 (Figure 10E). The as-prepared N-doped CNTs
film exhibited high tensile strength of 690 MPa and electrical
conductivity of 410 S cm−1. Owing to the full combination of
CNTs and graphene, the resulting electrode for LIBs displayed
high capacity of 390 mAh g−1. Song et al.[136] developed a coaxial
fiber-type LIBs wrapped with CNTs films, cotton core yarn, and
a nanoweb separator. Compared with cable-type battery, using
CNTs films as a current collector, the battery was more light
and smaller. Due to the high conductivity and flexibility of
CNTs films, this coaxial fiber battery displayed a stable perfor-
mance under bent with a high coulombic efficiency of 95% and
a volumetric energy of 144.82 mWh cm−3.
Carbon films can also serve as a stable artificial SEI layer for
LBs anodes, accommodating the large volume changes of elec-
trodes upon cycling. Carbon film stabilizes Li metal based on
its high mechanical strength and ion transfer ability, offering
an alternative route to protect Li anodes by physically isolating
the reactive Li from electrolytes.[135,137] For instance, carbon
film incorporated Si nanostructure with abundant space can
restrict the growth of the SEI layer, decreasing the charge
transfer resistance and suppressing pulverization of Si.[138] This
obtained Si/C composite manifested the enhanced rate capabil-
ities varying from 1286 to 671 mAh g−1 as the current densities
increased from 0.5 to 10 A g−1, respectively. After 200 cycles, the
capacity remained up to 93.6% at 1 A g−1.

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The doping of heteroatoms including N,

B, S, P, ant F is an important approach to
modify the electrochemical properties of
carbon cloths.[146] Balogun et al. used ther-
mally reduced Fe and Co oxide precursors
to improve the lithium storage capability
of N-doped carbon cloth.[147] The doping of
nitrogen onto edges or defect sites could
improve the electrochemical activity and
conductivity. Furthermore, the employment
of carbon cloth avoided the block of active
sites even in case of potassium ions with
the radius of 0.38 nm. The interconnected
3D porous network together with the reach
oxygen-containing groups also enhanced the
contact between active materials and current
collector.

2.3. 3D Carbon Hierarchical Nanostructures

Figure 10.  A–C) SEM images of 20 nm thick semitubular-carbon-coated electrode. Reproduced
with permission.[135] Copyright 2017, American Chemical Society. D) Schematic illustration Interconnected architectures coupling con-
for synthesis of aligned N-CNT film and structure of an N-CNT. E) Photographs of several ducting networks with enhanced physical
N-CNT films on a tip of asparagus fern and a freestanding N-CNT film. Reproduced with entrapment of active materials are consid-
permission.[136] Copyright 2016, Wiley-VCH. F) Schematic illustration of a) fast kinetics of WS2
ered among the most promising candidates
supported on the CCI (WS2/CCI). Reproduced with permission.[139] Copyright 2017, Wiley-VCH.
to promote the rate performance and energy
density of LBs.[148,149] 3D carbon nanostruc-
2.2.4. Carbon Cloths tures such as carbon monolith, mesoporous carbon, porous
carbon framework and corresponding nanocomposites owing
Another important macroscopic carbon-based nanomaterial to rich open space and exquisite hierarchical architectures, have
is carbon cloth, which is a class of woven textile fabricated by enabled the development of LBs with higher energy density,
carbon fibers oriented in reciprocal chiasma.[140] Among the lower cost, and stable performance.[150,151] It is demonstrated
available flexible electrochemical storage devices, carbon cloths that the structural and interfacial design of 3D carbon nano-
are widely served as current collector because of high conduc- structures can not only establish favorable lithium reservoir
tivity, good corrosion resistance, and adequate flexibility. Carbon but also enable lithium dendrite-free deposition.[152] Hierarchi-
cloths can serve as an artificial protective layer on the surface of cally porous carbon-based structures, which consist of multiple
electrode to avoid the uncontrolled formation of SEI film. It is porosities on different level, have become the first choice for
usually accepted to employ carbon cloth as the host to enlarge desired electrode materials owing to their large surface area and
the contact area and improve the electrochemical/mechanical superior conductive networks. That can shorten the Li+ inser-
properties of the electrodes for flexible devices.[141] Goodenough tion/extraction pathway, facilitate charge across the electrode/
and co-workers utilized carbon cloth connected to the cathode electrolyte interface. The continuous porous structure can also
current collector to support tungsten disulfide (Figure 10F).[139] smooth the diffusion of guest molecules, thereby enhancing
The carbon cloth provided both physical barrier blocking migra- the mass transport. The unique hierarchical architecture with
tion of polysulfide and collector of WS2 particles, allowing fast pores at micro/nanolevels can well accommodate large volume
electron transfer between the cathode current. WS2 was sup- expansion during charge/discharge processes.[153] Moreover,
ported on interlayers of carbon cloth and used as catalyst for the employment of 3D conductive carbon-based matrix for Li
hydrodesulfurization due to its strong adsorption of sulfur and hosting can greatly decrease the local current density, avoiding
sulfides.[142] The electrode with carbon cloth showed the high the formation of Li dendrites.
discharge capacity of 1201 mAh g−1 for 100 cycles. Due to the ordered structure and integration, 3D carbon
Particularly, the electrochemical properties of carbon cloths nanostructures have excellent contact with the building blocks,
are also associated with their crystalline texture, compositions enhancing the performances of lower dimensional structures
and nature of exposed surfaces.[143] Similar to other carbona- such as 1D carbon nanotubes and 2D graphene sheets.[154]
ceous materials, the integration of electrochemically active The transportation of ions and electrons inside 3D structures
materials with carbon cloths is a feasible way to promote electro- should be more smoothly than that in 1D or 2D structures
chemical properties.[144] Recently, Mao et al.[145] fabricated a thin because of the conductivity and porosity. There is no doubt
carbon cloth by combining metal organic framework (MOF) and that 3D structures have a well-controlled and integrated porous
CNTs following a confinement conversion. The formed struc- configuration that can be fully used for supporting active
ture provided the high conductivity and good structural integrity, materials and enhance electrolyte infusion along unique direc-
giving a strong sulfur confinement to achieve a long durability. tions. The intimate contact between framework and current

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collector realize homogeneous Li+ distri-

bution and electrochemical accessibility.
Without any conductive agent or binders,
the uniform pores can provide more space
to buffer large volume changes during
charge/discharge. Consequently, 3D carbon
nanostructures are a promising choice that
can streamline the conversion of lab-based
technologies into practical products.

2.3.1. Carbon Monoliths

Generally speaking, macroscopical (upwards

1 mm3) with continuous walls and 3D
shape can be suitably called as monolith.[155]
Carbon monolith made from graphene,
CNTs, CFs foams or networks possesses solid
nanostructures with nanometer-sized walls
and hierarchically interconnected voids pro-
vides accessible surfaces for the adsorption
and desorption of ions. The wall thickness of
carbon monolith is typically less than 50 nm,
which is highly desirable for anchoring active
materials and shorting ions transferring. The
3D structure without any binder further ben-
efit charge-transfer reaction rates because of Figure 11.  A) Schematic illustration of ice-templating method. Reproduced with permission.[158]
the well-interconnected wall structure with Copyright 2014, American Chemical Society. B–D) Foam-templating method. Reproduced
continuous electronic pathway. Thus, this with permission.[159] Copyright 2015, Elsevier. E–G) Hydrothermal route. Reproduced with
structure has been considered as one of the permission.[160] Copyright 2010, American Chemical Society.
most advanced energy storage media.
3D carbon monoliths are deemed as the excellent materials synthesis, a dispersion of the carbon precursor will be frozen
to improve the electrochemical properties of Li-based cath- under a single temperature gradient by using liquid nitrogen
odes, such as LiMn2O4, Li4Ti5O12, LiFePO4, and LiCoPO4, that as cooling center. Then, the growth of ice causes the entrap-
are the majority of cathode materials used in commercial LIBs. ment of suspended particles in between two cold fingers.
As the most significant cathode materials for LIBs olivine-type Subsequently, multiple ice crystal orientates perpendicularly
LiFeO4, their applications are still restricted by electron trans- along the freezing direction (Figure  11A). After freezing-dry
port kinetics and sluggish. The Li+ only diffuse along [010] and removing the ice template, porous monolith forms.[157]
direction (only from ordered-olivine structure), which leads to As we previously demonstrated that freezing rate is the main
capacity loss and low extraction efficiency. Reducing the size of factor, which could greatly affect the formation of the parallel
Li-based cathode and minimizing diffusion distance are effec- pores.[162] For the case of slow freezing rate (10–100 µm s−1),
tive approach to address this problem. The large surface areas metastability domains in cellular solidification of the sus-
and periodically pore structures of 3D carbon monoliths endow pension. At the slower freezing rate of 0.1–50 µm s−1, phase
the LiFePO4 nanoparticles with controllable size and enhance separation occurs and stratification of suspended particles
electrolyte–electrode contact. These 3D structures smooth forms around solid/liquid interface.
migration of Li+ and electrons around the embedded LiFePO4, Except for ice, many other foam templates including
improving rate capability and cycle stability. For example, Bai Ni-foam[163] and Cu-foam,[158] can be used to prepare carbon
et al. encapsulated LiFePO4 into 3D carbon nanowires network monolith through a thermal-induced in situ carbonization.
as the cathode for LIBs via an evaporative self-assembly This carbonization procedure allows the preparation of all
method.[156] The 3D conductive network connections attributed carbon frameworks, which can provide improved conductivity
to a low electrode polarization and outstanding cycling perfor- and allow in situ chemical decoration of heteroatoms for more
mance. The discharge capacity maintained at 128 mAh g1 after active sites of Li+ storage. As carbon atoms saturate the inner
100 cycles, higher than that of pristine LiFePO4 (62 mAh g ). 1 surface of the hard template at relatively high temperature
Hard- and soft-templating methods are the most efficient (usually above 1000 °C), they form a continuous and tunable
way to prepare 3D carbon monolith. In particular, freeze casting interconnected 3D structure.[164] For example, the deposition
(also referred as ice templating) recently rises as a simple of carbon atoms on the surface of a commercial available Cu
and universal method to fabricate monolith with aligned and filter membrane can be employed to prepare the monolithic
disordered 3D porous network.[161] The ice-templating process quasi-graphene framework (Figure 11B).[159] The as-prepared
is controllable and environmentally friendly. For a typical graphene monolith inherits the honeycomb-like structure of

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Cu foil (Figure 11C). Highly magnified SEM image displayed 2.3.2. Mesoporous Carbon Materials
the interconnected tunnels of the monolith (≈1.5  µm in
dia­
meter). After carbonization process, transparent quasi- In the past two decades, mesoporous carbon materials have
graphene sheets covered on the top of the interconnected attracted increasing attention because of high surface area,
tunnel (Figure 11D) was obtained. Meanwhile, nitrogen atoms large pore volume, tunable pore size, and easy-to-modified
can also be introduced into the carbon framework because of surface.[169,170] According to the definition from International
nitrogen-containing precursor. Union of Pure and Applied Chemistry (IUPAC), porous carbon
Soft templates with polymer colloids, such as polystyrene, materials with pore size distribution in the range of 2–50 nm
poly(methyl methacrylate) and surfactant assemblies have is classified as mesoporous carbon. Thanks to their fascinating
also attracted significant attention as a powerful alternative to properties, mesoporous carbon materials have shown great
form carbon monolith. One potential route is the pyrolysis of potential to solve some crucial problems in LBs.[171] On the one
microporous polymers from high internal phase oil-in-water hand, the unique mesoporous structure can shorten the trans-
or water-in-oil emulsion systems (with an internal phase portation length of electrons and ions and alleviate the huge
volume fraction exceeding 0.74[165] Polymerization of mono- volume expansion during charge/discharge process. On the
mers of rich carbon emerges in the continuous phase whereby other hand, the large surface area can also provide more con-
a small amount of cross-linker. After removal of the droplet tact and active sites for lithium storage, thus increasing the
phase and carbonization of the continuous phase, carbon electrochemical performances. For instance, Yu et al. employed
monolith can be produced. Pore structures can be tuned mesoporous carbon matrix (CMK-3) confined phosphorus (P)
through tuning the diameters of the droplets. For example, to improve both lithium storage and sodium storage perfor-
particulate emulsifiers generally stabilize larger droplets, mances of red P (P@CMK-3) by a vaporization condensation
yielding closed-cell structures. Based on this, Woodward et al. process (Figure  12).[172] The achieved P@CMK-3 electrode
produced an open- and closed-cell carbon monolith from showed a high reversible specific capacity of ≈2250 mAh g−1.
a microporous poly(divinylbenzene) precursor in a simple That is mainly attributed to the incorporation of CMK-3 with
water-in-oil system.[166] They employed both molecular sur- high conductivity and large surface area. Additionally, the
factant (Hypermer 2296) and particulate emulsifiers (silica ordered mesoporous channels of CMK-3 significantly short-
particles) to introduce pore throats during polymerization. ened the transport path of ions and accommodate the volume
A high specific surface area stabilized at 505 m2 g−1 after changes of red P. In contrast, pure P and carbon-coated red
carbonization. P suffered from large volume expansion during cycling. Saikia
Self-assembly based on hydrothermal reactions has also et al. encapsulated LiFePO4 nanoparticles into a 3D ordered
been recognized as one of the most effective strategies for the mesoporous carbon CMK-8 as the LIBs cathode.[173] Nanostruc-
fabrication of carbon monolith. Recent work has demonstrated tured mesoporous carbon downsized the LiFePO4 particles to
the success self-assembly of graphene sheet into complex improve the surface reactivity and reduces the diffusion path of
carbon monolith.[167] We have previously demonstrated that the Li+, and accommodated the volume change upon cycles. There
self-assembly of 2D graphene through a hydrothermal method was no any cracking occurring with the capacity retention of
is an important strategy to produce 3D networks.[159] 3D 96.7% after 1000 cycles. Jiang et al. prepared polyimide derived
graphene network could be easily obtained
by heating a 2 mg mL−1 of GO aqueous dis-
persion at 180 °C for 12 h (Figure 11E,F).
The diameter of the pores ranged from sub-
micrometers to several micrometers with
highly stacked graphene sheets as the walls
(Figure 11G). Very impressive and predomi-
nant elastic 3D monolith formed thanks to
the residual hydrophilic oxygen-containing
groups together with π-π stacking between
graphene sheets and the partial overlapping
of flexible graphene sheets. He et al. used
Pluronic F-127 as the surfactant to prepare
hierarchical nano-Si/N-doped/C/graphene
porous foam.[168] Self-assembly of the proto-
nated melamine through hydrogen bonding
results in the formation of 2D nanosheets,
which were further converted into a porous
network. Benefiting from the unique porous
structure and the good mechanical stability, a
superior cycling stability was obtained with a
Figure 12.  A) Schematic illustration of the preparation process for the P@CMK-3 material.
capacity fading rate of 0.045% per cycle. The B) Schematic illustration of the lithiation/sodiation process of red P particles, red P particles-
capability was remained at 1130 mAh g1 after carbon core–shell composite, and nanostructured red P confined in the channels of CMK-3 in
400 cycles. LIBs and SIBs. Reproduced with permission.[172] Copyright 2016, American Chemical Society.

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www.advancedsciencenews.com
N-doped hierarchical porous carbon spheres by using N-doped
porous carbon nanosheets as scaffold that allowed in-situ
modification of expanded molybdenum disulfide (MoS2).[174]
The continuous 3D porous structure along with the expanded
interlayer spacing offered continuous pathways for transport
of ions and electrons, as well as relieved volume expansion.
The resultant system delivered an excellent energy density of
120 Wh kg−1 after 4000 cycles.
Template-directed technique including soft-templating
and hard-templating routes is wide accepted for preparing
mesoporous carbon materials.[175] For soft-templating strategy,
the formation of mesoporous structures mainly comes from
the assembly of carbon precursors with the help of structure-
directing agents (SDAs), in which the porous structure and
pore size can be well adjusted by tuning the synthetic param-
eters including raw material, pH value, reaction temperature,
and the type of surfactants.[176] Among them, the type of sur-
factants is the most important factor, which directly determines
the porous structure and pore size distribution of the terminal
products. For example, poly(isoprene)-b-poly(ethylene oxide),
polystyrene-b-PEO and poly(ethylene-co-butylene)-b-PEO are
usually utilized to prepare mesoporous carbon with large pores
and rigid carbon frameworks.[177] Tian et al. synthesized a
series of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblocks
with different PS block lengths as the soft templates.[178] The
as-made PS-b-PEO micelles were spherical structure with
narrow size distribution ranging from 14 to 39 nm. PS-b-PEO
copolymers in tetrahydrofuran/ethanol/H2O mixed solutions
coassembled with dopamine through the hydrogen bonding,
followed by polymerization of dopamine, and further forming
the mesoporous carbon with different pore sizes.
Hard-templating approach offers another possibility for
synthesis of mesoporous carbon by taking advantages of
many rigid and specially designed inorganic templates. The
hard-templating preparation of mesoporous carbon generally
involves three steps: 1) preparation of porous template with
desired pore structure and targeted morphology; 2) impregna-
tion of carbon precursor into the pores; 3) after carbonization
and removal of template, mesoporous carbon is obtained, which
can precisely inherit the structure of the used template. Have to
say, nanocasting based on hard templates is the most signifi-
cant technique with high repeatability to prepare mesoporous
carbon with ideal pore size and structure. Recently, Shen
et al. synthesized hierarchical carbon coated vanadium sulfide
mesoporous spheres as anodes by a thermal sulfurization in
H2S atmosphere.[179] Owing to the highly efficient electro/ion
conductivity of carbon, the achieved product displayed a high
reversible capacity of 777 mAh g1 and an excellent rate capacity
of 410 mAh g1 at 4000 mA g1.
In terms of templating method, the carbon precursor should
be well adsorbed onto the surface of the preperformed tem-
plates, ensuring the subsequent polymerization. Considering
the interaction between the template and the monomers or the
initiators, it remains a significant challenge to fully replicate all
hierarchical levels of the templates. Furthermore, the prepara-
tion and etching of the templates make processing onerous
and environmentally unfriendly. More importantly, the parent
template greatly limits the shape and pore size of the resultant
mesoporous carbon. In an alternative way, the template formed
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simultaneously as the carbon source was added into the reac-
tion container, making the procedure more efficient. The key
point is the control of the reaction parameters or the molecular
engineering of monomers to realize the successful construc-
tion of mesoporous structures. Müllen et al. had established
such a facile protocol to prepare monodispersed mesoporous
carbon nanospheres.[180] The self-assembly behavior of colloidal
silica and aniline induced the large surface area and tunable
mesopores in the range of 7 to 42 nm. Khan et al. employed
ordered mesoporous silica as the hard template to produce
ordered mesoporous carbon for supporting LiFePO4.[181] The
volume changes associated with Li+ insertion and extraction
can be accommodated, resulting in a stable rate capability and
good reversibility. A stable discharge capacity of 140.4 mAh g−1
at 0.1 C was obtained after 100 cycles.
The self-assembly strategy discussed above requires further
carbonization and the removal of the template. Besides this,
mesoporous carbon materials can be produced from available
natural biomass through a versatile hydrothermal carbonization
approach at 100–300 °C. In this regard, carbon-rich precursors
are employed to facilitate the in situ hydrolysis and dehydra-
tion, subsequently forming chemically activated mesoporous
carbon.[182] Most biomasses containing abundant atoms can
also obtain in situ doped mesoporous carbon materials upon
carbonization treatment.[183] One successful example is the
utilization of GO nanosheets as the template and catalyst to
carbonize egg proteins via hydrothermal carbonization.[184] N2
adsorption/desorption isotherms appeared a distinct hysteresis
loop, indicating the presence of mesopores.[185] The pore sizes
distributed around 1 and 4 nm. In addition, Jain et al. utilized
ZnCl2 as an activating agent to produce mesoporous carbon
with a high surface area of 1775 m2 g−1 through hydrothermal
carbonization method from biomass.[186] Mesoporous carbon
could also be prepared by directionally carbonization of many
other natural products, for example, wood, which has a unique
anisotropic open channel along the up-growth direction.[187]
2.3.3. Hollow Carbon Spheres
Hollow carbon spheres integrate the advantages of carbon
materials with spherical colloids, endowing the amazing fea-
tures such as low density, large space, regular geometry, and
easy-functionalized inner and outer surfaces. Over the past
decades, explosive growth in the study of hollow carbon sphere
presents great utilitarian value for various applications.[188]
Many synthetic strategies have been presented for preparing
hollow/core–shell carbon spheres, including templating-route,
self-assembly, emulsion polymerization, and modified Stöber
method.[189] Current innovative methodologies allow for con-
trolling the pore orientation, surface area, particle size, and
structural order.
Similar with other porous structures, the hard-templating
technique is widely utilized to prepare hollow carbon spheres.
As shown in Figure 13A, the generation of the cavity is based
on a direct carting and removing process.[190] Currently,
one of the main challenges of the hard-templating method
is the tedious synthesis procedures and low yields. Further
simplifying the process and scaling-up the yields is highly
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capacity of 695 mAh g−1 after 300 cycles

Figure 13.  A) Illustration of the preparation of hollow carbon spheres via template method. bonization and selective removal of silica,
Reproduced with permission.[189] Copyright 2015, Nature Publishing Group. B) TEM image of
resorcinol formaldehyde resin and nickel silicate coated SiO2 with a diameter of about 530 nm. relatively large pore size of 7.5 nm was pro-
C) TEM image of hollow silica nanoparticles coated with Ni nanoparticles and carbon obtained
after carbonization in N2 atmosphere. Reproduced with permission.[191] Copyright 2017,
Wiley-VCH. D,E) TEM and SEM images of triple-shelled Mo-polydopamine hollow spheres. mesoporous carbon spheres could be simply
Reproduced with permission.[192] Copyright 2016, Wiley-VCH.
desirable. Ye et al. employed an in situ thermal reduction and
sulfidation approach to distribute nanosized NiS onto hollow
carbon spheres.[191] This hybrid structure could be obtained by
using uniform SiO2 nanospheres as the sacrificial template,
followed by coating nickel nitrate and resorcinol formaldehyde
resin (Figure 13B). After carbonization, Ni nanoparticles were
incorporated into the outer silica shell. Then, sodium sulfide
was introduced for in situ transformation of Ni to form NiS.
−
Noteworthy, the released OH during the sulfidation process
etched SiO2 cores, granting the formation of hollow spheres
(Figure 13C). Sulfur was further impregnated with a high
sulfur content of ≈72%. The strong chemical coupling between
NiS nanoparticles and hollow carbon spheres greatly enhanced
the charge transfer and the redox kinetics of the sulfur elec-
trode. The resultant hollow carbon sulfur hybrid displayed a
at 0.5 C.
In particular, an in situ generated hard
template method provides another way for
reducing operation procedures. Wang et al.
offered a facile method towards multishelled
hollow MoO2/carbon composites through
adding ammonia into the dispersion of solid
Mo-glycerate (MoG) spheres.[192] The layers
of shells could be tuned from one to four
by adjusting the MoG sizes (Figure 13D,E).
Generally, a multishelled hollow structure
endowed more increment of electrochem-
ical active sites compared with the single-
shelled hollow structure, further improving
the energy density and power density.[193]
The obtained triple-shelled MoO2/C hollow
spheres demonstrated a high reversible
specific capacity of ≈580 mAh g−1 at 0.5 A g−1
after 200 cycles.
Although hard templates have made
significant progress, this strategy requires
effective interaction between carbon precur-
sors and templates, hampering the deep
applications. Recently, Yu et al. reported a
one-pot synthesis of mesoporous carbon
hollow spheres by taking advantage of the
slower hydrolysis of tetrapropyl orthosili-
cate (TPOS) than tetraethyl orthosilicate
(TEOS).[194] The formation of core–shell
structure was attributed to the codeposi-
tion between silica core and the resorcinol-
formaldehyde oligomers at the beginning.
With a long lifespan of TPOS, primarily
formed silica interacted with oligomers
through weak hydrogen bonding. After car-
mesoporous carbon hollow spheres with a
duced. The pore sizes of the as-prepared
tuned by controlling the dynamic nature of
the aggregated silica primary particles. This
strategy paved a new way toward solving the
weak interaction between the core and the shell in case of hard-
templating method.
By contrast, soft-templating presents a simple and facile
procedure.[195,196] Organic surfactants, block copolymers and
emulsion droplets are usually adopted as SDAs for direct
generation of hollow structures via a self-assembly process.
The soft templates can be gently removed in the subsequent
washing or calcination procedure.[197] Zhou et al. produced
Fe/N-doped hollow carbon nanospheres with the assistance
of Triton X-100 as the soft template.[198] Importantly, soft-
templating method also offered an accessible way to fabricate
the asymmetric structure, which can be employed as essen-
tial building blocks for energy storage.[199] Some parameters
such as reaction temperature, pH value, and concentration
were often tuned to prepare particles with uniform shape and

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tunable size distribution.[189] The key to the success for this
method is to find a suitable agent, which can be responsive to
those parameters. For example, sodium oleate can hydrolyze
and produce oleic acid in dilute aqueous solution, then trans-
forming to emulsions as the sacrificial core.[200] That leads to
the formation of an asymmetric flask-like hollow carbonaceous
structure.
Despite the above successful examples of hollow carbon-
based materials, a significant challenge to synthesize monodis-
persed hollow structure through soft-templating still hinders
the practical application. Carbon precursors in the solution are
prone to interact with neighboring particles due to their weak
self-assembly ability. Nevertheless, the relatively simple soft
template strategy is still applicable for the fabrication of various
hollow carbon structures with complex surface functionalities.
3. Lithium Storage Applications
Lithium-ion batteries have been commercially applied in elec-
tric vehicles and portable electrical equipment owing to their
high capacity and good stability.[201,202] Meanwhile, the growing
demand also greatly promotes the rapid development of new
battery systems with higher energy density. Researchers mainly
focus on anode, cathode, separator and electrolyte to pro-
mote the overall performance of LBs. For example, separator
including polymer and ceramic between the positive and nega-
tive electrodes have to be employed and investigated to avoid
electrical short circuits.[203] Structure engineering of anode,
cathode and membrane is also critical to enhance ionic con-
ductivity and suppress the formation of Li dendrites.[204] Apart
from the well-known LIBs, Li–S batteries, and Li-O2 batteries
have gradually drawn much attention due to their unique
advantages in energy storage and conversion. Although signifi-
cant efforts have been made to increase the energy density, the
current LBs cannot meet the increasing requirements for high-
performance energy storage especially in great capability, high-
ratio discharge and absolute security. Therefore, increasing the
energy density and cycling durability is still a huge challenge
for expanding a wider range of commercial applications.
Dimensional design of carbon-based nanomaterials provides
great opportunity to expand the LBs application. 1D, 2D, and
3D carbon-based materials and their macroscopic assembly
including CNTs, CFs, graphene, carbon film, and mesoporous
carbon, have been extensively investigated as high-performance
LBs electrodes. Particularly, carbon-based materials are indis-
pensable in some cases of LBs. For instance, a porous carbon
cathode is necessary for a typical Li–O2 battery for the electrode
reaction to produce Li2O2 at the presence of O2.[205] Similar con-
dition can also be found in Li–S batteries, where carbon-based
materials are used as the cathode to improve the conductivity
of sulfur and trap soluble polysulfides during cycles.[206] In this
section, carbon-based materials used in three kinds of LBs are
systematically discussed.
3.1. Lithium-Ion Batteries
Carbon-based nanomaterials have been the most promising
anode materials for LIBs due to their abundant resource, high
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conductivity, and easy engineering. Carbon-based materials
with proper structure engineering show excellent lithium
storage performances, which could be further enhanced by
integrating various dimensional structures into a single one.
Specifically, carbon-based materials like 1D carbon fiber, 2D
graphene layers and 3D ordered hierarchical porous structures
are rich of long-range ordered structures for providing facile
electron transportation and infiltration. The efficient electrode/
electrolyte interactions thus achieve excellent electrochemical
performance. Component engineering like the introduction of
heteroatoms into carbon-based materials has also been widely
considered to boost their electrochemical properties. Last but
not least, the low density and flexibility of carbon-based nano-
materials allows the establishment of a flexible and arbitrarily
shaped battery with high energy density but low weight.
Based on the above-mentioned advantages, carbon-based
materials, such as graphite and/or graphene-based porous
structures are the most commonly used anode materials for
commercial LIBs. Of all the researches on commercial LIBs
anodes, carbon-based materials are the most successful ones.
The commercial modern LIBs were born based on the graphite
anode and a high voltage metal oxide cathode materials
(LiCoO2). Post commercialization, LIBs were revolutionized
with the cathode mostly unchanged and substantial modifica-
tion of anode and electrolyte. Graphite, hydrogen-containing
carbon and hard carbon are three distinct classes. On the other
hand, considering the variety and easy engineering of carbon-
based materials, the controlling of porosity, structure, and
morpho­logy on the nano/microlevel has attracted more and
more attention to promote the overall performance of LBs.
Current LIBs technologies mostly employ a transition metal
oxide cathode (e.g., LiCoO2, LiFePO4, or LiMn2O4), a graphite
anode, and an organic liquid electrolyte. The anode and cathode
are usually separated by polymer. The performances of both
cathode and anode depend on intercalation/insertion of Li+
during charge/discharge process.[207] For the commercial appli-
cations, graphitic carbon has been predominantly employed
as the choice of anode material. While the cathode is typically
an inorganic material able to intercalate Li+ (e.g., LiCoO2 or
LiFePO4[208]), with achieved energy densities of the order of
≈120–150 Wh kg−1. LIBs have one of the highest specific ener-
gies among rechargeable batteries, but the state-of-the-art
technology based on intercalation mechanism has a theoretical
specific energy of as high as ≈400 Wh kg−1 for both LiCoO2/
graphite and LiFePO4 system.[209]
Several technological challenges including high cost, insuf-
ficient life, and poor safety need to be tackled before grid
applications can occur.[203] One of the biggest problems is that
the stability of the lithium electrode and electrolyte under the
oxygen crossover condition. Substantial difficulties are faced
in the formation of a surface passivation layer (e.g., discharge
products or lithium peroxide), which leads to poor Coulombic
efficiency.[210] The growth of the Li dendrite during charge/
discharge and the fragile SEI also result in the safety problem
of LIBs. A prominent example is the severe capacity fading
caused by the inherently large volumetric expansion, leading
to cracking and pulverization of the Li-alloying anode mate-
rials during deep cycles. Carbon-based materials are the most
accepted electrode for the current research, while pore clogging
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Figure 14. Atomic-resolution cryo-electron microscopy images of Li
metal dendrites growing along the (211) A) and (110) B) directions.
Corresponding SAED pattern showing that the dendrites are single-
crystalline. The red and blue boxes are magnified correspondingly.
Reproduced with permission.[213] Copyright 2017, American Association
for the Advancement of Science (AAAS).
have to be balanced with the need for permeation of reactive
agents. Besides, the mechanism of the whole reaction is not
yet clear, which necessitates the development of practical LIBs.
With the rapid development of science and technology, a lot of
advanced technologies have been used to collect more informa-
tion during battery operation without cell disassembling, post-
treatment and interruption. Especially, some in situ techniques
such as cryo-electron microscopy, atomic force microscopy
(AFM), TEM, synchrotron radiation, X-ray diffraction, Fourier
transform infrared spectroscopy and Raman spectroscopy, etc.,
have shown excellent compatibility with current LBs configu-
ration to consecutively collect information of the intermediate
products during cycles.[211,212]
The growth of the Li dendrite has been schematically studied
by Cui et al.[213] Taking advantage of cryo-electron microscopy,
they revealed that Li metal dendrites begin grow along the
(111), (110) and (211) directions (Figure  14A,B) after the first
electrochemical deposition.
Although graphite is the most commercially applied anode
material for LIBs, its low theoretical capacity (only 372 mAh g−1)
and poor rate capability are holding back the development
of certain high-tech industries such as electric vehicles and
stationary energy storage.[214] Carbon-based materials including
graphite with tunable micro/nanostructure and various compo-
sitions have long been the main anode-active materials in LIBs.
It should be noted that the energy density of LIBs consisting of
cathode-graphite pairs is still considerably high. Impressively,
graphite and silicon composites have emerged with impressive
potential for next-generation LIBs. A prominent example is the
introduction of carbon-based materials circumvent cracking
and pulverization resulted from the inherent volumetric expan-
sion of active materials.[215] New carbon-based materials are
therefore being actively perused for high-performance LIBs.[216]
Furthermore, carbon-based materials with proper design of
dimensionality offer short ions/electrons diffusion length,
improving the reversible capacity.[217]
The flexibility and mechanical stability of 1D carbon-based
materials (CNTs and CF, etc.) presents an ideal platform to
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develop advanced electrodes without Li dendrites. A recent
impressive work firmly consolidated that this point is a 1D
MWCNTs/Cu composite anode, which exhibits high specific
capacities and Coulombic efficiency.[218] Further improvement
of specific capacities and Coulombic efficiency can be real-
ized by adding active materials.[91] Another example is a CF
composite proposed by Zhang et al. They prepared a coralloid
CF-based composite Li anode by electroplating silver particles
onto the surface of CF. Silver nanoparticles could not only
syphon molten Li, but also regulate the nucleation and growth
of Li. A CF/Ag–Li|LiFePO4 cells showed stable properties over
500 cycles at 0.1 C. A large capacity retention rate for Li–S cells
is of 64.3% after 400 cycles at 0.5 C.[219]
However, the transportation, striping, distribution, and
plating reaction of Li ions are impacted heavily by the interfaces.
Cooperation of 2D carbon-based materials in micro/nanostruc-
tured electrodes pave a feasible way for regulating interface
impedance, current density, and lithium nucleation overpoten-
tial. For instance, a two-step synthetic approach was used to
prepare an ultrathin 2D single-layered ordered heteromaterial
composed of mesoporous carbon and MoS2 (Figure 15A,B).[220]
One-layer mesoporous carbon with pore size of 9 nm grew
homogeneously on the surface of nanosheets (Figure 15C).
This formed heterostructure delivered an ultrahigh initial
capacity of ≈2750 mAh g−1 at 100 mA g−1 (Figure 15D), and
stabilized at 1140 mAh g−1 in the following cycles. Even at a
higher current density of 10 A g−1, a reversible capacity of
over 400 mAh g−1 was still maintained. The reversible capaci-
ties of mesoporous-carbon/MoS2 nanosheets (1750 mAh g−1)
were two times higher than that of pure MoS2 (710 mAh g−1).
The abundant mesopores and well-coupled interface provided
direct pathways for the fast diffusion of Li ions. The ultrathin
carbon flexible layers further allowed the stability of the sub-
stantial structure. In contrast, mesoporous carbon inhibited the
restack of MoS2 sheets, leading to a remarkable stability of the
composite electrode (Figure 15E).
2D carbon-based materials with high surface area can
significantly reduce the local current density and thus inhibit
the growth of Li dendrite. The unstacked graphene layers are
able to offer an ultralow local current density, which is five
orders of magnitude lower than that of the bulk counterpart.[221]
The interaction of 2D structures and Li+/Na+ or electrons tends
to shorten the length of diffusion, significantly improving
electrochemical performance of LIBs.[222] This results in a sta-
bilized capacity of higher than 1300 mAh g−1 and a notable
power density of 6500 W kg−1 with excellent cycling stability.[223]
The repeated and continuous carbon backbone also promises
a good transport path for electrons.[224] However, the irrevers-
ible restacking of graphene sheets through π-π stacking usually
induces the loss of active sites for Li storage.[225] The irrevers-
ible aggregation of graphene breaks the connected channels
for Li+ and electrons transportation.[226] As mentioned above,
N-doping is a widely used method to inhibit the restacking of
graphene sheets. Ai et al. presented an in situ fabrication of
N-doped graphene via annealing GO@melamine cyanurate
composite above 410 °C.[227] The decomposition of supramo-
lecular polymer released nitrogen containing gas served as
N source. The gas induced the separation of graphene sheets
from each other. Simultaneously, the removal of thermally labile
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 15.  A) TEM image and B) SEM image of mesoporous carbon/MoS2 nanosheets. C) TEM image of mesopores on the flat plane of heteronanosheets.
D,E) The rate capabilities of mesoporous carbon/MoS2 electrode for LIBs. Reproduced with permission.[220] Copyright 2016, Wiley-VCH.
oxygen functional groups from graphene sheets induced active
sites for in situ N doping. The reversible capacity of N-doped
graphene electrode was 900 mAh g−1 after 150 cycles, that is
almost two times higher than that of graphite. The increase of
capacity upon cycling could be assigned to the electrochemical
activation process, which leads to an improved accessibility
of Li+ into the inner area of the electrode, thus forming more
activated sites for Li storage.[228] The topological defects from
the N doping leaded to outstanding Li accommodation.[229]
Integrating nanoscale metal oxides into 3D structure offers a
promising technique for achieving high-performance electrodes
for LIBs. Jiang et al. developed a spatially confined Ostwald
ripening strategy to synthesize highly flexible 3D graphene/
metal organic framework aerogel.[230] The hierarchical structure
possessed highly interpenetrated conductive network, as well as
abundant buffer space. When used as LIBs anode, it remained
an ultrahigh capacity of 1129 mAh g−1 after 130 cycles and an
outstanding cycling stability with a capacity retention of 98%
after 1200 cycles. Another example of improving the mass
loading is to conjugate N-containing holey-graphene sheets
into a 3D hydrogel through evaporating the trapped water
(Figure 16A–C). The holey structure not only provided efficient
diffusion channels for Li+ and a highly conductive pathway
for electrons, but also provided more edges on the sheets to
enhance Li intercalation. Additive H2O2 and pyrrole were added
to oxidize the carbon atoms and to provide N sources. The
slow evaporation of trapped water in the graphene foam pro-
moted the formation of highly compacted mesopores and an
open microstructure. A high areal capacity of 2.68 mAh cm−2
could be achieved, once the areal mass loading reached to as
high as 2.75 mg cm−2. This highly compact architecture had a
volumetric capacity of 1052 mAh cm−3, which is three times
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higher than that of commercial graphite anodes (Figure 16D).
The N-containing holey-graphene sheets exhibited the best
cycling stability than most of the reported Si-based electrode
without graphene coating (Figure 16E). Vanadium oxide nano-
structures are popular cathode materials in full-cell batteries
due to their various valence states that allow more than one
lithium to insert and extract. However, lithium metal counter/
reference is needed because Li+ is not initially contained in
vanadium oxide. Most studies have focus on prelithiation in
the anode electrode for the sake of the construction of a safe
full cell with vanadium oxide. Son et al. directly grew NiCO2O4
and V2O5 nanowires on oxygen-containing 1D carbon fabrics
through hydrothermal method.[231] In the study, carbon fabrics
with V2O5 and NiCO2O4 were employed as current collector for
both cathode and anode, respectively. Carbon fabrics served as
a SEI film during the prelithiation process that avoids capacity
sacrifice. Under a potential window of 1.5–3.5 V, a capacity of
155 mAh g−1 was achieved, and 75% of the capacity was main-
tained after 500 cycles, showing a good reversibility.
3.2. Li–S Batteries
Considerable progress has been made toward carbon-based
nanomaterials, but fundamental drawbacks of carbon nano-
materials in LIBs still plague their practical applications, espe-
cially the low volumetric capacity due to low packing density
(<0.5 g cm−3) and high interparticle resistance. As a result, Li–S
batteries with high energy density and charge-storage capacity
have been intensively studied in recent years.[232] The concept
of Li–S batteries was established in 1960s even earlier than
LIBs. Li–S batteries usually consist of a lithium metal anode,
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 16.  Schematic of the preparation of N-containing holey-graphene hydrogel (NHGM).
A) First, NHGM was obtained by hydrothermal process. B) NHGH was then shrunk into a rigid
monolith by a drying process. C) NHGM was finally prepared by annealing the above product. commonly known shuttle phenomenon, that
D) Rate capacities of NHGM at different current densities. E) Volumetric capacity of the NHGM
electrode. Reproduced with permission.[231] Copyright 2017, Wiley-VCH.
organic electrolyte, and a sulfur composite cathode. Sulfur is
regarded as an appealing high-capacity cathode for recharge-
able LBs due to a high theoretical capacity of 1672 mAh g−1 and
energy density of 2600 Wh kg−1,[233] which is five times higher
than conventional LIBs.[234] Practically, the energy density of
Li–S batteries can reach as high as 600 Wh kg1.[235] The elec-
trochemical reactions of Li–S batteries mainly involves in two
stages. At the first stage, long-chain polysulfides (Li2Sx, x = 4–8)
is produced, followed by dissolving in the electrolyte and pre-
cipitating in the form of Li2S2 or Li2S at the second stage. An
electrical current is thereby generated as the Li+ move internally
to the positive electrode, while electrons move externally to the
positive electrode. Li–S batteries overcome the limitations of
charge storage, accommodating more ions and electrons. Those
advantages make them one of the most promising candidates
for the next-generation energy storage devices.
Different from the intercalation of Li+ in LIBs, Li–S batteries
involve the conversion of sulfur to lithium sulfides by accepting
electrons, which delivers a much higher energy density than
LIBs. As mentioned above, carbon-based materials provide
highly versatile cathode materials for Li–S batteries. Void space
built inside can provide reservoir for the repeated volume
expansion of sulfur, which is one of the severest problems for
Li–S batteries. The conductive carbon-based materials serve to
construct the internal circuitry of the cathode that is especially
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necessary for sulfur with low electronic
conductivities.
Although decades of intensive research
have been denoted, Li–S batteries have not
achieved comparable success in commercial
applications with LIBs. The primary reason
could be the highly complex electrochem-
ical reaction routes and the free migration
of soluble polysulfides. The special solid–
liquid–solid phase transitions in case of Li–S
batteries results in severe volume changes
because of the formation of a series of soluble
lithium polysulfide species. The commer-
cialization of Li–S batteries is also hindered
by the poor electronic conductivity of sulfur
and intermediate products. In addition,
these soluble polysulfides lead to harmful
side reactions and give rise to serious loss of
active materials.[236] The continuous reduc-
tion of Li2Sn moieties by Li anodes, which
decreases the S contents at the cathode side
upon charging. During a discharge process,
octasulfur (S8) is reduced, resulting in the
formation of longer-ordered polysulfides
(Li2Sx, 6 < x ≤ 8), low-order polysulfides (Li2Sx,
2 < x ≤ 6) and polythionate complexes (Sx O2− 6 ,
x  ≥ 3) at discharge plateaus of 2.3 and
2.1 V, respectively. The higher order lithium
polysulfides Li2Sx (6 <x ≤ 8) can freely migrate
between the cathode and anode. This is the
results in a low Coulombic efficiency of Li–S
batteries system and low utilization of active
materials.[237] The long-chain polysulfides
on the lithium metal side are electrochemically reduced to
low-order polysulfides, while they will be reoxidized as trans-
ferring back to the cathode side. This so-called shuttle effect of
polysulfides leads to low coulombic efficiency, as well as severe-
discharging upon cylces. The diffusion of polysulfides (Li2Sn)
during the charge/discharge process into the electrolyte solu-
tion and their reactions with the lithium negative electrodes
induced a strong self-discharge.[238] Even though many reported
polar metal oxides can be used to adsorb polysulfides and pro-
vide better cycling properties, the poor conductivity of those
metal oxides inhibits the reduction reaction of polysulfides. The
current study of those polar metal oxides as sulfur host can only
adsorb sulfur near the surface and those polar metal oxides
cannot be fixed in issue of high sulfur contents.
Various approaches have been demonstrated for improving
cycling stability and specific capacity of Li–S batteries, such as
coating sulfur with conductive materials, establishing LiPSs
blocking interlayers, and employing functional holder for
S atoms.[239] In these studies, carbon-based materials with high
conductivity, tunable porosity, chemical stability are considered
as desirable candidates for Li–S batteries, where S is widely
embedded in carbon matrix, such as mesoporous carbon
materials,[240] carbon film,[241] graphene[19] etc. Two key factors
are to enhance the conductivity of the sulfur cathode and
moderate the dissolution of LiPSs. To realize these, integration
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Figure 17.  A) The synthesis process of hollow carbon coated TiO and sulfur (TiO@C-HS/S) composite. B–E) TEM images of PS sphere, PS@TiO2
core–shell spheres, PS@TiO2@PDA spheres and TiO@X-HS spheres. Reproduced with permission.[243] Copyright 2016, Nature Publishing Group.
Scale bars in B1, C1, D1, and E1 are 500 nm. Scale bars in B2, C2, D2, and E2 are 100 nm.

of S in a conductive but spacious matrix has been demon-
strated to be desirable.[242,243] One practical way to integrate S
is employing hollow carbon-based materials with high conduc-
tivity (Figure 17A).[244] In the case, active carbon and sulfur were
thermally treated to prepare sulfur/carbon composites, exhib-
iting a reversible capacity of 440 mAh g−1 for nonaqueous Li–S
batteries (Figure 17B–E). The employment of carbon materials
made Li–S batteries showed much better cycling stability than
pure sulfur cathode. Sulfur was loaded inside a carbon-coated
TiO hollow sphere by vapor phase infusion method. Carbon
layer provided a conductive surface for high sulfur utilization
by promoting the reduction reaction and pathways for fast Li+
transportation. And the protective outer carbon layer was cru-
cial for controlling the crystal phase and size of TiO during
the thermal treatment. Meanwhile, the hollow nanostruc-
ture not only adsorbed LiPSs near the entrance to hinder the
deep-seated LiPSs from dissolve, but also accommodated the
large volume expansion during lithiation. Similarly, Ding and
co-workers supported titanium nitride mediator with carbon
dual-shell hollow nanospheres (C@TiN).[245] The multifunc-
tional polysulfide mediator achieved catalysis and confinement
for sulfur species simultaneously. A stronger binding energy
between TiN and polysulfides (by synergistic dual bonding)
than that of TiO2 was beneficial for the oxidation procedure and
facilitates electrons/ions transfer.
The cycling stability derived from the dissolution-deposition
reaction of sulfur cathode is key factor for practical applica-
tions of Li–S batteries.[246] The dissolution and migration of
polysulfide intermediates seriously lead to the corrosion of
the lithium electrode and the fast decay of capacities, thereby
deteriorating the Coulombic efficiency and cycling capacity.[247]
The common method is to physically confine sulfur in various
carbon materials. It has acknowledged that carbon-based mate-
rials composed of 1D and 2D nanostructures can provide more
polysulfide immobilization sites for sulfur cathode, and then
alleviate the migration and dissolution.[248,249] The heteroatoms-
doped CNTs and graphene are widely utilized for anchoring
polysulfides, because these heteroatoms are generally more
electronegative than carbon, which can facilitate the chemical
adsorption.[250] When the N-doped graphene and CNTs com-
posites used as the cathode for Li–S batteries, showing a high
reversible capacity of 1221 mAh g−1. Owing to the minimiza-
tion process of sulfur with the conductive structure, the elec-
trode delivered exceptional reversible capacities of 158 and
128 mAh g−1 after 1000 and 2000 cycles, respectively, with
high Coulombic efficiencies. The excellent electrochemical
properties are ascribed to more active defect sites introduced
by the doping of nitrogen. The designed hierarchical carbon-
based materials provided another desirable platform to improve
cycling performance by encapsulating/immobilizing S, thus
suppressing the loss of active materials. For example, a typical
mesoporous carbon (CMK-3) anchored on CNTs was served
as cathode for sulfur absorption due to the surface tension of
ethanol,[251] where sulfur was stored in the mesochannels of
CMK-3 with a high content of 20 mg cm−2 (Figure 18A,B).
The flexibility of 1D and 2D carbon-based materials also
opens a new window to create the highly flexible Li–S batteries.
For example, a flexible aligned CNTs sheets provided effective
conductive scaffolds with high mechanical strength.[252] The
lower cathodic voltage plateaus at 2.1 V, corresponding to the

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www.advancedsciencenews.com
Figure 18. Electrochemical performance of the aligned mesoporous carbon composite. reported sulfur cathodes demonstrated an
A,B) TEM images of CMK-3 before and after loading with S particles. C) CV curve at 0.1 mV s .
D) Voltage profiles at 0.1 C. E,F) Rate capability and cycling performance, respectively.
Reproduced with permission. [251]
Copyright, 2015 Wiley-VCH.
deposition of lower-order lithium sulfur compounds, con-
tributed a major fraction of the capacity. The upper plateau at
2.3 V was related to the formation of higher-order polysulfides
(Figure 18C,D). The hybrid cathode recovered its capacity
after running at high rates, manifesting a good reversibility
(Figure 18E). A high capacity of 919 and 400 mAh g−1 were
remained (Figure 18F) for 100 cycles and 1000 cycles at 2 C,
respectively.
Despite much progress has been made in carbon-based Li–S
batteries electrodes, the relatively weak interactions between the
nonpolar carbon and polar polysulfides are sometimes insuf-
ficient to immobilize the sulfur intermediates. As mentioned
above, the composition engineering, surface modification,
and heteroatom doping can enhance the interaction. Specially
noted, MOF with abundant and controllable pores, e.g., zeolitic
imidazolate framework-8 (ZIF-8), have been widely used as
sulfur matrix.[253] Importantly, MOF-derived carbon materials
with heteroatom doping can serve as electronic matrix with
higher efficiency to entrap polysulfides, resulting in an remark-
able cycling stability.[254] A recent example is a MOFs-derived
porous carbon homogeneously anchored on the surface of
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graphene.[255] The well-dispersed nitrogen-
doped porous carbon on the graphene sheets
with high conductivity were able to confine
and adsorb polysulfides. Consequently, a
high specific capacity of 1372 mAh g−1 was
remained, as well as a good cycling stability
over 300 cycles.
To solve the shuttle effect of Li–S batteries,
engineering of porous carbon materials to
serve as sulfur host are widely used. The
intermediate polysulfide can be efficiently
trapped in the carbon cathodes. Alternatively,
various binders could also act as Li–S cath-
odes to improve sulfur loading and cycle life.
Multifunctional binders instigate mechanical
interlocking between binders and dissolved
polysulfides, withstand volume change, as
well as provide overall electrode stability.[256]
Some binders such as guar gum, chitosan,
and polyvinylidene have served to mitigate
polysulfide shutting through the formation of
C–S bonds. As binders are applied to sulfur
cathodes, they can ensure efficient contact
between carbon structure and the active
materials, displaying smaller internal resist-
ances and maintaining structure integrity.[257]
By using conductive binders, the electronic
and ionic insulating nature of sulfur can also
be partially overcome.
From the perspective of applications, a
high areal sulfur loading is still challenging,
that is needed to be addressed before the ter-
minal commercial application. Most of the
−1
areal sulfur loading lower than 2 mg cm−2.
That is the reason of the low areal capacity
(less than 2 mAh cm−2).[258] Besides, there
is a tradeoff between increasing sulfur
loading efficiency and shortening the diffusion pathways for
electrons transportation. A thick sulfur cathode also causes a
higher possibility for cracking and peeling off from the cur-
rent collector. In this regard, 3D carbon-based materials with
hierarchical structure are excellent candidates to serve as
sulfur collector with high areal loading. The recent example is
a 3D sponge-like electrode architecture established by a highly
nitrogen-doped carbon fiber and graphene layer.[259] The former
enables to insulate and collect sulfur, while the later serve as
polysulfide interception. As a result, a high areal capacity up to
8.7 mAh cm−2 were attained over 500 cycles.
3.3. Li–O2 Batteries
Li–O2 battery (or Li–air battery) is currently viewed as the
most promising electrochemical energy storage technology
with the hope of realizing practical energy storage devices
in the near future, due to their high theoretical energy den-
sity.[260] To date, four types of Li–O2 batteries have been
reported including aprotic, aqueous, hybrid, and solid-state
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batteries.[261] The nonaqueous system has the highest energy
density and potentially high rechargeability. Typical recharge-
able Li–O2 batteries are composed of the porous oxygen dif-
fusion cathode, lithium metal anode, and Li+ conducting
electrolyte. Their electrochemical performances are associated
with the reversible reaction of lithium at the anode and air at
the cathode. In the discharge process, oxygen is drawn from
the air atmosphere and reduced by Li to form Li2O2 (oxygen
reduction reactions, ORRs). During the charge process, the
discharge products electrochemically decompose to Li+ and
oxygen (oxygen evolution reactions, OERs).[262] The charge/
discharge process could be understood by the storage pro-
cess O2  + 2e−  + 2Li+  ↔ Li2O2. The overall energy density is
determined by the amount of insoluble Li2O2 in the oxygen
electrode. Consequently, such a unique battery system can
provide a greatly increased specific energy density to a theo-
retical value of 5200 Wh kg−1.[263,264]
Carbon-based materials, which are commonly used as
cathode, have been developed to catalyze the Li2O2 formation
in Li–O2 batteries. The high conductivity, large surface area for
effective O2 and Li+ diffusion generally meet the requirement
for developing high energy density Li–O2 batteries. Owing to
the low catalytic activity and poor stability in presence of Li2O2,
carbon-based materials are commonly doped with heteroatoms
and/or modified with functional groups to modify the ORR and
OER performances. Additionally, metal or metal oxides deco-
rated carbon can also enhance the ORR and OER performance,
which attribute to strong Li2O2 or O2 adsorption.
Nevertheless, the research on Li–O2 batteries is still at initial
stage due to poor cycle stability and low energy efficiency. For
Li–O2 batteries, the desired reaction is 2 Li+  + O2  → Li2O2.
However, unavoidable reactions result in many by-products like
Li2O, LiCO3, ROCO2Li, and LiOH. Simultaneously, insoluble
Li2O and Li2O2 forming at the cathode hinders the diffusion of
the electrolyte and O2 pathways, which lead to low electrochem-
ical performance. Meanwhile, a large overpotential (>4.0 V)
occurs due to the difficult decomposition of lithium hydroxide
compound, the insoluble discharge products (Li2O2) and unde-
sirable formation of Li dendrite during the charge process. The
overpotential leads to poor cycling performance and low Cou-
lombic efficiency.[265] The main reason of those problems is
the high kinetic barriers of ORR and OER at oxygen electrode,
which arises from limited electron transfer and mass transport
efficiency.[265] To obtain high-performance Li–O2 batteries, a
cathode with plenty of reachable active sites to promote ORR
and OER, as well as sufficient void spaces to accommodate the
large amount of Li2O2 deposition are highly desirable.[266]
Toward tacking the critical issues of Li–O2 batteries, many
studies have been reported to give a fundamental under-
standing of Li–O2 batteries. By taking advantage of the
capability of the aberration-corrected environmental TEM,
Wang and co-workers enabled in situ atomic-level imaging of
the configuration evolution of the discharging/charging prod-
ucts of Li–O2 cell (Figure 19A).[267] A CNTs dressed with RuO2
(cathode) mounted on a platinum tip was connected with a
Li2O-covered Li metal on a tungsten tip, which was exposed to

Figure 19.  A) In situ observation of the morphological evolution of Li–O2 batteries in an environmental TEM chamber. B) The time-resolved high-angle
annular dark-field scanning TEM images depict the morphological evolution of the discharging/charging product. Reproduced with permission.[267]
Copyright 2017, Nature Publishing Group. C) SEM image of mesoporous CNTs (MCCs). D) TEM image of Ru@MCCs. E,F) Discharge curves of Li–O2
batteries with MCC and carbon black (CB) catalysts at different current densities in a LiClO4/DMSO electrolyte. Reproduced with permission.[268]
Copyright 2015, Wiley-VCH.

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an O2 environment. Seen from Figure 19B, the ORR on CNTs
initially produced LiO2, followed by the disproportionation into
Li2O2 and O2. A hollow nanostructure with Li2O outer-shell and
Li2O2 inner-shell surfaces was then created by the resulted O2.
After an incubation time of a few seconds, two hollow spheres
popped out and continuously grew at the three-phase junction
contact point of the CNTs from an initial diameter of ≈50 to
≈200 nm. During the OER process, the outer shell suddenly
inward shrank and collapsed after partial charge. On dis-
charging, Li+ diffused across the electrolyte to react with oxygen
to form LiO2 followed by the disproportionation reaction and
resulted Li2O2 and O2. The growth process of particles growth
process was sustained by continuous mass transport in the
outer and inners side shell.
At present, two major approaches have been utilized for
promoting the ORR and OER that are structure engineering and
the addition of effective catalyst. In fact, the amount of insol-
uble discharge products accommodated in the oxygen electrode
determines the overall energy density of Li–O2 batteries.[269]
Therefore, more stable carbon-based materials have been
regarded as the desired selections for reducing or avoiding side
reactions to boost the performances of Li-O2 batteries; Structure
engineering and active heterogeneous catalysts introducing
have been utilized to improve ORR and OER during the dis-
charge/charge processes.[270] Additionally, the tunable assembly
unit of the electrode provides abundant spaces to accommodate
insoluble Li2O2 clusters, contributing to the high capacity of
Li–O2 batteries. This is illustrated by a 3D hierarchical hollow
carbon-dolybdenum carbide sphere (HSC), composed of carbon
nanosheets imbedded with high-density molybdenum carbide
nanodots.[271] Figure 19C,D clearly displays the unique architec-
ture, where lots of mesopores interconnect with each other. The
homogenously dispersed molybdenum carbide incorporated
into graphitic carbon nanosheets could remarkably reduce the
charge and discharge overpotentials. The electrode achieved a
discharge and charge capacity of 26 100 and 16 090 mAh g−1,
respectively. These results were much better than that of CB
electrode (Figure 19E,F). A capacity retention rate of 46.3% was
recorded for MCC catalysts, which was higher than that of CB
(38.6%).
On the other hand, numerous electrocatalysts including
metal oxides and heavy metals can be used in Li–O2 batteries.
Since the initial ORR step is O2 adsorption due to the ther-
modynamics being favorable, followed by reduction of O2 on
the electrode, the catalytic promotion from Co3O4,[272] metallic
mesoporous pyrochlore,[273] noble metal,[274] and Ru2O,[270] can
decrease the polarization of the electrodes during the charge/
discharge process. However, the use of those catalysts can
also cause a serious loss in overall energy density. Among the
reported catalysts, heteroatom-doped carbon-based materials
have shown a preferable Li+ adsorption property and remark-
able catalytic activity for both ORR and OER.[275] From the
electrode point of view, 1D carbon-based nanomaterials enable
the facile design, easy in situ growth of active materials and
heteroatoms doping. The integration of 1D carbon-based nano-
materials into freestanding film or 3D hierarchical structure
guarantees the high output production of electrode materials
with superior mechanical strength and large surface area.
Ramakrishna et al. prepared N/O-codoped CNTs/CF films via
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a facile free-surface electrospinning technique.[276] This flexible
and robust structure combined high catalytic activity and
efficient mass-transport characteristics. As a proof-of-concept,
this newly designed Li–O2 battery had a positive half-wave
potential (0.87 V) for ORR and low overpotential (0.43 V) for
OER. Density functional theory calculations by Jing and Zhou
demonstrated that the strong electron withdrawing capability of
pyridinic-N, especially in-plane tetra-N pyridinic accelerated the
reaction paths of Li+ → Li → LiO2 → Li2O2 → Li3O2 → Li3O4 →
Li4O4 on the active sites.[277] Hence, the formation of LiO2 was
significantly inhibited, resulting in the formation of Li2O2 clus-
ters or films through a surface-growth path. Except for nitrogen,
S-doped carbon-based cathode materials could also modulate
the electrochemical properties of Li–O2 batteries. A more stable
CSC and CS structures in S-doped graphene than
the CN in N-doped graphene was demonstrated by Chen
et al. Thus, S-doped cathode material manifested better cycling
stability.[278] Additionally, B, Al, Si, and P doped carbon-based
materials were also reported. P-doped graphene showed the
highest catalytic activity in reducing the cell charge voltage by
0.25 V. And B-doped graphene exhibited the highest catalytic
activity in decreasing the oxygen evolution barrier by 0.12 V,
which is the lowest discharge and charge overpotentials in
aprotic Li-O2 batteries.[279]
Except for doping heteroatoms, chemical modification of
carbon-based materials, including oxygen containing func-
tional groups can tailor the ORR and OER performances,
effectively lowering the discharge and charge overpotentials.[280]
Oxygen containing functional groups on carbon-based mate-
rials facilitate the surface-based growth of Li2O2 particles,
deducing the potential for decomposition.[281] Additionally,
the surface modification with metal or metal oxides is consid-
ered to be an efficient way for addressing the issues of poor
reaction kinetics of OER and ORR for Li–O2 batteries.[282] As
shown in Figure 19C,D, the large amount of discharge products
can be deposited on the mesopores inside the Ru functional-
ized carbon nanocubes after discharging (Figure  20D). This
Ru functionalized mesoporous nanostructure demonstrated
a good cycling performance up to 120 cycles with capacity of
1000 mAh g−1. Ji et al. used a facile electrospinning route to
grow nonprecious transition-metal-based N/O codoped CNTs
on CFs films.[133] Benefiting from high catalytic activity of
Fe and effective transportation ability of 2D CFs film, the as-
prepared electrode exhibited high voltage of ≈3.4 V and a very
low overpotential of 0.15 V. The Fe-based particles presented
ORR catalytically active sites and greatly promoted the local
activity. Furthermore, the doping pyridinic N atoms and oxygen
atoms generated positively charged carbon, which favored the
adsorption of OH− and H2O, thus offering active sites for OER.
A lighter and more robust carbon-based electrode can
significantly improve the high energy density of Li–O2 batteries.
Unfortunately, the immobile nature of the solid/solid interface
between catalysts and discharge products limits the activity.
This implies that diffusible catalysts facilitate the decomposi-
tion of discharge products. Lim et al. combined a hierarchically
woven porous 1D CNTs fiber and a highly active redox mediator
(LiI) as diffusible catalyst to enhance the capacity and stability
of Li–O2 batteries.[283] On the electrode surface, iodide ions (I−)
were initially oxidized. The oxidized products (I3−or I2) then
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 20.  A) SEM image of discharge product on Ir–rGO (scale bar, 1 µm); inset is the TEM image of discharge product on Ir–rGO (scale bar,
200 nm). B) Voltage profiles of the rGO cathode. Cycle number of voltage plot is given by the color of the plotting symbol. Inset shows capacity as a
function of cycle number. Reproduced with permission.[291] Copyright 2016, Nature Publishing Group. C) Schematic illustration of the role of the redox
mediator (RM) in a Li–O2 battery system made using a hierarchical CNT fibril electrode. Reproduced with permission.[283] Copyright 2014, Wiley-VCH.
D) The deposition process of toroidal-shape Li2O2 on the mesoporous carbon nanocubes (MCCs) electrodes. Reproduced with permission.[268]
Copyright 2015, Wiley-VCH.

reacted with Li2O2 to produce Li+ and O2. Compared with con-
ventional CB electrode and Super P carbon, the as-made woven
porous CNTs fibril manifested an obviously reduced overpoten-
tial (Figure 20C). The hierarchically aligned CNTs prohibited
clogging by the discharge products and maintained a rapid
electron pathway.[284] This synergistic effect of CNTs and redox
mediator could decrease the polarization, further enabling
rechargeability and stability. This novel electrode delivered a rel-
atively high reversible capacity of 1000 mAh g−1 over 900 cycles.
The stability of electrolyte and electrode materials involved in
the cycling process should be another critical limitation. This
problem can be partially solved by rational design of a suitable
pore structure of the oxygen electrode to enhance the rate and
stability of Li2O2 formation/decomposition reactions.[285] The
in situ formation and decomposition of insulator Li2O2 during
charge/discharge process is a unique characteristic of Li–O2
batteries.[286] This discharge product inhibits progress of occur-
ring reaction, resulting in a low Coulombic efficiency. Due to the
limited solubility of Li2O2 in aprotic solvents, the growth of Li2O2
on the surface of carbon cathode surface passivates the cathode
and leads to the cell death and low rates.[287] The sluggish oxida-
tion of solid and insulating Li2O2 at the positive thus occurs.
Accordingly, a high potential is needed for charging Li–O2
batteries, leading to low voltaic efficiency and degradation of
battery components. More seriously, on discharging a Li–O2
battery, LiO2 film grows on the cathode, passivating the reaction.
The formation of Li2CO3 at the interface between the Li2O2 and
the cathode further exacerbate this passivating process.[288]
Carbon-based nanomaterials have shown great advantages
for Li–O2 batteries, but an onset of carbon corrosion as low
as 3.5 V brings another major problem.[289] Dangling bonds,
polymer binders, and oxygen-containing surface groups of
those carbon-based materials facilitate the generation of reac-
tive species and by-products during battery operation. A
decrease in the oxygen-containing functional groups and addi-
tives and the increase in the graphitization degree are believed
to improve the cycling stability of carbon-based structures in
Li–O2 batteries. Because of the disproportionation, LiO2 easily
transforms to Li2O2. The introduction of thermodynamically
stable LiO2 in pure form into Li–O2 batteries can decrease the
charge potential and ensure an enhanced cycling ability.[290]
Lu et al. demonstrated that solid LiO2 can be stabilized using
graphene-based cathode. The key is the utilization of iridium
nanoparticles on graphene, which is responsible for the growth
of crystalline LiO2 (Figure 20A).[291] The Ir-rGO electrode had
a very low charge potential of ≈3.2 V, which up to 3.5 V over
40 cycles, leading to more than 85% efficiency in this system
(Figure 19A). Without Ir nanoparticles, rGO showed a much
higher charge potential of ≈4.2 V, which was higher enough
to decompose carbon cathode, displaying a low efficiency
of ≈67% (Figure 20B). SEM images showed that the Ir-rGO
based cathode consisted of needle- or rod-like morphology
(Figure 19A). The Ir-rGO discharge product by different current
density gave an average O2 formation rate of 1.3 × 10−9 mol s−1.
Since both Ir and rGO were good ORR material, they presented
good ORR sites, promoting nucleation and growth of LiO2.

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www.advancedsciencenews.com
Simultaneously, the Ir-rGO cathode suppressed the dispropor-
tionation of LiO2 to Li2O2.
The low oxygen partial pressure in air limits the diffusion
of O2 to access the cathode.[292,293] Such a system has been
restricted to pure oxygen atmosphere. A cathode with highly
porous structure for oxygen transfer is very ideal. The easy
modulation of porosity of carbon-based materials endow them
the most attractive candidate as cathode materials to accom-
modate insoluble/insulating Li2O2 for Li–O2 batteries. The
precisely designed structure promotes the transport efficiency
of Li+ and oxygen in spatial positions. Those engineered
structure with high conductivity form the effective active sites
for catalyzing the formation and decomposition of Li2O2.[294]
At the meanwhile, a proper engineered structure inhibits the
build-up of excessive Li2O2 over the depth of discharge process,
avoiding the collapse of the cathode architecture. The developed
carbon coating for the lithium anode only allow the pass of Li+,
which can limit side reactions in a Li–O2 battery.
4. Conclusions and Outlook
Carbon-based nanomaterials have attracted tremendous
research interests for LBs applications in recent years, and
various reports on these topics further signify the importance.
Comparison with non-carbon electrode materials, it is evident
that carbon-based materials make it possible to enhance the
characteristics of LBs and meet practical requirements.[295]
Their structural, dimensional, electrical and chemical pro­
perties directly determine the power density, energy density,
cycling stability and safety of next generation lithium energy
storage devices. Hierarchical porosity, structure engineering,
and hybridization can lead to the boosted lithium storage
capability. The facile assembly of 1D, 2D, and 3D nanostruc-
tures can increase the conductivity and structural integrity.
Additionally, the doping of heteroatoms (such as N, P, B, and
O, etc.) into carbon-based materials can also well modify the
electrochemical properties of electrodes benefiting from the
enhanced conductivity and more defects. The full combina-
tion of active materials (such as TiO2, MoS2, CoS2, Fe2O3,
etc.) and carbon-based materials provides a good choice to
further promote the gravimetric and volumetric capacities
of LBs.
As mentioned above, carbon-based nanomaterials is still
the best choice for LBs electrodes, the existing problems
need to be further solved such as low Coulombic efficiency,
poor rate performance, and cycling stability. Such conclusion
stems from the increasing understanding of the fundamental
structural mechanism of electrodes. To best of our knowledge,
1) flexible 1D carbon structure can provide excellent platform
to integrate with active materials, which can be developed
as wearable, stretchable devices; 2) 2D carbon materials are
capable of supporting active materials due to the large sur-
face area and superior conductivity. These 2D structures can
establish a stable SEI layer and enable homogeneous lithium
absorption free from dendrite-related problem; 3) 3D hierar-
chical structures with proper dimensional engineering can
ensure efficient electrolyte flux to the electrodes and pro-
mote the electrochemical reactions. Importantly, the precisely
Adv. Energy Mater. 2020, 1903030 1903030  (27 of 34)
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designed 3D structure can shorten the diffusion pathway of Li+
and electrons, and effectively buffer the large volume changes
during cycling.
Nevertheless, terminal performance strongly depends on
the structural characteristics. For example, interconnected 1D
structure blocks the paths of Li+, especially at high current
density. Although reported performance far exceed the com-
mercial available ones, economic problem for the large-scale
and standard production still gap laboratory research and
industrial manufacturing. The effects of multidimensional
structures on the LBs performances require a deeper under-
standing, and the functions of heterogeneous structures should
be studied in detail, aiming to inspire more ideas for design
of advanced carbon-based nanostructures with superior prop-
erties. Investigations into dimensional structure, porosity,
morphology, and active materials may suggest solutions to
these issues. More attention should be paid to the construction
of exquisite dimensional structure whereby Li+ and electrons
can be appropriately reacted and transferred.
Another critical aspect is the integration of active materials.
As listed in Table  1, the lifespan, rate capability, and energy
density can be remarkably improved after the introduction
of active materials in various dimensional carbon structures.
Certain species of insert carbon like graphene and CNTs
do not react with Li+ and electrons, but serve as regulator of
specific electroactive materials. The identification of electroac-
tive materials that determine the fundamental electrochemical
performance of LBs requires more emphasis to obtain desirable
properties including large window of potential, high energy
density, and good stability.
However, the stagnation of improvement suggests the
absence of feasible approach of the employment of active mate-
rials. The irreversible loss of active materials still needs to be
eliminated. Furthermore, high costs, low yields, and complexity
of fabrication procedures are also key issues. The fabrication
steps should be further simplified and cut down expense by
developing facile, cost-effective, operable approaches as well
as selecting economic and environmental friendly starting
materials.
The functionalization of batteries aims to meeting the
modern requirement of wearable, flexible, and touchable instru-
ments with long lifespan and high capacity. On the other hand,
considering the theoretical energy density and gravimetric/
volumetric energy density, Li–S and Li–O2 batteries possess
many commendable advantages. For Li–S batteries, structure
engineering of carbon-based materials endows an effective host
for S atoms to inhibit the dissolution of polysulfides, leading
to a high conductivity. The unique multistage and multiphase
reaction nature of Li–S batteries with an outstanding energy
density also gives a good chance for energy-related applications.
Some intrinsic issues about Li–S batteries should be addressed
in the future: 1) the dissolution of sulfur and its intermediates
results in severe phase migrations and drastic structure col-
lapse; 2) severe volume fluctuation arises from the deposition
of Li2S with a much lower density than sulfur in electrodes;
3) polysulfur shuttle from electrolyte causes side reactions and
reduces the battery efficiency. A major approach is used to over-
come these obstacles by structure engineering of carbon-based
nanomaterials to achieve the higher mass loading of S in the
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Table 1. The electrochemical performances of carbon-based nanomaterials with different dimensionalities as the electrode materials for lithium
energy storage.

Dimensionality Component Application Discharge capacity [mAh g−1] Specific capacity [mAh g−1] Coulombic efficiency Cycle no. Refs.
1D Carbon nanotube fiber LIBs 145.9 100 [62]
1D Fiber-in-tube hierarchical LIBs 1042 1790 58% 300 [296]
nanostructure
1D Carbon nanotube/silicon LIBs 1460 100 [61]
composite fiber
1D Fe2O3-caron nanofibers LIBs 1406 812 81% 300 [81]
1D Graphene/carbon nanotube/ Li–S 762 1200 62.2% 100 [297]
sulfur composite fibers
1D Tube-in=tube carbon Li–S 918 652 50 [32]
1D Carbon nanotube composite Li–S 1270 857 99.5% 300 [298]
1D Nanosheet/carbon-nanotube Li–S 1240 450 1200 [299]
1D N-doped multiwalled Li–S 1363 950 100% 30 [300]
carbon nanotube
1D Au-decorated cracked Li–O2 5488 120 [301]
carbon tube array
1D Carbon wire coated with Li–O2 8200 >1000 130 [302]
carbon nanoparticles
2D Carbon nanotube films LIBs 335 50 [303]
2D Sn/SnO2/MWCNT paper LIBs 374 100 [304]
2D Si film/carbon nanofibers LIBs 2537 1000 100% 200 [83]
2D Aligned carbon nanotube– LIBs 1801 1494 75% 45 [134]
silicon sheets
2D Monolayer MoS2–carbon LIBs 1191 1100 76% 500 [305]
2D Si/C sheet-like carbon film LIBs 2127 1018 72% 200 [138]
2D Graphitic carbon nanosheets LIBs 734 722 64.9% 100 [306]
2D Porous graphene LIBs 1137 470 94% 3000 [308]
2D Mesoporous carbon nanosheets LIBs 3535 770 >90% 60 [14]
2D Graphene filling Li–S 1236 461 94.5% 200 [308]
coated by
N-doped porous
carbon layers
2D N-doped carbon sheet Li–S 1118 885 100% 100 [309]
2D Cassava-derived carbon sheet Li–S 640 811 100 [310]
2D Sheet-like carbon matrix Li–S 1118.6 722.5 92% 100 [311]
2D Metal oxide nanofibers and Li–O2 6300 1790 14 [312]
graphene nanoribbons
2D Dual-doped graphene and Li–O2 11 431 500 100 [313]
mesoporous carbon
2D Cobaltite oxide nanosheets Li–O2 4150 ≈84% 33 [314]
anchored graphene
3D Carbon-coated CuO hollow LIBs 1003 750 55% 300 [315]
spheres
3D Fe2O3 submicron spheres LIBs 1392 1200 >99% 50 [316]
coated with carbon layer
3D Nitrogen-doped porous carbon/ LIB 1223 1060 86.7% 100 [317]
Co3O4 nanocomposites
3D Sn nanowires encapsulated LIBs 1938.4 1308.8 75.4% 20 [318]
Al2O3 tubes in carbon matrix
3D Carbon–fiber monolith Li–S 1000 650 100 [319]

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Table 1. Continued.
Dimensionality Component Application Discharge capacity [mAh g−1] Specific capacity [mAh g−1] Coulombic efficiency Cycle no. Refs.
3D 3D graphene nanosheet@ Li–S 1049 639.1 200 [320]
carbon nanotube matrix
3D Carbon nanotube foam Li–S 1039 >500 200 [321]
3D Carbon nanofiber aerogel Li–S 1283 1042 99% 90 [322]
3D Platinum-coated hollow gra- Li–O2 5600 >800 18 [22]
phene nanocages
3D Nanocomposite of Fe2O3 Li–O2 1000 250 [323]
@C@MnO2
3D Oxygen- and nitrogen-doped Li–O2 500 30 [324]
carbon nanowebs

electrode, thus enhancing the capacity and power density for
Li–S batteries.
In terms of Li–O2 batteries, carbon-based nanomaterials are
ideal candidates to overcome safety issue, which is the ultimate
target for commercial purpose.[325] Although carbon-based
nanomaterials serve as obbligato component in Li–O2 batteries,
the decomposition of carbon cathode during Li2O2 oxidation
requires the denotation of efforts to this aspect. In addition,
carbon-based electrodes show sluggish reaction dynamics in
ORR and OER, resulting in the low charge/discharge round-
trip efficiency and battery death. The relatively low catalytic
activity of carbon-based materials seriously affects the perfor-
mances of Li–O2 batteries.
In the operation of a Li–O2 battery, ORR/OER reactions occur
within the electrode to generate a solid–liquid–air interface. To
develop the performance of Li–O2 batteries, it is necessary to
address the efficient air diffusion in the nonaqueous electro-
lytes and suppress passivation of the air cathodes. It is evident
that the capacity is in proportion to the surface area and related
to the pore size of the carbon-based materials. 1D structures
with large surface area, high tensile strength, and electric
conductivity provide sufficient space for Li2O2 deposition and
high catalytic activity (e.g., CNTs). Graphene and other fabric
2D structures with a lot of lattice defect sites play key roles
in the formation of Li2O2, resulting in a high capacity. Fur-
thermore, heteroatoms-doping and the formation of compos-
ites have been focused as strategies to improve the round-trip
energy efficiency and lower the discharge/charge overpotential.
To solve the safety problems caused by high concentration of
reactive O2, contaminant CO2 in ambient air, water, and den-
dritic growth of Li can fall back to the surface modification and
construction of an exquisite 3D structure.
Acknowledgements
H.Y.G. and Y.P. contributed equally to this work. The authors thank the
financial support from the Shuguang Program supported by Shanghai
Education Development Foundation and Shanghai Municipal Education
Commission (18SG035), Shanghai Pujiang Program (17PJD015), and
National Natural Science Foundation of China (51673026).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
carbon-based nanomaterials, electrochemical performances, lithium-
based batteries (LBs), structural designs, synthetic techniques
Received: September 16, 2019
Revised: November 26, 2019
Published online:
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