Nano Materials Science xxx (xxxx) xxx

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Nano Materials Science

journal homepage: www.keaipublishing.com/cn/journals/nano-materials-science/

The role of graphene in rechargeable lithium batteries: Synthesis,

functionalisation, and perspectives
Asad Ali a, b, 1, Fengxing Liang a, 1, Jinliang Zhu a, *, Pei Kang Shen a, **
a
Collaborative Innovation Center of Sustainable Energy Materials, MOE Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Guangxi Key
Laboratory of Processing for Non-ferrous Metals and Featured Materials, School of Resources, Environment and Materials, Guangxi University, Nanning, 530004, PR China
b
School of Chemistry & Chemical Engineering, Guangxi University, Nanning, 530004, PR China

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

Keywords: In recent years, the demand for high-performance rechargeable lithium batteries has increased significantly, and
Graphene many efforts have been made to boost the use of advanced electrode materials. Since graphene was first isolated
Functionalisation by Novoselov et al., graphene/graphene-based materials have become an active area of research and are
Lithium-ion battery
considered to be promising high-performance electrode materials. Graphene is a two-dimensional single-atom
Lithium-sulfur battery
Lithium-oxygen battery
carbon-packed material that possesses fascinating properties, including a large surface area, remarkable electrical
conductivity, extraordinary intrinsic electron mobility, high Young's modulus, superior mechanical strength,
optical transmittance, catalytic performance, and stability. Therefore, graphene is considered an attractive ma-
terial for rechargeable lithium-ion batteries (LIBs), lithium-sulfur batteries (LSBs), and lithium-oxygen batteries
(LOBs). In this comprehensive review, we emphasise the recent progress in the controllable synthesis, func-
tionalisation, and role of graphene in rechargeable lithium batteries. Finally, in this review, we aim to address the
most promising results, benefits, challenges, critical issues, research directions, and perspectives to explain the
developmental directions of graphene for batteries.

1. Introduction lithium-ion batteries (LIBs) [5,6], lithium-sulfur batteries (LSBs) [7,8],

Currently, energy production, energy storage, and global warming are
all active topics of discussion in society and the major challenges of the
21st century [1]. Owing to the growing world population, rapid economic
expansion, ever-increasing energy demand, and imminent climate
change, there is a substantial emphasis on creating a renewable energy
future for human beings while protecting our planet at the same time [2].
To achieve this goal, we should decrease our dependence on fossil fuels
and turn to low-cost, eco-friendly, and renewable energy sources, such as
solar, tidal, wind, biomass, and geothermal sources [3]. To make the best
use of these energy sources, advanced energy storage systems are
necessary that can store the excess energy and use it on-demand to sus-
tain a constant power supply to homes and industries [4]. Undoubtedly,
energy storage is a key issue to be addressed within this context, and
electrochemical energy storage systems are clearly the main facilitators.
Batteries can play a significant role in the electrochemical storage and
release of energy. Among the energy storage systems, rechargeable
and lithium-oxygen batteries (LOBs) [9] have attracted considerable in-
terest in recent years owing to their remarkable performance.
It is crucial to fabricate and design efficient electrode materials that
deliver high specific energy (energy per unit mass) and high energy
density (energy per unit volume) to fulfil the ever-growing demand for
electrical devices with superior performance, such as power consumption
devices (e.g., tablets, laptops, smartphones, and smartwatches) and
hybrid/electric vehicles [10]. For instance, a common property of these
energy storage technologies is that they contain two electrodes and an
electrolyte-impregnated separator where electrons and ions are neces-
sary for the electrochemically active nanomaterials involved. However,
the energy storage mechanisms of these batteries, which take advantage
of their electrode systems, are distinct from each other. Nanostructured
electrode materials with outstanding electrochemical features have been
recognised to be crucial for the future development of energy storage
devices [11]. Furthermore, nanostructured electrode materials possess
the preferable advantages of short length for electron and ion

* Corresponding author.
** Corresponding author.
E-mail addresses: jlzhu85@163.com (J. Zhu), pkshen@gxu.edu.cn (P.K. Shen).
1
These authors contributed equally.

https://doi.org/10.1016/j.nanoms.2022.07.004
Received 12 June 2022; Accepted 18 July 2022
Available online xxxx
2589-9651/© 2022 Chongqing University. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article as: A. Ali et al., The role of graphene in rechargeable lithium batteries: Synthesis, functionalisation, and perspectives, Nano
Materials Science , https://doi.org/10.1016/j.nanoms.2022.07.004
A. Ali et al.
transportation, large contact area for electrode/electrolyte, facile func-
tionalisation for solution wettability, and novel electrochemical reactions
that are not possible with their micro- and bulk-sized counterparts [12].
In recent years, the synthesis and design of nanostructured electrode
materials have been confirmed as necessary for achieving remarkable
improvements in energy storage devices. Specifically, graphene and
graphene-based composites have attracted interest and have been widely
studied as electrode materials for different energy storage technologies
[13].
Novoselov et al. [14] discovered an advanced aromatic single-atom
thick layer of carbon atoms in 2004, initially labelled graphene, whose
thickness is one million times smaller than the diameter of a single hair.
Graphene is a hexagonal two-dimensional (2D) honeycomb lattice
formed from chemically sp2 hybridised carbon atoms and has the char-
acteristics of the graphite precursor. In sp2 hybridised chemical bonds,
the in-plane sigma bond is the strongest and the out-of-plane π-bond is
made from delocalised electrons, causing electron conduction by offering
weak interactions between the graphene layers or between graphene and
the substrate [15–17]. The unique features of graphene make it an ideal
material for unlimited applications and have created a new chapter in the
advancement of materials science. Simultaneously, graphene is thermally
and electrically conductive and transparent. Importantly, graphene is
stronger than steel and is still highly flexible and lightweight. These
remarkable characteristics of graphene can lead to a progressive revo-
lution in modern society. In recent years, interest in graphene has
continuously increased, giving rise to what might be called the graphene
gold rush. In terms of application goals, graphene may have an extraor-
dinary number of industrial applications [18,19]. It is worth noting that
the large theoretical surface area (2630 m2 g
1), high Young's modulus
(1.0 TPa), breaking strength of 42 N m
1, selectivity, remarkable me-
chanical strength, superior electrical conductivity (5–6.4  106 S/m),
extraordinary intrinsic electron mobility (200000 cm2 v
1 s
1),
outstanding thermal conductivity (4.8–5.30  103 W m
1 k
1), optical
transmittance (~97.7%), density (<1 g cm
3), catalytic performance,
stability, and tunable properties of graphene have generated significant
interest for its use in rechargeable batteries [20–22].
Despite its remarkable characteristics, graphene is not readily avail-
able for large-scale industrial applications because the production of
high-quality graphene is costly. In recent years, many synthetic strategies
have been adopted to produce large-scale high-quality graphene,
including micromechanical cleavage, chemical oxidation of graphite, and
topological growth on metal and non-metal substrates [23,24]. Whether
working as a catalyst-supporting material or an active metal-free elec-
trocatalyst, the rational morphology of graphene facilitates the adjust-
ment of an electrocatalytic procedure in a favourable route in terms of its
remarkable electrochemical kinetics [25,26].
Recently, many basic and applied studies have been performed on
graphene. Notably, the use of graphene as a supporting material offers
promising electrocatalytic performance and stability [27]. To explain its
superiority, graphene is usually incorporated with other electrode ma-
terials that function more like additive agents. Accordingly, we also
focused on launching graphene as an additive agent (for a
graphene-based material) in electrodes for batteries. Additionally, we
take advantage of its different architectures, such as graphene cages and
graphene spheres, which not only increase electron and ion transport but
also provide an enclosure assembly to buffer or accommodate the volume
expansion of metal-host composites throughout the cycles [28]. For
example, our research group [29] successfully fabricated an efficient
sulfur host material for 3D graphene-carbon nanotubes (CNTs) via a
one-pot heat treatment method. Graphene nanosheets were
self-assembled into interconnected 3D porous frameworks, and CNTs
were anchored to the internal walls of the graphene nanosheets. The 3D
graphene-CNT architecture not only efficiently developed the activity
and use of sulfur for the sulfur-based cathode but also restricted the
mobility of polysulfides in the 3D porous architecture and lowered the
soluble species in the electrolyte. Similarly, our research groups [30]
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showed that 3D porous graphene provides a conductive network in
conjunction with a large surface area that supports MnO2 nanoparticles,
efficiently increases the mechanical strength of the hybrid during volume
changes, and suppresses the aggregation of MnO2 nanoparticles during
lithium ion insertion/extraction.
In recent years, several reviews related to batteries have been pub-
lished by different researchers [31–33] but not much attention has been
given to reviewing the role of graphene in electrochemical energy storage
batteries, for example, the role of graphene morphology. Therefore, a
comprehensive and timely review focusing on graphene applications is
urgently required. Our review covers the entire spectrum of
graphene-based battery technologies and focuses on the basic principles
as well as emerging strategies for graphene doping and hybridisation for
different batteries. In this comprehensive review, we emphasise the
recent advancements in the controllable synthesis, functionalisation, and
role of graphene in batteries. As the operation principles of
graphene-based materials have been depicted in detail, here, we focus on
recent research advancements in understanding the key challenges and
strategies for their commercialisation. More importantly, the regulatory
role of graphene in batteries such as LIBs, LSBs, and LOBs has been
comprehensively studied from the perspectives of essential electro-
chemical reactions, electrode morphology, and integral energy storage
cell design (Fig. 1).
Finally, perspectives on how graphene can further contribute to the
progress of electrochemical batteries are presented, and future research
directions for the use of graphene in various battery fields are considered.
2. Graphene synthesis
It is well recognised that graphene's characteristics greatly depend on
the synthesis route employed. Graphene nanomaterials with various
morphologies have been prepared, including graphene fibres, graphene
balls, graphene scrolls, graphene networks, graphene tubes, graphene
cages, graphene vertical sheets, and graphene with other architectures.
Generally, the synthesis of graphene is divided into two main categories,
namely, top-down and bottom-up techniques [34]. In recent years, many
chemical and physical methods have been proposed for the synthesis of
graphene materials, including unzipping of CNTs, reduction of graphene
oxide, microwave synthesis, epitaxial growth on single-crystal silicon
carbide, chemical vapour deposition (CVD) on metal surfaces,
liquid-phase exfoliation, micromechanical cleavage (the original
scotch-tape method), chemical coupling reaction, soni-
cation/intercalation, ball milling, and other techniques. An outline of the
graphene production methods is presented in the flowchart in Fig. 2 [35].
Owing to their high cost for large-scale production and limited scal-
ability, techniques such as bottom-up synthesis, synthesis of carbon, and
mechanical exfoliation impede the use of graphene in key applications.
CVD is a well-established technique for producing vertically-oriented
graphene nanosheet electrodes; however, owing to its low yield, mod-
erate product purity, and high cost, the CVD method seems unsuitable for
large-scale graphene production for electrochemical energy storage [36].
Liquid-phase exfoliation and reduction of graphene oxide are two widely
employed techniques for bulk production of graphene. In the reduction of
graphene oxide, which is an extremely defective form of graphene, it is
synthesised by the strong oxidation of pristine graphite, followed by
ultrasonication of graphite in a liquid medium. To re-establish the
π -network, graphene oxide must be reduced, which is a characteristic of
conductive graphene [37]. In the liquid phase exfoliation method,
expanded or pristine graphite particles are obtained via thermal expan-
sion of graphite intercalation compounds (typically called expandable
graphite), which are dispersed in a solvent to decrease the strength of the
intermolecular force between graphene layers [38]. Subsequently,
external driving forces such as an electric field, ultrasonication, or
shearing are applied to induce the exfoliation of graphite into
high-quality graphene sheets. More importantly, the high scalability and
low cost of liquid-phase exfoliation make it desirable for large-scale
A. Ali et al. Nano Materials Science xxx (xxxx) xxx

Fig. 1. Representative graphene-based electrocatalysts are used for batteries.

Fig. 2. Synthesis route flow chart of graphene. Reproduced with a license from ref. [35] Copyright (2016) Springer.

Fig. 3. The most familiar synthetic mechanism for constructing graphene-based nanomaterials (graphene oxide, graphene oxide-based compounds, reduced graphene
oxide, reduced graphene oxide-based compounds) for utilisation as electrode active nanomaterials in batteries. Reproduced with a license from ref. [41] Copyright
(2015) Macmillan Publishers Limited.

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A. Ali et al.
graphene construction. Chemical, electrochemical, and thermal tech-
niques are commonly used to produce reduced graphene oxide (rGO).
More specifically, owing to the existence of both extrinsic defects (H and
H-containing groups) and intrinsic defects (deformations and edges) in
the obtained material, these techniques allow high-yield and
cost-effective graphene production [39,40].
Several recent studies have explored graphene-based materials for
electrochemical energy storage. In many experiments, graphene was
produced from graphite. As seen in Fig. 3, expandable graphite can be
thermally expanded and then exfoliated to produce graphene. Graphene
also can be obtained via directly exfoliation of graphite in liquid
dispersant or first oxidation of graphite and then reduction of GO [41]. It
is worth noting that the morphology of graphene can be altered using
different strategies to adjust its characteristics and performance. Gra-
phene production techniques include (i) self-assembly of ordered nano-
composites, (ii) surface re-engineering of graphene nanosheets with
surfactant species, (iii) coating/deposition of metal, metal oxides, and
other electrochemically active materials on graphene nanosheets, and
(iv) direct fabrication of graphene nanosheets into porous electrode
materials [42].
3. Functionalisation of graphene
Owing to its unique morphology and exclusive properties, graphene
has been demonstrated as an attractive candidate for batteries, but it is
rare for graphene-based electrodes with desirable characteristics to also
have essential surface properties specific for certain applications [43]. In
several cases, functionalisation is the ideal approach to realise the
remarkable performance of graphene or graphene oxide. In this respect,
graphene and graphene oxide are modified by chemical or physical ap-
proaches via both covalent bonds and noncovalent interactions [44].
Usually, functionalisation through covalent interactions deals with the
sp2 configuration of graphene lattices, which results in defects and loss of
electronic characteristics [45]. Noncovalent functionalisation is gener-
ally favoured as it does not change the morphology and electronic
characteristics of graphene; in contrast, it introduces new chemical
groups. Electron donor-acceptor complexes, polymer wrapping, π
π
linkages, and weak van der Waals forces are common examples of non-
covalent functionalisation [46].
Subsequently, various functionalisation techniques including het-
eroatom doping, edge functionalisation, and topological/structural de-
fects (Table 1) have been developed for the synthesis of graphene-based
materials for batteries.
3.1. Heteroatom doping
Heteroatom doping through the insertion of heteroatoms (for
example, boron, phosphorous, nitrogen) into the graphene network
could trigger electron modulation to optimise the optoelectronic features
and those chemical activities are especially beneficial for electrochemical
energy storage systems [47–49]. In particular, the introduction of het-
eroatoms in graphene results in “extrinsic defects”, and the introduction
Table 1
Functionalisation of graphene.
Methods Feature Advantages Disadvantages
Heteroatom doping Heteroatoms into the Optimise the optoelectronic
graphene network features, obtain extrinsic or
intrinsic defects
Edge functionalisation Via reactive edge sites Provides abundant active
form covalent sites, maintain the
interactions physicochemical properties
Topological and structural defects Engender different Directly serve as
dimensions defects electroactive sites, provide
anchoring sites for active
species
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or removal of carbon atoms into or from graphene nanosheets gives rise
to edges, deformations, and vacancies, which are known as “intrinsic
defects” [50]. Therefore, it is very important to obtain chemically func-
tionalised graphene with controlled doping concentration for electro-
chemical energy storage applications [49,51].
For example, freeze-dried graphene oxide sheets were treated via
thermal nitridation in an ammonia atmosphere. After thermal nitrida-
tion, the oxygenated functional groups on the graphene oxide nanosheets
were decomposed and partially transformed into nitrogen functional
groups. As shown in Fig. 4, the functionalised nitrogen functional groups
of N-doped graphene nanosheets are excellent for trapping intermediate
higher-order lithium polysulfides and boosting their redeposition
mechanism upon discharge/charge via strong SXLi … N interactions [52].
Our groups [53] synthesised functionalised 3D graphene powder
material by metal sulfide catalytic growth followed by KOH chemical
activation for application in electrochemical energy storage in super-
capacitors. Owing to its large surface area of 1687.8 m2 g
1, outstanding
3D framework, and abundant level of oxygen heteroatom doping of
7.76%, the as-prepared functionalised 3D graphene demonstrated a high
specific capacitance of 285.2 F g
1 at 1 A g
1 and remarkable electro-
chemical stability. Furthermore, our groups [54] successfully demon-
strated the functionalisation of graphene via doping. Three-dimensional
(3D) crumpled nitrogen and boron co-doped graphene nanosheets
(NBGs) were fabricated using a heat treatment method. Owing to the
doping of nitrogen (7.72%) and boron (7.18%), as well as the unique 3D
crumpled morphology, the NBGs ensure a large number of lithium ion
storage sites and fast electron transfer and lithium ion transportation. In
another study, our research group [55] explored the role of functionali-
sation in which the highly dense (HD) TiO2 N-rich rGO (N-rGO) monolith
electrode demonstrated high volumetric lithium/sodium storage,
remarkable rate, and superior ultralong cycle performance. The syner-
getic effect between TiO2 and N-rGO and the novel compact monolith
electrode design are described in Fig. 5. The N-rich surface of the N-rGO
material can provide a large number of coordination sites for stable
anchoring, and the uniform growth of TiO2 is considered for the
long-term cycling stability of the hybrid monolith. Moreover, the small
TiO2 nanoparticles anchored on N-rGO can significantly shorten the ion
diffusion length in the solid phase and promote more active electro-
chemical reactions. The porous compact hybrid monolith offers an in-
tegrated electrode with high compact density and fast electron/ion
transportation, thereby accomplishing rapid and high volumetric lith-
ium/sodium storage.
3.2. Edge functionalisation
Surface functionalisation is important for fabricating graphene-based
materials with excellent bulk and surface features, which are essential for
efficient storage systems. More significantly, graphene edge sites are
more reactive and are responsible for the covalent interactions of several
chemical species. The graphene structure and characteristics can be
largely retained after edge functionalisation with minimal damage to the
carbon basal plane, unlike graphene functionalisation of the basal plane,
Ref.
Cause structural deformation and change the electronic band structure [47–51]
Lead to defects and loss of electronic characteristics [45,56]
Emerge a distortion of the graphene π-network [58]
A. Ali et al. Nano Materials Science xxx (xxxx) xxx

Fig. 4. Schematic of the creation of S@NG hybrid and nitrogen functional groups for trapping Li2Sx. Reproduced with a license from ref. [52] Copyright (2014)
American Chemical Society.

Fig. 5. Diagram showing the morphological merits and remarkable lithium/sodium storage mechanism of the HD-TiO2-N-rGO electrode in a battery system.
Reproduced with a license from ref. [55] Copyright (2019) American Chemical Society.

which often causes distortion of the π–π conjugation and related physi-
cochemical characteristics. Both theoretical and experimental studies
have demonstrated graphene materials' specific edge chemistry and
characteristics. Edge functionalisation is carried out via many methods,
such as edge functionalisation of graphene oxide, edge functionalisation
of graphene by chemical exfoliation, edge functionalisation of 2D cova-
lent organic polymers, and edge functionalisation of graphene by ball
milling [56].
For example, Park et al. [57] synthesised edge-functionalised gra-
phene nanoplatelets using a ball-milling method (Fig. 6a). The SEM
image (Fig. 6b) shows stacked pristine graphite flakes. The SEM image
(Fig. 6c) of the rGO sample exhibited a typical defective structure with
wrinkled graphene nanosheets because of defects in the basal plane. As
shown in Fig. 6d, the edge-functionalised graphene nanoplatelets show a
smaller grain size than pristine graphite, which indicates the successful
cleavage of graphitic C–C bonds. It can be concluded that oxygen defects
mainly exist at the edge sites of edge-functionalised graphene
nanoplatelets. Therefore, the effective location of oxygen defects accel-
erates fast electron transfer and mass transport.
3.3. Topological and structural defects
Structural and topological defect functionalisation has emerged as a
promising strategy for enhancing the performance of graphene. Struc-
tural defects directly serve as electroactive sites or provide anchoring
sites for other active species such as metals and heteroatoms. Defects in
graphene have a direct impact on its properties. Similar to macroscopic
crystalline materials, graphene's structural and topological defects have
different dimensionalities.
Multiple defects in graphene have been used to improve graphene
performance (Fig. 7). Like the case of macroscopic crystalline materials,
structural defects in graphene have different dimensionalities. Zero-
dimensional point defects consist of Stone Wales, vacancies, adatoms,
and substitutions. Due to the reduced dimensionality, one-dimensional

5
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Fig. 6. (a) Schematic of the edge-functionalised graphene nanoplatelet synthesis process. SEM images of (b) pristine graphite, (c) reduced graphene oxide (rGO), and
(d) edge-functionalised graphene nanoplatelet samples. Reproduced with a license from ref. [57] Copyright (2015) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 7. Summary of topological and structural defects in graphene. Reproduced with a license from ref. [58] Copyright (2018) Elsevier.

line defects emerge in different situations from those in bulk crystals. Not
only edge dislocations but grain boundaries are 1D lines along which
atoms are arranged anomalously. Interstitials between the layers can
bridge the adjacent layers, forming higher dimensional structures.
Stacking fault is another typical defect in few-layer graphene [58].
4. Roles of graphene in lithium batteries
Owing to the mysteries that graphene involves, it is also called a
wonder material. Notably, graphene can be an effective material when it
takes part in the electrochemical energy storage system [59].

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Furthermore, graphene has the capability to boost lightweight, durable, Table 2

stable, and high-capacity electrochemical energy storage batteries with Graphene-based materials for Li-ion batteries (LIBs).
quick charging time. Graphene has the capability of charging smart- Graphene based Capacity performance Cycling stability Ref.
phones with electricity in a short time. For example, the traditional materials (After the number of
lifecycle of LIBs can be enhanced, and they can be charged in a short cycles)
time, stocking more power for a prolonged period. Graphene-based Ni7S6/graphene Reversible capacity of 95% capacity [65]
electrodes are so lightweight and flexible that they can be stitched nanosheet 1010 mAh g
1 at a retention at a current
comfortably into the dress of soldiers who used to carry approximately current density of density of 120 mA
0.12 A g
1 g
1 (2000 cycles)
7.25 kg of batteries. More importantly, graphene increases the energy 3D graphene/CuO Reversible capacity of 99% capacity [66]
power of planes and cars and decreases the weight compared to con- 409 mAh g
1 at a retention at a current
ventional devices. Recently, graphene-based nanomaterials have been current density of 100 density of 1600 mA
developed for different types of batteries, such as LIBs, LSBs, and LOBs. mA g
1 g
1 (50 cycles)
MoS2/SnS2-graphene Reversible capacity of 722 mAh g
1 at a [67]
1244 mAh g
1 at a current density of
4.1. Lithium-ion batteries current density of 150 0.75 A g
1 (200
mA g
1 cycles)
LIBs have dominated solid-state electrochemical research and the 3D MnFe2O4/CN- Reversible capacity of 73% capacity [68]
NG(0.4) 1032 mAh g
1 at a retention at a high
advancements in portable electronics for the past twenty years [60]. LIBs
current density of 0.1 current density of
are widely used in the emerging electrical/hybrid vehicles and power A g
1 1.0 A g
1 (800
consumption devices (e.g., tablets, laptops, and smartphones) and have cycles)
dominated the current rechargeable battery market owing to their great BDT/3D graphene Reversible capacity of 80% capacity [69]
longevity and high energy density [61]. Furthermore, much attention 210 mAh g
1 at 0.1C retention at 0.5C
(200 cycles)
needs to be paid to the development of reliable LIBs with high energy,
LTO/N, S-PG Rate capability of 130 83.1% capacity [70]
large capacity, and power density, as well as a prolonged lifetime. Sig- mAh g
1 at 80 C retention at 20 C
nificant developments in battery performance and cost reductions are (4000 cycles)
expected to come from new battery chemistries based on different con- SnO2/graphene material Reversible capacity of 97% capacity [71]
1420 mAh g
1 at a retention at a high
figurations at the cell and system levels as well as different storage
current density of 0.1 current density of
mechanisms at the material level [62]. Various innovative materials are A g
1 1.0 A g
1 (230
flourishing to replace traditional electrodes, providing substantial po- cycles)
tential for next-generation high-power LIBs. Graphene, which has the SnO2@reduced graphene Reversible capacity of 67% capacity [72]
advantages of excellent structural stability, outstanding electrical con- oxide 1149 mAh g
1 at a retention at a high
current density of 0.2 current density of
ductivity, tunable surface functionality, and good mechanical properties,
A g
1 0.2 A g
1 (130
has attracted considerable research attention in the field of LIBs [63,64]. cycles)
Graphene can act as an efficient track for electron transportation, thereby few-layered Reversible capacity of 76% capacity [73]
boosting electron transport between the electrode active materials and NbSe2@graphene 1142 mAh g
1 at a retention at a high
current collectors. This can reduce the internal resistance of LIBs and current density of 0.1 current density of 10
A g
1 A g
1 (1000 cycles)
improve their output power. In addition, graphene's superior mechanical P–SnO2@graphene Reversible capacity of 94% capacity [74]
properties benefit electrode materials' stability, leading to enhanced rate 860 mAh g
1 at a retention at a high
capability and cyclic stability. We reviewed the role of graphene in LIBs current density of 0.5 current density of
by studying its potential to address the issues of new battery chemistries A g
1 0.5 A g
1 (50 cycles)
Graphene encapsulated Reversible capacity of 843 mAh g
1 at a [75]
and the problems associated with graphene-based materials. Recently
nanosheet-assembled 1094 mAh g
1 at a current density of
reported graphene-based materials for LIBs are listed in Table 2. ZnO–Mn–C current density of 100 2000 mA g
1 (1000
Crumpled graphene scaffold (CGS) balls are remarkable building mA g
1 cycles)
blocks for the synthesis of high-performance Li-metal anodes. In this PM reduced graphene Reversible capacity of 100% capacity [76]
work, CGS was accumulated on demand by facile solution casting using oxide 1075 mAh g
1 at a retention at a high
current density of 50 current density of
arbitrary solvents. The high Coulombic efficiency and ultralong stable mA g
1 2000 mA g
1 (400
cycling Li within the CGS are ascribed to the high conductivity, light cycles)
weight, lithiophilicity, and chemically robust stability [79]. Similarly, 3D TiO2 nanorods/rGO Rate capacity of 205.1 353.6 mAh g
1 at a [77]
flexible nanohybrid foams consist of graphene foam@CNTs loaded with composite mAh g
1 at a current current density of
density of 2 A g
1 0.1 A g
1 (100
MoS2 nanoparticles for LIBs. The 3D architecture of the graphene hybrid
cycles)
foam increases the electrode and electrolyte contact, decreases the Li-ion 3D graphene/Fe2O3 Rate capacity of 1129 98% capacity [78]
diffusion distance, and affords an internal void space to accommodate the mAh g
1 at a current retention at 5 A g
1
enhanced volume change caused by the MoS2 nanoparticles. CNTs density of 0.2 A g
1 (1200 cycles)
encapsulated by graphene foam are a promising conductive material to
facilitate electron/ion transport within the hybrid foam and increase its
graphene layers by the larger d-spacing due to the created functional
flexibility [80]. Furthermore, our research groups [81] explored the role
groups.
of graphene in the NiCo2S4@graphene nanosheet hybrid, in which gra-
To construct flexible LIBs with high capacity and rapid charge and
phene nanosheets with rich mesoporous network architectures can
discharge rates, Li et al. [83] integrated highly conductive porous and
function as a conductive matrix and a shielding layer to suppress the
flexible graphene with Li4Ti5O12 (LTO) and LiFePO4 (LFP) as the anode
volume expansion of NiCo2S4 nanoparticles. Ershadi et al. [82] devel-
and cathode, respectively, as shown in Fig. 8. More significantly, the 3D
oped an efficient and facile process for the stitching and functionalisation
porous graphene network was directly used as a highly conductive
of graphene oxide (GO) nanosheets and ethylenediamine (EDA). EDA
channel for electrons/lithium ions and current collectors for LIBs without
was used as a factor to regulate the 3D morphology of the graphene
the use of conventional metal current collectors, carbon black additives,
nanosheets, as well as a nitrogen source to produce N-doped graphene.
and binders.
The porous channels of the GO-EDA composite were considered for the
The multilayer graphene films, which were conformally and directly
transportation of Li ions. Furthermore, the enhanced electrochemical
grown on industrial Al foil using a plasma-enhanced CVD technique,
performance was attributed to the increased Li-ion transport within the

7
A. Ali et al.
Fig. 8. Schematic of a flexible lithium-ion battery (LIB) containing an anode and cathode made from 3D interconnected graphene. Reproduced with a license from ref.
[83] Copyright (2012) Proceedings of the National Academy of Sciences.
worked as an extraordinarily conductive shield that could efficiently
thwart the attacks of the anions or other coordinating species to Al3þ
ions. Consequently, the possibility of coordination between Al3þ ions and
other species was drastically minimised or even disabled. As shown in
Fig. 9, the Al foil encapsulated in a conductive graphene sheath exhibits
significantly reinforced resistance against anodic corrosion. Additionally,
using LiMn2O4 as a model system, cells using graphene-encapsulated Al
foil as current collectors exhibit enhanced electrochemical performance,
including outstanding long-term cycling performance at a low rate,
relieving self-discharge propensity, and remarkable rate/power perfor-
mance [84].
Hollow and hierarchical porous interconnected frameworks have a
large number of pores and, owing to their large surface area, they
decrease the ion/electron diffusion distance, enhance the transportation
rate, and improve the buffer penetration of Li ions for remarkable elec-
trochemical performance. Zhang et al. [85] applied a facile method to
prepare 3D hollow carbon spheres encapsulated on rGO composite
(DHCSs/rGO) for high-performance LIBs. Based on density functional
theory (DFT) and a newly proposed atom pair adsorption strategy, Wu
et al. [86] studied the mechanisms and performance of nitrogenated
holey graphene C2N monolayer anodes for high-performance LIBs.
Notably, the carbon atoms' P-shell electrons hybridising with the
Fig. 9. Schematic of graphene encapsulated aluminium foil with a remarkable anticorrosion property used as a current collector for LIBs. Reproduced with a license
from ref. [84] Copyright (2017) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
8
Nano Materials Science xxx (xxxx) xxx
nitrogen atoms' lone pair electrons create many accessible active sites.
Furthermore, a large number of attracted metal atoms are observed due
to the relatively lightweight elements and the holes in C2N, resulting in
dangling of the adjacent N-atoms. Wang et al. [87] developed an easy
strategy to prepare cobalt boron nanoparticles fabricated on rGO
(Co–B/rGO) with active boron as Li-ion storage sites. The 2D morphology
of rGO can efficiently enhance electrode/electrolyte contact and boost
the transportation of Li ions. The morphology of Co–B/rGO remained
unchanged after cycling (Fig. 10a) and it exhibited structural stability
after charging/discharging. A comparison of the specific capacities re-
ported in previous studies at distinct current densities is shown in
Fig. 10b. Furthermore, Fig. 10c illustrates the structure and lithiation
process of Co–B/rGO as an anode material for LIBs. Significantly, the
amorphous 2D architecture and substantial pseudocapacitive perfor-
mance during lithiation/delithiation also increase the diffusion of elec-
trons and Li ions. Co–B/rGO delivers high rate, high capacity, and
long-lifetime electrochemical characteristics for LIBs.
In recent years, red phosphorus has gained wide attention for LIBs,
but its low electrical conductivity and large volume expansion have
hampered large-scale applications. Therefore, Jiao et al. [88] designed
red phosphorous/crumpled N-doped graphene (P/CNG) nanocomposites
with excellent rate performance and high capacity density as anode
A. Ali et al.
Fig. 10. (a) TEM image of Co–B/rGO electrocatalyst after cycling. (b) Assessment of the rate activity of the cobalt-based anode in this and previous studies. (c)
Schematic of the Li-ion transfer activities within the Co–B/rGO and lithiation process. Reproduced with a license from ref. [87] Copyright (2018) Elsevier.
materials for LIBs. The nanohybrid morphology of P/CNG enhances the
electron conductivity and alleviates the volume change of red phos-
phorus. The restacking of rGO nanosheets limits their rate performance
and capacity in LIBs. To address this issue, Meng et al. [89] prepared an
rGO sandwiched N-doped carbon (rGO@NDC). The implantation of NDC
nanoparticles on the surface of rGO nanosheets protects the restacking of
rGO nanosheets, increases the interlayer space of rGO to ease Li-ion
transportation inside the composite, decreases the number of superfi-
cial oxygen-containing functional groups, and reduces side reactions
during battery cycling. Xiong group's [90] described an easy hydrother-
mal method for the synthesis of functionalised N-doped graphene
nanosheets (Fig. 11a). The as-prepared N-doped graphene was employed
as a cathode in LIBs and delivered remarkable rate potential, promising
reversible capacity, and long-life cycling stability owing to its unique
active oxygenic functional groups, high nitrogen doping, and 3D porous
morphology. The promising progress of a self-standing 3D inter-
connected cellular morphology of S-doped graphene is based on a facile
method involving the soft assembly of polymer chains, followed by
thermal treatment. Atomic hybrid orientation and nanostructured
morphology are promising developments for S-doped graphene that offer
excellent performance for LIBs. The ultra-light 3D cellular morphology of
S-doped graphene, with eco-friendly and economic nanomaterials, ex-
hibits potential for wearable and advanced portable electronics and the
assembly of batteries for large electric vehicles [91]. Liu et al. [92]
developed an economical, clean, and scalable method to construct
nitrogen-doped graphene nanosheets (NGNS) from urea with solid
ball-milled graphite. The N-doping content of NGNS is mostly of pyrrolic
and pyridinic types, which are located at the edges of graphene nano-
sheets. Compared to undoped graphene, the as-prepared NGNS showed
enhanced rate potential and cycling stability for LIBs. Luan et al. [93]
reported the arch-discharge synthesis of prime quality fluorine-doped
graphene as an anode for LIBs (Fig. 11b). The as-prepared F-modified
graphene showed excellent electrical conductivity, high atomic C/O
ratio, wrinkles, and crumpled surfaces. It is worth noting that the in situ
synthesis of LiF nanoparticles during the first Li-ion insertion mechanism
promisingly impedes the restacking and agglomeration of graphene
nanosheets, ensuring the interlayer spacing, which provides sufficient
voids for rapid Li-ion insertion/extraction. Therefore, the as-prepared
F-modified graphene delivered high reversible capacity, outstanding
rate potential, and excellent cycling stability for LIBs. Chen and
9
Nano Materials Science xxx (xxxx) xxx
co-workers [94] developed N-doped graphene/MoS2/N-doped graphene
heterostructures via a low-cost and scalable in situ thermal decomposi-
tion reduction process. The as-prepared NDG/MoS2/NDG showed inti-
mate interface interactions/full NDG encapsulation and a high degree of
crystallisation of the MoS2 nanoparticles. Furthermore, the N-doped
graphene coating layers exhibit remarkable advantages for solving the
polysulfide shuttling problem. A high-quality N-doped mesoporous gra-
phene (HNMG) electrode was developed for fast-charging and
high-energy LIBs. The unique morphology of the HNMG composites is
responsible for sufficient active sites for ion storage, effective ion and
electron transportation, and electrochemical and structural stability,
leading to remarkable rate performance, high energy capacity, high
Coulombic efficiency, and ultra-long lifetime cycling [95]. Multilayered
graphene (MLG) plays a significant role in LIBs (Fig. 11c). The SiOx/TiO2
composite encapsulated by multilayered graphene (denoted as SiOx/-
TiO2@MLG) exhibited a high capacity of 1484 mAh g
1 and an ultralong
lifespan of over 1200 cycles at 2 A g
1. MLG can develop electrical
conductivity, mitigate electrolyte decomposition, and effectively alle-
viate the volume effect of SiOx [96].
4.2. Lithium-sulfur batteries
Owing to the reversible storage of substantial electrical energy at low-
cost, LSBs have emerged with a theoretical energy density of 2500 Wh
kg
1 as promising candidates in the lithium energy storage field [97,98].
Sulfur is inexpensive, abundant in nature, and is produced in large
quantities as a waste product of the gas and oil industries [99]. Signifi-
cantly, the electrochemical reduction of sulfur gives a theoretical ca-
pacity of 1672 mAh g
1, comparable to that of the state-of-the-art lithium
ion cathode materials [100]. Furthermore, replacing LIBs in an electric
vehicle with LSBs of equal energy storage capacity promisingly decreases
the vehicle's weight [48,101]. However, LSBs suffer from low rate
capability and poor cycle stability, which limits their practical applica-
tions. Graphene, which has a large surface area and remarkable catalytic
properties, is a key material for LSBs. Graphene serves as a porous
backbone for supporting sulfur to improve the conductivity and hold the
polysulfide products formed during the discharge process in LSBs. We
review recent advances in graphene for addressing a fundamental issue in
LSBs, that is, the dissolution of polysulfides, focusing on both computa-
tional and experimental methodologies to tailor the chemical
A. Ali et al. Nano Materials Science xxx (xxxx) xxx

Fig. 11. (a) Schematic of the N-doped functionalised graphene. Reproduced with a license from ref. [90] Copyright (2017) American Chemical Society. (b) Schematic
of the fluorine modified graphene synthesis process. Reproduced with a license from ref. [93] Copyright (2019) Elsevier. (c) Schematic configuration of the lithium-ion
full battery. Reproduced with a license from ref. [96] Copyright (2020) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

interactions between polysulfides and sulfur host materials. The config-
uration, role of graphene, and performance of the LSBs are listed in
Table 3.
The excellent flexibility and lightweight advantages of rGO substrates
make them promising for flexible high-energy-density LIBs. To assess the
practical viability of 3D rGO foam@S as a cathode and rGO@Li as an
anode, Li et al. [114] engineered and demonstrated its performance in
Li–S batteries (Fig. 12a). It is worth noting that highly flexible LSBs with
such a specific topographic feature show a high specific energy density of
754 Wh kg
1 and a power density of 377 W kg
1. Our research group
[109] prepared 3D hierarchical nanoporous carbon materials obtained
from cationic resins and used them as an intermediate layer to boost the
rate performance and cyclic stability of LSBs. Consequently, stereotaxi-
cally constructed multiporous graphene with a large number of pores, a
large specific area (824 m2 g
1), and excellent conductivity (1.6  103 S
m
1) has been used in cathodes to improve the conductivity of sulfur,
enhance the electrolyte contact, and increase Li-ion transportation. Based
on experimental data, we concluded that the remarkable performance is
due to the confinement of lithium polysulfides by the mesoporous and
microporous morphology of the hierarchical composite. The sluggish
redox kinetics and diffusion of polysulfides (LiPSs) affect the rate capa-
bility and cyclability of the LSBs. To solve these issues, Kong et al. [108]
designed porphyrin-derived graphene-based nanosheets (PNG) for LSBs.
The PNG surface was coated with lithiophilic sites to offer robust
chemisorption to LiPSs and enhance electrolyte wettability. More
significantly, the graphene substrate affords fast electron transport to
accelerate the redox kinetics of sulfur species. As shown in Fig. 12b, the
PNG composite with spatially modulated dopant dispersion is a
remarkable host for sulfur compared with homogeneously N-doped
graphene (NG) and undoped graphene nanosheets with weak attraction
to LiPSs, which suffer from low electrical conductivity. Fan et al. [111]
designed a selective interlayer structure to reduce the charge transfer
resistance and control the shuttling issue by coating the cathode surface
with a thin film of boron nitride nanosheet/graphene. The novel inter-
layer provides a remarkable approach for increasing the performance of
LSBs. As a proof of concept, the specific capacity and cycling stability of
LSBs with a cathode of S-containing porous CNTs have been improved
owing to the ultralight and thin interlayer (Fig. 12c). Hu et al. [115]
reported a new approach to suppress dendrite growth in LSBs with high
sulfur deposition by hosting graphene quantum dots (GQDs) in the
electrolyte. In this work, the GQDs provided heterogeneous sites for
uniform nucleation and controlled the continuous regulation of
dendrite-free lithium deposition. Notably, high loading LSBs using the
GQD-modified anolyte exhibited stable 99% Coulombic efficiency at a

10
A. Ali et al. Nano Materials Science xxx (xxxx) xxx

Table 3 LSBs. It is worth noting that amphiphilic polymer binders in combination

Configuration, role of graphene, and performance of LSBs. with porous graphene are considered to have large pore volumes, high
Graphene based materials Initial capacity Remaining capacity (After Ref. surface areas, engineered functional layers with excellent electrical
the number of cycles) conductivity, and remarkable strength for chemisorption of polysulfides.
TiN@C/Graphene 1490.2 mAh 635.8 mAh g
1 at 1 C [99] Therefore, LSBs with porous graphene separators and sulfur loading of
g
1 at 0.1C (600) 1.8–2.0 mg cm
2 showed high sulfur use at a very low self-discharge rate
3D hierarchical N-doped 1465.1 mAh 849.1 mAh g
1 at 2.0C [102] and enhanced rate capability. In working Li–S cells, dynamic and static
graphene/CNTs g
1 at 0.1C (500) suppression of the shuttle effects of hybrid separators occurs via both the
3D N-doped graphene/ 1510 mAh g
1 1267 mAh g
1 at 0.5C [103]
TiN at 0.5C (100)
chemical binding of intermediates on a binder and the physical trapping
S@exfoliated B-doped 1018 mAh g
1 838 mAh g
1 at 1 C (130) [104] of polysulfides onto porous graphene. Zhang et al. [110] prepared
graphene sheets at 1 C S-doped graphene using a CVD technique, followed by ball milling. The
N-doped graphene–CNTs 1221 mAh g
1
1
321 mAh g at 0.2C [105] mechanical milling effect to dope sulfur into the graphene lattice
hybrid at 0.2C (1000)
promises graphene affinity for the entire S-species and increases con-
ALDVO@3D N-Graphene 1256 mAh g
1 1113 mAh g
1 at 0.5C [106]
at 0.5C (100) ductivity for high-performance LSBs. Notably, excellent heterojunctions
Ni@ nitrogen-doped 1598 mAh g
1 612 mAh g
1 at 10.0C [107] were found between the S-doped graphene and sulfur nanoparticles,
graphene at 0.1C (500) promising for the transportation of ions and electrons.
Porphyrin-derived 1135 mAh g
1 798 mAh g
1 at 0.5C (300) [108] Zhang et al. [107] designed a uniform distribution of single nickel
graphene nanosheets at 0.5C
Stereotaxically 1008 mAh g
1 532 mAh g
1
at 1 C (300) [109]
atoms on N-doped graphene (Ni@NG) with a Ni–N4 structure and
constructed graphene at 0.5C, introduced it to modify the separators of LSBs. The oxidised Ni sites of the
S nanoparticle/S-doped 1216 mAh g
1 666 mAh g
1 at 0.5C (300) [110] Ni–N4 nanostructure reversibly catalysed the conversion of LiPS by
graphene at 0.1C forming S2
x … Ni–N bonds. Furthermore, the novel Ni–N4 nanostructure
FBN/graphene interlayer 1100 mAh g
1 278 mAh g
1 at 3 C (1000) [111]
of Ni@NG induced large binding energy, which robustly limited the
at 3 C
N-doped hierarchical 868 mAh g
1 403 mAh g
1
at 2 C (800) [112] dissolution of LiPS and the shuttle effect. The remarkable kinetic con-
graphene at 2 C version of LiPS on Ni@NG was ascribed to the low decomposition energy
rGO-La(OH)3 1160.4 mAh 541.7 mAh g
1 at 1 C [113] of the Li2S nanoparticles. Moreover, the Ni@NG nanocomposite immo-
g
1 at 0.2C (600) bilised LiPS and accelerated its kinetic conversion throughout the charge
and discharge processes. Zhang and co-workers [117] performed a sys-
current density of 3 mA cm
2. tematic study of graphene, N-doped graphene, Fe, and N co-doped gra-
Zhai et al. [116] developed an easy and scalable approach for con- phene nanomaterials for the sulfur cathode in LSBs to find new
structing porous graphene-modified separators for commercially stable chemically functional graphene with shuttling suppression abilities and

Fig. 12. (a) Schematic configuration of the

development of the 3D rGO foam@S cathode
and rGO@Li anode and configuration of the
Li-S full cell. Reproduced with a license from
ref. [114] Copyright (2019) WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim. (b)
Schematic of the vital responsibilities of
porphyrin-derived graphene-based nano-
sheets (PNG) for sulfur species. Conversion
graphene (G) with non-polar nature reveals
weak attraction to LiPSs. N-doped graphene
prefers LiPS attraction but is restricted by
low electrical conductivity. Furthermore,
PNG provides at the same time mediated
electron transfer and LiPS transportation for
the effective working of lithium-sulfur bat-
teries (LSBs). Reproduced with a license
from ref. [108] Copyright (2018)
WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim. (c) Schematic of a Li–S cell with
an FBN/G interlayer. Reproduced with a li-
cense from ref. [111] Copyright (2017)
WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.

11
A. Ali et al.
remarkable electrocatalysis. As a result, the Fe and N co-doped graphene
monolayer is an excellent nanomaterial, in which the four-member
Li–S–Fe–N ring nanostructure ensures the stability of adsorption and
allows the adsorption energy to be within a suitable range. Furthermore,
Fe–N4@graphene exhibits full discharge of LiPSs due to the catalytic
effect of the 3d electrons of doped iron and the low decomposition en-
ergies of lithium sulfides. The poor conductivity and intricate
charge-discharge reactions of sulfur reveal the significance of cathode
engineering for LSBs. Sun et al. [118] prepared porous spinal ZnCo2O4
nanoparticles fabricated on N-doped rGO (ZnCo2O4@N-rGO) via a
combined refluxing and hydrothermal treatment approach. The
as-prepared ZnCo2O4@N-rGO acted as an inimitable cathode scaffold to
suppress the shuttling of polysulfides through chemical confinement.
Owing to the new compositional and morphological characteristics, the
ZnCo2O4@N-rGO composite with 71% sulfur loading delivered high
specific capacity, excellent rate performance, and promising cycling
stability with exceptional initial Coulombic efficiency, exhibiting
remarkable use of sulfur.
Su et al. [105] converted Prussian blue to nitrogen-doped graphe-
ne/CNT nanohybrids using a facile one-step pyrolysis method. In an
electrochemical cell, the as-prepared composite was employed as the
sulfur scaffold for LSBs, which exhibited excellent electrochemical per-
formance, remarkable rate capability of 458 mAh g
1 at a rate of 5 C, a
high reversible capacity of 1221 mAh g
1 at 0.2C rate, and outstanding
cycling stability of 321 mAh g
1 at 10 C after 1000 cycles. The remark-
able electrochemical performance can be ascribed to the 3D morphology
and nitrogen doping, which create defects and active sites for enhanced
interfacial adsorption. Additionally, N doping allows the successful
trapping of LiPSs on active sites inside the cathode, leading to
outstanding cycling operations.
Generally, LSBs consist of an anode and cathode separated by a
12
Nano Materials Science xxx (xxxx) xxx
polymer separator. If sulfur/lithium polysulfides can be localised in the
cathode and efficiently reused during cycling, the rate capability and
cycling stability of LSBs will be improved. Based on these considerations,
Zhou et al. [119] engineered a novel cathode with pure sulfur sand-
wiched between graphene membranes. As shown in Fig. 13a I–IV, the
graphene membrane was used as a collector with sulfur coated on it as
the active material, and the other graphene membrane was coated on a
commercial polymer separator. The conductive and flexible graphene
layers on both sides of the sulfur cathode provide remarkable electrical
conductivity, and the sandwiched architecture can adjust the large
volumetric expansion of sulfur during lithiation. Sulfur migrates inside
the graphene layers which causes the graphene current collector (GCC)
and graphene separator (G-separator) to serve as sulfur reservoirs in
addition to the current collectors. Compared with the conventional
configuration (Fig. 13b), the shuttle effect can be significantly reduced by
Zhou's designed LSBs (Fig. 13c).
High-quality heteroatom-doped graphene effectively encapsulates
sulfur and fabricates a remarkable performance electrode for LSBs. Shi
et al. [104] developed exfoliated boron-doped graphene nanosheets, in
which the doped boron atoms unambiguously generated more active
sites for trapping polysulfides via chemical adsorption. The highly porous
conductive N-doped graphene in the 3DNG/TiN composite provides
efficient pathways for both electrons and ions. The unique structure
significantly increased the electrical conductivity of the electrode and
efficiently retarded the shuttle effects owing to the strong chemical
adsorption of LiPSs, which can potentially increase the rate performance
and cycle stability of LSBs [103]. Duan et al. [120] proposed an in situ
hollow cathode discharge treatment strategy to synthesise 3D porous
N-doped graphene frameworks. The as-prepared 3D porous N-doped
graphene framework used as a cathode in LSBs exhibited a remarkable
specific discharge capacity of 1186 mAh g
1 at 0.1C. Furthermore, the
Fig. 13. (a) Schematic of the electrode con-
figurations of I) an Al foil, sulfur cathode,
and commercial separator, II) a graphene
current collector (GCC), sulfur cathode, and
commercial separator, III) an Al foil, sulfur
cathode, and graphene separator (G-sepa-
rator), and IV) a GCC, sulfur cathode, and G-
separator. (b) Schematic of an LSB with
electrode configuration a-I. (c) Schematic of
an LSB with electrode configuration a-IV.
The paler yellow colour represents the
reduced shuttle effect. Reproduced with a
license from ref. [119] Copyright (2014)
WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.
A. Ali et al. Nano Materials Science xxx (xxxx) xxx

flexible 3D porous morphology of N-doped graphene adjusts the sub- Table 4

stantial volume change of the active material during lithium insertio- Configuration, role of graphene, and performance of LOBs.
n/extraction, enhancing the ultralong electrochemical performance. Gao Graphene based materials Discharge capacity Current density Ref.
et al. [121] developed a well-organised approach to anchor soluble LiPSs (mAh g
1) (mA g
1)
via a combination of chemical and physical synergy using V2O5 hollow NiO/Ni-graphene 25986 100 [122]
spheres (VOHS) encapsulated in N-doped graphene (NG) as the sulfur Ru-decorated VGNS@Ni 14461 200 [123]
host. The N-doped graphene network offers remarkable conductivity and foam
rapidly traps LiPSs with high specific areas. Li et al. [112] prepared Ru/3D N-rGO 23922 100 [124]
Ru NPs/N-doped rGO 17074 100 [125]
nanosheets such as nitrogen-doped hierarchical graphene (N-HG) sepa- RuNC/CoSA-3D N-doped 25 632 100 [126]
rators for LSBs. Benefiting from the devious inner channel architecture, graphene
high surface area, and plentiful N-doping of CVD-grown N-HG networks, Dendrite-free fluorinated 6520 100 [127]
the derived separator promisingly synergises physical confinement and graphene
3D hierarchical porous N- 7300 50 [128]
chemical immobilisation toward polysulfides followed by smooth Li-ion
doped graphene
diffusion. CMF-graphene-Co/CoO 4292 200 [129]
Pt-coated hollow graphene 5600 100 [130]
4.3. Lithium-oxygen batteries nanocages
Hierarchical graphene-based 19800 1000 [131]
electrode
LOBs, which utilise oxygen from the air, have the highest theoretical N and S co-doped graphene 11431 100 [132]
specific energy of any rechargeable battery and can transform electro- nanosheets
chemical energy storage if a practical device can be accomplished [9]. Porous graphene quasi-solid 33230 1000 [133]
Rechargeable LOBs have received great attention for use in state
NCO@N-rGO 6716 200 [134]
next-generation high energy density storage applications. The effective
operation of LOBs in an organic electrolyte requires reversible growth
and decomposition of insoluble Li2O2 on the cathode surface during approach to electrolyte and fast oxygen diffusion. Lin group's [138]
charging and discharging. The large overpotential limits the efficiency of presented graphene-based air electrode performance, fabrication, and
LOBs and should be lowered for commercial viability. The adsorption mechanistic investigations for LOBs. Such types of air electrodes could be
behaviour of electrolytes is a significant parameter in the charging pro- constructed in a short time under binder-free and solvent-free environ-
cess and the diffusion of oxygen. In addition, the porosity of the electrode ments via molding/compression of holey graphene because of their dry
in LOBs plays a vital role in enhancing their oxygen diffusion rate and compressibility feature related to pale holes on graphene nanosheets.
electrochemical performance and allows for ultralong cycle life. Gra- Impressively, dry-pressed holey graphene electrodes exhibit a promising
phene, which has a large surface area and remarkable catalytic proper- architectural plan with excellent performance, high capacity, and prac-
ties, is a key material for LOBs. The porosity, defect sites, and conduction tical significance for air cathodes in LOBs. Luo et al. [139] reported a
of graphene can promote oxygen diffusion and selective Li2O2 deposition free-standing microporous graphene@graphitic carbon nitride hybrid air
during the discharge process of LOBs. We evaluate the latest de- cathode in which microporous graphene nanosheets offer space for the
velopments in understanding the role of graphene in the electrochemistry deposition of Li2O2 and enhance electron transportation. Therefore, the
that governs the operation of LOBs, especially the electrochemical re- graphene@g-C3N4 hybrid is a favourable material for low-cost, high--
actions at the cathode. We also present opinions on the stability of energy, and prolonged cycle life LOBs. Wu et al. [140] designed an ul-
graphene-based cathodes and study design principles for superior LOBs. trasmall Pt-covered hollow graphene nanocage cathode for LOBs. The
The configuration, role of graphene, and performance of LOBs are listed novel hollow graphene nanocage matrix offers a large nanoscale
in Table 4. tri-phase area as an electroactive site for remarkable oxygen reduction
Cui et al. [135] reported a facile two-step self-assembly approach to and provides a sufficient number of mesoscale pores for fast oxygen
synthesise 3D porous polyaniline/rGO foams (PPGFs) with various pol- diffusion. In addition, ultrasmall Pt provides nucleation sites for Li2O2
yaniline contents. In the cell of a LOB, the PPGFs with 50% polyaniline with a remarkable atomic-level absorption of oxygen. Furthermore,
used as a cathode delivered a discharge capacity of 36010 mAh g
1 and owing to the synergetic effect between the nanosized Pt and the hollow
outstanding cycling stability of 260 cycles at 1000 mAh g
1. Guo et al. graphene nanocages, the as-prepared cathode exhibits remarkable elec-
[136] prepared a flexible protective membrane of rGO encapsulated on trochemical performance.
non-woven fibres (rGO@NWF) for stable lithium metal anode/elec- Zhang et al. [141] reported an effective approach for the fabrication
trolyte interfaces by easy dipping penetration and in situ electrochemical of core-shell Co/CoO nanoparticles encapsulated in 3D graphene-loaded
reductions. The rGO@NWF hybrid decreased the deposition over- carbon foam using 3D melamine foam as the primary backbone for LOBs
potential of Li and protected Li metal from corrosion during cycling for (Fig. 14a–d). The synergetic effect between graphene and Co/CoO indi-
over 550 h. Huang et al. [133] designed graphene-based quasi-solid-state cated that Li2O2 was loaded on the Co/CoO surfaces and decreased side
LOBs composed of a 3D porous graphene cathode, porous graphene/Li reactions. The CMG-G-Co/CoO electrode delivered a large capacity and
anode, and redox mediator-modified gel polymer electrolyte. These in- remarkable rate capability, revealing its excellent potential for LOBs.
tegrated prototype LOBs simultaneously achieved a low charge over- Notably, graphene acts as a bridge in the ternary hierarchical architec-
potential, large capacity at stable cycling, and excellent rates in both ture and provides large spaces for lead preservatives. The CoO-based
large-scale pouch-type and coin-type batteries. More importantly, these preservative with high LiO2 adsorption energy can persuade Li2O2 to
LOBs deliver volumetric and gravimetric energy densities that are higher grow mostly on the surfaces of the preservative instead of the graphene
than those of commercial lithium-ion polymer batteries. surface, which will decrease the side reaction between carbon and Li2O2
The porosity of the cathode in LOBs plays a vital role in enhancing the (Fig. 14e).
oxygen diffusion rate, electrochemical performance, and cycle life. Reducing the charge overpotential promises to increase the efficiency
Notably, the adsorption of electrolytes is a significant parameter in the and cyclability of LOBs. Hou et al. [142] successfully predicted a reduced
charging and oxygen diffusion processes. Jung et al. [137] developed a charge potential using B-doped graphene as a catalytic substrate. Based
restacking-constrained film cathode composed of highly porous and on perspective calculations of kinetics and thermodynamics, the results
corrugated reduced graphene flakes, which delivered remarkable ca- reveal that the electrochemical oxidation of Li2Oþ 2 ions is carried out
pacity and cycle life. The as-prepared free-standing graphene cathode more quickly than the chemical oxidation of the Li2O2 molecule.
film provided rich voids, spaces for oxygen-related reactions, and a facile

13
A. Ali et al.
Furthermore, the oxidation of (Li2O2)0,þ was facilitated by B-doping in
pristine graphene. Owing to the large theoretical specific capacity of
lithium, metallic lithium is considered the ultimate choice of a negative
electrode for LOBs. Unfortunately, interfacial side reactions and poor
safety/cyclability caused by lithium dendrite growth have hindered its
practical application. Cheng et al. [127] designed a fluorinated
Fig. 15. (a) Schematic demonstration of the stepwise engineering of Co3O4 nanoparticles incorporated into nitrogen-doped graphene (CNG). (b) Schematic of the
Li–O2 cell reaction mechanism with a CNG cathode. Reproduced with a license from ref. [145] Copyright (2019) The Royals Society of Chemistry.
14
Nano Materials Science xxx (xxxx) xxx
Fig. 14. (a–d) Schematic of the synthesis of
CMF-G-Co/CoO electrocatalyst. The figures
circled in (a), (b), and (d) are the micro-
structural illustrations of MF, Co2þ in the
graphene oxide solution and the final elec-
trocatalyst, respectively. The figures with the
deep background are the optical pictures of
MF, MF adsorbed by graphene oxide and
Co(NO3)2 6H2O, and CMF-G-Co/CoO. (e)
Schematic of the essential role of the pre-
servative in the discharge procedure. Repro-
duced with a license from ref. [141]
Copyright (2016) WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim.
graphene-modified lithium negative electrode (LFG) for LOBs. The
as-prepared LFG with the introduction of 3 wt% FG led to a remarkable
increase in the rate capability and cycling life of lithium electrodes.
Chong et al. [143] prepared porous N-doped graphene fibre webs
(N-GFWs) by an easy wet-spinning process. The wet chemical strategy
simultaneously promoted surface wrinkling and N-doping of the
A. Ali et al.
graphene fibres in a one-step method. Furthermore, the electrical con-
ductivity and atomic structure of N-GFWs can be tailored by modifying
the degree of N-doping and the thermal reduction of battery charge
storage in LOBs. He et al. [144] developed N-doped 3D graphene (3D
N-G) with enhanced electrocatalytic performance and a tuned pore
structure by simple hydrothermal and annealing approaches. The 3D N-G
is employed as a free-standing cathode in LOBs and has a distinct 3D
morphology with many active sites, pore volume, mesopores, and mac-
ropores, which promise to promote discharge product deposition, oxygen
diffusion, and electrolyte infiltration. Kim et al. [132] synthesised mes-
oporous carbon on N and S co-doped graphene nanosheets (NSGC) for
LOBs. The remarkable performance of NSGC facilitates the effective
composition and decomposition of Li2O2 on the air cathode. Further-
more, the lithium-oxygen electrochemical cell configured with the
NSGC-based air cathode exhibited a high initial discharge capacity of
11431 mAh g
1 and showed outstanding cycling stability.
Liu et al. [145] developed an easy bottom-up technique to prepare
Co3O4 nanoparticles incorporated into nitrogen-doped graphene (CNG)
composite (Fig. 15a). A schematic of the LiO2 cell reaction mechanism
with the CNG cathode is shown in Fig. 15b. The unique structure offers
distinctive features for oxygen cathodes, high catalytic performance, a
large number of active sites, available surface area, and porous features
for the accommodation of discharge products. Shu et al. [146] developed
a metal-free mesoporous N-doped graphene/carbon nanotube (NGC)
hybrid for LOBs. The favourable hierarchical NGC composite delivered
round-trip efficiency and outstanding cyclability.
In recent years, researchers have used nitrogen-doped graphene as a
cathode for LOBs; however, the cathode reaction mechanism of lithium
and oxygen has remained uncertain, including the mechanism of the
oxygen reduction reaction by ionic lithium and the surface of various
defective catalytic sites, such as pyrrolic, pyridinic, and graphitic sites.
Therefore, it is important to study the effects of ionic lithium and oxygen
gases at every defective catalytic site in N-doped graphene. Yun et al.
[147] adopted DFT calculations to investigate the atomic scale of a
defective catalytic site that serves as a cathode. Impressively, the
graphitic N site was found to be the most defective catalytic site for the
oxygen reduction reaction by ionic lithium in LOBs owing to the
electron-accepting reaction of Li–O formation.
5. Conclusions and perspectives
In this review article, we comprehensively highlight recent research
developments in the synthesis of graphene, the functionalisation of gra-
phene, and the role of graphene in lithium batteries, such as rechargeable
LIBs, LSBs, and LOBs. Graphene is an attractive material that has received
increasing attention from the scientific community over the past few
decades. The extraordinary and superior properties (electrical, thermal,
mechanical, and structural) of graphene offer great promise for building
better batteries with higher energy densities, maximum power densities,
and ultralong cycle lives. Graphene is a promising carbon substrate for
the practical application of non-carbon materials because of its unique
atom-thick 2D structure, large and accessible surface area, easy consis-
tent dispersion of active components on its surface, and more efficient
transport channels for ions/molecules. Graphene and graphene-based
materials are particularly attractive because of the large number of
synthesis techniques, including reduction of graphene oxide, unzipping
of CNTs, thermal decomposition of silicon carbide, microwave synthesis,
liquid-phase exfoliation, CVD, and micromechanical cleavage (the orig-
inal scotch-tape technique). Functionalisation of graphene can be carried
out using covalent and noncovalent modification approaches. In both
cases, the surface modification of graphene oxide is followed by reduc-
tion to produce functionalised graphene. The electrochemical perfor-
mance of graphene-based electrodes can also be improved by increasing
the electrical conductivity, surface area, porosity, and doping/co-doping
with different nonmetal elements. Heteroatom-doped graphene can
create ubiquitous defects, disordered morphology, and improved
15
Nano Materials Science xxx (xxxx) xxx
electrical conductivity and thermal stability, which are also beneficial for
improving the electrochemical performance of batteries. Increasing the
number of graphene defects can improve their performance in batteries,
although it will also decrease their conductivity. Graphene-based elec-
trodes provide a large specific surface area and favour ion diffusion but
also have a lower volumetric capacitance owing to their relatively low
packing density. A large number of surface functional groups can cause a
decrease in the electrical conductivity of graphene; therefore, the loca-
tion and density of the functional groups need to be controlled.
Furthermore, graphene can be easily employed to form an interconnected
conductive network between active particles and within the entire
electrode. This conductive network stabilised the electrode during
cycling. Therefore, various graphene-based electrodes have been devel-
oped for use in batteries. To fulfil the industrial demands of portable
batteries, lightweight batteries that can be used in harsh conditions, such
as those for electric vehicles, flying devices, transparent flexible devices,
and touch screens, are required.
Innovative techniques have been developed to produce batteries with
new features that are not possible with the current state-of-the-art
technology. During the past few years, the role of graphene in batteries
has witnessed rapid progress and significant achievements; however,
there are still many challenges to be addressed to realise practical ap-
plications. During the next decade, research on graphene for batteries is
expected to continue to expand, with a promising role that will impact
our lives.
(i) The development of graphene, functionalisation of graphene, and
graphene-based electrodes for various batteries are still in the
early stages. Further research is required to understand the bat-
teries' atomic- and molecular-level growth mechanism, failure,
and limitations. Therefore, multidisciplinary tactics are required
to identify the correlation between materials science, electro-
chemistry, design, engineering, nanostructures, interactions, and
properties to overcome these batteries' substantial challenges.
(ii) The initial Coulombic efficiency, energy/power density, and
cycling stability of graphene-based electrodes require further
improvement.
(iii) DFT calculations and simulations of graphene-based electrodes,
their chemical/physical properties, and structural features are
needed to provide theoretical guidance for the production of
batteries. Combined experimental and theoretical research will
support the construction of novel electrode materials in terms of
rate capability and ultralong stability. As we know, batteries are
complex systems; therefore, it is significant to establish multiscale
modelling tools for basic understanding, diagnostics, and design
of novel electrochemical electrodes and their working conditions
to optimise overall battery performance.
(iv) Researchers should focus on better understanding the interaction
mechanism between active materials and graphene (such as the
synergetic effect) before designing a novel graphene-based elec-
trode with special morphologies and a high battery capacity.
Graphene-based materials with controlled morphologies, struc-
tures, and tailored properties will bring more exciting results in
batteries and a further step, their use can be extended to other
fields.
(v) The surface properties of graphene, such as thermostability, dis-
persibility in various solvents, and functional groups, should be
systematically studied. These properties play an important role in
the processing and synthesis of high-quality graphene-based
composites. There is still a fundamental gap between laboratory-
scale experiments and large-scale industrial production. In
particularly, a low-cost synthesis method for the large-scale pro-
duction of graphene has not been identified. Owing to their
peculiar nature, the electrochemical characteristics of graphene-
based materials depend on their production methods. In the
future, graphene's costly and environmentally unfriendly
A. Ali et al.
fabrication should be overcome. Therefore, feasible strategies for
well-defined interfacial and structural engineering, scalable and
economical production and convenient and green integration of
graphene-based electrodes must be developed before practical
implementation.
(vi) Owing to the ever-increasing demand for batteries, the design,
defects, and engineering of novel graphene-based materials need
to be promoted. However, in many studies, graphene and device
properties must be optimised for further enhancement. The
modification of graphene-based materials with higher utilisation
efficiency should not be ignored. Therefore, further studies on the
functionalisation of graphene are urgently needed to boost its
dispersibility and electrical conductivity and to address the
fundamental synthetic approach. Furthermore, researchers should
focus on controlling the structure (including doping, defects, and
functionalities), morphological homogeneity, and topological
distribution uniformity of the active materials to ensure consis-
tency in the performance of graphene-based composites for
batteries.
(vii) The main disadvantage of using graphene-based materials as an-
odes is their poor cycling stability due to the possible reaction of
ions with the oxygen-containing functional groups of graphene,
low Coulombic efficiency (particularly in the first cycle), and the
formation of solid electrolyte interphase in defects and nano-
cavities. Therefore, the capacity of graphene-based anodes can be
improved by functionalisation (e.g., heteroatom doping, edge
functionalisation, and topological/structural defects).
(vii) Graphene-based electrodes used in LIBs, LSBs, and LOBs but few
investigations on the mechanism have focused. Therefore, efforts
are required to explain the existing challenges using experimental
studies and theoretical calculations.
We hope that our review will inspire interest from the several disci-
plines that will benefit from the progress in graphene/graphene-based
materials for batteries.
Declaration of competing interest
There are no conflicts of interest to declare.
Acknowledgements
The work was supported by the National Natural Science Foundation
of China (51962002) and Guangxi Natural Science Foundation
(2022GXNSFAA035463).
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