1 s2.0 S2405829719309171 Main PDF

Energy Storage Materials 24 (2020) 22–51
Contents lists available at ScienceDirect
Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm
Graphene-based composites for electrochemical energy storage

Bo Wang a, b, *, 1, Tingting Ruan a, 1, Yong Chen a, Fan Jin a, Li Peng c, Yu Zhou b,
Dianlong Wang a, **, Shixue Dou d, ***
a
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of
Technology, 150001, Harbin, China
b
School of Materials Science and Engineering, Harbin Institute of Technology, 150001, Harbin, China
c
Department of Polymer Science and Engineering, Zhejiang University, Polymer Building, 38 Zheda Road, Hangzhou, 310027, PR China
d
Institute for Superconducting & Electronic Materials, Australian Institute of Innovative Materials, University of Wollongong, Wollongong, NSW, 2500, Australia
A R T I C L E I N F O A B S T R A C T
Keywords: Since the first exfoliation in 2004, graphene has been widely researched in many fields of materials engineering
Graphene due to its highly appealing properties. Recently, graphene-based composites have attracted increasing attention
Composite for electrochemical energy storage by combining the merits of graphene and other electrochemical materials to
Electrochemical energy storage
achieve superior electrochemical performances. In this review, we start with the properties and production
Capacitor
Battery
methods for graphene, summarize the recent research progress on graphene-based composites for electrochemical
energy storage from the structural and interfacial engineering viewpoints, and underscore the significance of the
dimensionality and compound interface characteristics in the rational construction and design of these com-
posites. We also discuss recent specific applications of graphene-based composites, from electrochemical capac-
itors and lithium-ion batteries to emerging electrochemical energy storage systems, such as metal-air and metal-
sulfur batteries. The new features and challenges of graphene-based composites for electrochemical energy
storage are also summarized and discussed. This review is specifically aimed at offering new perspectives on the
combination of graphene with other electrochemical materials to optimize their performances, and will outline
ways to further improve graphene-based composites towards the next generation of electrochemical energy
storage devices.
1. Introduction growing demands of both industry and society, advancing EES systems by
pursuing higher energy density, higher power density, and better cycling
Currently, realizing a secure and sustainable energy future is one of stability, is an important and pressing mission [5]. One of the critical
our foremost social and scientific challenges [1]. Electrochemical energy factors in realizing the abovementioned target is exploring ideally
storage (EES) plays a significant role in our daily life due to its wider and structured electrode composites with the desired synergistic effects be-
wider application in numerous mobile electronic devices and electric tween the different functional components [6].
vehicles (EVs) as well as large scale power grids [2]. Metal-ion batteries Recently, graphene has been attractive for broad application in EES,
(MIBs) and electrochemical capacitors (ECs) represent two important due to its unique properties from both physical and chemical aspects [7],
families of EES systems [3]. MIBs possess high energy density through including its outstanding electrical conductivity and extraordinary me-
storing charge and metal ions (especially Liþ and Naþ) in the bulk of chanical properties as well as large theoretical specific surface area, and
electrodes via comparatively slow faradaic reactions, while ECs provide reports from many groups have verified its potential to innovate the
high power density at the expense of energy density, due to their fast current EES landscape [8–11]. In theory, graphene presents a Liþ storage
surface or near-surface energy storage mechanisms [4]. To meet the capacity of 744 mAh⋅g1 and electric double-layer (EDL) capacitance of
* Corresponding author. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engi-
neering, Harbin Institute of Technology, 150001, Harbin, China.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (B. Wang), [email protected] (D. Wang), [email protected] (S. Dou).
1
These authors contribute equally to this works.
https://doi.org/10.1016/j.ensm.2019.08.004
Received 19 June 2019; Received in revised form 30 July 2019; Accepted 2 August 2019
Available online 6 August 2019
2405-8297/© 2019 Elsevier B.V. All rights reserved.
B. Wang et al. Energy Storage Materials 24 (2020) 22–51
Fig. 1. Schematic illustration of the outline for this review. GBCs represents graphene-based composites.
550 F g1 as the active material for Li-ion battery (LIB) anode and elec- composites (GBCs) for EES from the structural and interfacial engineer-
trochemical double-layer capacitor (EDLC) electrode, respectively [12]. ing viewpoints, and underscore the significance of dimensionality and
The current experimental results on the abovementioned applications compound interface properties in the rational construction and design of
differ significantly, however, from these theoretical values due to the these composites. We also discuss recent specific applications of
spontaneous re-stacking of graphene layers, which occurs during both graphene-based composites from electrochemical capacitors (ECs) and
the manufacturing and the repeated charging/discharging processes of LIBs to emerging EES systems, such as metal-air and metal-sulfur batte-
the electrode, leading to a significant reduction of the practical active ries. The new features and challenges of graphene-based composites for
sites for electrochemical reactions or charge storage processes [10]. EES are also summarized and discussed. This review is specifically aimed
Therefore, substantial efforts have been invested in exploring at offering new perspectives on the combination of graphene with other
graphene-based composites to inhibit the re-stacking of graphene layers electrochemical materials to optimize their performances, and it outlines
and increase the active sites and surface area [13,14]. methods for further improvement of graphene-based composites towards
Graphene-based composites [15], which can combine the advantages the next generation of EES devices. The outline of this review is illus-
of the graphene component and electrochemical materials to achieve trated in Fig. 1.
superior electrochemical performance, have thus been proposed for
application in various kinds of EES systems. Nevertheless, due to the 2. Properties and preparation methods of graphene
complexities in the microstructures and electrode processes of different
graphene-based composites, challenges for clearly understanding their 2.1. Properties of graphene
EES mechanisms have also appeared, which require systematic electro-
chemical analysis combined with adequate theoretical calculations and Graphene, a defect-free flat carbon monolayer with theoretical spe-
advanced operando techniques [16,17]. Moreover, the introduction of cific surface area (SSA) of 2630 m2 g1, is the basic unit of the 2-dimen-
graphene components will also introduce some new features into the sional (2D) carbon family, which includes family members with very
composites, such as flexibility, transparency, self-healing properties, etc. different properties based on different morphologies, defects, di-
[11] Some reviews have already been published on graphene-based mensions, and layers (Fig. 2) [10,30–32]. Because of the unique 2D
composites from viewpoints of preparation strategy or structure, or structure, the first Brillouin zone of monolayer layer graphene possesses
with a focus on specific EES or environmental applications [9,12,18–29], two inequivalent points (Dirac points) with a crossing band, which makes
but a comprehensive view of the graphene-based composites, combining graphene a zero-gap semiconductor with both semiconducting and
preparation strategies, structural designs and specific applications, as metallic properties [33–35]. However, bilayer graphene exhibits para-
well as emerging features and challenges for EES, is still missing. bolic bands without Dirac electrons, and trilayer graphene exhibits a
In this review, we start with the properties and production methods combined band structure of monolayer and bilayer. Generally speaking,
for graphene, summarize the recent research progress on graphene-based odd-layer graphene with AB stacking structure possesses a linear band.
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Fig. 2. Properties, preparation methods, defects and derivatives of graphene. (a) Various characteristics in terms of electrical conductivity, thermal conductivity,
mechanical behavior, opacity, SSA, and chemical behavior. (b) The most common graphene synthetic pathways in terms of graphene quality, cost, scalability, purity,
and yield. Reproduced with permission from ref. 10, copyright 2015, Nature Publishing Group. (c) Introduction of intrinsic or extrinsic defects in graphene. (d)
Schematic illustrations of the different structures of graphene derivatives. Reproduced with permission from ref. 31, copyright 2017, American Association for the
Advancement of Science. Reproduced with permission from ref. 32, copyright 2011, American Chemical Society.
With the increase of the number of graphene layers, the band structure phenomenon in twisted bilayer graphene (with a small angle of ~1.1 ),
becomes more complex with the overlap of the conduction and valence which could lead to insights into the physics of high-critical-temperature
bands [12]. superconductors and quantum spin liquids [38,39]. It should be
The carrier mobility of graphene at room temperature could reach mentioned that the electrical conductivity of graphene is significantly
15000 cm2 V1 s1 with the charge carriers adjustable between electrons influenced by the number of layers and the stacking orders, as well as the
and holes (up to a concentration of 1013 cm2) [33,35]. Moreover, mo- amount and type of defects with very complex influencing mechanism
bilities over 200000 cm2 V1 s1 have been achieved in suspended gra- [40–43]. High-temperature treatment (>2000 C) has been demon-
phene by minimizing impurity scattering [36]. Correspondingly, the strated could effectively reduce the defect concentration of graphene by
electrical conductivity of graphene is quite high, which is beneficial for healing the defect configurations to enhance its electrical conductivity
improving the electrical conductivity of the graphene-based composites [37,44]. In addition, foreign atoms doped graphene could also improve
for EES. For example, the electrical conductivity of a graphene film re- the electrical conductivity with appropriate doped position and quantity
ported by Chao Gao’s group reached ~106 S m1 [37]. Recently, Pablo [45]. Typically, Zhongshuai Wu et al. confirmed that the doped graphene
Jarillo-Herrero’s group found an interesting superconductivity with N and/or B atoms could enhance its electrochemical reactivity and
24
electrical conductivity with superhigh rate and large capacity for LIB electrical properties [53]. Moreover, It should be noted that an important
anodes [46]. derivative of graphene – graphene oxide (GO), is hydrophilic in nature,
The opacity of graphene is ~2.3% in a broad wavelength ranged from and thus, it has been widely used in combination with other materials in
ultraviolet to near infrared due to its special 2D microstructure with appropriate aqueous systems for the synthesis of graphene-based com-
single-layered atomic thickness [47,48]. An experimental transparency posites [65–67].
value in the visible range has reached ~97% [49]. On the other hand, the
researchers also found that the transmittance of graphene decreases 2.2. Preparation methods of graphene
linearly as the layers increase [50–52]. It is worth noting that, when the
input optical intensity is above a threshold value, the absorption becomes The most common preparation strategies for graphene are shown in
saturated, resulting in a non-linear optical behavior [53]. Because of its Fig. 2b, and these play crucial roles in determining the qualities and
superior optical properties, graphene is considered as a potential material properties of the products [68]. Among these strategies, mechanical
for transparent applications in the future, not only limited to EES devices, exfoliation [69], epitaxial growth on SiC [70,71], and bottom up syn-
but also for solar cells, smart windows, and other optoelectronic devices. thesis from organic precursors [72,73] have relatively limited scalability
The thermal conductivity of suspended graphene is very high combined with high cost, which restrict their large-scale application in
(4840–5300 W m1 K1), which is superior to those of other carbon both fundamental research and commercial applications. Although
materials (e.g., carbon nanotubes and diamond) [54,55], making it a chemical vapor deposition (CVD) of hydrocarbons (e.g., CH4, C2H2, etc.)
potential substance that can be used to enhance the thermal conductivity [74–77] is a mature technique for the preparation of graphene in in-
of electrochemical materials through different composite-forming pro- dustry, it is inappropriate for mass production for EES, due to its high
cesses, which is beneficial for dissipating the heat generated in the case of cost, relatively low yield, and mediocre product quality.
high current loads or abuse conditions for the final fabricated EES de- Apart from the above-mentioned methods, liquid-phase exfoliation
vices. Alexander A. Balandin et al. reported that, by including 5 and [78–80] and reduction of GO [81–83] are two general strategies for
10 vol% graphene, thermal conductivities could be improved by ~500% mass-production of graphene. In the first strategy, the treated graphite
and ~2300% for graphene-metal and graphene-polymer composites, particles (e.g., expanded graphite) are firstly dispersed in a suitable sol-
respectively, which mainly resulted from the intrinsically high thermal vent to lower the strength of van der Waals attraction between the
conductivity of the graphene component combined with its strong syn- adjacent layers. Then, an exterior driving force (e.g., ultrasonication
ergetic effects with metal and polymer components [56,57]. Similar to [78], electric field [79], mechanical shearing [80], etc.) is employed to
the electrical conductivity, the thermal conductivity is also largely exfoliate the graphite bulk into high-quality graphene sheets. Moreover,
influenced by the quality of graphene, such as the lateral size and defect this strategy is suitable for preparing graphene in bulk quantities because
factor [42]. Recently, Li Peng et al. reported a macroscopic graphene film of its high scalability and low cost. The existence of considerable amounts
composed of large-sized and defect-heald graphene sheets, which could of unexfoliated or less-exfoliated graphite results in a low yield for this
exhibit a high thermal conductivity of 1940 W m1 K1 after technique, however.
high-temperature (3000 C) and high-pressure (300 MPa) treatment In the second strategy, GO is first prepared by oxidizing pristine
[37]. graphite, followed by dispersing it in a liquid medium through stirring or
The mechanical properties of graphene are very excellent because of ultrasonication [84]. The product then needs to be reduced to recover the
the strong σ bonds (C–C bonds), in terms of having a high Young’s π network and electrical conductivity for application in EES [85].
modulus and strong fracture strength [58]. James Hone et al. demon- Correspondingly, many reduction processes (e.g., chemical [86], thermal
strated that graphene has a Young’s modulus of ~1 TPa, which seems to [87], electrochemical [88], etc.) have been adopted to obtain reduced
depend upon the layers and defects of graphene [58]. Moreover, the graphene oxide (RGO). Although the product yield of this strategy is high
breaking strength of graphene is almost 200 times higher than that of and the cost can also be effectively contained, the quality of the product
steel [58]. The superior mechanical properties of graphene make it a mainly ranges from low to average levels owing to the inevitable residue
great basic candidate for flexible and wearable EES devices. In addition, of both intrinsic (e.g., edges, deformations, etc.) and extrinsic defects
both experimental tests and theoretical calculations have demonstrated (e.g., O and H-containing groups), as shown in Fig. 2c. Actually, in
that uniaxial stress and anisotropic strain have different levels of influ- comparison with graphene (including RGO), GO is much easier to
ence on the electrical properties of graphene [48,59]. Keun Soo Kim et al. disperse into numerous solvents [89]. This peculiarity enables GO to be
studied the interplay of mechanical and electronic properties of gra- combined with other materials through different chemical routes to
phene. They found that the resistance in the bent direction increased construct GO-based composites, which could be applied directly or
almost one order of magnitude, which was due to the difference in alternatively (e.g., further reduction to RGO-composites) for EES
stretching along the parallel and perpendicular direction [48]. In another applications.
case, Mark A. Bissett et al. demonstrated that the mechanical strain could In addition, many other methods, such as carbon nanotube unzipping
change the structure of graphene, and dramatically improve the chemical [90] and direct arc-discharge [91], have also been reported for the syn-
reactivity of graphene [60]. It should be mentioned that the existence of thesis of graphene (or graphene derivatives, Fig. 2d) for laboratory
defects in graphene may remarkably influence its mechanical properties, research. Because of their high costs and low yields, however, these
which decrease as the number of defects increase. Normally, recon- strategies remain marginal and unsuited to mass-production. Actually, in
struction and healing of vacancy-type defects are the main strategies to order to realize the practical application of graphene in widespread
minimize these detrimental effects [61]. areas, exploring effective strategies to prepare high quality graphene in
In the case of chemical properties, perfect-structured graphene is large-scale quantities is still the most ambitious challenge [7]. This sit-
quite inert, so that it generally interacts with other components via uation is especially prominent considering the likely application of gra-
physical adsorption (e.g., π-π interaction) [62]. In order to realize higher phene in EESs for powering millions of electric vehicles (EVs) and hybrid
reactivity, defects (e.g., vacancies, edges, deformations, etc.), foreign electric vehicles (HEVs) in the future [1,8,68]. Recently, electrochemical
atoms (e.g., H, F, N, B, etc.), or surface functional groups (e.g., carboxyl, exfoliation of graphite has been considered as a promising strategy to
carbonyl, or amine groups, etc.) are usually introduced into graphene prepare graphene materials with high-quality on large scale at an
[46,63]. For example, the existence of defects in graphene may result in affordable cost, which normally introduces an electrical current for
locally curved structures, which could give rise to the local doping sites, encouraging structural deformation of a graphite working electrode in a
and thus influence its chemical reactivity [64]. When the foreign atoms liquid electrolyte [92–96]. Xinliang Feng and Klaus Müllen’s group re-
and functional groups are grafted into graphene, the highly extended π ported a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl-assisted electro-
electron cloud would be disrupted, leading to the change of its original chemical exfoliation method to produce graphene in large quantities
25
with high quality [93]. The obtained graphene sheets exhibited a large films, frameworks, sponges, etc.), as shown in Fig. 2d. In the following
lateral size (5–10 μm) and low Raman ID/IG ratio (<0.1). In addition, contents, we will discuss the corresponding strategies and the prepared
Zhong-Shuai Wu et al. further demonstrated the electrochemical exfoli- composites in detail.
ation could also realize the scalable production of high-quality hetero-
atom-modified (e.g., F) graphene [96]. Although the electrochemical 3.1.1. In-situ strategies for graphene-based composites
exfoliation approach has attracted widely interest, it is still in infancy, In-situ strategies for graphene-based composites have been used
which needs further endeavour from both industrial and academic fields extensively for EES specifically, which can be classified into three types:
to push this technology to maturity [92]. (i) one-step in-situ generation of other materials on graphene, (ii) multi-
From the perspective of industrial progress to obtain graphene, CVD, step in-situ conversion of other materials on graphene, and (iii) in situ
exfoliation of graphite and reduction of GO are still the main production growth of graphene on other substances (Fig. 3a). Among them, the one-
techniques so far by comprehensive consideration of technical maturity step in-situ method primarily concerns the direct growth of crystal nuclei
and cost [53,68]. Exfoliation of graphite and reduction of GO are the on an existing graphene substrate and with subsequent development into
most widely used methods for the industrial production of small gra- the desired materials with different dimensionalities, including nano-
phene sheets, and CVD is the most used strategy for the growth of gra- particles [97,98], nanowires [99], nanorods [100], nanoplates [101],
phene films [68]. With the significant progress in these approaches, the nanoflowers [102], etc. The main difficulty for this approach is avoiding
mass production of graphene materials with yields of thousands of tons of the use of protective surfactants or additional linker molecules, which
graphene powder (or suspensions) and hundreds of thousands of square normally requires a cumbersome synthesis program and influences the
meters of graphene film has been realized [53]. However, producing performance of the final obtained composites.
uniform monolayer and few-layer graphene sheets with high yield, high Various chemical and physical synthesis technologies, such as hy-
efficiency and controlled cost is still the universal challenge for all these drothermal and solvothermal processes [103–105], co-precipitation
mass production techniques. Rodney S. Ruoff’s group [53] and Huiming [106,107], gas-phase deposition [108,109], sol-gel treatment [110,
Cheng’s group [68] have made some excellent reviews of this field. 111], atomic layer deposition (ALD) methods [112,113], etc. [87,114,
115], have been applied for the in-situ strategy. In the literature, hy-
3. Synthesis and structural engineering of graphene-based drothermal and solvothermal processes are the most common reported
composites [116]. The one-pot method can be used to construct high crystallinity
materials without a following high temperature treatment [97,107]. For
3.1. Synthesis strategies example, Kening Sun’s group reported TiO2 quantum dots with diameters
of 4–8 nm that were in situ grown on the surfaces of graphene nanosheets
Over the last few years, significant efforts have been spent on through a facile one-step hydrolysis procedure [117]. Similarly, Chenxin
developing synthesis methods for preparing graphene-based composites Cai’s group designed a unique FePO4 hollow sphere/graphene composite
with all kinds of morphologies, dimensions, structures, and properties. via a hydrothermal route using urea as the precipitant [118]. Moreover,
The synthesis methods reported to date for graphene-based composites Yanwen Ma and Wei Huang’s group synthesized a graphene/polyaniline
could be divided into in-situ and ex-situ strategies, as illustrated in Fig. 3. (PANI) composite films using GO and aniline as the raw materials
The term graphene in this review is not only limited to monolayer gra- through a one-step large-scale electrochemical synthesis strategy [119].
phene with perfect crystallinity, but also includes graphene derivatives Unlike the one-step in-situ generation strategies, the multi-step in situ
(e.g., RGO, foreign-atom-doped graphene, bilayer and multilayer gra- conversion techniques usually include a pre-loading process for
phene, etc.) and graphene-based macroscopic structures (e.g., graphene anchoring the precursors on the surface of graphene and subsequent
Fig. 3. Schematic illustration of typical synthetic strategies for producing graphene-based composites with different dimensions. (a) In situ strategy including one-step
in situ growth, multi-step in situ conversion, and in situ growth of graphene on other materials. (b) Ex situ strategy.
26
conversion procedures to construct the desired composites. A variety of aminopropyltrimethoxysilane (APS) modified materials (e.g., SiO2
materials, e.g., Sn [120], SnS2 [121], TiO2 [122], Co3O4 [123], VN [124], [139], Co3O4 [139], LiFePO4 (LFP) [135], etc.) and subsequently, the GO
LiFePO4 [89], LiMn1-xFexPO4 [125], LiCoO2 [126], Li4Ti5O12 [127], component could be reduced to RGO through a subsequent physical or
carbon cages [128], etc., have been manufactured on graphene following chemical process without influencing the pre-constructed
this method. The desired composition and structure can both be simul- nanostructures.
taneously realized via rational design of the multi-step strategy, and thus,
could be used to fabricate complex architectures with ideal functions. 3.2. Structure and interface engineering
Recently, we demonstrated that pre-loaded Fe3O4 quantum dots on the
surfaces of graphene nanosheets could be transformed in-situ into It is well established that the structure of the active material and its
zero-dimensional (0D) amorphous carbon coated LiFePO4 (LFP) active interface exposed to electrolyte have a significant impact on the elec-
quantum dots [126]. Moreover, Bin Luo et al. realized the in-situ trans- trochemical performance of the final EES system [140]. In this section,
formation of the pre-loaded metal oxide nanoparticles into we will summarize the research advances on graphene-based composites
one-dimensional (1D) carbon encapsulated metal nanocables or 2D for EES from the viewpoint of structure and interface engineering, in-
metal/metal disulfide nanosheets on the surface of graphene [120,121]. clusive of the structural design of electrochemical materials and the
In another case, Junhong Chen’s group reported a technique that interfacial contact of the graphene component with the electrochemical
involved the pre-loading of zeolitic imidazolate framework-8 (ZIF-8) on materials, as well as the interfacial contact between the composite and
the surface of graphene, before using an in-situ confinement pyrolysis the electrolyte.
strategy for achieving ZIF-8 derived three-dimensional (3D)
nitrogen-enriched meso-microporous carbon nanocages on graphene 3.2.1. Structural design of electrochemical materials
[128]. It is expected that, in the future, the above-mentioned in-situ Electrochemical materials with ideal structures have been demon-
methods could be further extended to the design of various ideal strated with improved EES performance by increasing the active sites for
graphene-based composites with desired structures, which definitely interfacial reactions and enhancing the flux of ions across the electrode-
would encourage extensive applications in various EES areas [128]. electrolyte boundary [134]. Recently, the progress on graphene-based
In-situ growth of graphene on other materials is suitable in cases composites by effectively combining graphene with active materials
where the desired materials were prepared beforehand. This is an with a variety of dimensions (e.g., 0D nanoparticles [87,126], 1D
attractive method to encapsulate these electrochemical materials nanorods [108,120], 2D nanoplates [121,141], and 3D nanoflowers
through in-situ growth of graphene on their surfaces, which not only [128]), as illustrated in Fig. 4, has led to remarkable improvements in the
offers tight mechanical support of the preformed nanostructures, but also EES field.
improves electronic conductivity throughout the whole electrode. CVD Among them, 0D nanostructured electrochemical materials are
strategies have been most frequently introduced for in-situ generation of considered as the most likely ones for commercial EES applications
graphene on the surfaces of different electrochemical materials, such as because of their great mass-production potential. Adhering 0D nano-
Si nanowires [108], Si nanoparticles [129], Ge quantum dots [130], etc. structured materials onto 2D graphene sheets has been demonstrated as
In addition, the arc-discharge method [131] and the in-situ mechanical an effective method for improving the electronic conductivity of the 0D-
peeling process [132] have also been employed for in-situ coating of 2D composites, relieving the agglomeration of electrochemical materials,
graphene on active materials as well. and accommodating the volume changes of the electrode during the
charge and discharge reactions. Taking SnO2 material as an example,
3.1.2. Ex-situ strategies for graphene-based composites Liqiang Mai’s group have recently attached SnO2 nanoparticles onto
Ex-situ strategies mainly concern the preparation of objective elec- graphene sheets, which exhibited much improved EES performance as
trochemical materials with the ideal nanostructures and morphologies in LIB anode [142]. The introduced graphene component not only offers
advance, with subsequent modification and grafting to the graphene abundant electron transfer channels for electrochemical reactions, but
surface via covalent or noncovalent interactions (Fig. 3b) [133]. For also synergistically contributes to the total capacity. Recently, we
these approaches, either graphene or the desired component (or both) designed graphene modified LiFePO4 quantum dots (with diameter of
may need to be modified with functional groups. In contrast to the in-situ ~6.5 nm) as a composite through a microreactor strategy (Fig. 4), which
strategies, ex-situ approaches contribute to overcoming the in- exhibited an ultra-high-rate performance in LIBs [126]. Many other
compatibility between the processes for synthesizing precursors and active materials with this kind of 0D-2D structure have also been
composites. Generally, GO instead of graphene is preferred for combining designed, including metals (e.g., Sn [143], Ge [144], etc.), S [145], Si
with other materials because of its abundant oxygen-containing groups, [146], SiO [147], metal oxide (e.g., Fe3O4 [148], Co3O4 [149], Mn3O4
promoting connections with other functional groups through covalent [150], SnO2 [151], V2O5 [152], etc.), FeS2 [153], Na2/3Fe1/2Mn1/2O2
interactions [134,135]. For example, a graphene/Fe3O4 composite was [154], etc. In addition, graphene confined single metal atom composites
designed through self-assembly of partially reduced graphene (with an (e.g., Ni [155], Ru [156], Pt [157], Fe [158,159], etc.) have aroused
appropriate amount of functional groups) and Fe3O4 nanoparticles in widespread attention for the electrocatalysis field due to their enhanced
water by forming new bonds (e.g., –COO–) between them [136]. In electrocatalytic capability, which have also started to influence some
addition, many polymeric chains can also be easily grafted to GO, e.g., advanced EES systems, e.g., lithium-sulfur batteries and lithium-air
poly(ethylene glycol), polylysine, polyallylamine, poly(vinyl alcohol), batteries.
etc., for preparation of graphene-polymer composites [137]. 1D nanostructured electrochemical materials are potential candidates
Various kinds of non-covalent interactions, such as electrostatic, for EES, which could offer effective 1D electron transmission pathways
dispersive, and inductive interactions and exchange repulsion, have also and at the same time alleviate the generated mechanical strain during
been utilized to synthesize graphene-based composites [63,67]. Among charge and discharge. As with the 0D nanostructured materials, vast
them, electrostatic interactions have most frequently been used, because investigations have also been carried out that were focused on the
of the general potential for attaching different functional materials to structural engineering of similar 1D-2D composites [26]. Various 1D
graphene without disturbing its electrical network [63]. As is well nanostructures, such as nanowires [160] (e.g., Si [161], MnO [162], TiO2
known, both GO and RGO are intrinsically negatively charged due to [163], V2O5 [164], etc.), nanorods (e.g., MnO2 [165], TiO2 [166],
their oxygen-containing groups, which could easily be assembled with LaMnO3 [167], LiMn1-xFexPO4 [125], etc.), nanotubes (e.g., carbon
positively charged materials via electrostatic interactions [138]. For nanotubes (CNTs) [168], TiO2 [169], etc.), nanofibers (e.g., Li4Ti5O12
example, a facile electrostatic method to construct RGO-encapsulated [170], polyaniline [171], Co3O4 [172], etc.), and core-shell nanocables
composites was developed by an initial co-assembly of GO and or nanoscrolls (e.g., MnO2@N-doped graphene [160], Sn@C [120], Si@C
27
Fig. 4. Illustrations of graphene-based composites made by effectively compounding graphene with active materials with a variety of dimensions (0D, 1D, 2D and 3D),
taking LiFePO4/graphene composites as examples, 0D: Reproduced with permission from ref. 126, copyright 2017, Elsevier. 1D: Reproduced with permission from ref.
125, copyright 2011, Wiley. 2D: Reproduced with permission from ref. 184, copyright 2015, The Royal Society of Chemistry. 3D: Reproduced with permission from
ref. 198, copyright 2016, Wiley.
[108], etc.) have been successfully incorporated in composites by effectively trapped the free ions during the crystallization of LiFePO4
combining them with graphene components. For instance, Hongjie Dai’s [184].
group synthesized 1D LiFexMn1-xPO4 nanorods on reduced graphene Active materials with 3D hierarchical structures offer large surface
oxide via a two-step solution-phase reaction (Fig. 4) [125]. The resulting areas, well-distributed channels for electrolyte infiltration and mechan-
composite had high electrical conductivity and low ionic resistance, ical stability for electrodes [185]. Analogously, by combining graphene
leading to an excellent rate performance. We recently developed a and 3D hierarchical-structured active components, a variety of 3D-2D
core-sheath MnO@N-doped graphene scroll composite, in which 1D graphene-based electrode composites have been designed for EES
porous MnO nanowires were confined in tubular graphene scrolls [160]. through both in-situ and ex-situ strategies. Typically, hydrothermal and
This unique structural design not only realized enhanced electron/ion solvothermal processes have been most frequently employed to realize
transfer kinetics but also succeeded in addressing the structural and such a goal [186–195]. For instance, Zunli Mo’s group developed a
interfacial stability issues facing MnO-based electrodes. surfactant-assisted hydrothermal route for the synthesis of a 3D
2D materials (e.g., graphene) have drawn much attention recently on flower-like TiO2 microsphere decorated graphene composite based on
account of their unique properties arising from their ultrathin 2D char- the hydrothermal reduction of graphene oxide and the formation of TiO2
acteristics [173,174]. Correspondingly, a great deal of effort has been put microspheres in the presence of poly(vinyl pyrrolidone) [196]. In
into exploiting their possible deployment in many fields, including another work, Yu Zhu’s group designed a 3D hierarchical hollow NiO/-
electronics, optoelectronics, and EES devices [9]. By integrating gra- Ni/graphene composite derived from Ni-based metalorganic frameworks
phene with 2D nanostructured electrochemical materials, a wide range of (Ni-MOFs), in which, hierarchical NiO/Ni nanocrystals were covered
composites in the 2D-2D mode have been constructed for EES so far, with a graphene shell, with the hollow ball-in-ball nanostructure intact
either via in-situ growth of 2D electrochemical materials on graphene, or [197]. Moreover, our group also prepared a graphene modified 3D
via ex-situ self-assembly of 2D electrochemical materials with graphene. LiFePO4 composite with 3D hierarchical LiFePO4 nanoflowers supported
Due to the diversity of electrochemical materials, the reported 2D active by graphene sheets (Fig. 4) [198].
components combined with graphene could be classified into MXene
[175,176], phosphorene [177,178], metal [141], metal oxide [179], 3.2.2. Interface engineering of graphene-based composites
metal chalcogenide [180], layered double hydroxide [181,182],
layer-structured LiMO2 (M ¼ Co, Ni) [126], and phosphate nanosheet 3.2.2.1. Interfacial contact of graphene component with electrochemical
[183] or nanoplate [134,184] types. Recently, we reported a facile sol- materials. Obviously, the graphene inside the designed graphene-based
vothermal method using ethylene glycol as the solvent to prepare a composites plays an important role in gathering/transmitting electrons
2D-2D “plate-on-sheet” LiFePO4/graphene composite (LFP@GNs) with from/to the electrochemically active materials in the charge and
(010) facet oriented LiFePO4 nanoplates in situ grown on a graphene discharge processes. Thereby, obtaining an ideal interfacial contact mode
cross-linked network (Fig. 4) [184]. In this work, ethylene glycol not only of the graphene component with the electrochemical materials is also
induced the crystal orientation of LiFePO4 due to its strong binding effect quite important for decreasing the interfacial contact resistance between
towards the (010) facet, but also enhanced the interaction between the different components [140].
LiFePO4 crystals and the graphene sheets by building up a robust Considering the dimensions of the electrochemical materials
hydrogen bond network between the ethylene glycol and the GO, which compared to the lateral size and flexibility of graphene, the graphene-
28
based composites could be mainly divided into three types: graphene- graphene-mixed composites (combining the aforementioned two modes)
supported composites (which include graphene-anchored composites [114], as illustrated in Fig. 5 [10,29]. From the theoretical perspective,
[199], sandwich-like campsites [200], and layered structured composites the contact area of the graphene component and the second phase elec-
[171]), graphene-wrapped composites (which can be further divided into trochemical materials in the graphene-wrapped composites should be
partially wrapped composites and fully wrapped composites) [201], and larger than for the other two kinds of composites, and thus could improve
Fig. 5. Structural models of graphene-based composites, which can be mainly divided into three types: graphene-supported, graphene-wrapped, and graphene-mixed
composites (Reproduced with permission from ref. 10, copyright 2015, Nature Publishing Group). Supported: Active material particles are supported by graphene,
which include graphene-anchored composites (reproduced with permission from ref. 199, copyright 2010, American Chemical Society), sandwich-like composites
(Reproduced with permission from ref. 200, copyright 2014, Wiley), and layered structured composites (reproduced with permission from ref. 171, copyright 2010,
American Chemical Society). Wrapped: Active material particles are wrapped by graphene sheets, which can be divided into partially wrapped and fully wrapped
composites (reproduced with permission from ref. 201, copyright 2013, Elsevier). Mixed: graphene-supported and graphene-wrapped composites are mixed together
during the electrode preparation (reproduced with permission from ref. 114, copyright 2014, The Royal Society of Chemistry).
29
stability by avoiding peeling off of the second phase component from the Mei et al. used holey GO as one of the raw materials for designing 3D
graphene component [135,201]. For this mode, graphene acts as a pro- holey GA/Nb2O5 composite and realized a high mass-loading application
tective layer, preventing the aggregation of the second phase electro- as LIB anode material [208].
chemical materials more effectively compared with the other two modes. Improving the wettability between the graphene-based composites
Numerous graphene-wrapped composites, such as graphene wrapped and the electrolyte is another vital tool to accelerate the mass transfer
particles [87,135], hollow spheres [118], nanoplatelets [134] and dynamic process for EES [46]. Many attempts have been made to
nanowires [108] have been fabricated for EES. Considering of the mass improve the electrolyte-wettability of the graphene framework, for
(ion) transfer process inside these composites, however the graphene instance, modifying the surface of graphene with functional groups,
component may have some negative influence. For instance, Young Hee introducing the defects onto the graphene surface, and doping hetero-
Lee’s group demonstrated that the Liþ diffusion through a defect-free atoms into the plane structure of graphene [18,209–213]. Rodney S.
graphitic plane is limited from the theoretical calculation aspect [202]. Ruoff’s group reported poly(ionic liquid)-modified graphene electrodes
Moreover, Quanhong Yang’s group confirmed that the partially with much enhanced capacitive performance that used an ionic liquid
graphene-wrapped mode affords an optimal balance between improved (IL) electrolyte system for improving the electrolyte wettability [213].
electron transport and rapid ion diffusion, while the fully Later, Saikat Talapatra’s group studied the effect of 1-pyrene
graphene-wrapped mode isolates the active materials from the electro- carboxylic-acid (PCA) functionalization of graphene on its capacitive
lyte and blocks ion diffusion [201]. Therefore, the spatial obstruction of energy storage and found that the electrolyte wettability of the PCA
the mass transfer process should also be taken into consideration along modified graphene was much improved compared with pure graphene
with the electron transport kinetics in designing graphene-based com- using 6 M KOH aqueous solution as the electrolyte [212]. Recently,
posites for high-performance EES systems. Wencai Ren and Huiming Cheng’s group demonstrated that a heteroatom
From the perspective of dimensions, it should be mentioned that the (B and N) doping strategy could also improve the electrolyte wettability
1D electrochemical materials (e.g., nanotubes, nanorods, nanowires, for LIBs using organic electrolyte [46]. Following their research, many
etc.) and 2D electrochemical materials (e.g., nanosheets, nanoplates, subsequent works used the heteroatom (e.g., N, S, B, P, etc.) doped
nanofilms, etc.) can be grown either vertically [203–205] on or parallel graphene as the basic unit for fabricating high performance
[160,184] to the surface of the graphene component. Considering the graphene-based composites with improved electrolyte-wettability for
intrinsic 2D structure of graphene, a “face-to-face” contact mode between application in LIBs [134,160,209].
the graphene sheets and the other 2D electrochemical components shows Another way to improve the infiltration of the electrolyte is tuning the
the greatest potential among the various composite architectures, which orientation of the graphene component in the composite. Generally
could fully utilize the advantages of each component. In this context, speaking, the orientation of the graphene component for graphene-based
such a sandwich-like 2D-2D structure could effectively support both fast composites can be classified into three modes, including random orien-
electron and ion transport channels, and thus be favorable for the con- tation, parallel alignment, and vertical orientation. Considering the fact
struction of advanced EES systems. Recently, we proposed a general that many of the active ions (e.g., Liþ, Naþ, etc.) cannot pass through the
microreactor method for preparing graphene/2D LiCoO2 sheet compos- planar structure of defect-free graphene, the vertical orientation mode of
ites using sandwich-like graphene/Co(OH)2 nanosheets precursor, in the graphene component was considered to be the most efficient mode
which amorphous carbon coated LiCoO2 nanosheets adhered to both for the ion diffusion dynamics. Recently, CVD has been reported as an
sides of graphene [126]. For such a composite, the graphene substrate efficient method for producing vertically oriented graphene nanosheet
not only prevented the agglomeration of the adjacent LiCoO2 nanosheets, electrodes [214], although the packing density of the as-obtained gra-
but also provided abundant pathways for efficient electron transmission phene is very low [10,215]. Soon afterwards, Chengxin Wang’ group
based on their face-to-face contact mode. anchored several kinds of active nanomaterials (e.g., Sn [216,217], Si
[218], SnO2 nanoparticles [219], etc.) on both sides of the vertical
3.2.2.2. Interfacial contact between the composites and the electrolyte. It is aligned graphene sheets for EES and demonstrated the improved kinetics
well known that the mass (ion) transfer process is also very important for for both ion and electron transports.
EES, especially in high-power applications, and thus the interfacial
contact between graphene-based composites and the electrolyte are 3.2.3. Structure and dimensionality of graphene-based composites
discussed in this section to provide more detailed information [1]. The structures of the final designed graphene-based composites have
Basically, the reported strategies to improve the interfacial contact be- a significant influence on their application for various EES devices, which
tween graphene-based composites and the electrolyte could be divided cover all ‘four’ dimensions in terms of 0D particles, 1D wires, 2D films,
into three categories: (1) building porous structure into the 3D bulks, and potentially 4D self-healing or self-folding types [11], as
graphene-based composites; (2) improving the electrolyte wettability of demonstrated in Fig. 7. In this section, we will discuss how each mode
the graphene-based composites; and (3) tuning the orientation of the affects the properties and applications of graphene-based composites.
graphene component in the composites, as illustrated in Fig. 6. 0D graphene-based composites, such as irregular particles [139],
For building porous structure into the composites, methods such as spheres [220], and flowers [44], have the most potential to be used in
etching holes in graphene [206], constructing graphene aerogel (GA) EES markets for practical applications, because of their facile synthesis
structures [135], and building pores in the second phase [114] have been process and high tap density [220]. Recently, the spray-drying technique
successfully developed. Among them, constructing GA structure is the has been frequently used for preparing 0D graphene-based composites
most common one [207], which possesses unique advantages for pre- [221]. Zhaoping Liu’s group reported a graphene modified LiFePO4
paring 3D porous electrode materials, such as high porosity, large surface cathode material produced by a spray-drying technique combined with
area, and good electronic conductivity [134,135]. As a result, it provides annealing process, in which the LiFePO4 primary nanoparticles were
an ideal porous network for preparing graphene-based composites with embedded in microsized spherical secondary particles and were wrapped
3D ion diffusion channels and good electrical conductivity. Typically, with a graphene network [220]. In another case, Chao Gao’ group
Klaus Müllen’s group proposed a “two step” strategy to fabricate a 3D designed a graphene flower-like particle through a spray-drying process
graphene aerogel cross-linked with graphene pre-wrapped Fe3O4 nano- and high-temperature treatment [44]. When utilized as carbon host for a
spheres for LIB anodes [135]. Such hierarchical Fe3O4/graphene com- sulfur cathode, the graphene flower particle – sulfur composite delivered
posites provide double protection against the volume changes of Fe3O4 very impressive electrochemical performance in Li–S batteries (LSBs).
nanosheets during charge and discharge processes. Moreover, in order to 1D graphene-based composites, such as wires [120], scrolls [160],
further improve the infiltration of the electrolyte, Hongtao Sun and Lin and fibers [222], are also attractive due to their ability to integrate the
particular properties of individual graphene sheets and other functional
30
Fig. 6. Various strategies to improve the interfacial contact between graphene-based composites and the electrolyte, which could be divided into three categories: (1)
building porous structure in the graphene-based composites; (2) improving the electrolyte-wettability of the graphene-based composites (Reproduced with permission
from ref. 212, copyright 2011, American Chemical Society); and (3) tuning the orientation of the graphene component in the composites (reproduced with permission
from ref. 140, copyright 2015, The Royal Society of Chemistry).
materials into macroscopic assemblies with superior mechanical and cost, ease of processing, and performance. The unique characteristics of
electrical performances [223]. Moreover, 1D graphene-based composites graphene may endow the graphene film composites with excellent flex-
are favorable for constructing flexible and wearable EES devices, as they ibility, electrical conductivity, mechanical strength, and thermal con-
can be directly molded into fabrics and textiles [224]. Furthermore, 1D ductivity as well as optical transparency, depending on the properties of
graphene-based composites can be tailored to suit different EES devices the basic graphene-based-unit and the thickness of the as-obtained film
with unconventional architectures for special applications [21]. Typi- [171,232]. Recently, Dan Li’s group reported a flexible 2D
cally, Liming Dai’s group designed hierarchically structured graphene-polyaniline film electrode fabricated by in-situ chemical
graphene-carbon nanotube fibers and demonstrated their application for polymerization of aniline on the surfaces of chemically converted gra-
flexible all-solid-state micro-supercapacitors [222]. In another work, Wei phene sheets, which could provide a combination of high capacitance,
Huang’s group reported a flexible wire-shaped Li–S battery based on a excellent rate performance, and long cycling life [227].
graphene-sulfur composite fiber cathode [225]. Graphene-based nano- In the case of 3D graphene-based composites, various structures have
wire composite also displays immense potential for flexible and trans- been reported, such as aerogels [134], foams [233], and arrays [216].
parent electrodes with excellent optical and electrical properties as well These 3D graphene-based structure can support fast electron and mass
as high durability [226]. transfer, provide accessible surfaces for the adsorption and desorption of
2D graphene-based composites, such as sheets [141], films [227], and ions, and offer abundant pore volume for anchoring other functional
woven fabrics [228], represent an alternative applicable macroscopic materials, leading to EES systems with the desired performance. Apart
form on account of the high aspect ratio along its lateral direction, which from application in EES, the excellent electrical conductivity and
can usually be obtained by vacuum filtration, CVD, wet spinning process, biocompatibility of 3D graphene-based composites also enable their use
etc. [229–231] Actually, lamellar graphene components can be readily as scaffolds for tissue engineering and regeneration [234]. Substantial
assembled into 2D macrostructures with orderly packed sheets. Gra- research efforts are currently ongoing to control the morphologies and
phene film composites are particularly promising in film electrodes for the properties of 3D graphene-based composites for integration into
EES devices. Graphene-based film batteries and supercapacitors can be practical EES devices [235]. Typically, Huiming Cheng’s group designed
viable if they can equal or surpass current EES electrodes in regard of a 3D graphene foam-graphene/poly(dimethyl siloxane) composite with
31
Fig. 7. Configurational structures of the integral graphene-based composites in terms of 0D, 1D, 2D, 3D, and potentially 4D self-healing or self-folding types. In this
example, 0D forms include particles (reproduced with permission from ref. 139, copyright 2010, Wiley), spheres (reproduced with permission from ref. 220, copyright
2011, The Royal Society of Chemistry) and flowers (reproduced with permission from ref. 44, copyright 2017,Wiley); 1D forms include wires (reproduced with
permission from ref. 120, copyright 2012, Wiley), scrolls (reproduced with permission from ref. 160, copyright 2016, Wiley) and fibers (reproduced with permission
from ref. 222, copyright 2014, Nature Publishing Group); 2D forms include sheets (reproduced with permission from ref. 141, copyright 2012, Wiley), films
(reproduced with permission from ref. 227, copyright 2013, The Royal Society of Chemistry), and fabrics (reproduced with permission from ref. 228, copyright 2015,
The Royal Society of Chemistry); 3D forms include aerogels (reproduced with permission from ref. 134, copyright 2015, The Royal Society of Chemistry), frameworks
(reproduced with permission from ref. 233, copyright 2011, Nature Publishing Group), and arrays (reproduced with permission from ref. 216, copyright 2014,
Elsevier); 4D forms include self-healing (reproduced with permission from ref. 238, copyright 2018, Wiley) and self-folding types (reproduced with permission from
ref. 239, copyright 2015, American Association for the Advancement of Science).
high electrical conductivity through the CVD technique, which shows demand shape transformations. These 3D objects that change structure
great potential for flexible, foldable, and stretchable conductors [233]. over time are termed ‘4D materials’. A recent study has suggested that 4D
Afterwards, they used such a graphene foam in combination with printing of a ‘smart object’ may, one day, give rise to the development of
LiFePO4 and Li4Ti5O12 for fabricating 3D graphene foam composite such devices [237]. Recently, Takeshi Serizawa and Hongwei Zhu’s
electrodes for LIBs [236]. group designed a graphene oxide/poly(acrylic acid)/amorphous calcium
The future of this field lies in the progress on responsive graphene- carbonate (GO-PAA-ACC) composite via a facile
based structures that are adaptable to their surroundings. Generally, biomineralization-inspired process, which showed impressive reshaping
real-world objects, once produced, do not change their shapes or prop- and self-healing features and may meet some specific application re-
erties; a material that can transform and vary its configuration when quirements for self-healing or shape-changing EES devices [238]. In
subjected to an environmental change would be extremely useful, how- another case, Jiuke Mu and Chengyi Hou’s group designed a graphene
ever. This may lead to EES devices that are capable of self-healing or oxide-polydopamine/reduced graphene oxide (GO-PDA/RGO) compos-
changing shape in case of an accident or special requirement for on- ite film, which exhibited an interesting self-folding property and held
32
potential for a wide range of applications such as sensing, robotics, and 4.1. Electrochemical double-layer capacitors
self-folding EES devices [239].
In EDLCs, the amount of charge storage of the active materials is
4. Graphene-based composites for electrochemical capacitors proportional to the double layer contact with the electrolyte (Fig. 8a),
which can be evaluated per unit mass (F g1), volume (F cm3) or area (F
Electrochemical capacitors (ECs), also known as supercapacitors or cm2) [185]. In principle, graphene with a theoretical specific surface
ultracapacitors, with fast charge-storage mechanisms are more suitable area (SSA) of 2630 m2 g1 can reach a theoretical capacitance as high as
for high power density applications compared with other EES devices 550 F g1, which shows a great potential for boosting the energy density
(e.g., LIBs). The ECs can be classified into two main groups: electro- of such systems [242–245]. In practice, however, this does not seem to be
chemical double-layer capacitors (EDLCs) and pseudocapacitors [240]. the case, as the inaccessibility of the theoretical SSA of graphene results
In EDLCs, the energy is stored through a non-Faradaic process by phys- in a lower practical gravimetric capacitance [246]. Furthermore, spon-
ically adsorbing ions or charged particles on the surfaces of the elec- taneous graphene layer re-stacking, which occurs during both electrode
trodes, as illustrated in Fig. 8a [241]. In pseudocapacitors, the fabrication and cycling, significantly reduces the practical surface
electrochemical energy storage is realized by a fast and reversible Fara- available for charge storage (Fig. 3d, e) [247]. Various approaches have
daic process, such as a redox reaction, taking place between the interface been employed to mitigate these adverse impacts, such as designing
area of the electrochemically active species and the electrolyte (Fig. 9a) activated graphene with extended 3D meso- and microporous structure
[9]. [242], tuning the orientation of graphene so that it is perpendicular to
Fig. 8. (a) Schematic illustration of ion adsorption at the electrode surface for EDLCs. Structures and electrochemical characterizations of (b) graphene/fullerene
composite with 0D fullerene as the spacer (reproduced with permission from ref. 248, copyright 2015, Taylor and Francis Inc), (c) graphene/CNTs composite created
by incorporating 1D CNTs with graphene (reproduced with permission from ref. 254, copyright 2012, The Royal Society of Chemistry), (d) 3D graphene/carbon
nanotube sandwich-structured composite (reproduced with permission from ref. 255, copyright 2010, Wiley), and (e) 3D commercial activated carbon bulk material
combined with graphene (reproduced with permission from ref. 253, copyright 2012, The Royal Society of Chemistry).
33
Fig. 9. (a) Schematic illustration of charge transfer near the surface of the electrode for pseudocapacitors. In this example, RuO2/graphene composite has been chosen
as the active material. Structures and electrochemical characterizations of (b) 2,5-dimethoxy-1,4-benzoquinone/RGO composite xerogel (reproduced with permission
from ref. 288, copyright 2016, The Royal Society of Chemistry), (c) MnO2 nanoflake layer-coated vertical graphene composite (reproduced with permission from ref.
289, copyright 2016, American Chemical Society), (d) Graphene/MXene composite film (reproduced with permission from ref. 175, copyright 2017,Wiley), and (e) 3D
MnNi-LDH/graphene composite (reproduced with permission from ref. 284, copyright 2017, Elsevier).
the current collector plane [215], fabricating different types of graphe- activated carbon [253] have also been introduced for incorporation with
ne/carbon composites, etc. [222]. graphene to fabricate graphene-based composites with improved EDLC
Graphene/carbon composites can be prepared by combining carbon performance. Typically, Liming Dai’s group fabricated a self-assembled
species with other structures (e.g., fullerene [248], carbon black [249], graphene/CNTs composite film, in which the CNTs could insert be-
carbon nanotubes [168,222,250], porous carbon spheres [251], hollow tween graphene sheets parallel to its planar structure and form
carbon spheres [252], activated carbon [253], etc.) with graphene via in well-defined nanopores. This graphene/CNTs film electrode exhibited
situ or ex situ chemical and physical methods, gaining the advantages of great promise for EDLCs with a quasi-rectangular-shaped cyclic voltam-
each component towards improving the infiltration of the electrolyte and mogram even at an extremely high scan rate of 1 V s1 and an average
enhancing the electrical conductivity of the electrode. For instance, specific capacitance of 120 F g1 [229]. Afterwards, Dengsong Zhang and
Zhuangjun Fan’s group reported a graphene/carbon black composite Liyi Shi’s group designed a similar graphene/CNTs composite through a
prepared by the in-situ reduction method, in which the 0D carbon black modified exfoliation approach (Fig. 8c), which exhibited a much higher
acted as both the conductive agent and a spacer to increase the interlayer specific capacitance (230 F g1) than graphene (101 F g1) at a current
spacing between 2D graphene sheets for fast electron and ion transport density of 0.6 A g1 [254]. In another study, 3D graphene/carbon
[249]. Analogously, Xue Qin’s group used 0D fullerene as the spacer to nanotube sandwich structures with CNT pillars grown in between the
realize a graphene/fullerene composite, which could reach a capacity of graphene layers were been fabricated by the CVD technique (Fig. 8d).
135 F g1 at the current density of 1 A g1 (Fig. 8b) [248]. 1D carbon The special structure facilitated the high-rate transportation of electro-
nanotubes (CNTs) [168,222,250], 3D carbon spheres [251,252], and lyte ions and electrons throughout the electrode matrix, resulting in
34
excellent capacitive performance of this composite material [255]. capacity retention after 1400 cycles and a high energy density of
Additionally, Likun Pan’s group combined 3D commercial activated 47.29 Wh kg1 at the power density of 7473 W kg1 [284]. It seems that
carbon bulk material with graphene through a facile chemical method, the key to realizing the full potential of graphene in pseudocapacitors
and the resultant graphene/activated carbon composite could display a depends on the development of graphene-based composites that benefit
much improved specific capacitance of 181 F g1 (Fig. 8e) [253]. from the synergistic effects of the graphene substrate and the electro-
Although the strategies for introducing nanostructured carbons as the chemically active component to the maximum extent, combined with an
separators of graphene sheets are quite promising, further engineering of optimized spatial orientation of the graphene sheets [21,290].
graphene/carbon composites for EDLCs are required to reduce the pro-
duction costs for practical applications [20,256,257]. On the other hand, 5. Graphene-based composites for Li-ion batteries
most of the reported graphene/carbon composites for EDLCs possess a
large number of voids (especially macropores) leading to relatively low LIBs have attracted vast attention from both the scientific community
density, and these pores would be filled with the electrolyte, resulting in and the wider society as one of the most favored types of EES devices for
both high weight and volume in the final device [21,175]. Therefore, applications in different fields, owing to their high energy density
increasing the mass density of the graphene/carbon composite to reduce (compared with ECs), long cycling life, and low self-discharging [1,134].
the weight and volume of the final device is also very significant for the In LIBs, Liþ ions constantly shuttle back and forth between a
large-scale EDLCs required to power the next generation of electric ve- lithium-releasing cathode (e.g., layered lithium metal oxide or lithium
hicles and hybrid electric vehicles [11,246]. iron phosphate) and a lithium-receiving anode (e.g., graphite), as illus-
trated in Fig. 10a [140]. The amount of ions carried per gram of product
4.2. Pseudocapacitors determines the gravimetric capacity and energy of the battery.
In the case of pseudocapacitors, the presence of electrochemically 5.1. Graphene-based anode composites
active species in the electrode material (Fig. 9a), for instance, oxygen-
containing functional groups [258,259], conductive polymers [171], Similar to graphite, graphene can be applied in the anode for hosting
transition metal oxides [122] (or nitrides [260], sulfides [261–263], Liþ directly or as an active material in anode composites by combined
hydroxides [264], etc.), and MXenes [265], enables higher energy den- with other Li-hosting components. Unlike graphite, single-layered gra-
sities compared with EDLCs. Nevertheless, the electrochemical behavior phene has been theoretically calculated to host Liþ via an adsorption
of pseudocapacitors is inferior to that of EDLCs with respect to power mechanism on both sides with a stoichiometry of Li2C6, which results in a
density and cycle life because of the poor electric conductivity and poor specific capacity as high as 744 mAh g1, twice that of graphite
structural stability of the active materials [266]. In this regard, (372 mAh g1), with an Liþ intercalation mechanism between the
graphene-based composites could be available alternatives for improving stacked layers [46,291]. In addition, the inherent defects and nanopores
the performance of pseudocapacitors [240,267,268]. that are constructed by the randomly arranged graphene layers can also
Various graphene/conductive polymers (e.g., polyaniline [137,269], store Liþ ions according to the ‘house of cards’ model [292–294]. In order
polypyrrole [270,271], polythiophene [272], etc.), graphene/metal ox- to further clarify the Liþ storage mechanism of graphene, advanced in
ides (e.g., Mn3O4 [273–275], Co3O4 [276,277], SnO2 [278,279], etc.), operando techniques (e.g., in situ low-voltage transmission electron mi-
graphene/metal nitrides (e.g., VN [260,280], Ni3N [281], etc.), graphe- croscopy [295]) for obtaining direct evidence are still needed.
ne/sulfides (e.g., FeS2 [282], MoS2 [283], etc.), graphene/hydroxides Generally, graphene material typically exhibits a high irreversible
(e.g., MnNi-layered double hydroxide (MnNi-LDH) [284], NiCo-LDH capacity (even higher than 2000 mAh g1) during the first Liþ insertion/
[285], etc.), graphene/MXenes [175,286,287], etc., have been exploi- extraction process, well above the theoretical capacity of monolayer
ted and researched for pseudocapacitors. In these composites, graphene graphene [46,294]. This phenomenon is mostly caused by the irrevers-
provides a conductive substrate for the support or growth of the elec- ible reduction of the electrolyte to form a solid electrolyte interphase
trochemically active species at the nanoscale, which enables a large SSA (SEI) layer on the graphene surface, which is enhanced with a higher SSA
with more active sites and improved mechanical stability, thus enhancing and results in a fairly high initial irreversible capacity loss in comparison
the electrochemical performance of the final fabricated with graphite materials [46]. In the following de-insertion process, gra-
pseudocapacitors. phene displays a high reversible capacity, with potentials distributed in
Recently, Yury Gogotsi’s group reported a 2,5-dimethoxy-1,4-benzo- the range of 1–3 V vs. Li/Liþ, much higher than the classical potentials for
quinone (DMQ)/RGO composite xerogel (Fig. 9b), in which DMQ not graphite (0–0.4 V vs. Li/Liþ). This would cause an obvious voltage hys-
only provided stable redox-active centers but also served as a spacer to teresis between Liþ insertion and de-insertion processes (due to the
protect the RGO sheets from aggregation and construct a three- storage of Liþ on defect positions, such as vacancies, edges, and
dimensional (3D) hierarchical electrode architecture [288]. When a oxygen-containing groups) and lead to a poor energy efficiency for LIBs
binder-free 50 mm thick rolled film was tested as a pseudocapacitive using such graphene anodes. Moreover, the unavoidable re-stacking of
electrode, it exhibited an excellent capacitance of 650 F g1 at 5 mV s1 graphene will also lower the Liþ storage capacity during the repeated
(780 F cm3) in 1 M sulfuric acid and an excellent capacitance retention cycling processes [294]. Because of the above-mentioned factors, the
of 99% after 25000 cycles at 50 mV s1 [288]. In another work, a vertical cycling performance of graphene anodes is generally very poor, and
graphene composite coated with a MnO2 nanoflake layer was designed normally, the reversible capacity of graphene is rarely comparable to that
by Weng P. Kang and Shaozhi Deng’s group (Fig. 9c), with the vertical of the commercially available graphite. In this regards, pre-lithiation
structure and open architecture designed for fast ion transport pathways, [296], surface modification with functionalized groups [297] and,
providing high pseudocapacitive performance, with the overall areal especially, designing ideal graphene-based composites [20] are consid-
capacitance of 500 mF cm2 at the scan rate of 5 mV s1 [289]. More- ered as effective strategies for preventing initial Liþ consumption and
over, Jun Yan et al. designed a graphene/MXene composite film (Fig. 9d), graphene re-stacking [10].
which could deliver an ultrahigh volumetric capacitance (1040 F cm3) To date, various graphene-based anode composites with different
at 2 mV s1, excellent rate capability, and long cycle life. When a sym- structures have been developed through in-situ or ex-situ methods for the
metric supercapacitor was assembled from it, a high volumetric energy purpose of improving their cycling performance and increasing their
density (32.6 Wh L1) could be achieved in aqueous electrolyte [175]. In energy density compared with bare graphene [140]. The large capacity
addition, Songhun Yoon’s group reported a 3D MnNi-LDH/graphene contribution from other active components (e.g., metal oxides [117,138,
composite with MnNi-LDH impregnated into the interlayers of gra- 151,191], metals [120,141], etc.), can offer reversible insertion (e.g.,
phene nanosheets (Fig. 9e). It exhibited a stable performance with 90% TiO2 [117]), alloying (e.g., SnO2 [151], Sn [141], etc.) or conversion
35
Fig. 10. (a) Schematic illustration of the working principle of LIBs based on the graphene-based electrodes. In this example, Fe2O3/graphene and LiFePO4/graphene
composites have been chosen as the anode and cathode materials, respectively. Structures and electrochemical characterizations of (b) 3D interconnected porous
nitrogen-doped graphene foam with encapsulated Ge quantum dots (reproduced with permission from ref. 130, copyright 2017, Nature Publishing Group), (c) 3D
holey-graphene/Nb2O5 composite (reproduced with permission from ref. 208, copyright 2017, American Association for the Advancement of Science), (d) graphene
modified LFP quantum dot composite (reproduced with permission from ref. 126, copyright 2017, Elsevier), and (e) 3D porous LiFePO4/N-doped GA composite
(reproduced with permission from ref. 134, copyright 2015, The Royal Society of Chemistry).
(e.g., Fe3O4 [191], Co3O4 [138], etc.) reactions with Liþ and thus provide yolk-shell nano-architecture for LIB anode (Fig. 10b), which exhibited
considerably higher capacities. Also, the introduced electrochemically high reversible specific capacity (1220 mAh g1), long cycling capability
active nanostructures are beneficial for blocking the re-stacking of gra- (over 96% reversible capacity retention from the 2nd to the 1000th cycles)
phene layers by reducing the van der Waals forces [147,260]. Therefore, and ultra-high rate performance (over 800 mAh g1 at 40C) [130].
these composites are less affected by the agglomeration that takes place Moreover, Xiangfeng Duan’s group designed a 3D hole-
both in electrode preparation and cycling tests. More importantly, the y-graphene/Nb2O5 composite (Fig. 10c) by systematically tailoring the
efficient conductive carbon matrix constructed from the graphene layers porosity in the holey graphene backbone. The charge and mass transport
not only improves the electronic conductivity of the composite, but also in this fabricated architecture were optimized to deliver ultrahigh-rate
buffers the volume changes during charge and discharge [141]. Despite energy storage performance at practical levels of mass loading
these promising properties, however, the graphene-based anode com- (>10 mg cm2) [208]. In addition, some promising reversible capacities
posites still suffer from low Coulombic efficiency, which is mainly in the are also achieved for silicon/graphene (1400 mAh g1) [298], Fe3O4/g-
range between 50-70% for the first cycle with a large charge consump- raphene (1060 mAh g1) [135], and Co3O4/graphene (1029 mAh g1)
tion of 30–50%, similar to the Coulombic efficiency of bare graphene [123] composites. Nevertheless, further optimization of the structural
[135]. The performance achieved so far with graphene-based anode configuration and mass ratio distribution between graphene and the
composites are quite inspiring for high-energy LIBs. Recently, Runwei Mo other active components are still critical issues that should be addressed
et al. designed a 3D interconnected porous nitrogen-doped graphene to achieve better electrochemical performance in term of reversible ca-
foam with an encapsulated Ge quantum dot/nitrogen-doped graphene pacity, rate performance, cycling life, etc. [12,140].
36
5.2. Graphene-based cathode composites (1 wt%-3 wt.%) [302]. Therefore, further optimization of the graphene
conductive network (with more effective electron and Liþ pathways) and
For LIBs cathodes, LiFePO4 [299], LiCoO2 [300], and LiMn2O4 [301] a lower graphene weight ratio are still the most important challenges for
are the most common active materials for the current commercial mar- graphene-based cathode composites.
ket, which are mixed with low-cost carbon conductive additives, such as
carbon black, acetylene black, etc. [302] Due to their amorphous struc- 6. Graphene-based composites for electrochemical energy
ture, however, these conductive additives usually have a relatively low storage beyond electrochemical capacitors and Li-ion batteries
electronic conductivity and poor mechanical strength compared with
more graphitic carbon materials (e.g., CNTs and graphene) [198]. Hence, 6.1. Na-ion batteries
the rate capability and cycling life of these electrodes are still limited by
the fact of slow kinetics for electron and Liþ transport as well as severe Na-ion batteries (NIBs) recently have attracted extensive attention
structural degradation during repeated charge and discharge [303]. owing to the plentiful reserves and low cost of sodium, so that the NIBs
Accordingly, graphene materials as superior conductive and flexible are considered as the potential alternatives to LIBs [307,308]. The
matrices has been the object of considerable study for constructing working principle of NIBs is similar to that of LIBs, with Naþ migrating in
cathode composites to improve the electronic and ionic conductivity (by the electrolyte between the electrodes (cathode and anode) while the
forming a bi-continuous conductive network) of the electrode and alle- electrons are transmitted through the outer electric circuit, as illustrated
viate the stress/strain for preserving electrode integrity [125,134]. in Fig. 11a [309]. To date, some materials have been reported for NIB
For synthesizing graphene-based cathode composites, in-situ methods electrodes, including hard [310] or graphitic carbons [311], NaxM alloys
(e.g., the hydrothermal or solvothermal method) are normally superior to (M ¼ Si, Sn, Ge, Sb, P, etc.) [312] and transition metal oxides [313] or
ex-situ strategies (such as the mechanical mixing strategy), because the sulfides [314] as anode materials, and layered oxides [315], polyanionic
former ones could effectively suppress the crystal growth (to shorten the phosphates [316,317], or pyrophosphates [318] as cathode materials.
Liþ transport distance in the crystals of active materials) and form much Compared with Liþ, however, the relatively larger ionic size of Naþ
stronger chemical bonds as fast electron transport pathways (supported greatly limits the available kinds of host materials for NIB electrodes, and
by theoretical calculations in some previous reports) [184,304]. In gen- the search for more appropriate host materials is still ongoing [319].
eral, GO is most frequently employed as the raw material to construct the Pristine graphene is rarely directly used as an anode materials for
porous networks (leading to improved Liþ diffusion kinetics) in the NIBs because of its lack of defects (e.g., residual oxygen-containing
in-situ synthesis process because of its hydrophilic property, electro- groups) and poor Naþ adsorption property, which is very modest
negativity, and abundant functional groups, which is subsequently compared to hard carbon or other active carbonaceous materials in terms
reduced to graphene to improve the electronic conductivity, while of Naþ storage capacity [200]. Although creating defects in graphene
simultaneously, the cathode precursors would turn into active materials seems can dramatically improve the Naþ storage capacity of
with various nanostructures (e.g., nanoparticles, nanowires, nano- graphene-based anodes, the presence of defects represents low
ribbons, etc.) [164,220,305]. For instance, our group previously pre- Coulombic efficiency for NIBs as well [320]. Similar to LIBs,
pared a graphene modified LiFePO4 quantum dot (~6.5 nm) composite graphene-based anode composites also show great potential in NIBs,
through an in-situ microreactor strategy (Fig. 10d) [126], which had a where they enable better electrochemical performance (e.g., higher
large SSA for charge adsorption and plentiful active sites for faradaic specific capacity, better rate capability and longer cycle life) compared
responses, as well as desirable kinetic features for both electron and ion with bare graphene materials. Different types of anode active materials
transmission. It thus exhibited extremely fast, surface-dynamics have been combined with graphene, including transition metal oxides
controlled lithium storage behavior, imitating the pseudocapacitive (e.g., SnO2 [321], Fe3O4 [322], MgFe2O4 [323]), transition metal sulfides
mechanisms in terms of outstanding rate capability (78 mAh g1 at 200C) (e.g., SnS2 [324], MoS2 [314]), metals or metal alloies (e.g., Sb [325], P
and remarkable cycling stability (~99% capacity retention over 1000 [326]), phosphorene [327], and NASICON-type NaTi2(PO4)3 [328], for
cycles at 20C). On the other hand, based on the density functional theory fabrication as promising anode composites for NIBs. Typically, Yi Cui’s
(DFT) calculations, it was found that the heterointerfaces of graphene group reported a phosphorene/graphene composite made by sandwich-
and LiFePO4 had an efficient hybridized electronic structure near the ing phosphorene layers between graphene layers (Fig. 11b), which
Fermi level with optimal charge distribution, which increased the active showed a specific capacity as high as 2440 mAh g1 (based on the weight
sites in this region and further enhanced the electrochemical activity. of phosphorene) under a current density of 0.05 A g1 and capacity
In addition, some previous reported works on graphene-wrapped retention of 83% after 100 cycles in the voltage window of 0–1.5 V (vs.
structured cathode composites (e.g., a 3D porous LiFePO4/N-doped GA Na/Naþ) [327]. The presence of graphene layers in the composite
composite developed by our group [134], Fig. 10e) have demonstrated ensured electrical highways for electron transport and elastic buffer
that the graphene layer could protect the active materials from direct space for accommodating the volume changes of phosphorene during
contact with the electrolyte and thus alleviate the side reactions and cycling. In another case, Yunhui Huang’s group synthesized a 3D com-
dissolution of the active materials [184,201]. Nevertheless, it also was posite of graphene decorated with NaTi2(PO4)3 microspheres through a
revealed that Liþ ions are hard to pass through the graphene layer. facile spray-drying method combined with post calcination (Fig. 11c)
Taking LiFePO4 for example, Wei Wei et al. have demonstrated that a [328]. By combining the advantages of nanosized particles with the 3D
completely graphene-encapsulated LFP composite has almost no capacity graphene conductive network, the ionic, electronic and mechanical
[201]. Regardless of the high cost of graphene materials, when the properties of the composite were significantly improved, and it thus
graphene-based cathode composites are used as the electrode material, possessed the high reversible capacity of 130 mAh g1 at 0.1C and
the weight ratio of the graphene component should also be considered for excellent rate capability (38 mAh g1 at 200C) as well as great cycling
practical applications. This is because too little graphene makes it stability (77% capacity retention over 1000 cycles at 20C.
impossible to construct an effective conductive network and too much For NIB cathodes (e.g., layered oxides [315], polyanionic phosphates
graphene would block the Liþ transport to some extent in the electrode. [316,317], pyrophosphates [318], etc.), similar to their LIB analogues,
Moreover, the graphene component is almost inactive in the potential their relatively poor electronic conductivity is the key factor limiting
windows of LIBs cathodes and makes a negligible capacity contribution, their rate capability [319]. In this regard, although graphene components
which will reduce the energy density of the final electrode [87,114,306]. are generally inactive for SIB cathodes, many graphene-based cathode
The graphene weight ratios for the reported cathode composites are composites (combining graphene materials with FeF3 [329],
mainly distributed in the range of 5 wt%-20 wt%, which are much higher Na3V2(PO4)3 [330], Na2/3Fe1/2Mn1/2O2 [154], etc.) have been designed
than the commercial standard for using conventional carbon additives by taking advantages of the high electronic conductivity of graphene,
37
Fig. 11. (a) Schematic illustration of the working principle of NIBs based on graphene-based electrodes. In this example, NaTi2(PO4)3/graphene and Na3V2(PO4)3/
graphene composites have been chosen as the anode and cathode materials, respectively. Structures and electrochemical characterizations of (b) phosphorene/gra-
phene composite created by sandwiching phosphorene layers between graphene layers (reproduced with permission from ref. 177, copyright 2015, Nature Publishing
Group), (c) composite of 3D graphene decorated with NaTi2(PO4)3 microspheres (reproduced with permission from ref. 328, copyright 2016, Wiley), (d) FeF3–Fe-RGO
cathode composite (reproduced with permission from ref. 329, copyright 2014, Elsevier), and (e) 3D Na3V2(PO4)3@C@RGO hierarchically porous composite
(reproduced with permission from ref. 330, copyright 2015, Wiley).
which all show improved rate performance compared with the bare reaction between Li anode and S cathode, as illustrated in Fig. 12a [331].
cathode materials. For example, Yu Zhang’s group synthesized an For Li anode, despite its advantages in terms of low electrochemical
extraordinary FeF3–Fe-RGO cathode material with high discharge ca- potential and high theoretical specific capacity (3860 mAh g1), its main
pacity (150 mAh g1 under a current density of 50 mA g1), good cycling drawback is the easy formation of dendrites during repeated Li deposi-
stability, and high-power performance at room temperature, which tion and dissolution processes [332]. Once these Li dendrites impale the
resulted from the homogeneous conductive architecture composed of separator, a serious safety problem will exist. Some strategies have been
metallic Fe and RGO (Fig. 11d) [329]. In another work reported by Yan proposed to resolve the Li dendrite issue through (i) liquid electrolyte
Yu’ group, a 3D Na3V2(PO4)3@C@RGO hierarchically porous composite additive (e.g., LiF [333], LiPF6 [334], Csþ [335], etc.), (ii) polymer and
with bicontinuous ion/electron pathways could realize fast charge/di- solid electrolyte (e.g., liquid-like solid electrolyte [336], Li7P2S8I [337],
scharge performance (e.g., 91 mAh g1 at 80C and 86 mAh g1 at 100C, single-ion polymer [338], etc.), (iii) artificial SEI (e.g., Cu3N nano-
Fig. 11e) and long cycle life (64% capacity retention after 10000 cycles at particles joined together by styrene butadiene rubber [339], Li3PO4
100C) [330]. [340], poly(vinylidene-co-hexafluoropropylene) and LiF composite film
[341], etc.), (iv) membrane modification (e.g., Li6.75La3Zr1.75Ta0.25O12
6.2. Li–S batteries coated polypropylene separator [342], mussel-inspired poly-
dopamine-treated-polyethylene separator [343], N and S co-doped gra-
Li–S batteries (LSBs) possess remarkably high theoretical specific phene nanosheets on polymer separator [344], etc.), and (iv) anode
energy (2600 Wh kg1 or 2800 Wh L1) via a reversible electrochemical structure optimization (e.g., conductive nanostructured graphene
38
Fig. 12. (a) Schematic illustration of the working principle of LSBs with graphene-based electrodes. In this example, lithium/graphene and sulfur/graphene com-
posites have been chosen as the anode and cathode materials, respectively. Structures and electrochemical characterizations of (b) partially reduced GO/lithium film
composite (reproduced with permission from ref. 349, copyright 2016, Nature Publishing Group), (c) freestanding lithium alloy/graphene composite (reproduced with
permission from ref. 352, copyright 2017, Nature Publishing Group), (d) S/graphene-graphitic carbon nanocage composite (reproduced with permission from ref. 145,
copyright 2016, Wiley), and (e) conductive porous vanadium nitride nanoribbon/graphene composite (reproduced with permission from ref. 124, copyright 2017,
Nature Publishing Group).
scaffold [345], patterned reduced graphene oxide anode [346], 3D cur- lithium metal anodes (Fig. 12c). With the protection of graphene sheets,
rent collector with a submicron skeleton and high electroactive surface the foil is stable in different atmospheres and exhibit stable cyclability
area [347], etc.), etc. [348]. (400 cycles with 98% capacity retention) [352]. Further, Jiayan Luo’s
Recently, it was found that the graphene materials with appropriate group designed a patterned RGO/Li composite anode with electric field
oxygen-containing groups could exhibit a good “lithiophilicity”, detoured to the edges of the patterned anodes and Li horizontally cen-
providing abundant active sites for the formation of Li crystal nuclei, and tripetal plating in the patterned voids, which could be cycled for more
thus alleviate the dendrite phenomenon [349,350]. In this regard, gra- than 2000 h and maintained stable voltage profiles at a large current
phene with oxygen groups has been introduced to combine with Li for the density of 10 mA cm2 [346]. On the other hand, Qiang Zhang’s group
construction of composite anodes [351]. Typically, Yi Cui’s group [353] and Nikhil Koratkar’s group [354] demonstrated that the N-doped
designed a partially reduced GO/Li film composite electrode (Fig. 12b), atoms and defects in graphene were also lithiophilic, which could induce
in which Li metal is stored in the interspaces of graphene layers through uniform Li nucleation and smooth Li plating. Moreover, the high surface
lithiophilic capillarity, and it displayed stable Li plating/stripping area of the conductive graphene matrix can effectively enhance the
behavior and high Coulombic efficiency [349]. Soon after, they reported surface area and then reduce the local current density and suppress the
a free-standing lithium alloy/graphene composite foil as an alternative to growth of Li dendrite. For example, Rui Zhang et al. designed a high
39
surface-area graphene framework (1666 m2 g1) with large pore volume electrocatalytic performance (for the low-cost catalysts), generation of
(1.65 cm3 g1) and good electrical conductivity (435 S cm1), when used irreversible Li2O2 by-products, undesired side reactions (between elec-
in Li anode, it was beneficial to regulate the Li depositing morphology trolyte/Li and H2O/CO2 from the atmosphere), etc. Among the many
with a high Coulombic efficiency of 93% at 0.5 mA cm2 [345]. In factors influencing the performance of LABs, the properties of the air
another case, Shan Liu et al. reported a crumpled graphene ball matrix electrode (cathode) are especially important for achieving high energy
with large surface area to stabilize the dendrite-free Li metal anodes density, which is strongly influenced by the loading mass and catalytic
[355]. Additionally, Dong-won Kim’s group demonstrated that the N and activity of the catalysts as well as the morphology and amounts of the
S codoped graphene modified membrane could maintain a uniform ionic final discharge products [332,367]. In this regard, employing
flux on the Li metal surface and leading to the effectively suppressing graphene-based catalyst composites with large SSAs and porous nano-
dendrite growth and stabilized cycling performance [344]. structures seems to be an ideal strategy to address these issues for LABs
As for S cathode, although it has many advantages including abun- [369]. So far, various nanostructured noble and transition metals (or
dance, low cost, environmentally benignity, and high theoretical specific oxides), such as Pt (Fig. 13b) [370], Co3O4 (Fig. 13c) [172], MnCo2O4
capacity (1672 mAh g1), it is affected by several drawbacks: (i) very low (Fig. 13d) [371], Nd0.5Sr0.5CoO3δ (Fig. 13e) [372], etc., have been
electronic conductivity of the redox reaction products (e.g., S, Li2S, etc.) incorporated with different graphene materials and exhibited improved
leading to sluggish electrochemical kinetics; (ii) the “shuttle effect” of the performance in LABs compared with the bare catalytic materials,
soluble intermediate reaction products (polysulfides), resulting in low although the achieved capacities are still far below those expected from
Coulombic efficiency and poor cycle life; (iii) large volume changes the theoretical energy density. Furthermore, in some previously reported
during charge and discharge processes, giving rise to degeneration of the work, the researchers found that the functional groups and defects of
electrode [356]. Correspondingly, in order to address these problems, graphene materials can also play a catalytic role in the formation of
various graphene materials (e.g., GO [357], RGO [358], discharge products [369,373]. In order to develop more efficient
heteroatom-doped graphene [359], porous graphene [360], etc.) and graphene-based catalyst composites, however, major studies are still
graphene-based composites (e.g., graphene/transition metal oxide [361], needed to further clarify the nature of the synergistic effects between the
graphene/polymer [362], graphene/micro or mesoporous carbon [363], graphene components and other catalytic materials in the composites.
etc.) with different physical and chemical properties have been proposed
as both anode candidates and separators for trapping the soluble poly- 6.4. Others
sulfides and alleviating the “shuttle effect” [364–366]. Recently, Yuguo
Guo’s group synthesized a S/graphene-graphitic carbon nanocage The recent outbreak of graphene-based composites in the EES field
(G-GCNs) composite with S nanoparticles encapsulated within GCNs have spurred research into other novel EES systems, such as magnesium-
(Fig. 12d) [145]. Due to the high conductivity and the physical constraint ion batteries (MgIBs) [374] and Al-ion batteries (AIBs) [375,376].
effect of the G-GCNs network, the S/(G-GCNs) composite achieved Compared with Li and Na, Mg and Al are low-cost, environmentally
improved S utilization (with a high specific discharge capacity of friendly and stable in atmosphere, and more importantly, they are much
1375 mAh g1) and superb high-rate capability (765 mAh g1 at 5C) as safer as metallic anodes, being without dendrite formation in the
well as a long cycle life of 1000 cycles. In another case, Feng Li’s group repeated plating and stripping processes. Although MgIBs and AIBs have
reported a conductive vanadium nitride nanoribbon/graphene compos- been proposed as emerging EES devices with high energy density for
ite with porous structure that could accommodate the catholyte as future EES applications, the development of these batteries has been
cathode for LSBs (Fig. 12e), which provided strong chemical adsorption hindered by the limited choice of appropriate electrode materials.
of polysulfides and electron transport highways for fast polysulfide Recently, a few pristine graphene and graphene composite materials
conversion [124]. The obtained composite exhibited a high initial ca- have been reported as electrode materials for both MgIBs and AIBs,
pacity (1471 mAh g1) and good cycling stability (85% capacity reten- although the achieved electrochemical performances still fall far short of
tion after 100 cycles at 0.2C). practical requirements [374,375]. In fact, the research on using
Although many previous reports on graphene-based composites for graphene-based composites for the abovementioned two multivalent
LSBs demonstrated attractive electrochemical performance in terms of metal-ion batteries is still in its early stages, and more investigation needs
capacity and Coulombic efficiency, the achieved cycling performances to be focused on this field for achieving better electrochemical
are still very modest compared with LIBs, and further research to improve performance.
LSB techniques is required (such as further improvement of the stability Graphene-based composites have also been reported as air electrodes
of graphene/sulfur and graphene/lithium interfaces). for Na-air batteries (NABs) [377] and Zn-air batteries (ZABs) [378], and
as active materials for vanadium redox-flow batteries (VRFBs) [379],
6.3. Li-air batteries which were introduced in order to improve their performance. Similar to
LABs, NABs and ZABs also have some technical challenges hindering
To meet the growing demand for energy, it is imperative to develop their practical application, and it appeared that graphene-based com-
more advanced EES devices with greater energy densities than composites could enhance the catalytic properties of both ORR and OER
mercial LIBs. In this regard, the Li-air battery (LAB) with exceedingly processes for these metal-air batteries through the synergistic effects
high theoretical energy density of 5200 Wh kg1 is believed to be one of between graphene materials and other catalytic components [18]. These
the most promising candidates [332]. In general, LABs are composed of a technologies for NABs and ZABs are in their very early stages and require
metallic lithium anode, an Liþ ion-conducting electrolyte, and a porous much deeper research. In the case of VRFBs, although this type of EES
air cathode, as illustrated in Fig. 13a. The discharge process, corre- device is quite promising for practical applications, current techniques
sponding to the reduction of oxygen (O2) at the cathode exposed to air for synthesizing their electrodes and membranes cannot satisfy high re-
and the oxidation of metallic Li at the anode with the generation of LiO2 quirements. Graphene-based composites have also been employed in
and/or Li2O2, is commonly called the “oxygen reduction reaction” VRFB electrodes to improve their electronic conductivity and reversible
(ORR). In reverse, the charge process, i.e., electrochemically decom- kinetics [379]. Graphene materials (GO or graphene) have also been used
posing Li2O2 and/or Li2O into Li and O2, is called the “oxygen evolution as additives to VRFB ion-exchange membranes to reduce the vanadium
reaction” (OER) [332,367]. permeation and prevent ionic cross-mixing [380]. Nevertheless, the
Since the pioneering studies by Bruce and colleagues in 2006 [368], techniques for using graphene-based composites in VRFBs are also too
the recharging of LABs has been intensively investigated. Unfortunately, immature for commercial applications.
the LABs suffer severely from short cycle lifetimes, inefficient energy In addition to these aforementioned EES systems, graphene-based
utilization, and poor rate capability, caused by their limited composites have also exhibited great potential in numerous of other
40
Fig. 13. (a) Schematic illustration of the working principle for LABs containing graphene-based electrodes. Structures and electrochemical characterizations of (b) Pt
nanoparticles/graphene composite (reproduced with permission from ref. 370, copyright 2012, Elsevier), (c) Co3O4 nanofibers/graphene composite (reproduced with
permission from ref. 172, copyright 2013, American Chemical Society), (d) MnCo2O4 nanoparticles/graphene composite (reproduced with permission from ref. 371,
copyright 2012, The Royal Society of Chemistry), and (e) Nd0.5Sr0.5CoO3-δ nanorods/graphene composite (reproduced with permission from ref. 372, copyright 2016,
The Royal Society of Chemistry).
emerging EES devices, including, but not limited to K-ion batteries (KIBs) from flexible solar cells to flexible displays as well as wearable elec-
[381], Mg–S batteries (MSBs) [382], Mg-air batteries (MABs) [383], tronics, is rapidly expanding [413]. The rise of this market is mainly due
Al-air batteries (AABs) [384], and hybrid systems (such as Li-ion ca- to the further requirements from consumers and the fast progress in
pacitors - LICs) [385], because of their promising physical and chemical research on flexible materials [413]. In the EES field, almost all of the
properties with synergistic effects between different components for commercial batteries and capacitors are inflexible and unbendable (since
efficient EES. The reports on graphene-based composites for the afore- bending them to any large extent may cause electrolyte leakage or even
mentioned emerging EES systems in this section are summarized in structure damage). This is because the present EES devices are mainly
Table 1. based on particulate-like active materials with very poor flexibility. With
the rise of graphene, which is considered as an ideal flexible material
7. Emerging properties of electrochemical energy storage devices (due to its intrinsic properties), and graphene-based composites could
fabricated from graphene-based composites further inherit this advantage. In this regard, numerous flexible EES
systems (e.g., rollable [414], twistable [415], stretchable [416], and
7.1. Flexibility wearable [417] ECs and LIBs) with tunable shapes, dimensions, and
properties are being studied based on these materials. For example, 2D
The market for flexible electronics, with products currently ranging graphene-based composite films (e.g., a graphene hydrogel/polyaniline
41
Table 1
Summary of graphene-based composites for the emerging EES systems.
EESa) Graphene-based composites Electrochemical performance Ref.
1
Rate capability (mAh g ) Cycling stability (cycles)
MgIBs MgMn2O4/RGO 211.8 (50 mA g1)/140.1 (1 A g1) 119.5 mAh g1 at 1 A g1 (1000) [386]
Mo6S8/GO/Al Unmentioned 80 mAh g1 at 50 mA g1 (10) [387]
Mg1.1Mn6O12⋅4.5H2O/graphene 194.1 (20 mA g1)/112 (100 mA g1) 88.5 mAh g1 at 100 mA g1 (400) [388]
Mo6S8/Cu/graphene 82 (1.2 A g1) 100 mAh g1 at 120 mA g1 (30) [389]
FeVO4 0.9H2O/graphene 183.8 (50 mA g1)/86.6 (500 mA g1) 98 mAh g1 at 100 mA g1 (50) [390]
AIBs Al0.16V2O5/RGO 122 (3 A g1) 247 mAh g1 at 300 mA g1 (50) [391]
VS4/RGO 80 (100 mA g1)/60 (300 mA g1) ˃ 80 mAh g1 at 100 mA g1 (100) [392]
TiO2/graphene Unmentioned 33 mAh g1 at 6.25 A g1 (100) [393]
NABs MnCo2O4/N-doped graphene Charge-discharge voltage gap of 0.39 V at current density of 0.13 mA cm2 [394]
RuO2/B-doped RGO Charge-discharge voltage gap of <0.72 V at current density of 0.05 mA cm2 [395]
Graphene nanosheets loaded with Pt nanoparticles 7574 (0.1 mA cm2) Discharge and charge voltage plateaus at about 2.38 V and [396]
3.6 V at 0.1 mA cm2 (10)
VO2/RGO Charge-discharge voltage gap of 0.64 and 1.05 V at current density of 0.01 and 0.05 mA cm2 [397]
α-MnO2 nanowires/RGO/carbon microfibers 1200 (30 mA g1) Charge-discharge voltage gap increased from 0.7 to 0.84 V at [377]
15 mA g1 (20)
ZABs CoMn2O4 nanoparticles anchored on N-doped Unmentioned Charge-discharge voltage gap increased from 0.70 V to [398]
graphene nanosheets 0.86 V at 20 mA cm2 (100)
MnNiFe metal oxide/graphene Charge-discharge voltage gap of 1.09 V at current density of 50 mA cm2 [399]
3D Fe/N/S-doped graphene 53.9 mW cm2 (50 mA cm2) Unmentioned [400]
Ni3Fe/N,S-doped CNT/graphene 180 mW cm2 (350 mA cm2) Charge-discharge voltage gap of 0.75 V (60) [401]
RGO/carbon black/cobalt borate ~76 mW cm2 (0.3 A cm2) Unmentioned [402]
Ni3Fe/Co9S8/graphene Open circuit voltage (1.45 V), a peak power density of 125 mW cm2 [403]
VRFBs GO nanosheets/multi-walled carbon nanotubes Peak potential separation of 0.15 and 0.21 V at scan rate of 5 and 100 mV s1 [379]
RGO/graphite felt 23.9 Ah L1 (150 mA cm2) Unmentioned [404]
TiNb2O7/RGO 2400 mAh (40 mA cm2)/1700 mAh 2100 mAh at 120 mA cm2 (200) [405]
(160 mA cm2)
KIBs Mn3O4/graphene 83 (1 A g1) ~130 mAh g1 at 0.1 A g1 (100) [406]
SnS2@RGO 448 (50 mA g1)/247 (1 A g1) 205 mAh g1 at 1 A g1 (300) [407]
MSBs Graphene/sulfur nanocomposite 885 (5 mA g1)/108 (45 mA g1) 219 mAh g1 at 20 mA g1 (50) [382]
MABs Mn3O4 nanowires/3D graphene/single-walled Open circuit voltage (1.49 V), a high plateau voltage (1.34 V), and a long discharge time (4177 min) at [408]
carbon nanotube 0.2 mA cm2
α-MnO2 Nanowires/graphene 96 mW cm2 at 140 mA cm2 [409]
AABs ZnO/ZnCo2O4/C@RGO Open circuit voltage (1.53 V), a high plateau voltage (1.29 V), and a discharge capacity (42.6 mAh g1) at [410]
1 mA cm2
LICs Fe3O4/graphene//3D graphene 147 Wh kg1 (150 W kg1)/86 Wh kg1 70% retention at 2 A g1 (1000) [411]
(2587 W kg1)
NICs Polyimide-graphene//RGO 55.5 Wh kg1 (395 W kg1)/21.5 Wh kg1 ~60% retention at 100 mA g1 (1000) [412]
(3400 W kg1)
a
MgIBs, AIBs, NABs, ZABs, VRFBs, KIBs, MSBs, MABs, AABs, LICs, NICs represent Mg-ion batteries, Al-ion batteries, Na-air batteries, Zn-air batteries, vanadium redox-
flow batteries, K-ion batteries, Mg–S batteries, Mg-air batteries, Al-air batteries, Li-ion capacitors and Na-ion capacitors, respectively.
composite film developed by Dan Li et al. [227]) are very popular to 7.2. Transparency
application in flexible ECs [269,418].
Among the various flexible EES systems, wearable EES devices are Recently, transparent devices have attracted substantial attention.
quite attractive, which can be incorporated into clothing and accessories Benefiting from the research advances on transparent materials and
for fabricating wearable electronics [419]. T These smart garments are techniques, various transparent devices have been demonstrated for
expected to collect information from the users in real time [420]. Zhenan successful application in different fields, including touch screens, smart
Bao’s group first designed textile-based ECs in 2011 through coating windows, solar cells, etc. However, the development of transparent
graphene/MnO2 composite onto porous textile fibers [421]. Recently, power sources as a key component for fully integrated transparent de-
great research efforts have been devoted to the development of vices remains a challenge, mainly because of the difficulty in simulta-
core-sheath and coaxial electrodes, which combine the current collector neously realizing the transparency of each component [424]. Actually,
and active materials in a single yarn that is ready for knitting or weaving the traditional multilayer structure for power source systems (e.g., LIBs)
directly into textiles [422]. For instance, Chao Gao’s group reported contains electrode (anode and cathode), electrolyte, separator, pack-
polyelectrolyte-wrapped graphene/CNT core-sheath composite yarns aging, etc. Among them, only the electrolyte is intrinsically transparent,
with good flexibility and weavability that were produced via a whereas the other components are opaque, and the electrode is the most
wet-spinning method, which could exhibit a much improved areal difficult component for realizing transparency [11].
capacitance up to 269 mF cm2 (Fig. 14a) [423]. To make a transparent electrode, one approach is to reduce its
thickness to the nanometer scale, although this strategy would sacrifice
42
Fig. 14. A schematic diagram showing the emerging properties of EES devices fabricated from graphene-based composites. (a) Flexibility: Polyelectrolyte-wrapped
graphene/CNT core-sheath composite yarns (reproduced with permission from ref. 423, copyright 2014, Nature Publishing Group). (b) Transparency: Graphene/CNTs
composite film (reproduced with permission from ref. 428, copyright 2010, American Chemical Society). (c) Free-standing property: Graphene/LiFePO4 quantum dot
composite film (reproduced with permission from ref. 126, copyright 2017, Elsevier). (d) Fast-charging property for batteries. (e) High-energy density for ECs. (f)
Electrochromism: Electrochromic polyaniline/graphite oxide nanocomposite film (reproduced with permission from ref. 437, copyright 2013, Elsevier). (g) Self-
healing: GO/poly(acrylic acid) (PAA)/amorphous calcium carbonate (ACC) composite (reproduced with permission from ref. 238, copyright 2018, Wiley). (h) All
graphene-based structure: A unique sandwich structure with pure sulfur between two graphene membranes (reproduced with permission from ref. 439, copy-
right 2014,Wiley).
much of the capacity [425]. Another strategy is to design a patterned materials with conductive agents (e.g., carbon black) and polymeric
electrode with feature dimensions below the resolution limit of the binders (e.g., polytetrafluoroethylene) in suitable solvents. The obtained
human eye [426]. With these two methods, graphene-based composites slurries are coated on appropriate current collectors, normally copper foil
all have great potential for fabricating the desired transparent electrodes, for the anode and aluminum foil for the cathode. After drying, the
because of the inherent transparency of graphene (97.7% transmittance) electrodes are put through a mechanical pressing process to adjust the
and its tunable dimensions on both the micro- and the macroscale. For pore volume and density. In the electrodes, the conductive agents are
example, Aldo J.G. Zarbin’s group used an innovative, single-pot syn- used to improve the electronic contact between the active particles,
thesis to chemically produce graphene/polyaniline composite film, whereas the binders are intended to glue the active materials to the
which exhibited good transparency and flexibility, and could be easily current collectors [134]. For industrial preparation technologies, how-
transferred to many kinds of ordinary substrates for practical applications ever, the mass ratio of inactive conductive agents, such as binders and
(Fig. 14b) [427,428]. When this composite film was employed to current collectors, range between 20-30 wt%, which would lower the
construct a transparent supercapacitor device, it could display excellent energy densities of the fabricated electrodes. Moreover, the inhomoge-
pseudocapacitive behaviors with specific capacitance of 267.2 F cm3. neous distribution of insulating polymeric binders would block the
Therefore, it is believed that graphene-based composites will play more transport pathways for both electrons and ions, and thus result in poor
and more important roles in the field of transparent power source sys- rate capability and low power density [126].
tems in the future. Many previously reported works have demonstrated that graphene-
based composites (e.g. graphene/Si film [429], graphene/metal oxide
7.3. Free-standing property paper [430], graphene/LFP film [126], etc.) can be directly employed as
free-standing electrodes for various EES devices without the addition of
Generally speaking, the electrodes of commercial EES devices such as conductive agents and binders, because of their free-standing properties
capacitors and batteries are fabricated by mixing particulate-like active combined with excellent conductivity, tunable porous structures, and
43
outstanding mechanical flexibility. For example, we previously reported detail, with the aim of increasing the energy density of ECs to the level
a graphene/LFP quantum dot composite film with good mechanical achieved in batteries without sacrificing their high power capability
flexibility (Fig. 14c), which could delivered a specific capacity of (Fig. 14e) [257]. For example, Guangming Wu’s group designed a 3D
~80 mAh g1 at 100C as an LIB cathode, even at a relatively high mass hierarchical porous V2O5/graphene composite aerogel for super-
loading condition (6 mg cm2) [126]. Considering the superior proper- capacitors, which demonstrated a high energy density of 68 Wh kg1
ties of graphene-based composites, future free-standing EES devices (comparable to lead-acid batteries) in a symmetric two-electrode systems
based on these materials are expected to be more integrated and effective using 1 M Na2SO4 aqueous solution as the electrolyte, attributed to their
with higher energy and power densities. high electronic conductivity and unique hierarchical porous structure
[435]. In another example, Tsung-Wu Lin’s group fabricated an asym-
7.4. Fast-charging property for batteries metric supercapacitor based on NiOOH/Ni3S2/3D graphene and
Fe3O4/graphene composite electrodes, which could be operated revers-
In the case of battery systems (e.g., LIBs and LSBs), with the slow ibly between 0 and 1.6 V with a maximum energy density of 82.5 Wh
faradaic reactions generally taking place in the bulk of electrochemically kg1 at a power density of 930 W kg1 [264]. In addition, apart from the
active materials, they usually suffer from low ion transfer kinetics, thus high energy density achieved in the form of mass energy density for ECs,
leading to a long charging times, typically in hours, whereas the cus- many other works have also focused on improving the volumetric energy
tomers are looking forwards to a much shorter charging time, in minutes density by tuning the porous structure of graphene-based composites.
or even seconds. Taking LIBs for example, which were first commer- Typically, Richard B. Kaner’s group demonstrated 3D high-performance
cialized in 1991 by the Sony Corporation, they always take several hours hybrid supercapacitors based on graphene/MnO2 composites. Volu-
to reach the fully charged state [431]. With the development of metric energy densities as high as 42 Wh L1 were achieved by rationally
graphene-based composite in this field, however, the graphene provides designing the electrode microstructure and combining the active mate-
fast ionic and electronic transport pathways in the electrode and thus rials with electrolytes that operate at high voltages [436].
decreases the charging time of the LIBs (Fig. 14d). Recently, we have
demonstrated that a three-dimensional porous nitrogen-doped graphene 7.6. Other properties
aerogel/LiFePO4 cathode composite could realize a charged capacity of
145 mAh g1 in 60 s with a charge efficiency of 97% [126]. In another Apart from the properties discussed in the above sections, there are
case, David Rooney’s group designed an anatase TiO2 also some other unique properties that have been emerging for EES de-
quantum-dot/graphene nanosheet anode composite, which could be vices fabricated from graphene-based composites, such as electro-
successfully charged and discharged at 50C, corresponding to a fast chromism [437], self-healing [258,265], all-solid-state [438], all
charge and discharge process within 72 s [117]. Moreover, Huiming graphene-based structure [236,439,440], etc. For example, Zhanhu
Cheng’s group reported a full LIB fabricated by using a graphene Guo’s group reported an electrochromic polyaniline/graphite oxide
foam/Li4Ti5O12 composite anode and a graphene foam/LiFePO4 com- nanocomposite film with durable EES performance (Fig. 14f) [437]. A
posite cathode without any further introduction of binders and conduc- coloration efficiency of 59.3 cm2 C1 and an areal capacitance of
tive agents [236]. Because of the outstanding electronic conductivity and 25.7 mF cm2 were obtained simultaneously. In another case, Nishuang
open porous structure of the composite electrodes, the designed LIB Liu and Yihua Gao et al. designed a highly stretchable and self-healing
could be fully charged in only 18 s. supercapacitor using RGO based springs (Fig. 14g), which were
In addition, the fast-charging property has also been achieved by composed of polypyrrole (PPy)-decorated RGO/multiwalled carbon
other battery systems based on graphene-based composites. For instance, nanotubes (MWCNTs) [258]. The constructed supercapacitor exhibited
Qiang Zhang’s group reported an unstacked double-layer templated 82.4% capacitance retention with a large stretching capacity (100%) and
graphene/S composite as cathode material for LSBs, which achieved a 54.2% capacitance retention at the third healing. This work provides an
fast charge/discharge process at 10C (corresponding to 6 min) because of important method for the design and fabrication of stretchable and
its excellent electron and ion transport kinetics [432]. In another work, self-healable supercapacitors for next-generation multifunctional elec-
Lianzhou Wang’s group designed a MoS2/graphene nanosheet composite tronic devices.
as anode material for NIBs using commercial MoS2 bulks and graphite as The multifunctionality of graphene-based composites, which can be
the raw materials, which exhibited a remarkably high rate capability purposefully designed to form different kinds of components for EES
with capacity of 201 mAh g1 at 75C, corresponding to a fully charged devices, such as current collectors [441] and separator [442], has
state in 48 s [433]. Actually, the fast-charging property is not only limited resulted in all graphene-based and all-solid-state EES devices [438–440].
to batteries, the fast charge (and discharge) property of capacitors can For example, the existing LIB techniques generally adopt metal foil as the
also be improved by using graphene-based composites. In 2012, Douglas current collectors (with thickness mainly ranging between 20-80 μm),
Natelson and James M. Tour’s group fabricated a microsupercapacitor which occupies a relatively large weight ratio (~10–20 wt%) of the de-
based on a 3D graphene/carbon nanotube composite carpet, which could vice and contributes no capacity, reducing the overall energy density.
be charged and discharged in only 0.195 ms comparable to commercial Correspondingly, some strategies have been developed for fabricating
Al-electrolytic capacitors (AECs) for alternating current (ac) line filtering graphene-based films with light weight and high conductivity (both
applications [434]. This microsupercapacitor, however, could deliver a electronic conductivity and thermal conductivity), which could be cho-
much higher volumetric energy density of 2.42 mWh cm3 (in the ionic sen as ideal current collectors for EES devices [37,441]. For instance,
liquid), more than 2 orders of magnitude higher than that of AECs, which Zhong-Shuai Wu’s group reported the on-chip construction of
may make it possible to realize smaller and lighter electronic devices in all-solid-state planar integrated LIBs with robust flexibility, high energy
the future. density, and extraordinary integration, in which high-quality graphene
was employed as metal-free current collector [443]. In another case,
7.5. High-energy density for electrochemical capacitors Wencai Ren’s group demonstrated integrated micro-supercapacitors
based on in-series screen-printed graphene on various substrates, with
Currently commercial supercapacitors are mostly based on active metal-free current collectors, high-voltage output, exceptional electrical
carbon electrodes and organic electrolyte with the working voltage double-layer capacitive behaviors and outstanding flexibility [451].
ranging from 2.3 V to 2.8 V, which possess excellent cycling stability and There are also some reports focused on graphene-based separators for
high power density, although their energy density is quite low (5–7 Wh permselective mass transport, especially in the LSB field for reducing the
kg1) compared with battery systems (one order of magnitude lower). In “shuttle effect” of soluble polysulfides [442]. Furthermore, Huiming
recent years, graphene-based composites have been studied in great Cheng’s group constructed some sandwich-like all graphene-based
44
structures for LSB cathodes, which showed great potential in term of high from these graphene-based composites. Although graphene-based com-
energy density, long life, and ultrafast-charging performance (Fig. 14h) posites for EES have witnessed substantial achievements and rapid
[439,440]. In addition, recently, Chunsheng Wang’s group [445] and development in the past few years, there are still many challenges that
Xinliang Feng group [446] successfully fabricated all-solid-state LSBs and need to be addressed before practical applications of such EES in different
pseudocapacitors, respectively, based on graphene-based materials, fields (Fig. 15).
which all exhibited excellent electrochemical performance and superior First, the lack of feasible techniques for the mass production of both
safety. More details about the emerging properties discussed in this high-quality graphene materials and graphene-based composites limits
section are summarized in Table 2. their potential applications in the EES field to a great extent (Fig. 15a).
For example, although the strategy involving the reduction of GO to RGO
8. Conclusion and outlook (which is a common raw material for graphene-based composites) is
relatively cheap and promising for mass production, the inevitable
In this review, we have summarized the recent progress on graphene- presence of both extrinsic (e.g., O, H, and other foreign atoms) and
based composites for EES, focusing on their rational structural design, intrinsic (e.g. vacancies and deformations) defects in RGO strongly af-
interfacial engineering, and energy storage mechanisms for different EES fects its physical properties (e.g. electronic conductivity) and the elec-
applications as well as the emerging features of EES devices fabricated trochemical performance of the final obtained composites. Therefore,
Table 2
Emerging properties of graphene-based composites for EES devices reported in the literature.
Features EESa) Composites Performance Ref.
Rate capability (mAh g1) Cycling stability (cycles)
Flexibility ECs Graphene/MnO2 nano-textiles ~315 F g1 (2 mV s1) ~95% at 2.2 A g1 (5000) [421]
ECs Polyelectrolyte- graphene/CNT core- Capacitance retentions of 98 and 111% for bending 200 and 1000 times [423]
sheath fibres
ECs Cellulose/RGO/Ag 683.8 mF cm2 (5 mA cm2)/347.9 mF cm2 99.6% at 60 mA cm2 (10000) [447]
(40 mA cm2)
LIBs Si/RGO 1210 (100 mA g1)/253 (2 A g1) 1
43% at 1 A g (1000) [448]
ECs RGO/polymer dots 95.3 F g1 (0.1 A g1)/68 F g1 (10 A g1) 90.6% at 0.5 A g1 (1000) [449]
NIBs 3D carbon/Fe7S8/graphene 2.12 mAh cm2 (0.25 mA cm2)/1.12 mAh 95% at 6 mA cm2 (500) [450]
cm2 (10 mA cm2)
ECs Polyaniline/graphene 4.9 mF cm2 (2 mV s1)/3.16 mF cm2 91.1% at 0.2 mA cm2 (10000) [444]
(500 mV s1)
ECs Screen-printed graphene 1 mF cm2 (5 mV s1)/0.58 mF cm2 91.8% at 0.2 mA cm 2
(10000) [451]
(500 mV s1)
Transparency ECs Graphene/polyaniline 267.2 F cm3 (10.8 μA) 88% at 10.8 μA (400) [427]
Free-standing property LIBs Graphene/Si film Unmentioned 708 mAh g1 at 50 mA g1 (100) [429]
ECs Nb2O5/graphene papers 47 Wh kg1 (393 W kg1)/15 Wh kg1 ~93% of the initial energy at 0.25 A g1 [452]
(18 kW kg1) (2000)
LIBs LFP quantum-dots/graphene 135 (20C)/78 (200C) ~99% at 20C (1000) [126]
ECs RGO/PPy 226 mF cm2 (2 mA cm2)/116.9 mF cm2 73.2% at 3 mA cm2 (10000) [453]
(6 mA cm2)
LIBs V2O5/N-graphene 290 (100 mA g1)/162 (2 A g1) 134 mAh g1 at 1 A g1 (500) [454]
KIBs S-doped RGO sponges 435 (50 mA g1)/224 (1 A g1) 229 mAh g1 at 1 A g1 (500) [455]
Fast-charging property LIBs 3D N-doped graphene aerogel/LFP ~155 (0.2C)/78 (100C) 89% at 10C (1000) [134]
LIBs TiO2 quantum-dot/graphene 161 (5C)/101 (50C) 190 mAh g1 at 1C (100) [117]
LIBs Graphene foam/Li4Ti5O12//graphene 170 (1C)/135 (200C) ~96% at 100C (500) [456]
foam/LFP
LSB Double-layer graphene/S ~1200 (0.5C)/713 (10C) 530 mAh g1 at 5C (1000)/380 mAh g1 [432]
at 10C (1000)
1 1
NIB MoS2/graphene 284 (20 A g )/201 (50 A g ) 95% at 0.3 A g1 (250) [433]
ECs 3D graphene/CNT 115 W cm3 (400 V s1) 98.4% at 0.5 mA cm2 (8000) [434]
High-energy density ECs 3D porous V2O5/graphene aerogels 68 Wh kg1(250 W kg1) 90% at 10 A g1 (20000) [435]
ECs NiOOH/Ni3S2/3D graphene//Fe3O4/ 82.5 Wh kg1 (930 W kg1)/63.1 Wh kg1 26% at 1 A g1 (2000) [264]
graphene (6.9 kW kg1)
ECs Graphene/MnO2 22 Wh L1 (~10 kW/1) 96% at 1 V s1 (10000) [436]
Electrochromism ECs Polyaniline/GO film Coloration efficiency of 59.3 cm2 C1, 53.1% capacitance retention at 3 mA cm2 (1000) [437]
Self-heal property ECs PPy-decorated RGO/MWCNTs 82.4% capacitance retention after a large stretch of 100%, and 54.2% capacitance retention [258]
after the third healing
All graphene-based LSBs Graphene-S sandwich structure 1340 (300 mA g1) 70% at 1.5 A g1 (300) [457]
structure LSBs All-graphene/S cathode 1500 (0.34 A g1)/1039 (1.68 A g1) 841 mAh g1 at 0.34 A g1 (400) [440]
All-solid-state LSBs Amorphous S/RGO 1525.6 (0.05C)/204.7 (5C) at 60 C 830 mAh g1 at 1C (750) [445]
ECs 2D thiophene nanosheets/graphene 326 F cm3 (10 mV s1)/123 F cm3 ~86% at 100 mV s1 (10000) [446]
(100 V s1)
LIBs Li2TiO3/graphene//LFP/graphene 67.7 mAh cm3 (0.2C)/47.7 mAh cm3 (2C) no apparent degradation at 5C (3300) [443]
a
ECs, LIBs, NIBs, KIBs, LSBs represent electrochemical capacitors, Li-ion batteries, Na-ion batteries, K-ion batteries and Li–S batteries, respectively.
45
Fig. 15. Challenges that need to be addressed before

practical applications of graphene-based composites
in different EES fields. (a) Mass production. Repro-
duced with permission from ref. 80, copyright 2014,
Nature Publishing Group. (b) Optimized compound
mode. Reproduced with permission from ref. 126,
copyright 2017, Elsevier. (c) Optimized porous
structure. (d) Balanced electron and ion transport. (e)
Fundamental understanding. (f) Practical applica-
tion. Reproduced with permission from ref. 5, copy-
right 2016, Nature Publishing Group.
advanced material preparation strategies for synthesizing graphene and densities of graphene-based composites by optimizing their porous
graphene-based composites with the desired physical and electro- structure for further commercialization in supercapacitors (Fig. 15c).
chemical properties will continue to gain substantial research interests in Fourth, in fact, graphene-based composites have been substantially
the future. studied in various metal-ion batteries (e.g., LIBs, NIBs) and metal-sulfur
Second, although there are several reported compound modes and batteries (e.g., LSBs, MSBs) with outstanding electrochemical perfor-
structures of graphene-based composites (e.g., electrochemically active mance, which mainly benefit from their high electronic conductivity,
materials anchored to the surface of graphene, sandwiched between large surface area, unique nanoporous architecture, good stability for the
graphene sheets, wrapped or encapsulated by graphene layers, etc.) with formation of SEI film, etc. In most cases, however, the mass ratio of the
improved electrochemical performance, mainly because of the proposed graphene component is quite large in these composites, normally larger
“synergistic effects” between the graphene component and the other than 10 wt%, which may lower the packing density and energy density of
electrochemical active materials, however, it is still not clear which of the batteries. Moreover, too much graphene would more easily block the
these structures could provide the best electrochemical performance in transport of ions (e. g., Liþ, Naþ), especially in a high mass-loading
specific EES applications. Therefore, more effects are required to condition, due to the limited diffusion through the basal plane of per-
fundamentally understand the molecular interaction between graphene fect graphene. Therefore, more efforts should be focused on achieving an
and the other components in the electrode/electrolyte interface and optimized balance between electron transport and fast ion diffusion
inner bulk under device working conditions from both experimental and (Fig. 15d). In addition, the low Coulombic efficiency for the first cycle of
theoretical aspects (Fig. 15b). This would permit the production of graphene-based composite anodes, mainly caused by their high surface
unique graphene-based composites with customized properties for area and the existence of defects in graphene, is another challenge that
practical applications in different EES systems. needs to be addressed for their practical application in metal-ion batte-
Third, the high surface area of graphene-based composites plays a ries (e.g., LIBs).
significant role in their application for supercapacitors, both EDLCs and Fifth, metal-air batteries (e.g., LABs, NABs) with extremely high
pseudocapacitors. Specifically, a variety of graphene-based composites theoretical energy density are considered to be likely to lead a revolution
with diverse structures and dimensionalities, for instance, graphene/ in EES history. Although several graphene-based composites (e. g., gra-
CNTs, graphene/transition metal oxides (or sulfides), and graphene/ phene/Pt and graphene/Ru) have been designed with improved perfor-
polymer composites have achieved a degree of success. The high surface mance, the achieved capacities are still far away from the theoretical
area combined with the enhanced electronic conductivity, appropriate energy density. The key fundamental chemistry problems associated with
porous structures, and steric hindrance effect (between two components) graphene-based composite application in metal-air batteries, especially
endows these composites with boosted supercapacitor capabilities. The the synergistic effects between the graphene component and the other
porous structure, however, significantly degrades their volumetric en- catalytic materials in the composites, are still not completely understood.
ergy density. In this regard, there is still room to enhance the packing It is important that future work must be focused on solving and
46
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Energy Storage Materials 24 (2020) 22–51

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Energy Storage Materials

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