Renewable and Sustainable Energy Reviews 120 (2020) 109656

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Renewable and Sustainable Energy Reviews

journal homepage: http://www.elsevier.com/locate/rser

Graphene materials in green energy applications: Recent development and

future perspective
Chi Him Alpha Tsang a, b, Haibao Huang a, Jin Xuan c, **, Huizhi Wang d, ***, D.Y.C. Leung b, *
a
School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou, PR China
b
Department of Mechanical Engineering, The University of Hong Kong, PR China
c
Department of Chemical Engineering, Loughborough University, Loughborough, UK
d
Department of Mechanical Engineering, Imperial College London, London, UK

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

Keywords: Graphene, composed of single-layered sp2 graphite, with its superb physical and chemical properties, has
Graphene attracted scientists in different areas, including electronics, medicine, and chemicals. Its applications in green
Fuel cell energy were extensively studied in the past two decades. Results from different studies show that graphene-based
Supercapacitor
products with different structures (2D and 3D graphene) can effectively enhance green energy conversion and
Battery
Solar cell
storage compared to traditional energy materials like metal and metal oxides. This review focuses on the his­
3D printing torical development of graphene, the variation of graphene products, and mainstream researches in graphene-
based green energy applications carried out in recent years, such as fuel cell, solar cell, lithium-ion batteries
(LIBs), supercapacitor, dye-sensitized solar cell (DSSC), and photoelectrochemical water-splitting cell. The
development of graphene-based materials integrated with different 3D printing technology and the application of
their products in green energy are also discussed together with a forecast on the development of graphene-based
materials in the future.

structures. However, most of the research on graphene-based products

covered 2D structured graphene; and the 3D structured ones in bulk
1. Introduction
form were relatively fewer [7–9]. The import of 3D printing technology
in recent years widens the development potential of 3D structured
Graphene is an allotrope of graphite composed of single-layered sp2
graphene for different applications [10–13].
graphite with hexagonal planar carbon ring arrangement structures. It is
There is a variety of research on graphene-based materials applied in
a 2D nanosheet structured material, which is a derivative of 3D giant
green energy such as fuel cell, solar cell, lithium-ion batteries (LIBs),
covalent structured graphite [1,2]. These materials have attractive
supercapacitor, dye-sensitized solar cells (DSSC), and photo­
properties of strong electrical conductivity (106 S cm 1) [3], strong
electrochemical cell for hydrogen evolution via water splitting. This
thermal conductivity (5000 W m 1 k 1) [4], high mechanical strength
type of research was conducted extensively in the past decade. Even
(~40 N m 1), with Young’s module of 1 TPa [5], and large specific
though much effort has been devoted to it, most of the works were still in
surface areas (~2600 m2 g 1) [6]. Furthermore, its special chemical
the fundamental laboratory scale. Only few real applications were re­
reactivity towards foreign materials compared to the bulk carbon like
ported [7–9]. Importing new technology for graphene fabrication (i.e.
charcoal makes it not replaceable by other nanocarbons, such as carbon
3D printing) may provide a breakthrough in the limitation of traditional
nanotubes and fullerenes. The development of graphene as new prom­
fabrication techniques for graphene-based device preparation [10–13].
ising materials became solidified in the past decade, especially in the
This review is focused on the historical development of graphene and
area of catalysis.
graphene products in the first part. The second part describes the
Due to the attractive properties mentioned above, a variety of
mainstream researches on graphene-based materials applied in green
graphene-based materials like metal, metal oxide, or non-metal element-
energy, such as fuel cell, solar cell, LIBs, supercapacitor, DSSC, and
doped graphene products were developed. They exist in 2D and 3D

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (J. Xuan), [email protected] (H. Wang), [email protected] (D.Y.C. Leung).

https://doi.org/10.1016/j.rser.2019.109656
Received 12 July 2019; Received in revised form 15 November 2019; Accepted 3 December 2019
Available online 15 December 2019
1364-0321/© 2019 Elsevier Ltd. All rights reserved.
C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

List of abbreviations Graphene-Co3O4@C Graphene-cobalt (IV) oxide on carbon

ZnO/rGO, ZnO/RGO Zinc oxide nanosheet/reduced graphene oxide
LIBs Lithium-ion batteries composite
DSSC Dye-sensitized solar cells ATN/RGO anatase TiO2 nanosheet/reduced graphene oxide
CVD Chemical vapor deposition composite
GO Graphene oxide 3D CMG/MnO2 3D porous chemically modified graphene/MnO2
LPE Liquid phase exfoliation foam
NMP N-methylpyrrolidone GA/TiO2 graphene aerogel/TiO2
DMF N,N0 -dimethylformamide Ni(OH)2⋅(GN) Ni(OH)2 nanoparticles in graphene
DMSO Dimethyl sulfoxide GNS/LDH, graphene/NiAl–LDH chemically converted graphene
2D Two dimensional nanosheet/Ni2þ/Al3þ layered double-hydroxide (LDH)
3D Three dimensional composite
HR-XPS High resolution-X-Ray photoelectron spectroscopy 3D-ARGON/NiAl-LDH 3D activated reduced graphene oxide
rGO, RGO, G, GNPs Reduced graphene oxide (nanoplates) nanocup/nickel aluminum layered double hydroxides
GH Graphene hydrogel composite
EGS Expandable graphene sheets GNS/CoAl-LDH graphene nanosheet/CoAl-layered double
VC L-ascorbic acid/vitamin C hydroxide
GA Graphene aerogel Co–Al LDH-NS/GO Co–Al layered double hydroxide nanosheets/GO
NF Ni foam Gr/SnO2 graphene/tin dioxide nanoparticles composites
PNWs PVP-metal nanowires hybrid PANI@3DGFs PANI loaded three-dimensional graphene-based
G-Gel/NF, G-gel@NF Graphene hydrogel/Ni foam frameworks
M/GN Metal modified graphene SRGA S-incorporated RGO aerogel
MOx/GN Metal oxide modified graphene STEM Scanning Tunnel Electron Microscopy
EG Ethyl glycol GNFs Graphene nanoflake films
PD 1,2-propanediol ORR Oxygen reduction reactions
IPA Isopropyl alcohol MOR Methanol oxidation reaction
Nf Nafion solution EtOH Ethanol
NCs Nanocrystal EOR EtOH electrooxidation
NGA, N-GA N-doped graphene aerogel GOR Glucose electrooxidation
GN-GH nitrogen doped graphene hydrogel FOR Formic acid electrooxidation
NG/NF nitrogen-doped graphene on nickel foam DEFC Direct ethanol fuel cell
a-MEGO activated microwave exfoliated graphite oxide DGFC Direct glucose fuel cell
aG-O film activated graphene oxide film HOR Hydrogen oxidation reaction
NSGAs nitrogen and sulfur dual-doped graphene aerogels Li-Air, Li–O2 Lithium-air
α-MnO2/RGO MnO2 nanowires/Reduced graphene oxide HGF Holey graphene framework
3DE/Au gold loaded three-dimensional printed electrode OCV Open circuit voltage
Ru/r-hGO mesh ruthenium loaded reduced 3D printed holey ZGR ZnO graphene
graphene oxide mesh GT Graphene-TiO2
3D G/MnO2 3D printed graphene aerogel/MnO2 SLA Stereolithography
B-G Boron doped graphene FDM Fused deposition modeling
BT-rGO Boron-doped and thermally reduced graphene oxide DIW Direct ink writing
nanoplatelets IGF integrated graphene network
BCN graphene Boron and nitrogen co-doped graphene MOG MnO2 loaded 3D printed IGF
SP-AG Sulphur and phosphorus co-doped 3D macroporous, NOG NiO loaded 3D printed IGF
activated graphene aerogel PLA Polylactic acid
NP Nanoparticle PVA Polyvinyl alcohol
NF(s) with Metal (M) prefix Metal Nanoflower(s) PVB Polyvinyl butyral
CFP Carbon fibre paper
GF Graphene foam or 3D graphene frame work Nomenclature
GQD Graphene quantum dot KMnO4 Potassium permanganate
GA@NF graphene aerogels on NF NaNO3 Sodium nitrate
HrGO/NF hydrothermal reduced graphene oxide/nickel foam P2O5 Phosphorus pentoxide
3D-NiGO(M) 3D Ni foam-supported graphene oxide (support for K2S2O8 Potassium persulphate
MnO2) H2O2 Hydrogen peroxide
GCA@NF graphene/CNT hybrid aerogels on NF CO2 Carbon dioxide
rGH reduced graphene hydrogel C¼O Carbonyl group
RGOA reduced graphene oxide aerogel O–C¼O Carboxyl group
GO-RFA-P pyrolyzed GO-loaded RF (resorcinol and formaldehyde) C-Obonds Ether link
aerogels Zn Zinc
SGH, SGHs Self-assembled graphene hydrogel NH3 Ammonia
GH-Hz8 Graphene hydrogels prepared via hydrothermal reduction N2H4, Hz Hydrazine
with hydrazine (8 h) BH4 Boron hydride species/borohydride
FGSs Functionalized graphene sheets PtCl26 Hexachloroplatinate (IV)
FAG 400 3D self-assembly of holey graphene (reduced at 400 � C) LiAlH4 Lithium aluminum hydride
Graphene-Fe3O4@C Graphene-iron (IV) oxide on carbon CO Carbon monoxide

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PANI polyaniline B, N-doped or BN-codoped Boron-nitrogen codoped

Pd Palladium HClO4 Chloric (VII) acid
Pt Platinum H2SO4 Sulphuric Acid
Jf anodic sweep current density NaOH Sodium hydroxide
LITFSI Lithium bis(trifluoromethanesulfonyl) imide KOH Potassium hydroxide
LiPF6 Lithium hexafluorophosphate Co3O4 Cobalt (IV) oxide
Nb2O5 Niobia Jsc Short circuit Current
S Sulphur TiO2 Titania or P25
P Phosphorus Au Gold

Fig. 1. a) Photograph of a reduced GO wet gel before drying (left), after supercritical drying (middle), and after ambient drying (right). For reference, the wet gel is
in a 20 mL vial. Inset shows a GDC cylinder (cast), prism (machined), and pyramid (machined). SEM images of fracture surfaces of b,c) the GMA and d,e) GDC at b,d)
low and c,e) high magnification. f) TEM images of commercial graphite at high magnification. Inset is a zoom-in of white box area and is 10 nm in width. g) TEM
image of GDC at high magnification. Inset is a zoom-in of white box area and is 10 nm in width. h) Low magnification TEM image of GDC [64]. (Reproduced with
permission from Wiley Interscience).

photoelectrochemical cell. The recent development of graphene-based and chemical oxidation were chosen as representative synthesis
materials by integration with different 3D printing technologies and methods.
their applications in green energy were discussed in the third part fol­ CVD has become a majority method for graphene synthesis since
lowed by a forecast on the future development of graphene-based 2009 [18]. This method is carried out by the use of highly volatile
materials. carbon sources under a high-vacuum and high-temperature (~1000 � C)
environment with the use of an inert carrier gas. Common carbon pre­
2. History of raw graphene synthesis cursors for the CVD graphene synthesis include gaseous (methane,
acetylene, ethylene) [19], liquid (ethanol [20,21], methanol [18,
With the development in past decades, graphene synthesis has 22–24]), and solid (bio-carbon [25,26], polymer [27], waste plastic
become a mature technology. There are two major pathways of gra­ [28]). Since graphene is obtained from secondary substrates [18–28],
phene synthesis: ‘Bottom-up’ and ‘Top-down’ methods [14–17]. ‘Bot­ CVD is classified as ‘bottom-up’ synthesis [14–17]. Generally, the elec­
tom-up’ is synthesis by depositing the carbon precursor vapor onto trical conductivity of graphene synthesized by CVD is higher than that
secondary substrate as seed for the growth of graphene, while the synthesized by the chemical method [22], and no reduction process is
‘top-down’ method is carried out through exfoliation by mechanical or needed. The product is therefore very suitable for electronic devices.
chemical pathways to separate the carbon layer from the giant structure However, the approach also suffers from the shortcomings of low pro­
of graphite oxide, or through the knocking down of the graphite struc­ duction yield and high cost [14,29], which make this method unsuitable
ture into a single graphene sheet as the final product [14–17]. In this for large-scale graphene synthesis.
review, syntheses of raw graphene via chemical vapor deposition (CVD) In contrast, the chemical method is relatively simple with a higher

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Fig. 2. a) Fabrication of GHCs and GHC sandwiches; Optical images of b–d) GHCs with different GA wall thicknesses, t, ranging from 0.25 to 1 mm, and e–g) the
corresponding GHC/PDMS composites; SEM images of h) GHC and i) GHC/PDMS composites [66]. (Reproduced with permission from Wiley Interscience).

Fig. 3. SEM images of (a) NF, (b, c) as-prepared GOA@NF at different magnifications, and (d–f) as-prepared GA@NF at different magnifications [33]. (Reproduced
with permission from ACS).

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Fig. 4. Photographs of (a) GO aqueous dispersions, (b) GO hydrogel with the insert of a NF sheet, and (c) NF, GOA@NF, and GA@NF [33]. (Reproduced with
permission from ACS).

yield, which makes it popular for raw graphene production [14,16]. The exfoliation, the method was classified as ‘top-down’ in graphene syn­
Hummer’s method is the most commonly used pathway, and the raw thesis [14–17].
graphene obtained by this method is graphene oxide (GO). It was The liquid-based shear-driven method is another common ‘top-
developed in the middle of the 20th century, when the graphitic oxide down’ approach for graphene synthesis, which is also called the liquid
was the major product [30]. This method involved direct oxidation of phase exfoliation (LPE) method [15–17,54,55]. Graphite was converted
graphite powder by a strong oxidation agent such as potassium per­ into graphene by shearing of graphite in different kinds of solvent,
manganate (KMnO4) to obtain graphite oxide, which can be said to be including (1) organic solvents like N-methylpyrrolidone (NMP), N,
the origin of GO synthesis. However, the method also suffers from the N0 -dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and so on
weakness of poor product quality due to the formation of incomplete [16]; (2) water [55]; and (3) ionic solvents like fulvic acid [54] as the
oxidized GO/graphite core/shell particles as final products throughout first step, followed by mechanical post-treatment like ultrasonic,
the graphite oxidation [31]. As a result, modifications of Hummer’s high-speed shear mixer, microwave, and so on [16,54,55]. Graphene
reaction were proposed by different groups for quality improvement. In was produced by the ‘shearing’ of graphite layers with the help of sol­
this method, the graphite was preoxidized into preoxidized graphite vents to weaken the van der Waal’s force between graphite layers.
oxide by a mild oxidizing agent such as sodium nitrate (NaNO3) or a Finally, a mixture of mono-layer and few-layer pristine graphene was
strong oxidizing agent like a mixture of phosphorus pentaoxide (P2O5) obtained when NMP was used as the solvent [16]. A similar result can
and potassium persulphate (K2S2O8) in sulphuric acid as the first step also be achieved by the use of ionic liquid as demonstrated by Yang’s
[32–35], which was the so-called Hummers and Offmann’s method [36, team (1–5 layers graphene flakes with low defects) [54]. Liquid phase
37]. After neutralizing and drying, the cleaned preoxidized product was exfoliation from graphite was hard to achieve when using water as a
then further oxidized into GO by a second oxidation with the use of solvent, which required the use of a stabilizer to avoid re-aggregation of
KMnO4, followed by quenching with hydrogen peroxide (H2O2) at the the exfoliated graphene flakes [54]. Further studies were then carried
end of the oxidation [31–40]. The quenched products were then cleaned out to solve this problem. One of the most recent demonstrations was by
by hydrochloric acid and water in sequence, followed by dialysis Tian et al. [55] who successfully synthesized graphene through water
cleaning in water. However, the use of NaNO3 may have the problem of graphite exfoliation by replacing graphite powder with graphite oxide
toxic NOx evolution in the Hummer’s reaction. Some research groups powder. The quality of graphene obtained can be improved and
like Marcano et al. [41] further improved the process by using a larger controlled by adjusting the ultrasonic time, speed of the homogenous
amount of KMnO4 in H2SO4/H3PO4 solution without using NaNO3. This disperser, and centrifugation rate [16,55]. Since the amount of chem­
results in an increase in the total amount of hydrophilic oxidized GO icals required for this process is relatively low and exfoliation can be
when compared with those synthesized from traditional Hummer’s achieved by the mechanical method as post-treatment, such a method
method [41]. The purified raw GO was obtained by (1) simple filtration was then regarded as a simple and low-cost method for large-scale
by water [41]; (2) freeze-drying the cleaned aqueous GO or direct low-defect pure graphene when compared with the chemical
storage without further treatment [42–46]; (3) oven-drying under vac­ redox-pathway [16,54]. However, this method is a double-sided sword
uum or in an ambient environment [47,48]; or (4) drying in the air [32, as it is also instrument- and solvent-sensitive, which may cause a
49]. The purified GO and exfoliated GO were very stable up to months lowering of the quality of the graphene produced, such as the defect
and years [31]. However, such method exhibits a weakness of the formation in graphene flake [16,55].
metastability of the raw GO, especially under a low-temperature range
of room temperature up to 50 � C [50–52]. It is caused by the defects 3. Graphene-based products
presented in the GO due to the CO2 elimination [51,53]. As a result,
some research groups modified the synthesis conditions to obtain a In the past decades, various kinds of graphene-based products for
better quality GO, for example, by reducing the reaction temperature to green energy research were developed by different techniques. These
10 � C in the KMnO4 oxidation step, reducing the dosage of KMnO4, and methods included chemical reactions, physical methods, and CVD.
increasing the reaction time from 3 h to 16 h [50]. Since GO was formed Different methods of preparing graphene-based products have been used
from the insertion of oxidized functional groups throughout the graphite to fit the specific needs and applications in green energy research. A
oxide preparation, and the final GO nanosheets were obtained by detailed description of the nature of the reactions for graphene modifi­
separating the oxidized graphite oxide sheets by further oxidative cation will be discussed in detail.

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Table 1
List of the M/graphene-based products produced by chemical reduction with corresponding reducing agent and surface properties.
(Catalyst)/Graphene host Reducing agent (Green/Toxic) Electrochemical active surface area (m2 g 1) Ref

Pd/rGO; PdRu/rGO; PdSn/rGO; PdIr/rGO BH4 (Toxic) 58.1; 52.0; 64.9; 61.6 [44]
Pd (10 nm)/rGO; Pd (3 nm)/rGO BH4 (Toxic) 182.56; 162.56 [48]
Pd1Cu1/rGO BH4 (Toxic) 86 [76]
Pt/rGO BH4 (Toxic) 141.6 [86]
Pt/rGO BH4 (Toxic) 44.6 [91]
Pd1Ni1-NNs/rGO; Pd/rGO BH4 (Toxic) 98.2; 67.2 [96]
Pd–Au(1:1)/rGO; Pd/rGO BH4 (Toxic) N/A [99]
Pd–Ag (1:1)/rGO-SB BH4 (Toxic) N/A [100]
rGO-Pd; rGO-Pt BH4 (Toxic) N/A [102]
Pt/rGO BH4 (Toxic) 98 [109]
Pd/3DGA BH4 (Toxic) N/A [113]
Ni/2D-rGO; Ni/3D-rGO N2H4 (Toxic) 463 (BET); 883 (BET) [61]
Pt@Pd/rGO; Pt/rGO; Pd/rGO N2H4 (Toxic) 15.11; 10.42; 10.59 [79]
Pd–Pt ANFs/rGO N2H4 (Toxic) 200.32 [80]
Ni/rGO N2H4 (Toxic) N/A [84]
Pd/Cu/rGO N2H4 (Toxic) 20.22 [92]
rGO/Pd N2H4 (Toxic) N/A [103]
PtPd NFs-rGO N2H4 (Toxic) 26.33 [107]
Ni/GA N2H4 (Toxic) N/A [111]
3DGFs N2H4 (Toxic) N/A [162]
Pd70Ag30@rGO N2H4 (Toxic) 13.58 [125]
Pd/rGO Oleylamine (Toxic) N/A [97]
Au/GH Triethylenetetraamine (Toxic) N/A [112]
Pt75.4Cu24.6 Alloy/rGO Hydroxylamine hydrochloride (Toxic) N/A [124]
Pt68.2Cu31.8 Alloy/rGO Hydroxylamine hydrochloride (Toxic) N/A [124]
Pt/GH hybrid L-ascorbic acid (Green) N/A [38]
Pd@Pt/rGO; PdPt/rGO L-ascorbic acid (Green) 29.94; 37.55 [43]
Pd/rGO, Pt/rGO, Au/rGO, Ag/rGO L-ascorbic acid (Green) N/A [45]
Au@Pd-G, Au-G, Pd-G L-ascorbic acid (Green) N/A [81]
rGOs-PtPd NHs L-ascorbic acid (Green) 18.5 [82]
Pt1Pd3NPs/rGO; PtNPs/rGO; PdNPs/rGO L-ascorbic acid (Green) 23.34; 21.93; 13.87 [83]
PdNCs/rGO; PdNPs/rGO L-ascorbic acid (Green) 50.28; 25.64 [94]
PtPd/rGO; Pt/rGO; Pd/rGO L-ascorbic acid (Green) 83.1; 16.3; 12.5 [104]
Pd/GA/NF L-ascorbic acid (Green) N/A [164]
Pd1Pt1.03/GA/NF L-ascorbic acid (Green) N/A [165]
Nd2O5/GF; Nd2O5/HGF Sodium ascorbate (Green) 63 (BET); 83 (BET) [8]
PtNFs-rGO Ethanol (Green) 72.1 [46]
Pd/N-3D-rGO Ethanol (Green) 390 (BET) [75]
PtPdNPs/rGO; PdNPs/rGO; PtNFs/rGO Ethanol (Green) N/A [93]
PtNCs@NGA EG (Green) 1750 (BET), 871 [73]
Pt/rGO EG (Green) 36.27 [87]
Pt/ND/rGO-1500; Pt/ND/rGO-1200 EG (Green) 137.9; 125.1 [88]
rGONP/Pt; rGO/Pt EG (Green) 63.0; 53.6 [89]
Pd–Ag/rGO; Pd/rGO; Ag/rGO EG (Green) N/A [90]
Pd–Cu/rGO; Pd/rGO; Cu/rGO EG (Green) N/A [101]
Pd–CuNC/rGO EG (Green) 49.2 [105]
rGO-Pd; rGO-Pt EG (Green) 544.3 (BET); 478.3 (BET) [108]
Pt/rGONP EG (Green) ~40 [110]
40%Pd–10% Ru/rGO; Pd/rGO EG (Green) N/A [163]
Pt/rGO-5; Pt/rGO-10 PD (Green) 85.71; 65.61 [85]
Pt/HGF EG/IPA (Green) 340.65 (BET), 92.58 [78]
rGO-Pt; rGO-PtPd Formic acid (Green) 38.6; 23.6 [72]
PdPt@Pt/rGO; PtPd/rGO; Pt/rGO; Pd/rGO Formic acid (Green) 58.9; 20.5; 17; 14 [106]

3.1. Graphene derivatives from a wet chemical reaction 3.1.1. Pure reduced graphene derivatives
Pure graphene is obtained by the chemical reduction of GO obtained
Among different kinds of graphene-based product preparation from from the ‘top-down’ reactions like Hummer’s method mentioned above,
raw GO mentioned above, chemical synthesis was the mainstream of the where the oxidized carbon functional groups (e.g. C– – O, O–C–– O and
methodology. It makes use of the special chemical properties of GO by C–O bonds) in pure GO were reduced by the reducing agent. This phe­
the presence of oxidized carbon functional groups, which has been nomenon was proved by the reduction in the intensity of HR-XPS peaks
mentioned previously. So far, most of the chemically modified graphe­ of the oxidized carbon groups (e.g. C–
– O, O–C–– O and C–O bonds) from
nes are 2D structured, while 3D structured ones are relatively few in XPS characterization of these products against that from the corre­
numbers due to its brand new nature. The difference between these two sponding pure GO samples [56–60]. The process is the same for 2D or 3D
groups of graphene is that 2D graphene nanosheet-based products are graphenes. The chemically reduced product is called reduced graphene
composed of 2D nanosheets, while the 3D structured graphene products oxide (rGO), while its 3D bulk block form is called graphene hydrogel
are composed of bulk blocks via stacking of the 2D graphene nanosheets (GH). The origin of such difference was the process because 2D rGO was
throughout the 3D graphene network formation. These two categories of obtained from the chemical reduction of graphene under stirring [56,
graphene can be further classified into 2 groups based on the nature of 61], while 3D GH was obtained from stationary reduction, mainly the
the chemical modification. They are pure reduced graphene and foreign hydrothermal or chemical reduction [57–63]. In the early years, strong
materials modified graphene. Details are discussed below. reducing agents like hydrazine (N2H4), boron hydride (BH4 ) species,
lithium aluminum hydride (LiAlH4), amine group compounds,

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iodine-containing compounds, hypophosphorous acid, or formaldehyde

were common reducing agents to achieve the goal ([41,56,61] (2D) and
[57–64] (3D)). Its major advantage is that the reaction time needed is
short, but it has the adverse effect of strong toxicity arising from the
reducing agent itself. In addition, due to the strong reaction between GO
nanosheets and some of the reducing agents mentioned above, the for­
mation of CO2 gas bubble during the reduction of GO into reduced
graphene would take place throughout the GH formation, which results
in the breaking of GH under hydrothermal reduction [59]. As a result,
the use of a green or a non-toxic reducing agent is the alternative, which
includes L-ascorbic acid or the so-called vitamin C (VC), ethanol, and
ethylene diamine [32,38,42,59,65,66]. The product obtained by this
group of reducing agents has the advantages of having no toxic residue
after reduction [32,38,42,59,65,66], and the shortcoming of GH
breaking throughout the reaction can be avoided [42,59]. Final bulk
graphene aerogel (GA) was obtained by freeze-drying GH synthesized
from methods previously mentioned [42,57–60,62,63,65,66]. Some of
the cases did not even require the use of a reducing agent for the GA
synthesis [67,68]. The shape of the GA can also be customized by the
shape of the reactor or the use of a regular pillar pattern throughout the
hydrothermal reaction as demonstrated by Worsley’s group [64] and
Wang’s group [66] from illustrations in Figs. 1 and 2, respectively. Such
a technique can also be used in the GA/Ni foam (NF) synthesis [32,33,
67–71], as reflected in the digital images and microscopic image of
GOA/NF and GA/NF shown in Figs. 3 and 4 [33]. The demonstrations
Fig. 5. (a) HRTEM and (b) TEM images (inset, size-distribution histogram) of
mentioned above provided the possibility of designing a substrate-free
PtNCs in NGA; (c) SEM image (inset, photograph of bulk PtNCs@NGA) and (d)
electrode with shape and pattern customized for the battery research
magnified SEM image of PtNCs@NGA [73]. (Reproduced with permission
from RSC).

Fig. 6. Low and high magnificent SEM images of (a) and (b) of GAs, and (c) and (d) of GA/Pd NP hybrids. (e) Dark-field TEM and HR-TEM images of GA/Pd NP
hybrids. Inset of SAED pattern of GA/Pd NP hybrids [122]. (Reproduced with permission from Elsevier B. V.).

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elements doped)-loaded graphene was obtained by direct chemical

reduction of foreign materials. Generally, metal modified graphene (M/
rGO) [38,43–46,48,60,61,72–126] and metal oxide modified graphene
(MOx/rGO) [7,127–137] were synthesized from the reaction between
metal ions and GO. Similarly, MOx/rGO can also synthesized by reacting
MOx with GO [22,23,138–143]. Non-metal elements-doped graphene
was obtained from a reaction between GO and non-metal (B, N, or S)
dopants [7,56,73,144–157]. Such a principle applies to both 2D and 3D
graphene substrate structures. The only difference is that foreign
materials-loaded 2D graphenes are obtained by the continuous mixing of
GO with foreign materials via a stirring environment with different
treatment techniques. Among them, stirring under heating was the most
commonly used technique for the M/rGO [43–46,48,61,72,76,77,84,86,
87,90,93,97,100,102,115–117,123,126], MOx/rGO [7,127–135,
140–142], and non-metal element-doped rGO [56,145–154], while
some of the continuous stirring synthesis under heating was (1) a reflux
reaction [45,109,110,119], (2) use of the gaseous reducing agent of CO
[36,158], or (3) ion displacement reaction [114,115] for M/rGO prep­
aration. Some of the 2D structured graphene products via thermal re­
action synthesis do not require the use of stirring; these reactions include
(1) hydrothermal reaction [89,98,124,155], (2) microwave-assisted
synthesis [85,88,137], and (3) heat flux with inert gas [159]. In
contrast, 3D graphene-based products like GA-based products were ob­
tained under a stationary environment for a period in terms of hours
once a reducing agent was added to the GO/loading materials mixture
Fig. 7. (a, b) Low-magnification STEM images of 2.1 nm thick Pt nanoclusters [38,60,73,78,111,113,121,122,144,156,157,160,161]. The dry prod­
coated GNFs. Inset is the corresponding EDS spectrum taken in SEM. High-
ucts from chemical synthesis were obtained by normal drying under heat
resolution STEM (c, enlarged image of the marked square area of (b)) and
[7,56,61,75–77], or freeze-drying [73,78,121,122,138,142,144,156,
HAADF (d) images of 2.1 nm Pt nanoclusters on GNFs, revealing 2–4 nm
monolayer Pt nanoclusters well intercoupled on both basal and edge planes of 157,160,161]. Similar to the reduced graphene, chemically synthesized
high-quality GNFs [20]. (Reproduced with permission from ACS). foreign materials-loaded graphene are obtained from a reducing agent
composed of N2H4, amine-based compounds, or BH4 via simultaneous
reduction under hydrothermal reaction environment as listed in Table 1
at the device level.
[44,48,56,60,61,76,79,80,84,86,91,92,96,97,99,100,102,103,107,109,
111,113,124,125,157,162]. However, a problem similar to the pure
3.1.2. Foreign materials modified graphene
reduced graphene preparation exists, such as the use of a toxic reducing
Foreign materials (i.e. metal/metal oxide base, or non-metallic
agent in nature under harsh reaction conditions, which violate the

Fig. 8. (a) Lower- and (b) higher-magnification SEM images of as-electrodeposited Pd on the rGO/CFP electrode, (c) HRTEM image, and (d) electron diffraction
pattern of as-electrodeposited Pd [47]. (Reproduced with permission from RSC).

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 9. TEM images of FS-Pd/GO composites in different scales. The inset of (A) is the size-histogram of FS-Pd [118]. (Reproduced with permission from Elsevier
B. V.).

Table 2
List of the monometallic Pt loaded graphene-based electrocatalysts in MOR and EOR.
2
Graphene host Pt precursor Oxidation Type Jf (Area basis) (mA cm ) Jf (Mass basis) (mA mg 1) If/Ib Year Ref

2D rGO Pt NPs MOR N/A 199.6 1.1 2009 [91]

Pt NPs MOR 30 N/A 0.8 2010 [87]
Pt NPs MOR 7.4 N/A 1.8 2010 [187]
Pt NPs MOR N/A 195 1.3 2010 [188]
Pt particles MOR N/A 590 1.0 2011 [85]
Pt NPs MOR 2.5 N/A 1.9 2011 [86]
Pt/NFs MOR N/A 523 1.2 2012 [46]
Pt/Nf EOR 2.3 N/A 1.1 2012 [49]
Pt/ND MOR N/A 98.7 0.9 2012 [88]
Pt NPs MOR 44.2 N/A 0.9 2012 [89]
Pt NPs MOR 57.7 N/A 1.2 2012 [89]
Pt NPs MOR 0.5 N/A 1.9 2013 [102]
Pt cluster MOR 22.9 N/A 2.2 2013 [159]
Pt particles MOR N/A 2540 4.2 2014 [43]
Pt NPs MOR 16.5 N/A 3.3 2014 [79]
Pt NPs MOR 0.9 N/A 6.6 2014 [82]
PtNPs MOR 1.7 N/A 5.6 2014 [83]
PtNF EOR 9.1 N/A 1.0 2014 [93]
Pt NPs MOR 23 N/A 3.6 2014 [104]
Pt NPs EOR 12 N/A N/A 2014 [104]
Pt NPs EOR N/A 26.7 4.8 2014 [106]
Pt NF MOR 1.8 N/A 2.5 2015 [80]
Pt PNWs MOR N/A 394 1.0 2015 [117]
Pt NPs MOR 1.0 N/A 1.4 2015 [158]
Pt NPs GOR N/A 14 N/A 2016 [74]
PtNPs MOR 5.1 N/A 3.8 2017 [78]
3D GF Pt-NPs MOR 1.6 N/A 2.3 2012 [192]
3D HGF PtNPs MOR 8.2 N/A 4.2 2017 [78]

concept of user-friendliness in the graphene products synthesis. Green [122], which have an appearance similar to those synthesized by the
elements, such as VC, ethanol, ethyl glycol (EG), 1,2-propanediol (PD), a traditional pathway (i.e. reducing agent-assisted reaction) described
mixture of ethyl glycol/isopropyl alcohol (EG/IPA), and formic acid, above [122]. This is illustrated in the SEM and TEM images shown in
were then imported to foreign materials-loaded graphene. These were Fig. 6, where Pd NPs are highly distributed on the surface of graphene
reducing agents commonly used for M/rGO or M/GA products as listed nanosheets in the GA/Pd NP array [122].
in Table 1 [38,43,45,46,72,73,75,78,81–83,85,87–90,93,94,101,
104–106,108,110,163,164], or dopant itself for the foreign
elements-doped graphene products [7,144–147]. The quality of these 3.2. Graphene derivatives from CVD method
graphene-based products was comparable to those obtained from
traditional reducing agents [43,45,73]. This is revealed from an example Relative to the mainstream of the chemical method for the synthesis
shown in Fig. 5, where the bulk platinum nanocrystal-loaded N-doped of the graphene derivatives, the CVD method is an alternative that was
graphene aerogel (PtNCs@NGA) after the simultaneous reduction of GO, used for the synthesis of 2D and 3D graphene derivatives, such as pure
PtCl26 and dopant (dopamine) by EG under hydrothermal condition was graphene foam (GF) [166,167], metal modified [20], MOx modified
a black cylindrical block [73]. At the same time, the successful loading of graphene [24,168], and foreign elements-doped graphene [21,169,
high crystalline metal nanoparticles (PtNCs) was proved by the presence 170]. In general practice, the substrate was required for the synthesis of
of black spots on the surface of the graphene nanosheet from the foreign materials-loaded graphene via CVD, which was similar to the
HR-TEM image of PtNC/NGA [73]. In contrast, some of the metal-loaded procedure in CVD-synthesized pure graphene. Examples include Cu foil
GA products are reducing agent-free reaction [121,122], such as [21], NF [168,170], silicon wafer [20], and glass plate [24]. The size of
Pd-loaded graphene aerogel (GA/Pd NP) synthesized by Yun et al. the template used was also small in size (2 cm2–6.3 cm2) [20,21,24].
There was an exception that boron nitrile-doped graphene quantum dots

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Table 3 mixing in an ambient environment [69,74,75,118,120,125]. These

List of common monometallic non-Pt and bimetallic graphene-based electro­ methods were mainly used for the foreign material-loaded graphe­
catalysts and their structure. ne-based materials, especially metal (2D graphene [37,47,49,74,75,118,
Catalyst type M/GNs Graphene Ref 120,182–188,193–195]) or MOx (2D graphene [128,139,189,190,
Structure 197–200]:, 3D graphene [22,23,69,196]) modified graphene. In
Monometallic Ag/rGO 2D [90] contrast, such a method was seldom used for preparing foreign
Au/rGO 2D [81,182,194] element-doped graphene [191]. Another common feature is that the
Cu/rGO 2D [101] final graphene products were either in liquid media [37,74,75,118,120,
Ni/2D-rGO, Ni/rGO (Ar 2D [61,84]
139,184,189,193–197] or deposited on a secondary substrate for 2D
protect)
Ni/3D-rGO, Ni/GA 3D [61,111] graphene [47,49,128,182,183,185–188,190,191,198–200]; and 3D GA
Pd/rGO, PdNCs/rGO, 2D [37,44,48,49,79–83, [69] and porous 3D GF products [22,23,192]. From the comparison of
FS-Pd/rGO, Pd/rGONP 90,93–104,106,114, TEM images of the metal-loaded graphene synthesized by electrodepo­
115,118,119,158, sition (Pd on rGO/CFP [47]) and direct mixing (FS–Pd/GO [118]) as
163,184,194]
Pd/GA, Pd/GA/NF 3D [113,164]
shown in Figs. 8 and 9, there was almost no difference in the morphology
Bimetallic Ag/Au/rGO 2D [182] of Pd-loaded graphene. This showed the feasibility of the foreign
Au/Ag/rGO 2D [182] materials-loaded graphene synthesized by totally physical pathways.
Pd–Ag/rGO, 2D [90,95,100,125] The fabrication of modified graphenes by this method was compara­
Pd70Ag30@rGO
tively easy, which made it suitable for device fabrication. Even though
Au@Pd/rGO, Pd–Au/ 2D [81,99,194]
rGO, rGO-AuPd@Pd such methods are relatively easier than CVD or the traditional chemical
Pd1Cu1/rGO, Pd/Cu/ 2D [76,92,101] synthetic pathway, as mentioned in previous sections, process require­
rGO, Pd–Cu/rGO ment was also complicated when using such materials for device fabri­
PdIr/rGO 2D [44] cation. Such a drawback is especially obvious for the application of
PdNi-NN/rGO 2D [96]
metal- or metal oxide-loaded GF as DSSC or fuel cell electrodes because
PdPt/rGO, Pd@Pt/rGO, 2D [43,49,79,80,82,83,
PdPt@Pt/rGO, 93,104,106,107,126, removal of the NF skeleton is required [22,23,192].
Pt60Pd40/rGONP 158,195]
Pd1Pt1.03/GA/NF 3D [165,202] 4. Graphene-based materials for green energy applications
PdRu/rGO 2D [44,163]
PdSn/rGO 2D [44]
Pt–Co/rGO 2D [185] 4.1. Fuel cells and metal-air batteries
Pt75.4Cu24.6 Alloy/rGO 2D [124]
PtIr PNWs/rGO 2D [117] The foreign materials-loaded graphene played an important role in
PtRu/GF 3D [201] green energy research. The main reason is that the interaction between
graphene nanostructure and loaded materials is usually enhanced upon
(BN-GQD)/G and BN-doped graphene (BN-G) synthesized by CVD were modification with graphene. Electrocatalytic fuel cell and battery
carried out in a quartz boat throughout the synthesis, and the product research is a hot topic in green energy development. Fuel cells can
was directly collected in powder form [169]. The dopant used can be reduce fossil fuel demand by generating electricity via electrochemical
solid (e.g. Zn, boric acid) [24,169], or gaseous dopant (e.g. NH3) [21, oxidation of renewable alcoholic fuels like methanol, ethanol, and
169]. By definition of graphene synthesis mentioned in the previous glucose, as well as gaseous fuel hydrogen produced by water-splitting. In
section [14–16,19,171–178], the synthesis of these chemically modified addition to the strong catalytic activity of fuel cell catalysts, such as
graphenes can be regarded as an extension of ‘bottom-up’ graphene monometallic metal and bimetallic precious metal catalysts, as well as
synthesis. Appearances of the CVD-synthesized foreign materials-loaded easy modification properties of graphene with those materials,
graphene products were similar to those synthesized by chemical syn­ graphene-based materials have become a very popular candidate as an
thesis, which is mentioned in the previous section. It was revealed from electrocatalyst. Graphene-based electrocatalysts, no matter whether
the STEM of Pt-loaded graphene nanoflake films (GNFs) illustrated in they involve 2D or 3D graphene, are classified into two main groups. The
Fig. 7 [20], where Pt nanoclusters were evenly distributed on the GNFs first corresponds to anodic catalysts for alcoholic fuel (methanol,
surface. Even though it was instrumental in the compact-sized electrode ethanol, and glucose) in alcoholic fuel cells or hydrogen oxidation in
research, this technique has the shortcoming that only limited product hydrogen fuel cells. The second corresponds to cathodic catalysts for
size can be synthesized on the substrate. Also, such a method is costly oxygen reduction reactions (ORR) for alcoholic fuel cells, hydrogen fuel
and low yield for device fabrication [29,179–181]. These limited its cells, or metal-air batteries.
application in large-sized energy devices.
4.1.1. Direct alcohol fuel cells
First, in the alcoholic fuel electrooxidation, methanol oxidation re­
3.3. Graphene-based products by other methods action (MOR) was the most popularly studied topic. In the past decade,
metal-loaded 2D graphene (M/rGO) and metal-loaded graphene aerogel
Besides chemical synthesis and CVD methods, other non-chemical (M/GA) were the most popular electrocatalytic materials for the MOR.
methods like physical methods have also been developed for the syn­ Platinum was the most commonly used metal candidate for the 2D M/
thesis of graphene-based products, such as (1) electrodeposition [37,47, rGO [43,46,79,80,82,83,85–89,91,102,104,117,158,159,187,188], or
49,128,182–192], (2) ultrasonic synthesis [139,143,193–196], (3) 3D graphene-based [78,192] anodic electrocatalysts (Table 2). Results
direct mixing with simple heating [22,23,197–200], and (4) direct from different groups showed that the Pt-loaded graphene-based

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Table 4
List of the monometallic non-Pt and bimetallic graphene-based electrocatalyst performance in MOR, EOR, FOR and GOR.
Metal catalyst Metal precursor/Graphene host Type of oxidation Jf (Area basis) (mA cm 2) Jf (Mass basis) (mA mg 1) If/Ib Year Ref

Mono-metallic Ag/rGO EOR 0 N/A N/A 2012 [90]

Au/rGO MOR 0.1 N/A N/A 2014 [81]
Au/rGO MOR 0 N/A N/A 2014 [194]
Au/rGO GOR 7.4 N/A N/A 2014 [182]
Au/rGO GOR N/A 27 N/A 2016 [74]
Cu/rGO MOR N/A 0 N/A 2015 [101]
Ni/rGO (Ar protect, 500 � C) MOR 20 N/A N/A 2012 [84]
Ni/GA EOR 16.3 N/A N/A 2013 [111]
Ni/3D-G MOR 62 N/A N/A 2017 [61]
Pd (10 nm)/rGO FOR N/A 210 N/A 2011 [48]
Pd (3 nm)/rGO FOR N/A 300 N/A 2011 [48]
Pd/rGO FOR N/A 213 N/A 2011 [114]
AP-Pd/rGO FOR N/A 466.3 N/A 2011 [114]
Pd NPs/rGO EOR 46.7 N/A 0.9 2012 [37]
Pd/rGO EOR 0.56 N/A 4.0 2012 [49]
Pd/rGO EOR 22 N/A 0.9 2012 [90]
Pd/LDrGO MOR 27.6 N/A 6.6 2012 [98]
Pd/rGO MOR 15.0 N/A 4.5 2012 [98]
Pd/LDrGO FOR 61.6 N/A N/A 2012 [98]
Pd/rGO FOR 34.6 N/A N/A 2012 [98]
Pd/rGO MOR 360.8 N/A 4.3 2013 [99]
Pd/rGO EOR 897.6 N/A 1.2 2013 [99]
Pd/rGO MOR 0.8 N/A 16.7 2013 [102]
Pd/rGO EOR 3.8 N/A 1.2 2013 [102]
Pd/rGO MOR N/A 522 6.1 2013 [115]
FS-Pd/rGO GOR N/A 0.056 N/A 2013 [118]
PdnD/rGO MOR 0.5 N/A 7.5 2013 [119]
PdnS/rGO MOR 0.1 N/A 1.7 2013 [119]
40%Pd/rGO MOR 47 N/A 5.2 2013 [163]
Pd/rGO MOR 96.1 N/A 1.9 2014 [79]
Pd/rGO MOR 0.2 N/A N/A 2014 [81]
Pd/rGO MOR 0.4 N/A 5.7 2014 [82]
PdNPs/rGO MOR 1.2 N/A 3.2 2014 [83]
PdNP/rGO EOR 7.5 N/A 1.0 2014 [93]
Pd/rGO FOR 3.2 N/A N/A 2014 [97]
Pd/rGO MOR N/A 311 1.4 2014 [100]
Pd/rGO EOR N/A 835 1.2 2014 [100]
Pd/rGO MOR 0.4 0.9 4.2 2014 [103]
Pd/rGO EOR 1.5 3.4 1.4 2014 [103]
Pd/rGO MOR 22 N/A 1.7 2014 [104]
Pd/rGO EOR 23 N/A 0.6 2014 [104]
Pd/rGO EOR N/A 13.7 N/A 2014 [106]
Pd/GA/NF MOR N/A 798.8 3.1 2014 [164]
Pd/GA/NF EOR N/A 874 2.9 2014 [164]
Pd/rGO MOR 12.5 N/A 2.8 2014 [194]
2
Pd/rGO MOR 0.1 (mA m ) N/A 2.1 2015 [44]
2
Pd/rGO EOR 0.3 (mA m ) N/A 1.4 2015 [44]
Pd NF/rGO MOR 1.9 N/A 2.7 2015 [80]
PdNCs/rGO EOR N/A 429.8 1.8 2015 [94]
Pd/rGO EOR 6.5 N/A 0.8 2015 [95]
Pd/rGO FOR N/A 308.4 N/A 2015 [96]
Pd/rGO MOR N/A 358.5 11.7 2015 [101]
Pd/GA MOR N/A 8000 1.2 2015 [113]
Pd/rGO MOR 0.1 N/A N/A 2015 [158]
Pd/rGO FOR 13.8 3990 N/A 2015 [184]
Pd/rGO GOR N/A 16 N/A 2016 [74]
Bi-metallic Ag/Au/rGO GOR 15.2 N/A N/A 2014 [182]
Au/Ag/rGO GOR 16.2 N/A N/A 2014 [182]
Pd–Ag/rGO EOR 90 N/A 1.4 2012 [90]
Pd–Ag/rGO MOR N/A 630 3.2 2014 [100]
Pd–Ag/rGO EOR N/A 1601 1.6 2014 [100]
PdAg/rGO EOR 11.5 N/A 1.2 2015 [95]
Pd70Ag30@rGO Butan-1-ol OR 16.0 106.0 7.0 2019 [125]
Pd–Au/rGO MOR 1218.4 N/A 1.1 2013 [99]
Pd–Au/rGO EOR 2218.7 N/A 1.0 2013 [99]
Au@Pd/rGO MOR 0.7 N/A N/A 2014 [81]
AuPd@Pd/rGO MOR 29 N/A 2.8 2014 [194]
Au90Pd10/rGO GOR N/A 37 N/A 2016 [74]
Pd/Cu/rGO EOR N/A 392.6 3.0 2014 [92]
Pd–Cu/rGO MOR N/A 1153.4 2.9 2015 [101]
Pd–Cu/rGO EOR N/A 2105.4 1.4 2015 [101]
Pd1Cu1/rGO FOR N/A 1390 (A gPd1) N/A 2017 [76]
2
PdIr/rGO MOR 0.1 (mA m ) N/A 3.5 2015 [44]
2
PdIr/rGO EOR 0.2 (mA m ) N/A 1.0 2015 [44]
(continued on next page)

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Table 4 (continued )
Metal catalyst Metal precursor/Graphene host Type of oxidation Jf (Area basis) (mA cm 2) Jf (Mass basis) (mA mg 1) If/Ib Year Ref

PdNi-NN/rGO FOR N/A 604.3 N/A 2015 [96]

Pd–Pt/rGO EOR 7.7 N/A 5.5 2012 [49]
Pd@Pt/rGO MOR N/A 4972 2.1 2014 [43]
PdPt/rGO MOR N/A 3824 2.3 2014 [43]
Pt@Pd/rGO MOR 130.4 N/A 2.3 2014 [79]
Pt–Pd/rGO MOR 28 N/A 7 2014 [82]
Pt1Pd3NP/rGO MOR 2.3 N/A 2.5 2014 [83]
PdPtNP/rGO EOR 22.4 N/A 1.8 2014 [93]
PtPd/rGO MOR 252 N/A 1.1 2014 [104]
PtPd/rGO EOR 228 N/A 0.9 2014 [104]
PdPt@Pt/rGO EOR N/A 74.2 0.8 2014 [106]
PtPd/rGO EOR N/A 37.6 1.2 2014 [106]
Pt3Pd1/rGO MOR N/A 7.1 1.0 2014 [195]
Pt2Pd1/rGO MOR N/A 8.0 1.1 2014 [195]
Pt1Pd1/rGO MOR N/A 14.4 1.3 2014 [195]
Pd–Pt ANF/rGO MOR 2.2 N/A 3.3 2015 [80]
PtPd NFs/rGO EOR 52.3 N/A 2.2 2015 [107]
PdPt-03/rGO MOR 4.4 N/A 1.2 2015 [158]
Pd1Pt1.03/GA/NF GOR N/A 379.4 N/A 2017 [165]
Pt60Pd40/rGONP MOR 0.3 197 1.3 2017 [126]
Pd1Pt1.03/GA/NF EOR N/A 3408.7 1.2 2019 [202]
40%Pd–5%Ru/rGO MOR 118 N/A 3.1 2013 [163]
2
PdRu/rGO MOR 0.2 (mA m ) N/A 2.4 2015 [44]
2
PdRu/rGO EOR 0.5 (mA m ) N/A 1.4 2015 [44]
2
PdSn/rGO MOR 0.1 (mA m ) N/A 2 2015 [44]
2
PdSn/rGO EOR 0.4 (mA m ) N/A 1.6 2015 [44]
Pt–Co/rGO MOR 12.3 N/A 2.3 2014 [185]
Pt75.4Cu24.6 Alloy/rGO EOR 12.3 2.9 1.3 2018 [124]
Pt68.2Cu31.8 Alloy/rGO EOR 11.5 2.30 1.4 2018 [124]
PtIr PNWs/rGO MOR N/A 543 1.1 2015 [117]
PtRu/3D GF MOR 109.3 N/A 1.1 2014 [201]
PtRu/3D GF EOR 79.6 N/A 1 2014 [201]

catalysts (Pt/rGO or Pt/GA based) exhibited stronger electrochemical [101] or 2219 mA cm 2 [99] in EOR, respectively, as well as the best
activity in the MeOH half-cell scaled electrooxidation than the com­ If/Ib ratio of 11.65 in MOR [101] and 5.45 in EOR [49] as summarized in
mercial Pt/C, Pt/carbon black or even pure Pt, as reflected in the Table 4. Besides MOR and EOR, butan-1-ol OR [125], FOR [48,76,
maximum anodic sweep current density (Jf) of 2540 A g 1 (unit mass) 96–98,114,184], and GOR [74,118,165,182] catalyzed by
[43] or 30 mA cm 2 (unit area) [87], with strong tolerance towards CO graphene-based catalysts were another focus in recent years. However,
(If/Ib) as high as 6.6 [82]. However, due to the toxicity of methanol it­ systematic study in such topic was less relative to MOR and EOR, and
self, ethanol (EtOH) has become an alternative fuel in the electro­ non-platinum and bimetallic M/graphene-based electrocatalysts were
oxidation study. Same as the case of MOR, Pt-based graphene the mainstream in this topic [48,74,76,96–98,114,118,125,165,182,
electrocatalyst was extensively used in the past years, showing strong 184]. The results showed that the M/rGO- or M/GA-based electro­
activity in EtOH electrooxidation (EOR) [49,93,104,106]. The metal catalysts exhibited strong activity in the butan-1-ol OR (Maximum Jf:
candidate was replaced by non-platinum monometallic catalyst or 15.59 mA cm 2 or 105.98 mA mg 1 [125]), FOR (Maximum Jf: 61.6 mA
bimetallic catalyst at a later stage for the elimination of carbon mon­ cm 2 [98] or 3390 A g 1 [184]), and GOR (Maximum Jf: 16.2 mA cm 2
oxide (CO) poisoning from MOR and EOR in the Pt/graphene-based [182] or 0.056 A g 1 [118]) as listed in Table 4, but only a few reports
anodic catalyst due to the blockage of the active surface site of Pt by focused on the stability of the electrocatalysts after prolonged servicing
the CO molecules, which shortens the lifetime of the Pt/graphene cat­ (500–1248 cycles) [165,182].
alysts. Non-platinum monometallic catalysts like Pd ([37,44,48,49,74, Up to date, most of the graphene-based electrocatalyst research was
79–83,90,93–104,106,114,115,118,119,158,163,184,194] (2D M/rGO) done via the fabrication on a secondary substrate platform, such as a
[113,164], (3D M/GA)), Ni ([61,84] (2D M/rGO) [61,111], (3D M/GF glassy carbon electrode. These works involved the use of binding or
and M/GA)), Cu [101], Ag [90], Au [74,81,182,194] or bimetallic stabilization agents like Nafion solution with ultrasonic treatment for
electrocatalysts ([43,44,49,74,76,79–83,90,92,93,95,96,99–101,104, the catalyst ink production. Such a technique has the adverse effect of
106,117,124–126,158,163,182,185,194,195] (2D M/rGO) [165,201], destroying the graphene nanosheets structure; this is especially obvious
(3D M/GA or M/GF)) then became the alternative as summarized in for 3D graphene nanostructures. The use of a conductive binder also
Table 3. These graphene-based electrocatalysts loaded with such metals results in the reduction of the catalytic active surface by the binder. To
showed much stronger electrochemical activity in the half-cell scaled maximize the activity, the use of a binder-free graphene electrode has
MOR ([43,44,61,79–84,98–104,115,117,119,126,158,163,185,194, become an alternative in recent research. Binder-free graphene elec­
195] (2D M/rGO) [61,113,201], (3D M/GF)), EOR ([37,44,49,90, trode has several strengths over the traditional electrode, especially the
92–95,99–104,106,107,124] (2D M/rGO) [111,201], (3D M/GF and following. (1) The specific capacity and conductivity of the electrode can
M/GA)), butan-1-ol electrooxidation (butan-1-ol OR) [125], glucose be increased when compared to those requiring the use of non-
electrooxidation (GOR) ([74,118,182] (2D M/rGO) [165], (3D M/GA)) conductive and active binders. (2) Electron transfer inside the elec­
and formic acid electrooxidation (FOR) [48,76,96–98,114,184] with trode can be strengthened with the help of interconnected or stacked
strong tolerance towards CO poisoning. These graphene-based electro­ graphene nanosheet throughout the self-assembly, which forms a strong
catalysts also showed stronger activity than monometallic Pt/Graphene conductive and robust network. (3) Effective contact between the elec­
in the MOR and EOR. This point was reflected from the high anodic peak trolyte and the electrode interface due to the large specific surface area
current density recorded from the best output current density with of the electrode results in the reduction of the diffusion resistance [29].
values of 4972 A g 1 [43] or 252 mA cm 2 [104] in MOR, 2105.4 A g 1 With reference to the binder-free pure GA/NF synthesis for direct

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 10. (a) CV curves of GM-Co-B-N in O2- and N2-saturated electrolyte. (b) Polarization curves of G-Co, G-Co-B, G-Co-N, G-Co-B-N, and GM-Co-B-N at 1600 rpm
rotation speed in O2-saturated electrolyte. (c) LSV curves of GM-Co-B-N in different rotation speeds in the range from 400 to 2500 rpm, inset shows the K L plot of
GM-Co-B-N. (d) Electron transfer numbers of catalyst samples. (e) The durability of electrodes and (f) current density loss-time CA responses of GM-Co-B-N and Pt/C
electrodes at 0.3 V in oxygen-saturated electrolyte at rotating speed of 1200 rpm. The arrow indicates the addition of 3 M methanol into the electrochemical cells
[7]. (Reproduced with permission from ACS).

Fig. 11. (a) Chronoamperometric responses of the PtNCs@NGA and commercial Pt/C catalysts for 12 h in an O2-saturated aqueous solution of 0.5 M H2SO4. (b)
Chronoamperometric responses of the PtNCs@NGA and Pt/C catalysts in an O2-saturated aqueous solution of 0.5 M H2SO4 to injection of 1 M methanol [73].
(Reproduced with permission from RSC).

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

electrode preparation techniques with high stability of 150 cycles over

1248 cycles in the prolonged GOR, and 100–500 cycles over 1456 cycles
in the prolonged EOR, respectively [164,165,202]. Relative to the basic
half-cell scaled electrode analysis mentioned previously, systematic
research of the graphene-based electrocatalyst in the fuel cell unit or
battery scale was relatively little [7,203,204]. Types of fuel cell unit
covered were also limited to the direct ethanol fuel cell (DEFC) [203]
and direct glucose fuel cell (DGFC) units [204]; the results showed that
the output power density and current density were higher than the
existing non-graphene catalyst-driven DEFC and DGFC units. More
importantly, the binder-free Pd1Ptx/GA/NF electrode plate driven DEFC
and DGFC units exhibited stronger cell unit activity than the
Nafion-modified Pd1Ptx/GA/NF plate in the same DEFC (29.4% of
binder-free) and DGFC (66.5% of binder-free) under identical fuel
combination and working environment [203,204].

4.1.2. ORR catalysts for hydrogen fuel cells or metal-air batteries

Hydrogen fuel cells and metal-air batteries are operated by ORR at
cathode and hydrogen oxidation reaction (HOR) at the anode, but ORR
was the major focus of graphene-based electrocatalyst-driven hydrogen
fuel cell and metal-air battery research throughout the past decade. M/
rGO (M ¼ Pd, Pt, Au–Pd, Pd–Pt, PdPt@Pt Pt-Ag) [72,73,75,77,105–107,
109,110,118,122,158,194], MOx/rGO [7,127], and metal-free foreign
element-doped graphene-based materials [56,144,149,151,152,154,
169,205] were commonly studied targets in either acidic (HClO4 and
H2SO4) [72,73,77,106,107,109,110,118,122,158,194] or basic (NaOH,
KOH) [7,56,75,105,144] media. These catalysts showed stable activity
in the ORR as reflected in their high current density output. An example
is the result obtained from Wang et al. [7] using BN-codoped graphene
nanomesh/Co3O4 catalyst in the KOH solution (see Fig. 10). Some
research groups also investigated the crossover effect towards the ORR
performance of the cathodic electrode in the presence of alcohol (e.g.
methanol) [7,56,73,105,144]. The results showed that the
graphene-based ORR catalysts had strong tolerance towards the meth­
anol added to the cathode area compared to commercial Pt/C cathode,
which was illustrated from the representative results demonstrated by a
few research groups, including Wang’s group in the Zn-air battery
research using BN-codoped graphene nanomesh/Co3O4 catalyst in KOH
[7], Xie’s group using PtNCs@NGA catalyzed ORR in H2SO4 [73] and
Lv’s group using Pd–Cu NCs/rGO catalyzed ORR in KOH [105] as shown
in Figs. 10–12, respectively.
Same as alcohol fuel cell research, the demonstration of graphene
catalyst-driven hydrogen fuel cell or metal-air battery in the device scale
was rare. A representative example was the demonstration of MOx/rGO
as the electrode materials for the zinc-air battery (Zn-air battery), with
BN-codoped graphene nanomesh/Co3O4 chosen as the cathodic material
by Wang’s group [7]. The battery showed comparable activity to the
commercial Pt/C cathode-driven Zn-air battery after prolonged
servicing for 10 h, which is reflected by the battery performance in a
single cycle prolonged operation as shown in Fig. 13 [7].

4.2. Lithium ion and lithium metal batteries

Fig. 12. CVs of Pd–Cu NCs/RGOs (A), RGOs (B), and Pd black (C) modified Besides the huge effort on the graphene-based fuel cell catalyst
electrodes without (curve a) and with (curve b) 3.0 M methanol in 0.1 M KOH research, the use of graphene in lithium-ion battery (LIBs), lithium-air
at the scan rate of 50 mV s 1 [105]. (Reproduced with permission from Elsevier (Li-Air) battery and supercapacitor research has also been a popular
B. V.). topic in recent years. It is because graphene exhibited strong electrical
conductivity with their large specific surface area, which is beneficial for
supercapacitor electrode [32,33], a metal-loaded GA/NF direct elec­ the charge transfer in the LIB and Li-Air battery operation [8,9,21,126,
trode was then developed by the same reaction pathway [164,165, 128,130,137,141–143,155,161,206–210]. Pure graphene [206], metal
202–204]. The results showed that strong activity was recorded in MOR loaded graphene [126], metal oxide-loaded graphene [8,128,130,137,
(Maximum Jf ¼ 798.8 A g 1) and EOR (Maximum Jf ¼ 862 A g 1) for 141–143,161,207,209,210], and the metal-free foreign elements (B, N,
binder-free Pd/GA/NF electrode [164]; EOR (Maximum Jf ¼ 3408.7 A S)-doped graphene [9,21,155,208] (2D rGO [21,126,128,130,137,
g 1) [202] and GOR (Ja2 ¼ 379.4 A g 1) [165] for binder-free 141–143,155,206–210] and 3D GA [8,9,161]) were commonly used
Pd1Ptx/GA/NF electrode, respectively, as shown in Table 4. Such a materials for LIBs and Li-Air battery anode preparation. They showed
finding was outstanding relative to those fabricated by traditional high specific capacities in the LIBs and Li-Air battery discharge step in

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 13. (a) Open-circuit voltage of GM-Co-B-N-based Zn-air battery. (b) Typical galvanostatic discharge curves of Zn-air batteries with GM-Co-B-N and Pt/C as
cathode catalysts at 10 mA cm 2 current densities. (c) Long-term galvanostatic discharge curves of Zn-air batteries and (d) galvanostatic discharge-charge cycling
curves, current density 10 mA cm 2, 20 min for each state [7]. (Reproduced with permission from ACS).

Table 5
List of graphene-based LIBs, Li-Air battery electrode materials.
(Catalyst precursor and) Graphene host Battery Type Discharge capacitance (mAh g 1) Charge capacitance (mAh g 1
) Cycle (Depreciation) Year Ref

N-Graphene LIBs 0.1 N/A 50 (40%) 2010 [21]

FGSs Li–O2 15000 N/A N/A 2011 [206]
α-MnO2/RGO LIBs 154 N/A 20 (0%) 2012 [210]
TiO2(B)/rGO LIBs 635 613 100 (6.5%) 2013 [141]
P25/graphene LIBs 319 322 50 (12.2%) 2013 [142]
Porous graphene-Co3O4@C LIBs 780 N/A 100 (0%) 2013 [207]
Porous graphene-Fe3O4@C LIBs 1391 N/A 100 (19.2%) 2013 [207]
ATN/rGO LIBs 298.1 N/A 200 (13.9%) 2014 [130]
N-GA LIBs 2602.4 N/A 100 (79.4%) 2015 [9]
ZnO/rGO LIBs 1724 N/A 200 (79.2%) 2015 [128]
B-rGO LIBs 723 801 60 (30%) 2015 [208]
NS-rGO Li–O2 1000 N/A 40 (~0%) 2016 [155]
Nb2O5/HGF-2.0 LIBs 125 N/A 10000 (10%) 2017 [8]
Pt40Pd60-rGONPs LI-O2 1000 N/A 80 (~0%) 2017 [126]
PSCMnOx@rGO LIBs 1072 N/A 500 (6% increase) 2018 [143]
Fe3O4 NWs/GA LIBs 1296 905 100 (30.6%) 2018 [161]
Co3O4/rGO LIBs 47 42.7 100 (~0%) 2019 [137]
LTO/HG LIBs 117 N/A 1000 (~6.7%) 2019 [209]

the range of 0.06–15000 (mAh g 1) [8,9,21,126,128,130,137,141–143, density of 500 mAh g 1, and 2–3 times stronger discharge activity than
155,161,206–210], with high stability and a large number of operation the pure graphene aerogel as shown in Fig. 14. Sun et al. [8] achieved
cycles (20–10000 cycles) in the non-aqueous Liþ-based (Lithium bis even stronger stability via the use of Nb2O5-loaded holey graphene
(trifluoromethanesulfonyl) imide (LITFSI), lithium hexa­ framework (Nb2O5/HGF-2.0) as LIBs anode, where the capacity reten­
fluorophosphate (LiPF6), Lithium triflate (LiCF3SO3), or Lithium nitrate tion achieved was 90% after 10000-cycle operations [8]. Even though
(V) (LiNO3)) electrolyte solution as summarized in Table 5 [8,9,21,126, the specific discharge capacitance was not very high (~150 mAh g 1)
128,130,137,141–143,155,161,206–210]. Among them, Meng et al. [9] compared to N-GA developed by Meng’s group (500 mAh g 1) [9], such
developed the most stable graphene anodic materials for LIBs as the HGF anode was directly used without the assistance of binder and
discharge specific capacity could keep stable for 400 cycles at a current conductive additives, which showed the advanced point of binder-free

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 14. First three charge/discharge curves of GA (a) and N-GA (b) at 100 mA g 1; Cycling performances of GA and N-GA at 100 mA g 1 (c) and 500 mA g 1
(d);
Rate capability at different current density (e) and Nyquist plots (f) of GA and N-GA [9]. (Reproduced with permission from Elsevier B. V.).

free-standing bulk 3D graphene framework as direct electrode for LIBs conventional coin cells without treatment when compared to 2D gra­
or green energy storage devices [8]. This hypothesis was proved from phene electrode materials [8,9]. Studies carried out by Sun [8] and
the large difference in specific capacitance recorded in the control Meng [9] showed that the Nb2O5/HGF and N-doped GA can be directly
sample of 2D Nb2O5/G (~60 mAh g 1) against the 3D Nb2O5/HGF-2.0 assembled into traditional coin cells (CR 2016 and CR 2025) for the
(145 mAh g 1) under the same Nb2O5 loading (6 mg cm 1) in the same electrochemical analysis of the GA anodes without the use of binder and
electrochemical analysis. conducting additives [8,9]. Sun even showed that complicated fabrica­
The capability of the graphene products as anodic materials for de­ tion treatment process with the use of additives was required when 2D
vice scale LIBs was an important index for the application; bulk cylin­ Nb2O5/G was used for the LIBs anode assembly [9]. Excellent electro­
drically shaped 3D GAs products were especially suitable to fit into the chemical properties, as well as an easy and clean assembly process for

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Table 6 Table 7
List of graphene-based materials for supercapacitor electrode. List of graphene-based supercapacitor electrode performance.
2D graphene-based Ref 3D graphene-based Ref (Precursor)/Graphene Specific Cycle Year Ref
supercapacitor materials supercapacitor host capacitance (F (Depreciation)
materials g 1)

Pure rGO [211,214, Pure GH [32,42,57, SGH 160 N/A 2010 [216]
215] 58,65,162, Graphene aerogel 128 N/A 2011 [42]
216] GH-Hz8 220 2000 (8%) 2011 [58]
RGON [217] Pure GA [32,33,42, SGHs 240 N/A 2011 [65]
57,62,67, Nanomesh graphene 255 2000 (5.9%) 2011 [211]
134,213] a-MEGO 165 10000 (3%) 2011 [212]
Microwave exfoliated [212] 3D RGO/Ni foam [68] G-Gel/NF 41 (mF cm 2) 10000 (10%) 2012 [32]
GO (MEGO) aG-O film 120 2000 (5%) 2012 [214]
Co3O4/rGO-C [136] GCA@NF [33] Porous PGNs 154 5000 (12%) 2012 [215]
Graphene-MnO2 [129] 3D-NiGO [69] GA@NF 366 2000 (15% (2 A 2013 [33]
MnO2/3D CGM [196] HrGO/NF [70] g 1))
NF/G/MnO2 [168] rGO@Ni foam [71] rGH 232 100 (4%) 2013 [57]
Gr/SnO2 [133] MnO2/GF [23] RGOA 212 (KOH) 1000 (~5%, 2013 [62]
ZnO/GNs [131,132, 3D-NiGOM (MnO2 [69] 279 (H2SO4) KOH)
190] nanowires) 1000 (1.5%,
Ni2þ/Al3þ(GNS/LDH), [218–220] Mn3O4/GAs [160] H2SO4)
graphene/NiAl-LDH, 3D- G-gel@NF-2 152 2000 (~23%) 2014 [71]
ARGON/NiAl-LDH 3D-NiGO 236 1000 (5%) 2015 [69]
Co–Al LDH-NS, GNS/CoAl- [221,222] Ni(OH)2/Graphene [116] HrGO/NF 334 1000 (0.4%) 2015 [70]
LDH GO-RFA-P 56 N/A 2015 [213]
B/GNs [153,224] Co/GA [121] FAG 400 442 1600 (5%) 2016 [67]
N/GNs [224] GA/TiO2 [134] RGO/Ni foam 207 10000 (2.6%) 2016 [68]
BCN/GNs [224] B-doped GA [148] composite
N-doped GA [145,148] RGON 33 N/A 2017 [217]
N-doped GH [146] GCA@NF 207 2000 (20% (10 A 2013 [33]
NG/NF [150] g 1))
S-doped GA [225] PANI@3DGFs 932 5000 (29.8%) 2015 [162]
BN co-doped GA [148] B-GAs 228 1000 (0%) 2012 [148]
PS co-doped GA [223] BT-rGO 448 3000 (0%) 2015 [153]
NS-GA [157] B-graphene 83 N/A 2015 [224]
SNG aerogel [156] N-GAs 190 1000 (0%) 2012 [148]
GN-GH 190 4000 (4.8%) 2013 [146]
NGA 223 2000 (~8%) 2015 [145]
the LIBs anode exhibited by Nb2O5/HGF against 2D Nb2O5/G mentioned N-graphene 111 N/A 2015 [224]
NG/NF 223 3000 (0%) 2016 [150]
above, clearly showed the strength of free-standing GA electrode for
NS-GA-5 (GO:S ¼ 5:1) 203 3000 (10%) 2018 [157]
green energy. SNG aerogel 254 5000 (16.5%) 2018 [156]
BN-GAs 239 1000 (0%) 2012 [148]
BCN graphene 131 2000 (2.5%) 2015 [224]
4.3. Supercapacitors SRGA 446 1500 (26.6%) 2015 [225]
SP-AG 381 10000 (6.6%) 2016 [223]
GNS/LDH 782 200 (22.6% 2011 [218]
Relatively, effort in supercapacitor research was large, pure gra­
Increase)
phene [32,33,57,58,62,67–71,162,167,211–217], metal [121], metal Co–Al LDH-NS/GO 880 2000 (~0%) 2012 [221]
hydroxide [116], layered double hydroxide [218–222], metal oxide GNS/CoAl-LDH 712 2000 (19%) 2012 [222]
([23,69,129,131,132,134,136,160,168,190,196]), foreign elements (B, Graphene/NiAl-LDH 214 250 (9.3%) 2013 [219]
N, S, or P)-doped pure graphene [145,146,148,153,156,157,223–225], 1000 (~0%)
3D-ARGON/NiAl-LDH 2713 5000 (1.1%) 2013 [220]
and carbon nanotube [33]. These were the most commonly studied Co(II) ion-modified r- 387 1000 (~0%) 2014 [121]
materials as summarized in Table 6 (2D graphene: ([129,131–133,136, GO aerogels
153,168,190,196,211,212,214,215,217–222,224]), 3D graphene [23, Co3O4/rGO-C 709 6000 (8.8%) 2019 [136]
32,33,42,57,58,62,65,67–71,116,121,134,145,146,148,150,156,157, Graphene–MnO2 310 15000 (4.6%) 2010 [129]
composite
160,162,213,216,223,225]), which exhibited strong specific capacity in
MnO2/GF 670 N/A 2014 [23]
the range of 40–2100 (F g 1) with high stability of 20–15000 service 3D-NiGOM 1186 1000 (22%) 2015 [69]
cycles with low capacitance depreciation as listed in Table 7 [23,32,33, 3D CMG/MnO2 421 1000 (3%) 2015 [196]
42,57,58,62,65,67–71,116,121,129,131–134,136,145,146,148,150, NF/G/MnO2 723 (F cm 2) 2300 (2.4%) 2017 [168]
153,156,157,160,162,168,190,196,211–225]. In the ordinary super­ Mn3O4/GAs 162 5000 (11.2%) 2019 [160]
Ni(OH)2⋅(GN) 533 2000 (~0%) 2013 [116]
capacitor electrode analysis, liquid- or gel-like electrolyte like KOH, Gr/SnO2 323 (NaCl) 50 (4.9%, NaCl) 2014 [133]
NaOH and H2SO4 was used in the supercapacitor electrode performance GA/TiO2 143 (NaCl) 1000 (~0%, 2013 [134]
analysis [23,32,33,57,58,62,67,69–71,116,121,129,131,132,136,145, 245 (KOH) NaCl)
146,148,153,156,157,160,162,168,190,196,211–225], and a few of the ZnO/rGO composites 308 1500 (6.5%) 2011 [131]
ZnO/RGO 60 180 (~6%) 2015 [132]
cases were carried out at Na2SO4 solution [68]. However, an investi­
ZnO/GNS 291 1000 (32.5%) 2015 [190]
gation carried out by Yin et al. [134] was special in that the GA/TiO2
electrode showed strong specific capacitance in simulated saline water
(0.1 M NaCl solution) with a range of 50–150 F g 1 under different
those achieved by pure GA and neat activated carbon. These excellent
scanning rates (5–1000 mV s 1). However, it achieved almost zero
performances were reflected in Fig. 15 [134]. Even though the low
retention in capacitance in the simulated saline water after 1000 cycles
specific capacitance retention (4.9%) of Gr/SnO2 in NaCl solution was
of operation in 0.1 M NaCl [134]. GA/TiO2 electrode also showed strong
short lasting (50 cycles) from demonstration by El-Deen AG et al. [133]
desalination efficiency after reaching equilibrium at 200s with strong
in 2014, it still achieved 83% salt removal efficiency from NaCl solution.
regeneration efficiency over 10 cycles, which was much stronger than

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 15. (A) CV curves of AC, GA, GA/TiO2 in 0.1 M NaCl solution at a scan rate of 100 mV s 1; (B) The specific capacitance of AC, GA, GA/TiO2 at different scan
rates; (C) Cycling performance of GA/TiO2 at a scan rate of 100 mV s 1, inset presents the CV curves before and after the 1000 cycles. (D) Desalination capacity of AC,
GA and GA/TiO2 with different equilibrium concentrations and the corresponding Langmuir isotherm fitted curves; (E) Desalination efficiency of AC, GA and GA/
TiO2 in 500 mg/L NaCl solution at different times; (F) Electrosorption and regeneration cycles of GA/TiO2 in 500 mg/L NaCl [134]. (Reproduced with permission
from Wiley Interscience).

Fig. 16. (a) Schematics of ZGR based DSSC (b) Typical energy levels of various components of ZGR based DSSC employing an iodide/triiodide based redox elec­
trolyte and N749 as a sensitizer [199]. (Reproduced with permission from Springer).

Such demonstrations provided the possibility of using metal oxide/GA into conventional graphene-based DSSC materials involves the use of
as the fresh water generation materials via the desalination of seawater MOx-loaded 2D or 3D graphene support [22,24,138,140,197–199], or
using supercapacitor operation. metal-loaded graphene [78,186,226]. It should be noted that all the
above works were carried out at a pressure 50% higher than the atmo­
spheric condition. Most of the device scale graphene-based photoanode
4.4. Solar cells driven DSSCs were similar to each other [22,199]; this was illustrated in
Fig. 16 assembled by Siwach’s group with a corresponding operation
Relative to the traditional battery research on graphene-based ma­ scheme [199]. Some research groups used 2D graphene-based materials
terials, the use of such materials in solar-related green energy was also a as electrode for MOx-loaded graphene-based DSSC [24,138,140,197] or
popular research topic in recent years, including solar cell (mainly the blocking layer of the photoanode [198], while some applied the 3D
DSSC) [22,140,186] and photocurrent generation via hydrogen evolu­ GF [22]. The performance from different research works showed that
tion by photocatalytic water splitting reaction [139]. Due to the low cost the 2D graphene-driven DSSC exhibited strong cell performance, as re­
and high conversion efficiency (~12%) achieved by DSSC, research into flected in the short circuit current (Jsc) range of 11.6–15.90 mA cm 2,
such area was very popular since the 1990s [22]. Up to date, research

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 17. J–V curves of DSSCs based on (a) ZGR 0.25 (b) ZGR 0.5 (c) ZGR 1 and (d) ZGR 0 nanocomposite films [199]. (Reproduced with permission from Springer).

ZnO-loaded 2D graphene-based DSSC electrode, sometimes it did not

Table 8 show any activity [24], while some of the cases showed strong activity
List of best performance of graphene-based DSSC.
[199]. This may be due to the difference in the nature of ZnO/graphenes
Graphene photoanode Jsc (mA OCV Efficiency Year Ref synthesized by CVD and the sol-gel method, which caused a change of
cm 2) (V) (%)
the chemical structure of the resulting ZnO/graphene. The performance
3DGN (1 wt%)-P25 15.4 0.67 6.6 2013 [22] of MOx-loaded graphene-driven DSSC was associated with the relative
0.75 wt% RGO-P25 12.2 0.67 5.5 2013 [140] MOx loading in MOx-loaded graphene photoanode. Wei’s group and
Pt/rGO 11.6 0.78 3.9 2013 [186]
co-workers observed that the performance of graphene-TiO2 (GT-x, x ¼
Pt-HGF 12.3 0.68 5.6 2017 [78]
GB-1.0 15.3 0.74 7.5 2017 [198] 0–2.5 mL rGO) composite driven DSSC was enhanced when the amount
ZGR 0.25 11.6 0.76 3.2 2017 [199] of rGO increased from 0 to 1.0 mL, and then depreciated when x > 1.0
S–Co3O4/rGO 15.9 0.76 8.2 2018 [138] mL in the raw mixture for GT synthesis [197]. The origin of DSSC per­
Graphene (1.0 wt 15.0 0.72 7.1 2018 [197]
formance depreciation was the formation of a recombination center by
%)/TiO2 (GT-1.0)
TiO2/Graphene-Ag NPs 14.3 0.71 6.0 2018 [226]
excessive rGO surrounding the surface of TiO2 nanoparticles (NPs) in the
GT DSSC, which results in longer charge migration route or electron
directly coming into contact with electrolyte for dark current formation
open-circuit voltage (OCV) range of 0.72–0.78 V, and an efficiency [197]. As a result, the optimum amount of graphene used for DSSC
range of 3.2–8.2% when MOx/rGO with optimum composition of GO photoanode preparation should be fully considered. Some research
and photosensitive metal oxides were used [138,140,197–199]. Fig. 17 groups like Tang’s team [22] used 3D structured graphene synthesized
illustrated a J-V curve example where ZnO graphene (ZGR) was used from CVD, followed by chemical modification of GF with P25 and
with different graphene loadings as the photoanode of the DSSC fabricated on a conductive glass for the photoanode preparation. The
assembled by Siwach’s group [199]. Interestingly, in the case of the performance of the DSSC assembled by this 3DGN-P25 photoanode

Table 9
List of green energy research materials involving the use of 3D printed GA based materials against traditional GA based products.
1
Precursor Type GA-based composite Synthesis method Specific capacitance (F g ) Stability (Depreciation) Year Ref

None GA@NF Chemical reduction 366 2000 cycles (15% (2 A g 1)) 2013 [33]
RGO/Ni foam Hydrothermal 137 10000 cycles (~0%) 2016 [68]
Graphene/PLA 3D printing (FDM) 5 120 cycles (N/A) 2017 [10]
MWCNT GCA@NF Chemical reduction 207 2000 cycles (20% (10 A g 1)) 2013 [33]
Graphene/MWCNT MDHA 3D printing (DIW) 27 10000 cycles (10%) 2018 [12]
PANI PANI@3DGFs Hydrothermal, electrochemical deposition 932 5000 (29.8%) 2015 [162]
PANI0.4/RGO 3D printing (DIW) 423 1000 cycles (25%) 2018 [13]
M 3DE/Au 3D printing (FDM) 98 1000 cycles (87.9%) 2018 [232]
MOx 3D-NiGOM Sol-gel reduction 1186 1000 (22%) 2015 [69]
3D G/MnO2 3D printing (DIW) 239 20000 cycles (7.1% (2 mm)) 2019 [247]
2
MOG 3D printing (DIW) 121 (F cm ) 10000 cycles (13.4%) 2019 [248]
NOG 3D printing (DIW) 400 10000 cycles (13.9%) 2019 [248]

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 18. Electron transfer mechanism in ZnO nanoparticles and graphene/ZnO nanocomposite on irradiation [200]. (Reproduced with permission from Elsevier
B. V.).

Table 10
Advantages and disadvantages of the existing 3D printing methods for graphene-
based green energy applications.
3D printing Advantages Disadvantages
method

SLA High printing resolution [250] Too long printing time [250]
Strict reinforce solvent option
for both graphene and SLA resin
[235]
FDM Fast printing time [232] Complicated self make filament
Low cost [232] ink preparation process [231]
Market available filament [10] Spray of metal catalyst to the
printed product [232]
DIW Simple printing process [246] Required secondary loading
Low cost [246] process [246,247]
Can achieve binder-free GA Required the use of additive
monolith printing with proper [242] with harsh additive
rheological properties [245] removal process [13]

performance of TiO2-driven DSSC [78,226]. Based on the summarized

results shown in Table 8, both MOx-loaded graphene and metal-loaded
Fig. 19. Mechanism of hydrogen production in the GO-TiO2 composite system graphene have strong potential for being solar cell electrode materials.
[139]. (Reproduced with permission from Wiley Interscience).
4.5. Solar-driven water splitting reactions

Metal oxide-loaded graphene-based materials also played an

showed stronger output and efficiency than that driven by pure P25,
important role in the water-splitting reaction with improved perfor­
achieving 15.4 mA cm 2, 673 mV, and 6.58% for Jsc, OCV, and effi­
mance of the photocurrent production when compared to the corre­
ciency, respectively [22].
sponding pure metal oxides [139,200]. From the investigation carried
For the case of metal-loaded graphene, one of the examples was
out by Ghorbani and Gao’s group [139,200], the photocurrent gener­
graphene-Ag NPs supported on TiO2 (TiO2/Graphene-Ag NPs) fabri­
ated throughout the water-splitting reaction catalyzed by ZnO/graphene
cated by Huang’s group [226], which exhibited strong electrical prop­
porous structure (ZnO/GO(1 wt%)) and (GO-TiO2-3) was 1.0 mA cm 2
erties with a Jsc recorded value of 14.3 mA cm 2, OCV of 0.71 V, and
and 32 mA cm 2, respectively. These values were around approximately
conversion efficiency of 6%. Another example involves the use of
12 times that of pure ZnO (0.09 mA cm 2) and 3 times that of TiO2 (10
Pt/rGO as counter-electrode, which showed enhanced activity
mA cm 2), respectively [139,200]. The hydrogen evolution rate recor­
compared to that of the counter-electrodes composed of Pt and rGO. This
ded by GO-TiO2-3 (305.6 mmol h 1) was also much larger than that of
is reflected in the high output values of Jsc of 11.6 mA cm 2, OCV of
TiO2 (23.5 mmol h 1) [139]. Both groups suggested the improved
0.78 V, and efficiency of 3.9% for the Pt/rGO-driven DSSC studied by
charge separation within the MOx/graphene products upon irradiation
Chen’s group [186]. Recently, Yu’s team even showed that metal-loaded
by the light source [139,200], which is reflected from the examples of
3D GA-like products can also act as both the MOR electrocatalysts and
the charge transfer scheme as shown in Figs. 18 and 19 [139,200]. These
strong counter-electrode for DSSCs [78]. The performance recording the
materials showed the potential of graphene-based products as electrode
Pt/HGF-driven DSSC assembled from this electrode showed that it
materials for hydrogen water-splitting cells in the future.
achieved a 5.6% conversion efficiency with Jsc and OCV of 12.3 mA
cm 2 and 0.68 V, respectively. These results were comparable to the

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 20. Common light- and ink-based 3D printing methods. a, The light-based 3D printing method known as continuous liquid interface production (Diagram
adapted from Ref. [250]). b, Light-based selective laser sintering of powders. c, Light- and ink-based photocurable inkjet printing of photopolymerizable resins. d,
Ink-based fused deposition modeling of thermoplastic filaments. e, Direct ink writing using viscoelastic inks [249] (Reproduced with permission from Nature group).
f, Fabrication illustration of BN-GAs hydrothermal process and freeze-drying process. g, Digital images of two pairs of GO solutions with different volumes in the vials
and N/B co-doped graphene hydrogels before and after hydrothermal self-assembly. Inset: digital images of the BN-GAs obtained after freeze-drying [148]
(Reproduced with permission from Wiley Interscience).

Fig. 21. (A) Tensile strength comparison of cast and 3D-printed parts. SLA-printed complex-shaped GO nanocomposites: (B) nested dodecahedron and (C) diagrid
ring [239]. (Reproduced with permission from ACS).

5. Recent developments and applications of new technology for the support itself. It is difficult to synthesize large-sized customized
graphene-based materials GA-derivative electrodes by the traditional hydrothermal or mild
chemical reduction method due to the requirement of a specific reactor
Even though graphene-based materials are attractive materials for with the desirable size, resulting in high production cost. The contrac­
green energy development as mentioned previously [32,33,67–71,150, tion in product size due to the surface tension of the reaction mixture
164,165,202–204] and shape customized GA can also be obtained by the exhibited in the GA products throughout the self-assembly process also
use of a suitable shape reactor [64] or NF as template after a simple exists. Even though the GF synthesis can correct this shortcoming via
soaking with chemical reduction [32,33,67–71], several shortcomings CVD with the use of NF or Cu foil, the removal of CVD supports (Cu foil
still exist as a barrier to further development using traditional technol­ and NF) was also complicated and involved the use of a corrosive or
ogy. For example, a complicated process is necessary to fabricate toxic etchant, which makes the synthesis not user-friendly. All these
graphene-based materials or catalysts for electrode production, and the shortcomings may lead to actual activity not being reflected in the
risk of original structure destruction during ultrasonication exists. More operation and limit the value of binder-free GA-based green energy
importantly, such a process requires the use of surfactant to stabilize the materials for large-scale production and real device-level application.
graphene catalyst on the support surface, especially 3D GA-based To overcome this barrier, the importation of novel technology like
products. Using direct growth GA-based materials on support like NF 3D printing has recently become a new direction. It is because 3D
may also have potential problems for catalytic activity exhibited from printing technology can eliminate the weakness of GH size contraction

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

synthesized GA process between 3D printing and traditional chemical

reaction methods is illustrated in Fig. 20 [148,249], where Fig. 20a–c
belongs to SLA method, Fig. 20d belongs to FDM, Fig. 20e is DIW, and
Fig. 20f and g is traditional hydrothermal reaction for the 3D GA syn­
thesis with NSGAs as example. The major difference is that traditional
methods required the use of a specific shape container to achieve scal­
able GA [64], but the size contraction throughout self-assembly is un­
avoidable (Figs. 1a, 20f and 20g) [64,148]. Such phenomena do not take
place in the 3D printing process [250]. The only similarity is preparation
of GO-based dispersion is the first step of both techniques.
FDM is a printing technique involving the use of an ink-like plastic
filament. The 3D structure is formed by melting the filaments into a
paste-like thread at the nozzle of the printing head, followed by solidi­
fication on the printing platform to obtain the product [10,11,227–229,
232–234]. SLA involves the use of photolithographic resin with a
hardening of the resin and laser cutting of the resin slurry throughout
the synthesis [235–241]. DIW, an extrusion-based direct printing tech­
nique which is relatively simple since the liquid or paste-like graphe­
Fig. 22. Tensile strength as a function of GO loading [239]. (Reproduced with ne-based ink can be used directly in the printing process by a printer [12,
permission from ACS). 13,234,242–248]. The common characteristics of these printed products
were size and shape scalable by the computer program like CAD drawing
due to surface tension throughout the traditional GA synthesis [64,148]. and Solidworks [10–13,227–232,234–248]. An example is shown in
It can also achieve the size and shape scalable production by using Fig. 21 as demonstrated by Manapat’s group via the SLA technique
computer designed (CAD) shapes instead of using specific size of shape [239]. These products exhibited characteristics comparable to the
reactor [64,148]. It is extremely suitable for scalable free-standing bulk traditional GA, such as mechanical strength [227,228,234–236,
GA electrode synthesis. The most commonly used 3D printing technol­ 238–240] and electrical conductivity [10,228,230,231,236,241]. For
ogy for graphene synthesis includes three methods: fused deposition example, Manapat’s group found that the mechanical strength of the
modeling (FDM) [10,11,227–234], stereolithography (SLA) [235–241], SLA-printed GO-loaded products was enhanced when the amount of GO
and direct ink writing (DIW) [12,13,242–248]. The difference in the in the polymer resin increased, and the 3D-printed GO composites

Fig. 23. Physiochemical characterization. (a) Optical image of the 3D printing process, (b) 3D printed electrode used throughout the study. (c) FESEM image of 3DE/
Au electrode, and (d) corresponding magnified cross-sectional area [232]. (Reproduced with permission from Nature group).

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 24. Morphology and structure of graphene aer­

ogels. (a) Optical image of a 3D printed graphene
aerogel microlattice. SEM images of (b) a 3D printed
graphene aerogel microlattice, (c) graphene aerogel
without R–F after etching and (d) graphene aerogel
with 4 wt% R–F after etching. Optical image of (e) 3D
printed graphene aerogel microlattices with varying
thickness and (f) a 3D printed graphene aerogel
honeycomb. Scale bars, 5 mm (a), 200 mm (b), 100
nm (c, d), 1 cm (f) [243]. (Reproduced with permis­
sion from Nature group).

exhibited stronger mechanical strength than the casted GO products as properties of 3D-printed GA products [245]. Such properties are com­
revealed by the tensile strength variations shown in Figs. 21–22 [239]. parable to the ice-supported printed GA (Figs. 25–26). Both
Similar to SLA mentioned previously, FDM and DIW GA products ice-supported printing [244] and ambient printing [245] technique
also showed the size- and shape-customized nature, as reflected in the showed the advantage of shape and array customized properties. The
digital images and SEM images illustrated in Fig. 23 from Foo’s team printed GA exhibited strong mechanical strength (Young’s Modulus ¼
(FDM) [232] and Fig. 24 obtained from Zhu’s group (DIW GAs) [243] as 137 kPa (80% strain)-174.6 kPa (50% strain)) and electrical conduc­
representatives. So far, pure GA [12,232,242–246], metal (M) [12,232, tivity (15.4–41.1 S m 1) [244,245].
246], metal oxides [247,248], and metal sulfide (MS) [12], or organic FDM and DIW 3D printed graphene products played important role
molecule-loaded GAs [13] were demonstrated in both FDM and DIW in green energy research, include hydrogen evolution reaction [10], LIBs
method, which showed size-, porosity-, and shape-customized features. [10], supercapacitor [10–13,232,247,248], and photocurrent [232].
The loading uniformity of foreign materials (metal/metal sulfide) in the These products were pure graphene in nature [10–13,232]; only a few of
3D-printed GA array was also high [12,232,246,247]. them were foreign materials loaded 3D graphene via FDM (gold loaded
To the best of our knowledge, only a few studies focused on the size- three-dimensional Printed Electrode (3DE/Au)) [232] and DIW (3D
and shape-customized 3D-printed 2.5D and 3D pure GA blocks via the printed graphene aerogel/MnO2 (3D G/MnO2), NiO or MnO2 loaded
binder-free aqueous GO solution by ice-supported DIW method as integrated graphene network (IGF) (NOG, MOG)) [247,248] respec­
illustrated in Fig. 25, which showed mechanical and electrical properties tively. For example, Foster’s group demonstrated that the FDM
comparable to those synthesized by traditional methods [244]. This 3D-printed graphene/polylactic acid (graphene/PLA) exhibited strong
method has the advantage of a totally additive-free nature; its me­ electrochemical activity (Current density ¼ 0.4 A g 1 in 3 M KOH) and
chanical and electrical properties were hence wholly contributed from the capacitance (4.79 F g 1 in 3 M KOH) from the coin battery assembled
the pure graphene itself, as reflected by the real-time mechanical results with the graphene/PLA electrode (Figs. 29–30) [10]. Its strong hydrogen
reported by Zhang et al. (Fig. 26) [244] Recently, another demonstra­ evolution reaction activity (Onset potential ¼ 0.84 V (vs SCE)) was
tion carried out by Ma and his coworker showed the bulk GA can also be reflected from the strong current density output illustrated in Fig. 31 by
printed out under room temperature (ice mold-free printing) via the use comparison to other graphite-based materials [10]. DIW GA based
of concentrated aqueous GO paste [245]. Illustrations in Figs. 27–28 products also exhibited strong electrical conductivity (71.5–120 S m 1)
showed the flow of ambient environment GA printing, strong electrical [12,13,242], high specific capacitance (4.79–239.7 F g 1) and operation
and mechanical characteristics, and size- and shape-customized stability up to 1000–20000 cycles of operation [12,13,247,248], as

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 25. 3D printed GO aerogels. (a)–(c) Printed GO aerogels on catkin, and (d)–(f) designs of printed GO aerogels [244]. (Reproduced with permission from Wiley
Interscience).

Fig. 26. (a) Experimental setup for compression by DMA. (b) Loading and unloading process during compression test (50% strain) [244]. (Reproduced with
permission from Wiley Interscience).

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 27. LGO ink properties and schematic diagram of the fabrication process (a) Digital image of the LGO ink with a concentration of 20 mg/mL in a 30 cm3 barrel,
(b) Viscosity as a function of the shear rate for LGO ink, (c) G0 and G00 as a function of the shear stress for LGO ink, (d) the LGO ink extrusion through micro needle
(400 μm), (e) the model of printed 3D LGO monolith, (f) chemical reduction of LGO monolith by HI, (g) thermal annealing of monolith at 1000 � C in nitrogen, (h) the
optical image of the final low-density 3D graphene monolith, (i) the printed 3D letter FDU, (j) the electrical property of T-LGO monolith, (k) the compressive and
resilient property of T-LGO monolith [245]. (Reproduced with permission from Elsevier B. V.).

Fig. 28. The photograph of the printed 3D letter FDU, fork type and hexagon [245]. (Reproduced with permission from Elsevier B. V.).

reflected in the cyclic voltammetric results in the electrochemical per­ target [250], and the solvent for mixing both GO and SLA resin is limited
formance study carried out by Tang’s group (Fig. 32) [12]. By [235]. This makes SLA unsuitable for the GA based green energy elec­
comparing with those involving the GA based materials synthesized by trode fabrication. Second and the most critically, synthesis of such ink
traditional method as listed in Table 9, which showed that 3D printed required the use of surfactant (such as lactose, cellulose, polyvinyl
GA products have comparable activity and are new stars as replacement alcohol (PVA), or polyvinyl butyral (PVB)) with prolonged synthesis
materials of synthesized GA by traditional method in the green energy time or direct use of the market-available filament ink [10–13,231,232,
application. 242] to ensure the printable ink have proper rheological property. The
Even though the 3D-printed GA products showed strong activity in metal-loaded FDM graphene 3D electrode even needs the spraying of
the green energy applications, including LIBs, and supercapacitor gold and further fabrication of GO with the help of organic compounds
[10–13,232,247,248], the materials used still suffer from the weakness [232]. This is especially obvious for FDM products [10,11,231,232]. The
associated with the printing techniques. Firstly, even though the use of active catalytic sites would be blocked by the surfactant or resins, which
3D printing technology can produce high-resolution products in a may inhibit the contact between reactants and the loaded foreign ma­
low-cost way, SLA required long printing time (hourly) to achieve this terials in the 3D printed GA array [12,232]. Even though there is an

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 29. Schematic of the coin cell fabrication (A), charge-discharge profiles (B), cycling properties (C), coulombic efficiency (D) and rate capability of the 3D printed
anode (E) [10]. (Reproduced with permission from Nature group).

example of binder-free foreign materials loaded 3D printed GA monolith binder for the electrode fabrication in the traditional electrochemical
(ruthenium loaded reduced 3D printed holey graphene oxide mesh research (fuel cell, supercapacitor, LIBs, photovoltaic, etc.), which re­
(Ru/r-hGO mesh), 3D G/MnO2, NOG and MOG), it was synthesized by a sults in the low electrode activity and even high cost of electrode pro­
complicated 2-step synthesis via soaking of the as-printed r-hGO mesh duction. All these shortcomings limit the transfer of these techniques
into the metal solution followed by further chemical reduction [246], or from laboratory scale to industrial scale. As a result, importing new
electrodeposition of MnO2 or NiO to the DIW 3D printed GA [247,248]. technology has become an alternative to overcome the problem.
Such barriers need to be overcome for the GA-based materials via 3D Application of 3D printing technology has provided a possible solution
printing technology in green energy research. for the size- and shape-customized graphene products synthesis for the
Based on the advantages and disadvantages of the above-mentioned commercialization of the graphene-based energy devices materials,
3D printing technology for the graphene-based green energy research as especially the binder-free 3D GA based products. It is because besides
summarized in Table 10, use of DIW provides a solution of unleashing the limitations on the desirable design reactor for the size and shape
the potential of developing low-cost and binder-free freestanding customized binder-free free-standing GA based electrode material syn­
foreign materials-loaded 3D-printed GA based catalysts for direct fuel thesis mentioned previously, bulk 3D GA based materials synthesized by
cell, LIBs, supercapacitor, or solid oxide fuel cell electrodes in future. traditional chemical reduction or hydrothermal reactions have another
risk of uneven distribution of loaded catalyst (especially M, MOx, and
6. Conclusion and perspective dissolved polymer) in the 3D GA array due to the lengthy stationary
reaction. This may result in undesirable reactivity of the electrode
In the past two decades, 2D and 3D graphene products synthesized produced from current synthesis methods. In addition, the effect of
by different methods have played an important role in green energy foreign material (M, MOx, dissolved polymer) loading level to the
research. They exhibited strong activity in green energy research, like electrochemical activity of the foreign materials loaded 3D printed
fuel cell catalytic electrodes, LIBs, supercapacitor electrode, and pho­ graphene in battery research has also not been fully explored yet. Re-
tovoltaics (DSSCs and water splitting cell) research. However, most of aggregation of GO into the graphitic structure may also take place
these works were still at the fundamental activity analysis level. Per­ throughout the traditional self-assembly reaction which may reduce the
formance evaluation of such materials in the real device scale, such as porosity of the GA products, affecting the electron transfer within the GA
metal-air battery and coin cell scale, still occupy a small portion in total. array. Conducting polymeric additive used in time-consuming FDM and
Another challenge involves the graphene-based materials development SLA printed 3D graphene structures production may also cause problems
in green energy research due to the limitation arising from the tradi­ in the printed electrode due to the masking of the specific active sites on
tional synthesis and device fabrication techniques, such as (1) compli­ the catalyst surface by the additives. All these barriers are needed to be
cated procedure for ‘bottom-up’ CVD GF synthesis and the risk of uneven solved for the future establishment of low-cost graphene-based electrode
distribution of loaded catalyst in the 3D GA array by traditional chem­ ink with optimized material loading for large-scale production. Merging
ical reduction or hydrothermal reactions; (2) shape and size of the GA of DIW 3D printing in the cooling tank method with the use of direct
and GA/NF products was controlled by the shape and size of reactor foreign materials/GO ink, and taking the advantage of binder-free bat­
being used; (3) complicated process for the removal of supporting ma­ tery electrode materials probably can: (1) solve the problem of uneven
terials from the CVD synthesized GF; and (4) and the use of polymer distribution of loaded materials in the GA array due to sedimentation

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 30. Cyclic voltammetry (A) of the 3D-SC consisting of a 2 mm layer of solid electrolyte of PVA and 1.0 M H2SO4. Corresponding charge/discharge curves with
(C) and without (B) the Kampouris’ circuit in parallel are also presented. Scan Rate: 25 mV s 1. Inset to A is a schematic of the 3D-SC utilised throughout this study
[10]. (Reproduced with permission from Nature group).

Fig. 31. Comparative linear sweep voltammograms (LSV) (A) using 3DE compared to EPPGE, GCE, BDDE and platinum showing the onset of the HER. Stability
studies of the 3DEs (B) using LSV for the initial, 10th, 100th and 1000th scans. Scan rate: 25 mV s 1 (vs. SCE). Note: 3DEN ¼ 1 is upon the initial scan and 3DEN ¼
1000 is upon the 1000th scan [10]. (Reproduced with permission from Nature group).

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C.H.A. Tsang et al. Renewable and Sustainable Energy Reviews 120 (2020) 109656

Fig. 32. Electrochemical performance of the coin-type symmetric microsupercapacitors. (a) CV curves collected at scan rates of 20–100 mV s 1 in 6 M KOH
electrolyte. (b) GCD profiles collected at current densities from 4 to 40 mA cm 2. (c) Areal capacitance and capacitive retention versus different areal current
densities (4–40 mA cm 2). The inset shows optical images of the device before and after assembling. (d) Cycling stability measurements. The inset shows an optical
image of a green LED-lighted by three coins connected in series [12]. (Reproduced with permission from ACS). (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)

during the GA self-assembly reaction; (2) achieve a controllable porosity Appendix A. Supplementary data
in the GA array with the optimized foreign materials loading level for
maximizing the battery and solar cell device performance; and (3) Supplementary data to this article can be found online at https://doi.
reduce production cost due to the elimination of extra additives and org/10.1016/j.rser.2019.109656.
reactor free process throughout the synthesis. In short, DIW 3D printed
binder-free GA-based electrode synthesis with uniform catalyst distri­ References
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