Received: 1 March 2021 Revised: 2 June 2021 Accepted: 2 June 2021

DOI: 10.1002/er.6969

REVIEW PAPER

Application of graphene in low-temperature fuel cell

technology: An overview

Siti H. Osman1 | S. K. Kamarudin1,2 | Nabila A. Karim1 | Sahriah Basri1

1
Fuel Cell Institute, Universiti
Kebangsaan Malaysia, Bangi, Selangor,
Summary
Malaysia Fuel cells offer the possibility of zero-emission electricity generation and
2
Department of Chemical Engineering, increased energy security. However, fuel cell technology, particularly the low-
Faculty of Engineering and Built
temperature fuel cell, still has some major problems that hinder their commer-
Environment, Universiti Kebangsaan
Malaysia, Bangi, Selangor, Malaysia cialization, including costly components, durability issues, hydration, and an
efficiency loss of approximately 60% during operation. Recently, graphene has
Correspondence
S. K. Kamarudin, Fuel Cell Institute,
been introduced as a potential solution to enhance the performance of fuel cell
Universiti Kebangsaan Malaysia, 43600 systems. This article presents a review on the application of graphene in fuel
Bangi, Selangor, Malaysia. cell technology and the presentation of the electrochemical characteristic of
Email: ctie@ukm.edu.my
graphene. This article also summarizes the recent research trends in graphene
Funding information and its economic aspects, with a discussion on the modifications that increases
Universiti Kebangsaan Malaysia, Grant/
the graphene strength along with other benefits for the future development of
Award Number: DIP-2019-021
graphene technology. Finally, this work also addressed the current problems
and future advances in adopting graphene in a low-temperature fuel cell
system.

KEYWORDS
catalyst, fuel cell technology, graphene, membrane

1 | INTRODUCTION focusing on low-temperature fuel cells as described in

Fuel cells work by altering chemical energy directly into
electrical energy has a higher efficiency than a combus-
tion engine and emits much fewer emissions. Hence, fuel
cells are one of the greatest talented branches of technol-
ogy for resolving the global energy crisis and making the
living world more sustainable in the future.1 The basic
component is an electrolyte layer with two electrodes.
The fuel would be oxidized by the electrons released at
the anode surface by lowering the production of O2 at the
cathode and ensuring the circuit proper operation.
The O2 charge transfer between components (H+, OH ,
CO2 3, or O2 ) is reduced. Generally, the fuel cell could
be divided into two types depending on the operating
temperature which high-temperature fuel cell (≥500 C)
and low-temperature fuel (<300 C). This review will be
Figure 1. In low-temperature fuel cells, hydrogen is used
as the main fuel.2 Even though hydrogen is not a primary
energy source, but it is known as an energy carrier,
which in the long-term renewable energy sources impor-
tant sources for the production of hydrogen.3
Low-temperature fuel cells are promising candidates
that effectively transform hydrogen or alcohol into
energy for large-scale industrial, decentralized power
sources and mobile applications.4 Unfortunately,
Gottesfeld et al5 reported that the low-temperature opera-
tion gives the negative variation in free energy (ΔG) in
operation, this may cause CO poisoning which is affirma-
tive for CO adsorption on Pt (due to its affinity)
engineered electrodes. As a solution, carbon-based
nanomaterials such as carbon,6 graphene,7 carbon nan-
otubes (CNTs),8 and other types of carbon have been

Int J Energy Res. 2021;1–19. wileyonlinelibrary.com/journal/er © 2021 John Wiley & Sons Ltd. 1
2 OSMAN ET AL.
discovered to reduce the trace of CO simultaneously
reduces the usage of platinum (Pt) and the exceptional
properties of graphene will increase the performance of
fuel cells. Thus, it is expected, graphene-based materials
are essential for reducing the cost of fuel cells to alleviate
the high cost of general fuel cell systems.
Figure 2 shows that the grade of graphene is
heavily dependent on the quality of the components,
the form of defects, and the substratum, which are
strongly affected by the production method.10 The
development of this commercial segment can be seen
from the way most countries that supply graphene
allocate the product within several sectors as shown in
Figure 3.12
Graphene-based low-temperature fuel cell technology
offers many benefits, including a reduction in emissions
associated with electricity generation,10 an increase in
energy security,12 and a reduction in local air pollution.13
Graphene can be synthesized in large quantities using
different methods, and its production is becoming
cheaper every year. Interestingly, Liu et al14 revealed that
metal-free and heteroatom-doped binary carbon com-
pounds such as graphene, CNTs, and nanofibers
F I G U R E 1 Low temperature
of fuel cell [Colour figure can be
viewed at
wileyonlinelibrary.com]
F I G U R E 2 (A) Number of
publications since 2011 related
graphene in low temperature fuel cell
(B) Relative contribution of graphene
sources used as catalyst, catalyst
support and membrane in low
temperature fuel cell (Science Direct
search with combination of related
keyword). Sources 5 May 2021
[Colour figure can be viewed at
wileyonlinelibrary.com]
demonstrated an increase in oxygen removal
electrocatalytic behavior due to the mixture of carbon π
electrons and dopant lone pair electrons.15-17 While, Ji
et al,18 Meguro et al,19 and Khodaverdi et al identified
potential graphene in low-temperature fuel cell
technology.
Furthermore, almost all the findings of the study
demonstrated that graphene was combined with another
type of catalyst or membrane, which was significant for
its efficacy, either as a support or as the main factor, in
which the catalyst provides stabilization to achieve a uni-
form distribution of nanosized metal particles, resulting
in strong catalytic action.20 Besides, Antolini et al21 pres-
ented a review paper focusing on graphene nanosheets
used as supports for fuel cell catalysts. However, this
work presents the wide range of graphene application in
low-temperature fuel cell include catalyst, catalyst sup-
port, and membrane.
The first part of this study focuses on the claim of
graphene in the low-temperature fuel cell membrane.
The second part of the review explains the application of
graphene as catalyst support. This review also addressed
the problem and the advances of graphene application in
OSMAN ET AL.
F I G U R E 3 A, Global manufacturing of graphene by country; B, output of graphene in the industry11 [Colour figure can be viewed at
wileyonlinelibrary.com]
low-temperature fuel cells. Finally, this article also sum-
marizes the recent research trends in graphene and its
economic aspects.
2 | M E M B R AN E F OR FUEL CE L L
TECHNOLOG Y
Recently, polymer membrane transmitting protons have
been focused to progress fuel cell performance. The man-
ufacture of graphene-based membranes for fuel cells has
demonstrated its importance. An opportunity when
graphene is present as a paper or sheet, especially in the
manufacture of MEA, which has polymer matrix or filler
as used components.22 The modification of graphene
properties in low-temperature fuel cell membranes is dis-
cussed below in-depth to analyze the effect.
2.1 | Polymer electrode membrane
fuel cells
Offering energy conversion systems with high energy and
reduced greenhouse gas emissions, polymer electrode
membrane fuel cells (PEMFCs) have become an area of
research interest in the last decade. Yadav et al23
reviewed that graphene and GO enhanced the PEMFC
durability and efficiency up to 3.7 times and greatly
improves the ionic conductivity. Lee et al24 prepared
graphene oxide with sulfonated poly(arylene ether sulfo-
nate) (SPAAES) by employing a casting solution process.
The contribution of graphene to this preparation process
3
increased the compatibility of the filler with the polymer
matrix. The study of membrane PEMFCs attracted more
interest when Zakaria et al25 investigated the basic
poly(vinyl alcohol)/GO composite membrane reaction
and examined the passive direct ethanol-proton exchange
of membrane fuel cells (DE-PEMFCs) with minimal
ethanol permeable membranes. The optimal composite
membrane content of GO (15 wt%) had the greatest con-
ductivity of protons and decreased permeability of etha-
nol. A review by Farooqui et al26 summarized the
potential benefits and the latest advances in graphene-
based membrane synthesis and their impact on fuel cell
efficiency. Furthermore, this investigation was continued
by Janghorban et al,27 who altered sulfonate composites
of CNT/Nafion.
The nanocomposite membranes designed with Nafion
and (CNT@SiO2-SO3H) nanoparticles contrasted with
the reworked Nafion membrane, in which the proton
conductivity and water retention were increased, while
the methanol permeability was decreased. Abouzari
et al,28 using a solution casting process, fabricated GO
with polybenzimidazole (PBI). The durability was
enhanced, as the composite membrane showed increased
dimensional stability and chemical stability and an
increase in mechanical strength by 75%. Kim et al29 stud-
ied the sulfonated fluorinated multiblock copolymer
(SFMC), sulfonated (polyether ether ketone) (SPEEK),
and GO. As a supplement, high liquid absorption, ion
transfer potential, and gas transfer potential ensured
equal dimensional stability. Peng et al30 modified GO
and poly(2,5-benzimidazole)-GO (ABPBI-GO) grafted
with Nafion by a solution casting process and showed
4 OSMAN ET AL.
improved results due to the GO addition by air, mechani-
cal, and ionic performance uptake. In an innovative
study by Lin et al,31 protic ionic liquids were investigated,
and PIL-based hybrid PEMs were synthesized and
described with distinct [APMIm][Br]-GO contents. The
findings showed that the membranes had outstanding
thermal stability and high conductivity under anhydrous
circumstances at high temperatures.
Liu et al32 reported pioneering developments in both
theoretical and experimental chemistry for graphene-
based membrane engineering to develop a model for use
in manufacturing applications. Yang and co-workers33
studied ionic liquid-functionalized graphite oxide with
polybenzimidazole (PBI). In this study, the conductivity
and tensile strength of the protons increased due to the
addition of graphene in the polymer matrix. Kim and
team34 prepared triazole-functionalized GO with Nafion
by the casting method. The use of graphene enables mea-
suring proton conductivity, decreases the exposure to
ohmic heating, and preserves the vapor pressure. Lee
et al35 prepared polyoxometalate coupled with GO and a
Nafion polymer with a solution casting method. As
a result, the cell quality in terms of the platinum (Pt)-G
content was improved to be below 1.5%, and this compos-
ite had a positive influence on the membrane water
absorption and conductivity of protons.
Further work by Sharma et al36 reported the fabrica-
tion of platinum (Pt)-graphene/SiO2 with poly(vinyl alco-
hol) (PVA)/chitosan using the solution casting method
and concluded that the membrane function was affected
by the incorporation of graphene in terms of the conduc-
tivity, thermal and mechanical stability and elastic modu-
lus. Ko et al37 used a solution casting method to fabricate
silica-grafted sulfonated GO and sulfonated poly (arylene
ether sulfone). The effect of graphene integration was
increased as the proportion of graphene increased, show-
ing a strong electrical resistance, greater elongation, and
young's modulus and promising proton conductivity.
Yang et al38 prepared Nafion/platinum (Pt)-TiO2 GO
via the solution casting process. The implementation of
the GO membrane resulted in increased proton conduc-
tivity and an ICE value that is key to fuel cell efficiency.
Zarrin et al39 constructed a simple GO/Nafion polymer
membrane via the casting method. The findings indicated
that nanocomposites from GO/Nafion showed a substan-
tial enhancement in proton conductivity (a fourfold
enhancement) at 30% humidity throughout the free
nanocomposite and an elevated temperature of 120 C.
Cao et al40 discovered the use of poly(ethylene oxide)/GO
to maximize the power density without optimizing the
composition of the catalyst layer. The current progress
made in graphene-based membranes of PEMFCs has
been explored in depth. Graphene-based polymer
membranes have entered a significant point in their
development where they are being introduced. In
PEMFCs, graphene enhanced the filler compatibility,
strength, electrical resistance, elongation, young's modu-
lus, and proton conductivity.
2.2 | Direct methanol fuel cell
Many studies have been performed in terms of modifying
Nafion to explore alternative membrane materials; thus,
the implementation of newly developed PEMs has been a
focus over the years to solve several of the related
problems.
SPEEKs have drawn significant attention among the
several available PEMs due to their excellent mechanical
strength and increased chemical stability.28-30 According
to Rambabu et al,41 aspartic acid-functionalized GO
(ASPGO) diffusion via SPEEK nanocomposite mem-
branes are specific for methanol-containing electrolytes.
ASPGO addition positively affects the membrane struc-
ture, the transfer of protons, and the permeability of
methanol. Jiang et al42 studied GO sulfonated
organosilane-functionalized GO (SSi-GO) grafting with
3-mercaptopropyl trimethoxysilane and eventual oxida-
tion to modify the SPEEK filler. Figure 4 briefly shows
the procedure for synthesizing SSi-GO. Sulfonic acid
groups were used to add functionality.39 The composite
membrane with the ideal content of SSi-GOs has a higher
energy density than commercial membranes; in DMFCs,
these are appealing as alternative PEMs for DMFC
applications.
Besides, by dispersing in a Nafion matrix, sulfonated
GO (SGO) is a simple and efficient technique for generat-
ing small methanol crossover membranes. Chien et al43
examined a low-content SGO/Nafion mixture with unique
viscosity behavior that allows better SGO dispersion in
Nafion. In another study on Nafion membranes by
Prapainainar et al,44 Nafion-mordenite membranes and
GO were combined to improve the hybrid ability of metha-
nol fuel cells. Li et al45 suggested that nondestructive
sheared layers of GO (SGO) injected in situ through the
Nafion membrane function as bifunctional additives to
enhance the methanol-permeation resistivity and proton
conductivity. Recently, sodium alginate (SA) electrolyte-
sulfonated GO oxide bio-membrane was explored to
enhance proton conductivity and decrease methanol per-
meability by Shaari and co-workers.46 The presence of
SGO strengthened the SA/SGO membrane for industrial
membrane applications. In another study, Shaari and co-
workers47 investigated the crosslinking efficiency in
DMFCs using response surface methodology (RSM) opti-
mization to apply SA/SGO as a polymer electrolyte
OSMAN ET AL.
F I G U R E 4 Depiction of the SSi-GO synthesis protocol, morphology, and electrochemistry performance42 [Colour figure can be viewed
at wileyonlinelibrary.com]
membrane. Two SGO variables were analyzed: weight and
glycerol loading.
Yan et al48 designed a sandwiched monolayer
graphene composite membrane between two thin Nafion
membranes to benefit from the selective permeability of
monolayer graphene to only protons. This membrane
allowed a passive DMFC to display good efficiency even
at methanol concentrations as high as 10.0M. The new
advance built-in graphene-based membranes for DMFCs
have been further researched. Beydaghi et al49 applied
the solution casting method for (SGO)/Fe3O4 with
SPEEK/poly(vinyl alcohol) (PVA). The application of
graphene resulted in increased stability of the proton
mechanism and conductivity. Wang and his team9 stud-
ied GO and Nafion using the layer-by-layer (LbL)
method. The implementation of graphene membranes
was exceptional in terms of proton conductivity, showing
a decreased methanol permeability, thermal power stabil-
ity, ion exchange efficiency, and water absorption. Pan-
dey and co-workers50 fabricated sulfonated imitation GO
(SIGO) and sulfonated polyimide (SPI) by a water casting
method. Graphene changed the membrane and increased
the thermal, electrical, and oxidative capacities,
increased water retention properties, and achieved a high
ion exchange capacity (IEC) and improved proton con-
ductivity. The method by Chu et al51 was used to cast
solution zwitterion-coated GO (ZC-GO) and poly-
benzimidazole (PBI). The incorporation of graphene
5
improved the conductivity of the composite membrane
and improved the methanol permeability, liquid absorp-
tion, and swelling proportion. Recent work conducted by
Yin et al52 used a solution casting process to modify GO
SPEEK. The graphene addition positively modifies the
proton conductivity and the methanol permeability.
Shirdast et al53 redesigned the solution casting
method of SGO and chitosan/sulfonate chitosan (10/1).
The introduction of SGO led to increased thermal and
mechanical properties, improved proton conductivity,
decreased methanol permeability, and excellent selectiv-
ity. Shaari et al54 prepared SA/SGO using a solution cast-
ing process. The integration of SGOs resulted in an
increased water uptake capacity. More details were pro-
vided by Ranjani et al55 in a study on the preparation of
SGO with silica nanoparticles/chitosan by a solution cast-
ing process. Additionally, SGO positively affects thermal
stability, increases the number of channels for water
adsorption, and increases the power density. Additional
advances in related graphene works, Shukla et al56
reported graphene synthesis of nanoribbon-graphene
quantum dot (GNR-GQD) SPEEK hybrids via a simple
single-step process.
Membranes with graphene showed excellent water
absorption, ion exchange efficiency, and proton conduc-
tivity, and a reduction in methanol crossover.
Prapainainar and his team57 reported using GO and
Nafion in solution casting processes. The surface
6 OSMAN ET AL.
response methodology and the power density were
designed for optimal graphene operating conditions. Li
et al58 tested the nondestructive sheared GO swelling-
filling process with Nafion. In this process, SGO increases
the resistivity of methanol permeation and increases pro-
ton conductivity. Kim et al59 prepared vinyl group-
modified GO (FGO), vinyl group-modified montmorillon-
ite clay (F-MMT), and vinyl group-modified multiwalled
CNTs (F-MWCNTs) using a radiation-induced polymeri-
zation solvent casting process. Functionalized GO greatly
improved the physical and chemical properties of fuel
cells. Graphene as a membrane in a DMFC has a greater
contribution to the efficiency with multiple fabrication
processes, such as the solution casting process, particu-
larly enhancing proton movement for conductivity and
the methanol crossover reaction.
2.3 | Alkaline fuel cell
Over the decades, alkaline fuel cells (AFCs) have gained
attention. AFCs are preferred over proton-exchange
membrane fuel cells because various generalized alkaline
conditions boost the kinetics of the electrode reaction.60
According to Zarrin et al,61 nanocomposites of
quaternized GO can be used as fast hydroxide conduc-
tors. The manufactured materials were used in an alka-
line scheme to determine the functionality of a QAFGO/
pPBI nanocomposite. Ye et al62 reported a simple mixing
process by fully exfoliated graphene nanosheets and PVA
alkaline nanocomposite membranes. Figure 5 shows the
F I G U R E 5 A, Design of poly(vinyl alcohol) (PVA)/graphene composite membrane synthesis procedure; B electrochemisty performance
of PVA and PVA/graphene composite membranes62 [Colour figure can be viewed at wileyonlinelibrary.com]
preparation of PVA/graphene composite membranes in
conjunction with an internal PVA/graphene structural
model at each point of KOH solution doping. These
changes in transport characteristics lead to important
ionic conductivity changes (126%) and reductions in
the permeability of methanol (55%). This results in a
substantial improvement in the efficiency of the cell
(148% improvement in peak energy density). In low-
temperature fuel cells, the efficacy of graphene in mem-
brane modification shows its potential. The modification
abilities of graphene reveal that it is an attractive material
for future use in fuel cells.
3 | CATALYSTS FOR FUEL CELL
TEC HN O LO GY
3.1 | Polymer electrode membrane
fuel cell
Graphene has increasingly been used as an alternate cat-
alyst supply because of two-dimensional PEM fuel cells
at the anode and cathode side of the fuel cell.63-65
Hernandez et al66 studied the electrocatalysts PtRu and
PtRuMo on nitrogen-doped graphene nanoplatelets (N-
GNPs) using a polyol process and used them as anodes.
The results showed both higher CO tolerance and higher
electrochemical stability of N-GNP catalysts supported by
PtRu and PtRuMo than the industrial standard carbon
black (CB) supported by PtRu. Another study performed
by Alpaydin and his team67 focused on the performance
OSMAN ET AL.
of graphene and multiwalled CNT catalyst with HT-
PEMFCs. The best catalyst had a 0.280 W/cm2 peak
power density and 0.180 V in an H2/air atmosphere and
a 0.266 W/cm2 peak power density and 0.171 V in a gas/
air atmosphere. Iwan et al68 found that GO affects
selected properties of Nafion-based polymer fuel cells.
For PEMFCs with GO-based anodes at 60 C, a maximum
power density of 134 mW/cm2 with a current density of
374 mA/cm2 was achieved. Devrim et al69 reported that
graphene and chloroplatinic acid, H2PtCl6, have a chemi-
cal reduction function in ethylene glycol. The PEMFC
efficiency for the graphene-supported platinum catalyst
was better than the conventional Pt/C catalyst. Cho
et al70 discovered that when intercalated with CB, the
electrocatalyst Pt/GN (a single graphene nanosheet) pro-
vided a better electrocatalytic activity for hydrogen oxida-
tion and improved performance in PEM fuel cells,
especially in the field of activation of the polarization
curve and loss of mass transport.
Graphene-engineered at the cathode of PEMFCs
could generate a high-power density that increased the
current density by 38% and the ionic conductivity by
257%. Interesting research was performed to discover the
potential of graphene by Latif et al71 to test gold
nanoparticles mixed with MWCNTs supported by
graphene nanoribbons (Au-NT-G) as an effective reduc-
tion electrode for PEMFCs. For the highest concentration
of gold nanoparticles, the maximum power density of
242.29 mW/cm2 was reached. Park and his team72 stud-
ied the superior durability and stability of Pt electro-
catalysts on the nitrogen-doped graphene TiO2 hybrid
content for oxygen reduction using a simple hydrother-
mal technique. Single-cell tests showed that Pt/NG-TiON
has high stability and corrosion resistance with a perfor-
mance degradation rate of only 9% after 500 rapid dura-
bility test cycles, whereas the Pt/C efficiency decreased
by 83%. Marinoiu et al73 found that the simple synthesis
of functionalized rGO decorated with gold nanoparticles
(Au NP/rGO) was successfully achieved under mild reac-
tion conditions. A power density of 0.59 V was obtained,
which is a substantial voltage for the activity of fuel cells
and is equivalent to that of a commercial Pt-based
cathode.
Continued work by Pothaya et al74 reported
Pt/graphene catalyst formulations of PEMFCs using a
heavy electrostatic adsorption approach. The results
showed that there was greater interaction between the
supported Pt particles and carbon. Further research by
Das et al75 showed hybrid supports consisting of CB and
graphene nanoplatelets (GNPs) for Pt NP loadings with
various percentages. The hybridization of CB-based GNPs
can not only avoid the accumulation of these carbon
materials but also fully exploits the synergistic effects.
7
Chandran et al76 reported oxygen reduction reactions of
bimetallic alloy catalysts assisted by 1D-2D integrated
hybrid carbon nanostructures. The as-prepared electro-
catalysts showed an increased ORR activity due to the
high dispersion of catalyst nanoparticles on the CNTs.
Further analysis of graphene in fuel cells in the cathode
was conducted. Arici et al77 researched an efficient elec-
trocatalyst for PEM fuel cells based on platinum
nanoparticles assisted with GNPs and black carbon
hybrids. The electrochemically active surface area (ECSA)
value showed greater graphene-based support operation
with a value of 19 m2/g Pt for Pt/GNP and 55 m2/g for
Pt/CB. ORR experiments and fuel cell tests were in tandem
with these findings in which the Pt/CB-GNP hybrid elec-
trocatalyst reached the highest maximum power density of
377 mW/cm2. Boyaci et al78 optimized the PEMFC cathode
parameter settings in the presence of PtCo/CVD graphene
by a factorial design method. The optimization results pro-
vided an average current density of 1779.5 mA/cm2 and a
power density of 785.38 mW/cm2 at 79.99 C. Another
study by Sevim et al79 reported the synthesis and controlled
assembly of ultrasmall and monodisperse Pt NPs on
graphene-based supports, including rGO, commercial CB
and hybrid rGO-VC products.
High performance was achieved with the elec-
trocatalyst support reported by Kaplan et al80 on hybrid
carbon support networks where the CB function was to
prevent the restoration of rGO sheets, thus modifying the
graphene range efficiently and offering more active cata-
lyst sites in the electrocatalyst material. Yang et al81 dis-
covered that graphene doped with carbohydrate-like
components, including sulfur and selenium, led to the
catalytic activity under safer conditions in alkaline envi-
ronments compared with industrial Pt/C, implying that
doped graphene may be an excellent substitute for
platinum-based catalysts in FCs. Vinayan et al82 worked
on the synthesis of hydrogen-exfoliated graphene (HEG)
sheets by nitrogen doping. These sheets of graphene
doped with nitrogen (N-HEG) were used as catalyst sup-
port and platinum-cobalt alloy NPs synthesized through
a technique in which the modified polyol was decreased,
giving the catalyst NPs a uniform dispersion. Yun et al83
examined the electrochemical efficiency of fuel calls
exchanging protons by multiwalled platinum graphene
CNT (MWCNT)-reinforced cathodes. As shown in
Figure 6 indicates the polarization curves of a platinum-
CB cathode, the composite cathode platinum-graphene/
MWCNT, and the cathode platinum-graphene due to the
performance in PEMFC. Zhang et al84 implemented oxy-
gen reduction processes for fuel cells on nitrogen-doped
graphene. Doping with nitrogen presents an asymmetric
spin density, a density of nuclear load, and high
electrocatalytic activity of N-graphene for the ORR.
8 OSMAN ET AL.
F I G U R E 6 The architectures of the metal cathode Pt-graphene and Pt-graphene/MWCNT83 [Colour figure can be viewed at
wileyonlinelibrary.com]
It was observed that the PEMFC efficiency increased
by up to 3.7% when graphene was added, which
depended primarily on the electrolyte membranes but
was mainly focused on Nafion and PBI polymers due to
their enhanced conductive abilities and high durability.
3.2 | Direct methanol fuel cell
In a direct methanol fuel cell, electrical energy can be
generated directly from methanol. Methanol is a liquid
fuel with a high energy density that is simple to transport
and store, but it has a lower rate of electrochemical reac-
tivity than hydrogen.85 Platinum is widely used because
reaction mediators in the active site of the catalyst easily
block it. Enhancing the activity and durability of
graphene-based materials in MOR offers promising pros-
pects for launching platinum nanoparticles. Yoo et al 86
had discovered that the Pt/rGO catalyst has a higher
MOR performance with a CO adsorption rate that is 40
times lower than the Pt/CB catalyst. Instead of the strong
interactions between GNS and platinum atoms, high
Pt/rGO efficiency is achieved by reduce platinum parti-
cles size and increase catalytic activity. The outcome is
3 times using nitrogen-doped rGO as support, the MOR
current can be enhanced.87 The use of amino and pyri-
dine groups on nitrogen-doped rGOs as anchoring sites
for platinum nanoparticles results in a more uniform
dispersion.87,88 However, using Pd and Ni-based plati-
num catalysts in alkaline media MOR catalysts can result
in lower costs and higher CO tolerances.89,90 MOR activ-
ity was higher in Pd/GNS nanoparticles compared to
Pd/CNTs and Pd/nanocarbon particles in 1 mol/L KOH
due to the ECSA of nanoparticles.89 Furthermore, the
impact of rGO anchoring on highly dispersed Ni
nanoparticles, the Ni/rGO catalyst has an ultra-high mass
activity of 1600 mAmg 1 and strong anti-poisoning prop-
erties in 1 mol/L KOH for MOR.90 Graphene-based mate-
rials are well suited as support materials for bimetallic
MOR catalysts due to their surface area, specific electro-
conductivity, and versatile microstructure. Several highly
efficient bimetallic graphene MOR catalysts such as
Pd@NiS dopen graphene,91 Pt-Pd nanoflowers/rGO,92
and Pt Niporous rGO93 have recently been published.
3.3 | Direct alcohol fuel cell
The use of fuel cells, especially direct alcohol fuel cells,
has increased due to the ongoing use of fossil fuels and
the related increases in social and economic issues. Fuel
cell systems have incredible potential as a new generation
of power sources with high-energy conversion efficiency,
minimal pollutant emissions, and moderate operating
temperatures. Likewise, fuel cell technologies have excel-
lent potential as a new generation of power sources with
OSMAN ET AL.
features of high-energy conversion efficiency, low pollut-
ant emission, and low operating temperatures.71
Bhunia et al94 worked on a monodisperse PtPdNi
trimetallic GO hybrid platform integrated with
nanoparticles. The inclusion of Ni in the PtPd alloy
changes the electronic surface composition of the PtPd
alloy, enhances the electrochemical substrate, and adjusts
the kinetics. Cui et al95 reported a simple design for
ultra-small Pd nanoparticles in ultra-thin nanosheets
made of zeolite-templated monocellular graphene foam
(MGF) prepared using lamellar MCM-22 zeolite as a tem-
plate; then, using a stabilizer-free synthesis process,
ultra-small Pd NPs were easily cultivated on the template.
The kinetic reaction assessment revealed that the
Pd/MGF samples underwent an extended diffusion-
controlled method compared to Pd/C. Zheng et al96 stud-
ied the control of PtPd nanotube synthesis on graphene.
A solvothermal reduction strategy was used to evenly
prepare PtPd alloy NCs deposited with RGOs.
Agricultural foodstuffs or biomass may be used to
generate sustainable green energy sources, such as etha-
nol. According to this breakthrough, ethanol has a higher
mass-energy density (8.01 kWh kg 1) and lower toxicity
than methanol (6.07 kWh kg 1).97 The superior EOR per-
formance of Pt and Pd in the PtPd alloy is attributed to
their synergistic effects. Fonseca et al98 created a modi-
fied screen-printed electrode in a flow device to test
nanoparticle electroactivity for electrooxidation by alco-
hol. The modification offers new knowledge related to
the hydrodynamic current performance and the use of an
open device that is close to the actual value. Fathirad
et al99 studied carbon-supported (Vulcan XC-72) bimetal-
lic Pd-Mo nanoalloys. The efficiency of the nanocatalysts
in alkaline media has been assessed in terms of the
responses of methanol, ethanol, ethylene glycol, and glyc-
erol electrooxidation through cyclic voltammetry, linear
voltammeter sweeps, and chronoamperometric measure-
ments. Due to their distinct electronic structures, bime-
tallic Pd-Mo/VC catalysts have higher activity than
monometallic palladium. Zhang et al100 studied the
synthesis and catalysis of methanol and ethanol electro-
oxidation palladium-graphene nanocomposites. Commer-
cially supported Pd nanoparticles, Pd NP/PVP-graphene
(Vulcan XC-72) have excellent electrocatalytic behavior
and stability concerning alcohol electrooxidation.
In previous years, many attempts were made to build
direct methanol fuel cells (DMFCs) due to their inverter
performance, low operating temperatures, and easy han-
dling as an intermittent power supply.101 Models for the-
oretical simulation were also created to understand the
transport phenomena, cell features, and suitable geome-
tries for optimum fuel cell efficiency.79,80 The high
manufacturing costs have been an obstacle for the
9
effective marketing of DMFCs along with the slow kinet-
ics of the methanol oxidation reaction (MOR). The selec-
tion of an appropriate anode catalyst is anticipated to
considerably solve these problems.102 Platinum is being
used in DMFC systems as an anode catalyst because of its
outstanding catalytic characteristics; however, carbon
monoxide (CO) and other carbonaceous species produced
during methanol electrooxidation are readily poisoned,
and its action deteriorates.103 The cost of the platinum
catalyst alone is responsible for 38% to 56% of the total
cost of the production of fuel cells.104 These disadvan-
tages restrict the use of platinum as an electrocatalyst
with optimum results in DMFCs. Consequently, fast, per-
sistent, and minimal-cost MOR electrocatalyst design is
one of the main fuel cell engineering applications.84
Zhang et al105 described the increased methanol
electrooxidation activity of electrochemically exfoliated
graphene-Pt by the manipulation of polyaniline. The
complementary activity of platinum and N species can
promote the dispersion of platinum nanocrystals and the
transport of electrons via platinum hybrid structures,
thus enhancing the electrocatalytic activities of platinum
catalysts for methanol oxidation. Arukula et al106 opti-
mized the synthesis of reduced GO (rGO)/polyaniline
(PANI)/Pt-Pd composites for use as a prospective anode
catalyst in DMFCs to increase the methanol oxidation
ability. Improved catalytic activity was observed, and the
active carbon/conductive polymer facilitated the effi-
ciency and durability of DMFCs.
Chao et al107 investigated the innovative graphene-
assisted platinum/nickel phosphide electrocatalyst with
enhanced methanol oxidation behavior and stability.
They observed increased activity and stability, which
were attributed to the complex electron transfer among
platinum, Ni2P, and graphene, resulting in increasing the
kinetics of the adsorption of CO produced in
the electrooxidation reaction. Furthermore, Kwok et al108
investigated graphene/CNT composite aerogels with
Ru@Pt nanoparticles as porous electrodes for direct
microfluidic fuel cells, where the CNTs enhanced the
composite conductivity by linking the GO nanosheets
together. Toh et al109 reported an easy preparation
method for graphene-immobilized electrodes with ultra-
low platinum loads. ANOVA and a signal-to-noise assess-
ment (S/N) confirmed the ideal electrode position
requirements for GN-Pt NP electrodes, as predicted to
obtain the optimum conditions for electrode production.
Baronia et al110 developed a PtCo/rGO nano-anode
catalyst with the increased power density and decreased
crossover of methanol. An rGO nanocomposite with Pt-
Co NPs (with an optimized Pt:Co ratio) via bimetallic
synthesis was used as a catalyst for anodes. Eshghi
et al111 studied platinum (Pt) -irons supported by
10
decreased amounts of GO. Pt-Fe/rGo displays elevated
electrocatalytic activity, excellent CO poisoning catalyst
tolerance, and methanol electrooxidation catalyst dura-
bility in comparison to Pt/rGo and commercial Pt/C cata-
lysts. Further research performed by Chang et al112
showed strong electrocatalytic performance of graphene-
supported PtAu nanoalloys. PtAuNA/G can catalyze
methanol oxidation and enhance the electrocatalytic
activity based on the results of cyclic voltammetry and
chronoamperometry. Yuan et al113 studied a carbohy-
drate Pt-MnO2/catalyst for GO reduction. In situ carboni-
zation was further performed using L-ascorbic acid as a
carbon source to boost the effectiveness of the catalyst,
where GO (PMGL) reduced by Pt-MnO2 was prepared
due to its large electrochemical region and outstanding
catalytic activity for methanol oxidation. Ong et al114
studied the diffusion surface of an anode for graphene
applications. Pattanayak et al115 discovered composite
polymers, copper/polypyrrole GO (Cu2O/PPy-GO), by
manufacturing cost-effective nonnoble metal supports.
The study analyzed the main results from graphene-
assisted anode catalysts for DMFCs to provide more in-
depth information. Bao et al116 constructed Pt-Ru/verti-
cally oriented graphene (VG) via electrodeposition to
achieve higher MOR activity and improved anode stabil-
ity compared to PtRu/Vulcan.
In 2014, Yuan et al117 studied a graphene-CNT com-
posite layer for anodic diffusion. The crack-free anodic
MPL was obtained with graphene-CNTs, and the
improved cell performance showed a reduced methanol
crossover. Lu et al118 developed PtRu/nitrogen/boron-
doped graphene via single-stage heat treatment and
found higher MOR behavior in comparison to PtRu/
graphene in a DMFC catalyst test. Zhao et al119 prepared
PtRu/3D nitrogen-doped graphene aerogels (GAs) using
EG reduction assisted by microwaves. The increased
MOR resulted in better stability and good anodic perfor-
mance due to Pt-Ru/graphene, PtRu/C, and Pt/C in
DMFC experiments. Bin et al120 formulated the output of
PtRu/rGO/PVP using NaBH4 reduction. Related to Pt-
Ru/graphene and Pt-Ru/C, this formulation shows higher
MOR activity and better stability. Zhao et al121 performed
catalyst analysis of PtRu/rGO using microwave synthesis
to support the EG reduction process. A higher ECSA and
higher MOR activity were observed compared with those
of PtRu/C. It is important for the use of graphene as an
anode catalyst in DMFCs to react well in terms of the
ECSA, a higher MOR activity, and good impedance prop-
erties, all of which contribute to the performance. Kung
et al122 studied the synthesis of a PtRu/3D graphene foam
(3D GF) catalyst using NaBH4 reduction, which achieved
a higher MOR and better CO tolerance compared to Pt-
Ru/Vulcan and PtRu/graphene. Achieving more progress
OSMAN ET AL.
in this research, Xu et al123 used polyol Pt-Ru/nitrogen-
doped graphene as a catalyst to obtain a higher ECSA,
improved MOR, and better impedance compared to
PtRu/graphene. Wang et al124 investigated the small-size
characteristics and contact with graphene of Pt-WC
nanostructures. DFT calculations demonstrated the pres-
ence of a powerful covalent WC-graphene interaction. Pt-
WC/graphene has elevated catalytic effectiveness toward
the oxidation of methanol.
Jha et al125 studied multiwalled carbon composite
nanotube-assisted electrocatalysts. Measurements of the
fuel cell were carried out using Pt/Ru nanoparticles
deposited on a combination of functional graphene (f-G)
and multiwalled CNTs (f-MWCNTs) at different ratios,
such as the methanol oxidation electrocatalyst anode and
the cathode catalyst Pt/f-MWCNT, for the DMFC oxygen
reduction response. Qiu et al126 evaluated the manage-
able formation of graphene platinum (Pt) nanoparticles
as a direct fuel cell for methanol electrocatalysts. Lee
et al127 tested hydrothermal PtRu/graphene and found
that it had a higher MOR activity and higher CO toler-
ance compared to PtRu/MWCNTs. Zhao and his team128
reported PtRu/functionalized graphene sheets using a
carbon dioxide supercritical process. The study concludes
that the MOR operation is better than that of PtRu/Vul-
can in terms of stability. Li et al129 studied Pt/graphene
nanocomposite synthesis and electrochemical efficiency
by reducing graphite oxide and H2PtCl6 in one pot for
methanol oxidation. Certain precious metal nanoparticles
and bimetallic systems were also grown on GO and
showed superior catalyst activity.130 The high Pt catalyst
ORR activity, with rGO support, was analyzed.131
Farzaneh et al132 analyzed the high quality of nano-
structured nitrogen-doped rGO compared with commer-
cial Pt/C as a passive DMFC cathode electrocatalyst
layer. As a result, a higher ECSA and better catalytic
activity toward the ORR were achieved while, Xin
et al,133 studied the nitrogen-doped graphene using
hydrothermal and thermal solid-state techniques. This is
the first report on the use of graphene and its derivatives
for reducing oxygen as metal-free catalysts. Qu et al134
published the first study on the benefit of graphene and
its oxygen reduction derivatives as metal-free catalysts,
graphene (N-graphene) doped with nitrogen via chemical
vapor deposition of ammonia methane. As a metal-free
electrode, the resulting N-graphene was demonstrated to
have significantly increased electrocatalytic efficiency,
long-term functional reliability, and crossover resistance
effects when platinum (Pt) reduced oxygen in AFCs
through a four-electron route. Yoo et al86 explored Pt
nanoparticles supported by graphene nanosheets (GNSs).
The Pt/GNS density was better than the commercial Pt/C
density. This outcome shows the high tolerance of
OSMAN ET AL.
Pt/GNS for CO poisoning. As indicated, graphene modifi-
cations, where the performance output gives the maxi-
mum power density and fuel capacity, results in
improving the ECSA to provide good potential for cata-
lytic activity toward the ORR response.
3.4 | Microbial fuel cells
Modern electrical and chemical devices that directly con-
vert microbial metabolic energy to electrical energy are
defined as microbial fuel cells (MFCs). Electrochemical
technology has excellent potential in wide-ranging appli-
cations, such as wastewater treatment, implantable medi-
cal equipment,135 and biosensors.113-115
Huang et al136 formulated 3D-G electrodes that were
inflexible with a crumpled surface, macroporous compo-
sition (with dozens of micron-sized pores), high specific
surface area (188.32 m2/g), excellent conductivity with
affordable price, and they enhanced the effectiveness of
extracellular electron transfer and increased the bacterial
load capacity. The further 3D analysis was performed by
Zhao et al,137 who identified a 3D platinum (Pt) -coated
GA and nanoparticles (Pt NPs) as effective cantilevered
MFCs. For the first time in a driving timer, MFCs fitted
with the GA/Pt anode were implemented effectively.
Wang et al138 studied the conductive polymer surface of
graphene (G) and poly(3,4-ethylenedioxythiophene)
(PEDOT), and the G/PEDOT hybrid anode for the
Escherichia coli MFC was produced by galvanostatic
electropolymerization. Hou et al139 fabricated reduced
GO (ERGNO) by an electrochemical process and then
covered the carbon cloth (CC) surface with nanofibers of
polyaniline (PANI). The extremely enhanced and
strongly conductive support material also offers a wide
surface for PANI. Zhang et al140 investigated a graphene-
modified anode to improve the MFC efficiency. The con-
tinuous discharge experiments of MFCs were performed
to assess the discharge efficiency of distinct anodes. The
distinct anodes were tested at 0.01 mA/cm2 in a 5 mM
glucose solution, and the anode potential vs the moment
release was studied.
Liu et al141 prepared a graphene/CC anode. The bio-
compatibility and conductivity of graphene encourage
bacterial development as activation centers for more
direct electron transfer while generating more mediating
molecules, resulting in a greater electron transfer rate.
Kumar et al142 investigated nanotubular nanocomposite
α-MnO2/GO synthesized using a simple cost-effective
and time-efficient hydrothermal method. The MFC with
the cathode altered by MnO2 nanotube/GO
nanocomposites showed a rapid start-up and good dura-
bility relative to the other electrodes. A simple technique
11
used at a low temperature for synthesizing NG with a
denotation process in gram-scale amounts was reported
by Feng et al.143 It has been proven that synthetic NG
acts as an electrode that is free of metals with exceptional
electrocatalytic behavior and a long-term oxygen deple-
tion balance through the application of Bi and four-
electron loops. Wen et al144 studied a new low-cost, scal-
able, synthetic PNCN preparation technique for the car-
bonization of graphite oxide-polyaniline (GO-PANI) with
KOH trigger therapy. PNCN displayed outstanding cata-
lytic activity for the ORR due to its elevated nitrogen con-
centration and increased surface area.
Liu et al145 studied nitrogen-doped graphene (NG) as
a cathode catalyst that elevated the activity at a buffered
pH of 7.0 compared with the Pt/C counterpart in electro-
chemical measurements and MFCs. Xiao et al146 found
two graphic structures with very distinct morphologies
that were explored: periodic graphene for the modifica-
tion of anode and cathode electrodes in MFCs (similar to
flat sheets of paper) and crumpled particles (similar
to crumpled paper balls). Li et al147 studied graphene (Fe-
N-G) functionalized with iron and nitrogen as a source
for nonprecious metals. These were developed using a
simple salt, graphic carbon nitride (g-C3N4), and a
graphene hybrid via a heat treatment method.
4 | CURRENT PR OBLEMS AND
FUTURE DEVELOPMENT
The pure graphene honeycomb design is ideal. The dis-
tinct range of electrochemical characteristics has been
attributed to the 2D geometry of the carbon atoms in
graphene. Its wide electrochemically active area, rapid
carrier mobility, and high graphene conductivity tune the
properties of Pt to create new graphene-based structures
for membrane applications. Some of the current prob-
lems are highlighted:
1. Dramatically reduced crossover and improved longev-
ity of fuel cells
2. The fuel cell price is high, which prevents their
wide use.
3. Methanol crossover: 60% efficiency loss, heat, and
water management minimized,148 reduced lifetime,
and negative performance
Furthermore, for the fuel cell compartments, which
include catalysts and membranes, it is important to select
the best-performing materials. Graphene studies in terms
of membrane and catalyst performance based on the
fabrication-related properties have shown the reactivity
and electrochemical strength of graphene. Half-cell
12
experiments were used to evaluated graphene-based out-
put electrocatalysts. As a result, the activity and durabil-
ity cannot be reliably defined based on actual use.
Standard MEA is used to assess efficiency as a solution.
Furthermore, rather than being evaluated under moder-
ate simulation conditions, the conductivity and perme-
ability factors of graphene-based membranes, as well as
the corrosion resistance of graphene adjusted bipolar
plates, should be evaluated in a fuel cell environment.
Several variables might slow graphene adoption. One
of these is the restricted amount of manufacturing.
Although there are many ways to make different types of
graphene, the quantity of manufacturing remains small
for each of these techniques. One of the greatest prob-
lems in the graphene industry will be reaching volume
manufacturing over the next 2 to 5 years. Material consis-
tency and manufacturing costs will need to be the focus.
The cost has dropped significantly since graphene's first
commercial appearance. The cost of sheet graphene has
fallen to one-fifth of the original cost over the previous
2 years, while the cost of powdered graphene (including
fluid) fell to one-quarter of its original cost. However, the
original price of the material is high, along with
the supporting modifications that exploit various
graphene characteristics, leading to high-margin requests
being initially accepted.149
Graphene has a high proton conductivity and low fuel
permeation, and it can be used as an alternative electro-
lyte material in an activity fuel cell. However, carbon
electro corrosion becomes one of the performance reduc-
tions issues. In this regard, numerous studies have dem-
onstrated that carbon-based especially graphene can
reduce corrosion issues, especially on metallic bipolar
FIGURE 7 Future development of graphene [Colour figure can be viewed at wileyonlinelibrary.com]
OSMAN ET AL.
plates in fuel cell application.150,151 This is related to
graphene which has a very stable factor of outstanding
physical and chemical properties, such as its high specific
surface area (2630 m2 g 1) outstanding electrical conduc-
tivity, and extraordinary biocompatibility on graphene all
this can be used to solve corrosion issues with a simple
solution.
The task is to maintain the quality of graphene when
it is produced in large amounts. If the graphene mono-
layer carbon network has any flaws, the electrical con-
ductivity will be dramatically affected, along with the
transparency, thermal conductivity, permeability, and all
the other excellent graphene-specific characteristics.152
The future growth of graphene in the field of composite
products is shown in Figure 7. In 5 years, graphene com-
posites in sectors such as automotive and oil and gas are
anticipated to be used for very small parts. Besides, we
could even see graphene being used in aircraft
manufacturing in 10 years. Graphene marketing relies
strongly on the capacity to achieve high quality during
the upscaling stage. A roadmap to predict and implement
graphene-based materials based on the study results is
the main factor in the marketing of graphene products.
A logical interpretation usually requires knowledge of
the atomic and electronic structures of a given catalyst.153
However, the electrochemical oxygen elimination process
is rather difficult to understand. Furthermore, several
basic phases, apart from multielectron communication
processes, employ different intermediate species.154 For
the ORR process, there is still no underlying assumption
due to insufficient effective research verification methods
in terms of the intermediate surface developed during the
reaction. These aspects might be precisely described by
OSMAN ET AL.
laboratory analysis strategies155 and numerical catalytic
data that were introduced to some degree in previous
decades.
5 | C ON C L U S I ON
This report discusses the advanced research and innova-
tions of low-temperature fuel cell systems by resolving
problems related to costly components, durability issues,
hydration, and an efficiency loss of approximately 60%
during operation, with special emphasis on the contribu-
tion of scientists by introducing graphene as a material
solution. Researchers have practiced several adaptation
strategies. Thermal and optical properties. This empha-
sizes the membrane and catalyst uses of graphene in low-
temperature fuel cell devices. Based on these low costs,
high-grade materials are directly removed from the liquid
phase. Future studies in this interesting area would trans-
form the way future energy technologies are built, con-
tributing to a better fuel economy and a decrease in
harmful pollution. These new materials have shown
great potential for the viable marketing of graphene.
Graphene has a bright future, and the speed of its devel-
opment should not be limited to new technologies.
ACK NO WLE DGE MEN TS
The authors gratefully acknowledge the financial support
for this work by Universiti Kebangsaan Malaysia under
Grant No: DIP-2019-021.
ORCID
S. K. Kamarudin https://orcid.org/0000-0003-0383-5049
Sahriah Basri https://orcid.org/0000-0002-2453-562X
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How to cite this article: Osman SH,
Kamarudin SK, Karim NA, Basri S. Application of
graphene in low-temperature fuel cell technology:
An overview. Int J Energy Res. 2021;1-19. https://
doi.org/10.1002/er.6969