Journal of Power Sources 488 (2021) 229434

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Carbon corrosion mechanism and mitigation strategies in a proton

exchange membrane fuel cell (PEMFC): A review
Junjie Zhao a, Zhengkai Tu a, *, Siew Hwa Chan b
a
School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China
b
Energy Research Institute, Nanyang Technological University, 50 Nanyang Avenue, 637553, Singapore

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• An overview of carbon corrosion mech­

anism under three conditions was
addressed.
• Corresponding mitigation strategies for
carbon corrosion were presented.
• Future goals of mitigation strategies
about carbon corrosion were suggested.

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

Keywords: This paper presents an overview of the causes and consequences of the carbon corrosion mechanism and sum­
PEMFC marizes the corresponding mitigation strategies for various operating conditions. The high potential at the
Carbon corrosion cathode caused by the anode hydrogen-oxygen interface leads to the occurrence of carbon corrosion reactions
Mitigation
during the startup and shutdown process. System strategies, including gas purge and auxiliary load, have been
Startup and shutdown
developed to alleviate the performance decay during startup and shutdown processes. Improper water man­
Water flooding
Long-term ageing agement will cause local flooding to accelerate the carbon corrosion. Many novel flow fields have been proposed
to solve water management problems, such as an optimized 3D flow field, baffle flow field and porous media flow
field. The carbon corrosion under normal operation is not as serious as that under start-up and flooding, but it is
serious enough to affect the later performance of the PEMFC after long-term operation. Varieties of new supports,
such as mesoporous carbon, graphitized carbon, carbon nanotubes (CNTs), carbon nanofibers (CNF), and metal
oxides, have been developed to improve the durability of the catalyst support. This review aims to provide a clear
understanding of the carbon corrosion mechanisms, thereby helping researchers to prolong the lifetime of
PEMFCs.

1. Introduction chemical energy of a fuel and oxidant directly into electrical energy
under the action of a catalyst. It is not limited by the Carnot cycle and
The proton exchange membrane fuel cell (PEMFC) converts the has the advantages of a high energy conversion efficiency, high

* Corresponding author.
E-mail address: tzklq@hust.edu.cn (Z. Tu).

https://doi.org/10.1016/j.jpowsour.2020.229434
Received 1 June 2020; Received in revised form 7 November 2020; Accepted 28 December 2020
Available online 12 January 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
J. Zhao et al.
operational reliability, environmental protection and low noise. It is
considered as the most promising green energy conversion device to
replace traditional fossil energy [1]. As a new generation of automotive
power sources, PEMFCs have been regarded as strategic products by
major industrial countries [2,3]. Governments have formulated a series
of policies and regulations to actively encourage and promote the
industrialization and commercialization process of fuel cell vehicles
(FCVs). Through continuous global research and development, FCVs
have made significant progress in the international market. Nearly one
thousand FCVs have been demonstrated around the world, such as
Honda, Toyota, Hyundai, and General Motors automobiles [4]. How­
ever, if automotive fuel cell systems want to be competitive in the
market, they must have durability similar to automotive internal com­
bustion engines (ICEs). Durability, also known as lifetime, represents the
ability of PEMFCs to resist the long-term destructive effects of both
themselves and the natural environment. The United States Department
of Energy (DOE) has identified a durability target of 5000 h for 2020,
which means driving 150,000 miles with less than 10% loss of perfor­
mance, and PEMFC systems must be demonstrated with a long-term
durability (≥5000 h) under road ambient conditions [5]. As shown in
Table 1, The Technology Road map for Energy Saving and New Energy
Vehicles presented the development goals of Chinese automotive
PEMFC stack technologies [6]. At present, the lifetime of FCV in the
world has met the commercial requirements, but the system cost is high
due to the high Pt loading required on the cathode. Therefore, on the
premise of meeting cost requirements, the goal of reaching 5000 h of
automotive PEMFC lifetime is still challenging. However, it is still far
from the ultimate goal of 8000 h proposed by the DOE. In conclusion,
the research of PEMFC performance and durability is still the top
priority.
The catalyst and its membrane electrode assembly are the heart of
PEMFC. The catalytic layer is composed of catalyst, catalyst support and
Nafion polymer, and there are three-phase channels, including the
reactant and product transfer channels, the proton conduction channels
and the electron conduction channels. The PEMFC catalyst needs to have
a good electrical conductivity, electrochemical stability, and catalytic
performance [7]. At present, Pt nanoparticles, supported on a high
specific surface area carbon are widely used as PEMFC catalysts. How­
ever, carbon is not thermodynamically stable under the operating con­
ditions in PEMFCs, and the electrochemical oxidation of carbon is
accelerated at elevated temperature and potential. The performance
degradation is mainly caused by Pt detaching or agglomerating due to
the weakened interaction between Pt and the carbon support, which
leads to the loss of Pt surface area [8]. Studying the corrosion behavior
of the catalyst carbon support can deepen the understanding of the
corrosion mechanism of carbon support and improve the stability of the
catalyst, which can greatly increase the lifetime of PEMFC and promote
the commercialization of PEMFCs.
Due to the operating temperature of a PEMFC being low, the corro­
sion rate of carbon is generally low. However, during transportation
applications, there are certain operating conditions under which carbon
corrosion can be accelerated, such as high-water content, low pH (<1),
high temperature (50–90 ◦ C), high oxidation potential (0.6–1.2 V), and
so on [9]. Through a plethora of demonstration operations of FCVs, it
was found that there are three main conditions that cause carbon
Table 1
Development goals of Chinese automotive PEMFC stack technologies [6].
Characteristic Passenger vehicles Commercial vehicles
Time 2020 2025 2030 2020 2025 2030
Rated power (kW) 70 70 70 70 120 170
Lifetime (h) 5000 6000 8000 10,000 20,000 30,000
Volume specific power 3.0 3.5 4.0 2.0 2.5 3.0
(kW⋅L− 1)
Mass specific power 2.0 2.5 3.0 – – – r = kθvac θC# OH ref exp
(kW⋅kg− 1)
2
Journal of Power Sources 488 (2021) 229434
corrosion of PEMFC catalysts: (1) the high potential caused by frequent
startup and shutdown cycles, (2) reactant starvation caused by the water
flooding process, and (3) a cumulative-time effect of long-term normal
operation. To systematically understand the carbon corrosion mecha­
nism of PEMFC catalysts and mitigation strategies, this review has
classified and summarized the carbon corrosion mechanism of catalysts
under the three operating conditions. Through an abundance of litera­
ture investigation and analysis, we sorted out the latest research prog­
ress in new materials, new technologies, and system mitigation
strategies and pointed out that the lifetime goal of PEMFC commer­
cialization can be gradually achieved from two levels: on the one hand,
optimization the control strategy of the system to shorten the duration of
the attenuation condition, but this requires the addition of necessary
sensors and corresponding control units, which increases the complexity
and cost of the system; On the other hand, it is necessary to continuously
strengthen the development of new materials. When the performance
and durability of new materials can meet the requirements of PEMFC
automotive operating conditions, the system can be further simplified.
The lifetime target of automotive PEMFCs can be achieved on the basis
of new materials.
2. Carbon corrosion reaction and theoretical analysis
In recent years, with the development of PEMFC technology, the load
of Pt has dropped to approximately 0.2 mg cm− 2. The main reason for
this is the use of supported Pt catalysts. The extremely small Pt particles
are uniformly dispersed on the carbon support, thereby greatly
increasing the specific surface area of the catalyst. However, carbon is
thermodynamically unstable, the electrochemical oxidation of carbon
can be accelerated by increasing the potential. When the reversible
voltage is greater than 0.207 V, the carbon oxidation reaction shown in
equation (1) easily occurs.
C + 2H2 O→CO2 + 4H + + 4e− (0.207VRHE ，25◦ C) (1)
The relationship between the Gibbs free energy of equation (1) and
the reversible voltage is as follows:
Δgf = − nFE (2)
In equation (2), n is the number of moles of electrons transferred
during the reaction, F is a Faraday constant, and E is a reversible voltage.
At 25 ◦ C, E = 0.207 V can be calculated. That is, when the electrode
potential is higher than 0.207 V (the thermodynamic reversible poten­
tial of COR), the carbon corrosion reaction will theoretically occur [10].
When PEMFC is at a higher voltage, the carbon support will be
further oxidized to form CO, and the reaction product CO might poison
the catalyst.
C + H2 O→CO + 2H + + 2e− (0.518VRHE ，25◦ C) (3)
Makharia et al. [11] studied the effects of temperature, voltage and
time on CO2 corrosion current, and the following equation is applied to
describe the carbon corrosion kinetics:
iCO2 ∝10E/b e− Ea /(RT) − m
t (4)
where b represents the Tafel slope, Ea represents the activation energy, m
represents the time decay exponent. The above equation was validated
through experiments with measuring the mass loss of carbon on the
membrane electrode at 1.0 V, 1.1 V, and 1.2 V. The results showed that
when the potential was above 1.0 V, the corrosion rate of carbon may
increase by about one order of magnitude for every 0.1 V increasement
of potential.
Dhanushkodi et al. [12] proposed a simplified model to express the
rate of CO2 production by carbon corrosion:
( ) [
]
p0 αF
(V − U) (5)
p0 RT
J. Zhao et al. Journal of Power Sources 488 (2021) 229434

[
Ea,i
] apparent with no carbon support, indicating a drastic corrosion of
k = k0 exp − (6) carbon.
RT
GM researchers estimate that PEMFC in automotive applications will
where r is the rate of generation of CO2. θvac is the proportion of vacant experience approximately 30,000 start/stop cycles. Assuming that each
or free surface sites. θC# OH is the proportion of sites covered by C#OH. p0 start or stop time is 10 s, this requires the durability of the catalyst
support at a voltage of 1.2 V for approximately 100 h, and the output
and pref
0 represent the partial pressure and reference pressure (270 kPa)
voltage drop is less than 30 mV at 1.5 A cm− 2 [4]. Therefore, the impact
of water vapor, respectively. V and U respectively represent the elec­
of the startup and shutdown processes on the lifetime of PEMFC is
trode potential on the standard hydrogen scale and equilibrium poten­
important. Understanding the degradation mechanism under startup
tial. α is the transfer coefficient. In equation (6), k and k0 represent rate
and shutdown conditions can effectively improve the durability of
constant and preexponential rate constant, respectively. Ea,i is the acti­
PEMFC.
vation energy. Subsequently, they verified the accuracy of the model
through the carbon loss, and found an excellent agreement between the
experimental and calculated results. 3.1. Degradation mechanism
Stevens et al. [13] studied the time required to reach the same carbon
loss ratio under different Pt loadings, and found that the increase of Pt In 2005, Reiser [19] proposed that the hydrogen-air interface formed
loading will accelerate the reaction rate of carbon corrosion. The inside PEMFC would generate a high potential at the cathode, resulting
interface area between Pt and carbon increases with the increasing of Pt in the corrosion of carbon support. As shown in Fig. 1, it was found that
loading, which will increase the proportion of carbon in the reaction when a hydrogen/air interface was formed at the anode side, the cath­
zone and accelerate the rate of carbon corrosion reaction. Similarly, the ode potential was about twice that of the anode, and carbon corrosion in
carbon corrosion will accelerate the detaching or agglomerating of Pt the catalytic layer occurred easily at such a high potential [20]. At
particles. On the one hand, the generated CO2 or CO during carbon present, the reverse current decay mechanism is widely regarded as the
corrosion decreases the amount of carbon for Pt loading. On the other basis for the degradation of PEMFCs during the startup and shutdown
hand, oxygen functional groups generated on the carbon surface weaken processes. This mechanism explains the degradation mechanism of the
the interaction between the carbon support and the Pt particles, carbon support during the startup and shutdown processes. Before the
resulting in the shedding and failure of Pt nanoparticles [14]. start of PEMFC system, the anode flow channel is filled with air. When
the hydrogen enters the anode, there is a process of replacing air with
3. Carbon corrosion during startup and shutdown processes hydrogen, and a hydrogen-air interface forms in the anode flow field.
When the hydrogen and oxygen supply are disconnected, due to the
The startup and shutdown processes are two of the most important concentration gradient between the cathode and anode, residual oxygen
dynamic processes, which are unavoidable for PEMFCs in automotive in the cathode flow channel will diffuse through the proton exchange
applications. Compared with the steady-state process, PEMFCwill membrane to the anode, causing the formation of the hydrogen-air
experience different operating conditions during the startup and shut­ interface [21]. Simultaneously, external air enters the PEMFC through
down processes, such as temperature, gas humidity, and local gas anode channel, which is a very slow gas diffusion process. Therefore,
mixture. Park et al. [15] studied the corrosion of the carbon support compared to the startup process, the anode hydrogen-air interface exists
during the start-stop process under two standard accelerated test longer during the shutdown process. The formation of the hydrogen-air
schemes: the square wave cycle (E = 0.9–1.3 V vs. RHE, each E keeps 30 interface will result in extremely high electrode potentials in the cathode
s) and the triangle wave cycle (E = 1.0–1.5 V vs. RHE, the scan rate is catalytic layer. Such a high cathode interface potential difference will
0.5 V s− 1). It was found that the start-stop cycle first caused the surface lead to the oxygen evolution reaction and carbon corrosion reaction,
corrosion of the carbon support, and then the repeated start/stop cycles destroying the cathode electrode structure.
converted the crystalline carbon in the carbon support into amorphous Normal oxidation reduction reactions occur in the hydrogen-rich
carbon, which in turn led to the corrosion of the amorphous carbon. The region:
continuous corrosion process of the carbon support resulted in a sig­ Anode: 2H2→4H++4e− (Hydrogen Oxidation Reaction, HOR)
nificant reduction in the thickness of the cathode catalyst layer and se­
vere separation of the Pt particles from the carbon support, especially Cathode: O2+4H++4e− →2H2O (Oxygen Reduction Reaction, ORR)
under the square wave cycle. The results showed that the slower square
In the hydrogen-deficient region, the protons generated by the
wave cycle caused significant carbon corrosion on the surface and in­
anodic reactions on the cathode are consumed by the oxygen reduction
side, while the triangular wave cycle caused carbon corrosion to occur at
unstable surface defects.
Pei et al. [16] proposed an accelerated evaluation method for auto­
mobile PEMFC lifetime, which could calculate the performance degra­
dation rate of PEMFC under various working conditions, including
startup and shutdown cycles, idling cycles, load change cycles and
steady high power load cycles. The results showed that the load change
cycles and the startup and shutdown cycles were the main factors that
caused the decline in the performance of PEMFC, and one third of the
performance degradation was caused by startup and shutdown cycles.
Lin et al. [17] found that voltage reversal would occur at the outlet of H2
by analysing the current density distribution during a startup and
shutdown cycle. Cross-sectional SEM analysis showed that the thickness
of the cathode catalyst layer at the H2 outlet was severely degraded,
which also showed the above conclusion. Ishigami [18] used STEM
images to investigate the catalyst degradation at the cathode catalyst
layer after 500 cycles of the hydrogen/air replacement. The authors
found that the performance of PEMFC decreased as the number of gas
exchange cycles increased and holes near the inlet and outlet were Fig. 1. A schematic illustration of reactions in four distinct regions when an
air/fuel boundary is formed at the anode [20].

3
J. Zhao et al.
reaction at the anode. Hence, the phenomenon is referred to as the
“reverse-current” mechanism [19].
Anode: O2+4H++4e− →2H2O (Oxygen Reduction Reaction, ORR)
Cathode: C+2H2O→CO2+4H++ 4e− and 2H2O→O2+4H++4e− (Oxygen
Evolution Reaction, OER)
Kim [22] used an FT-IR spectrometer to identify and analyse the gas
products on the cathode side during the startup and shutdown processes.
It was found that when the potential was above 1.0 V, the amount of CO2
precipitation was proportional to the cathode potential, and above 1.2
V, CO and SO2 were generated, which had a very bad impact on the
performance of PEMFC. Schulenburg et al. [23] employed focused ion
beam/scanning electron microscopy (FIB/SEM) serial sectioning to
visualize porosity changes in the catalyst layers of PEMFCs after po­
tential cycling (24,000 cycles, 0.6 V-OCV) and start/stop cycling (1000
cycles). It was found that the carbon corrosion would cause changes in
the pore structure of the Pt/C catalyst layer. After start/stop cycling, the
proportion of macropores was significantly reduced, and pores with a
diameter <20 nm accounted for the vast majority. As shown in Fig. 2,
both degradation schemes resulted in the growth of Pt particles, and the
mean particle size increased from 2.3 nm in the pristine catalyst to 4.8
nm after potential cycling and 5.3 nm after start/stop cycling.
Since the high potential at the cathode during the startup and shut­
down process is much higher than the reversible potential of the carbon
corrosion reaction, the corrosion rate of the carbon support is much
higher than that under steady state conditions. Moreover, corrosion of
the carbon support weakens the bonding interaction between Pt parti­
cles and carbon support, causing Pt particles to peel off from the carbon
support, thus accelerating the growth of the Pt particles and dissolution
in the electrolyte [8]. After Pt particles are peeled off from the carbon
support, they will agglomerate together through the electrolyte, result­
ing in a higher electrolyte impedance [14]. Therefore, the corrosion of
the carbon support at high potential during the startup and shutdown
process is the main cause for the decay of the cathode catalytic layer of
PEMFC.
Fig. 2. TEM images of (a) the pristine cathode catalyst layer, (b) after potential cycling, and (c) after start/stop degradation. (d–f) Corresponding Pt particle size
distributions [23].
4
Journal of Power Sources 488 (2021) 229434
3.2. Mitigation strategies
Currently, many practical methods have been proposed to mitigate
the performance degradation caused by startup and shutdown cycles,
such as finding new carbon support materials, using no-carbon support
and applying system control strategies [24]. Although the first two
strategies are promising solutions to the startup and shutdown problem,
many alternative materials are still under development, which will be
introduced in detail in 5.2.1, 5.2.2 and 5.2.3. Thus, it may be more
practical to develop better control strategies for PEMFC systems. Many
automotive companies such as UTC, GM, Ford, Toyota, Nissan, and
Daimler Chrysler have proposed reasonable system strategies to deal
with the performance degradation of the PEMFC system during the
startup and shutdown processes, mainly including gas purging during
startup [25], an auxiliary load during shutdown [20], and so on [26].
The main purpose of these strategies is to avoid the generation of the
anode hydrogen-air interface and reduce the high potential of the
cathode.
3.2.1. Gas purge
Gas purge is an effective way to reduce the time that the hydrogen/
air interface exists. People have proposed many feasible gas purge
strategies, such as nitrogen purge [20], air purge [27], hydrogen purge
[24,28], and exhaust recycle [29].
Shen et al. [30] studied several startup and shutdown processes using
different strategies (Table 2), and the detailed schematic of PEMFC setup
is shown in Fig. 3. The researchers found that the duration of the
hydrogen/air interface was influenced by the flowrate of hydrogen and
air, and nitrogen purge during the shutdown process was not always
effective. It was found that purging with nitrogen during the startup
process and applying an auxiliary load during the shutdown process can
effectively avoid the formation of hydrogen/air interfaces.
Jia et al. [31] found that although a nitrogen purge eliminated the
hydrogen/air interface at the anode, reverse currents still occurred.
They proposed an air pre-filled starting strategy and a linear starting
strategy, which could effectively reduce or eliminate reverse current. As
shown in Table 3, Oyarce et al. [24] compared several of the most
common shutdown strategies, including air purge, H2 consumption, O2
consumption and H2 purge. They found that H2 purge of the cathode and
J. Zhao et al. Journal of Power Sources 488 (2021) 229434

Table 2 successful [33].

Details of the startup and shutdown processes in Shen’s experiment [30]. Yu et al. [34] investigated the effects of different dummy loads on the
Process System strategy Action current distribution during the shutdown process. It was found that
applying higher dummy load would eliminate the cathode high poten­
Startup Process Hydrogen was directly fed into the Valves 1, 2, and 3
1 anode filled with air. open, valves 4 and 5 tial more quickly. Yang et al. [35] used polarization curves, EIS, and
closed. segmented current density to analyse the effects of the auxiliary load
Process (2.a) Anode was first purged with Valves 5, 2, and 3 strategy. The results showed that the auxiliary load can effectively
2 nitrogen, open, valves 1 and 4 shorten the duration time of the hydrogen/air interface during the
closed;
(2.b) then, hydrogen was Valves 1, 2, and 3
shutdown process, thereby eliminating the generation of reverse cur­
introduced. open, valves 4 and 5 rent. A serious corrosion had happened at cathode outlet side in the
closed. unprotected group, and there was no obvious carbon corrosion in the
Shutdown Process Air diffused into the anode filled Valve 4 open, protected group. Yu et al. [36] used SEM and TEM to study the effect of
3 with hydrogen. valves 1, 2, 3, and 5
the gas shutdown sequence on the performance degradation when the
closed.
Process (4.a) Anode was first purged with Valves 5, 2, and 3 auxiliary load was introduced during the shutdown process, and the
4 nitrogen; open, valves 1 and 4 results showed that shutting down the air first significantly alleviated
closed; the loss of the electrochemical surface area. Lin et al. [37] studied the
(4.b) then air diffused in. Valve 4 open, shutdown process in a 5-cell stack with segment technology. The authors
valves 1, 2, 3, and 5
closed.
found that only applying the auxiliary load strategy may cause local gas
Process Dummy load was used to consume Valves 1, 2, 3, 4, starvation and the air purge can avoid this phenomenon. Therefore, they
5 the residual hydrogen, and then and 5 closed. designed a new strategy, which combined auxiliary load and air purge.
air diffused in. After adopting this strategy, the degradation of the stack after 1500
cycles was within the normal range, and the carbon corrosion in the inlet
was effectively reduced. Zhang et al. [38] found that using the tradi­
tional auxiliary load strategy during the shutdown process would lead to
local air shortage and uneven local current density. They proposed a
new two-phase auxiliary load shutdown strategy, which consisted of a
linearly decreasing main auxiliary load and a fixed small auxiliary load.
During the shutdown process, the main auxiliary load decreased linearly
with the decrease of oxygen concentration. When the voltage dropped
below 0.1 V, the small auxiliary load was connected to consume a small
amount of oxygen attached to the catalyst layer. Using this strategy
eliminated the lack of air and inhibited the recovery of the cell voltage.
After 900 start-stop cycles, the overall performance and ECSA of the
PEMFC hardly declined.

3.2.3. Other strategies

Fig. 3. Schematics of the fuel cell setup [30].
O2 consumption using a load were the most effective strategies. The H2
of the anode diffused to the cathode in the O2 consumption strategy and
H2 was directly introduced into the cathode in the H2 purge strategy,
which protected the cathode from a high electrode potential.
3.2.2. Auxiliary load
Gas purging can effectively prevent the formation of the anodic
hydrogen/air interface during the startup and shutdown processes.
However, the residual gas in the flow field and the residual reactants in
the gas diffusion layer (GDL) or the catalyst layer (CL) cannot be
completely eliminated [20,32]. Auxiliary loads, also called dummy
loads, are mainly used to consume residual O2 from the cathode or re­
sidual H2 from the anode, and have also been reported to be very
It was pointed out that the hydrogen-air interface is the main cause of
the local high voltage during the startup and shutdown processes.
Therefore, other strategies have been proposed to ease the generation of
the hydrogen/air interface. Eom et al. [39] investigated the effects of
anode Pt loading on the current distribution during the startup and
shutdown processes. It was found that reducing the anode Pt load from
0.4 mg cm− 2 to 0.1 mg cm− 2 reduced the reverse current, but had little
effect on the initial performance of PEMFC. They also proposed that the
increase of the residual oxygen partial pressure would accelerate per­
formance degradation under reverse current conditions. Therefore,
maintaining a low residual oxygen partial pressure was effective to
reduce the carbon corrosion during the startup and shutdown processes
[40]. Jia et al. [41] proposed a two-step startup strategy, which was
divided into two stages: first, the output voltage was reduced from OCV
to an intermediate value and further reduced to the operating voltage. It
was found that with the two-step startup strategy, local current densities

Table 3
Actions implemented in different shutdown strategies [24].
Strategy No purge Air purge H2 consumption O2 consumption H2 purge

Action 1. Fuel supply turned on
and run cell at OCV
2. Run cell at 0.5 A cm− 2
3. Shut off both fuel and air
supply (open exhausts)
4. Purge anode and cathode
with air
1. Fuel supply turned on and
run cell at OCV
2. Run cell at 0.5 A cm− 2
3. OCV
4. Shut off reformate supply
and purge anode with dry air
5. Purge anode and cathode
with air
1. Fuel supply turned on and run
cell at OCV
2. Run cell at 0.5 A cm− 2
3. Shut off reformate supply, start
pump and run the load program
4. Purge anode and cathode with
air
1. Fuel supply turned on 1. Fuel supply turned on
and run cell at OCV and run cell at OCV
2. Run cell at 0.5 A cm− 2 2. Run cell at 0.5 A cm− 2
3. OCV 3. OCV
4. Shut off air supply and 4. Purge cathode with
run the load program reformate
5. Turn load off and purge 5. Purge anode with dry air
anode with dry air 6. Purge anode and cathode
6. Purge anode and with humidified air
cathode with air

5
J. Zhao et al.
gradually changed to their steady state values and hydrogen starvation
was effectively alleviated.
Tokarz et al. [42] proposed a new shutdown strategy to alleviate the
high cathode potential during the shutdown process. The shutdown
strategy was divided into three steps: (I) turning off the hydrogen source
and supplying air to the anode, (II) stopping the supply of air to the
cathode, and (III) applying a large electrical load. The schematic dia­
gram is shown as Fig. 4. They noted that the combination of these three
steps could effectively reduce the degradation of the catalyst.
Yu et al. [43] used two single cells named the open-ended and closed
PEMFCs to investigate the effect of cathode exhaust conditions on the
degradation of the catalyst during startup and shutdown cycles. The
results showed that the ECSA loss rate of the open-ended PEMFC was
51.13%, which was about twice that of the closed PEMFC after frequent
startup and shutdown cycles. Therefore, closing the cathode outlet
would significantly reduce the degradation of the catalyst during
frequent startup and shutdown cycles.
In conclusion, the anode hydrogen-oxygen interface during the
startup and shutdown process causes the high potential at the cathode,
which leads to the occurrence of carbon corrosion reactions. The
methods to mitigate the performance degradation during the startup and
shutdown processes are mainly focused on the catalyst support materials
and system control strategies. Since many stable materials are still under
development, system strategies are relatively widely used in PEMFCs. At
present, most of the mitigation strategies are based on suppressing the
anode hydrogen-oxygen interface and reducing the cathode high po­
tential, such as gas purging, introduction of dummy load, reduction of
anode Pt load, step-by-step startup strategy and stopping oxygen supply
first when shutting down, etc. N2 purge during the startup process and
the application of a dummy load during the shutdown process have all
been proven to be effective. However, it is not convenient to carry ni­
trogen on actual vehicles, and purging with hydrogen will consume a lot
of fuel, it is necessary to develop an effective strategy without increasing
the complexity and cost of the system and test it in vehicular applica­
tions. The future works may focus on combining multiple strategies or
combining system strategies with novel corrosion-resistant carbon sup­
ports, which can achieve long lifetimes and meet the durability re­
quirements for PEMFCs.
Fig. 4. Schematic diagram of start/stop cycles involving measures I-III [42].
6
Journal of Power Sources 488 (2021) 229434
4. Carbon corrosion during water flooding
In PEMFC, the water generated by the electrochemical reaction is
transmitted to the gas flow channel through the diffusion layer under the
combined effect of evaporation, diffusion, and capillary force and is
discharged from PEMFC under the action of gas, thus ensuring the
normal operation of PEMFC [44]. “Water flooding” generally means that
excess water accumulates in the flow channel or porous electrode and
cannot be removed [45,46]. Most of the pore volume in the GDL has
been blocked, which prevents the reactants to reach the catalysts,
causing reactant starvation, as well as cell performance and lifetime
degradation [47]. The electrochemical reaction is carried out at the
water-gas-proton (electron) three-phase interface during the operation,
and the excess water will reduce the concentration of the reaction gas
and block the gas channel in the reaction area, thus affecting the per­
formance of PEMFC. PEMFC stacks need to face complex environments
and working conditions in automotive applications. Since the operating
temperature of PEMFC is less than 100 ◦ C, a part of the generated water
will exist in liquid form, which may block the porous gas transmission
channel in the MEA and reduce the performance of PEMFC. This situa­
tion can be well controlled under laboratory conditions, but it is much
more complicated in real vehicle operation condition. Especially when
operating at high current density, it is easy to cause water flooding of the
electrode, and the performance of the stack will drop sharply. At pre­
sent, in order to improve the specific power density of PEMFC and
simplify the humidification system, large FCV companies are greatly
increasing the operating current density of PEMFCs. At present, the
rated operating current density of PEMFC generally reaches 1600 mA
cm− 2 or higher. On the one hand, the water generation rate at cathode is
accelerated at high current density, which requires higher cathode water
management. On the other hand, the high concentration of water at the
cathode outlet will reverse diffuse to the anode, which is more prone to
cause anode flooding and carbon corrosion in the catalytic layer [45].
Yang et al. [48] developed a two-dimensional model to study the
carbon corrosion phenomenon under anode flooding conditions. It was
found that under high voltage, the maximum carbon corrosion rate in
CCL was only determined by the oxygen crossover rate; while under low
voltage, it was also affected by the kinetics of oxygen reduction reaction.
Ijaodola et al. [49] discussed the different water transport mechanisms
in PEMFCs and the effects of flooding in different regions of PEMFC; the
authors noted the importance of water transport mechanisms in opti­
mizing operation of PEMFC. Kim et al. [50] investigated anode flooding
by condensing the humidified anode gas, and it was found that the
performance degradation was mainly due to the loss of carbon support
in the anode. Zhang et al. [51] used the accelerated stress test (AST)
method to study the effect of carbon corrosion on mass transfer loss in
PEMFCs. It was found that carbon corrosion reduced the hydrophobicity
of the pores in the catalytic layer, making it more prone to flooding.
At present, most researchers focus on the problem of cathode
flooding [52]. Three mechanisms contribute to the flooding of the
cathode. (1) The oxygen reduction reaction generates water, and as the
current density increases, more water is generated. (2) The
electro-osmotic drag causes protons to pull water molecules from the
anode to the cathode through the membrane. (3) Excessive humidity of
the reactant gas will also accelerate flooding [49,53]. Meanwhile, the
anode’s hydrogen diffusion rate is faster, and water molecules of the
anode will migrate to the cathode with protons. In recent years, the
introduction of ultra-thin proton exchange membranes and 3D flow
fields have made breakthroughs in solving cathode flooding and anode
dehydration problems. The ultra-thin proton membrane has obvious
effects in improving proton conductivity and reducing resistance, but it
increases the flux of counter-diffusion water from the cathode side to the
anode side. At the same time, abundant liquid water will be accumulated
at the cathode exit, and high molar concentration differences will cause
water to diffuse back to the anode, resulting in anode water flooding
[48].
J. Zhao et al.
4.1. Degradation mechanism
When the anode is flooded, the hydrogen cannot enter the catalytic
layer, Hydrogen is no longer enough to be oxidized to maintain the
current, and the anode potential will rise enough to oxidize the water in
the anode. Simultaneously, at such a high anode potential, a small de­
gree of carbon corrosion occurs with oxygen evolution reaction [54].
Anode: C+2H2O→CO2+4H++4e− and 2H2O→O2+4H++4e− (Oxygen
Evolution Reaction, OER);
Cathode: O2+4H++4e− →2H2O (Oxygen Reduction Reaction, ORR).
The oxygen generated by the electrolysis of water in the flooded area
and the oxygen permeated from the cathode form a hydrogen-oxygen
interface with the hydrogen in the unflooded area. The electrode will
occur the carbon corrosion reaction similar to the startup and shutdown
process, forming a reverse current and causing irreversible damage to
PEMFC [50], as shown in Fig. 5.
Anode: O2+4H++4e− →2H2O (Oxygen Reduction Reaction, ORR);
Cathode: C+2H2O→CO2+4H++4e− and 2H2O→O2+4H++4e− (Oxygen
Evolution Reaction, OER).
When the cathode is flooded, protons from the anode will be oxidized
at the cathode to generate hydrogen [54]. The generated hydrogen
forms a hydrogen-oxygen interface with the oxygen in the unflooded
area, causing local hot spots in PEMFC, which may cause the detachment
of the platinum in the cathode [47]. The low cathode potential does not
cause some significant corrosion of cathode carbon support. However,
the use of ultra-thin proton exchange membranes increases the flux of
water from the cathode side to the anode side. The high molar con­
centration difference will cause water to diffuse back to the anode,
causing anode flooding and corrosion of the carbon support.
Anode: H2→2H++2e− (Hydrogen Oxidation Reaction, HOR);
Cathode: 2H++2e− →H2 (Hydrogen Evolution Reaction, HER).
Therefore, the corrosion rate of the carbon support under water
flooding conditions is substantially higher than that under steady state
conditions. Meanwhile, the electrochemical corrosion of the carbon
changes the chemical properties of the carbon surface, resulting in a
decrease in the hydrophobicity of the CL and GDL; this leads to a
decrease in their gas permeability and affects the water transport
mechanism, which will in turn accelerates water flooding [12].
4.2. Mitigation strategies
The accumulation of liquid water is the major cause of the gas mass
transport limitation in PEMFC. If the removal rate of water is lower than
the generation rate, excessive water will accumulate in the flow field,
thus, blocking the pores in the GDL and CL and hindering the transport
of gas [45]. The ultra-thin proton exchange membrane has low proton
Fig. 5. Carbon corrosion mechanism during water flooding.
7
Journal of Power Sources 488 (2021) 229434
conductivity resistance, which helps the liquid water generated at the
cathode diffuse back to the anode, thereby mitigating the cathode
flooding. If the counter-flow mode is adopted, hydrogen gas at anode
inlet can be wetted by the water diffused from the cathode, which can
not only prevent the anode from flooding, but also reduce the anode
humidification requirement. Meanwhile, Water flooding can also be
alleviated by changing operating conditions, such as reducing pressure,
increasing temperature, counter-flow operation, sub-saturated gas
streams, etc [52]. Compared with changing operating conditions, some
strategies can fundamentally solve the flooding problem from two as­
pects: inhibiting the accumulation of water in the flow channel and
improving the hydrophobicity of GDL and CL. Two classes of strategies
to mitigate flooding have been developed. The first is developing a novel
flow field, which can improve the uniformity and convection of gas
distribution to increase the water removal rate [55]. The second class is
treating GDL and CL with a hydrophobic material such as PTFE or FEP to
increase their hydrophobicity.
4.2.1. Optimize operating conditions
The operating conditions strongly affect the accumulation and dis­
tribution of water in the PEMFC, including gas flow rate, operating
temperature, inlet pressure, reactant humidity and so on. During the
operation of the PEMFC, improper setting of operating conditions will
lead to unbalanced water management. Liquid water will accumulate
inside the stack that cannot be discharged or the proton exchange
membrane will contain too little water that will affect the proton con­
ductivity. PEMFCs will enter the poor operating state of flooding and
membrane drying, which will cause the lifetime of the PEMFC to
decline.
Li et al. [56] calculated the cathode pressure drop of single-phase
flow and stable two-phase flow, and proposed a water management
strategy based on pressure drop. During the operation of the PEMFC,
when the actual pressure drop exceeded the calculated value, the flow
rate was increased to remove the liquid water and then returned to
normal. The authors pointed out that this water management strategy
could eliminate frequent voltage fluctuations caused by flooding and
extended the lifetime of PEMFCs. Li et al. [57] verified and compared
three methods to avoid flooding: increasing intake air pressure,
increasing temperature of PEMFC, and reducing intake air humidifica­
tion. When the PEMFC was flooded, increasing the inlet pressure by 25
kPa increased the voltage by 25 mV, and increasing the temperature by
2 K increased the voltage by 8 mV. However, the recovery was greatly
reduced by adjusting the inlet RH. It was pointed out that increasing the
inlet pressure was the most effective method. Hou et al. [58] discussed
the influence of different gas temperatures and cell temperatures on the
water distribution of cathode. When the gas was set to a constant tem­
perature, the increase of operating temperature removed excess liquid
water and reduced the relative humidity in the PEMFC. When the
operating temperature was constant, excessively high intake gas tem­
perature caused water vapor to condense inside the PEMFC, which
aggravated the flooding in the PEMFC. Therefore, the PEMFC operating
at high temperature and low gas temperature can effectively alleviate
J. Zhao et al.
the flooding problem. Anderson et al. [59] pointed out that the liquid
water of the cathode GDL could be removed by using dry hydrogen and
increasing the anode stoichiometry. They studied the anode stoichiom­
etry required at different operating temperatures and different cathode
relative humidity. At higher relative humidity of the cathode, a larger
anode stoichiometric number was required to reach the maximum
voltage, and at a higher temperature, only a smaller stoichiometric
number was required to remove the same water.
4.2.2. Novel flow field
The design of the flow field is a key factor affecting the performance
of PEMFC. A good flow field can guide the reaction gas to ensure that the
electrode can obtain enough reaction gas and discharge the liquid water
in the flow channel. If the reaction gas is unevenly distributed
throughout the electrode, it will cause the PEMFC to overheat locally,
and if the water generated in PEMFC cannot be removed quickly, the
electrode will be flooded, which will reduce the lifetime of PEMFC. For
the cathode flow field, its ability to distribute and transport oxygen
directly affects the rate of the cathode reduction reaction. There are two
main evaluation indexes for the gas distribution capability of PEMFC
flow field: uniformity and convection. Honda employs a wave configu­
ration flow field, a counter-current intake form, and a thinner MEA,
which achieve a uniform distribution of the CCM water content and
reduce the humidification requirement of the cell by 40%. This reduced
the water condensation and accumulation produced in the gas diffusion
layers, increasing gas diffusion performance [60]. Toyota first proposed
the 3D fine-mesh flow field structure. In the fish-scale structure of the
flow field, when the reaction gas flows through any baffle, a part of the
gas will be introduced into the area below the baffle and be promoted to
flow to the gas diffusion layer. The flow field is mainly based on two
considerations: (I) through the hydrophilic flow field design, the product
water is quickly eliminated and the water accumulation is suppressed;
(II) the ridges of the flow channel are narrowed to enhance the intensity
of convection and increase the air diffusivity [61].
In recent years, scholars have proposed many typical designs to
supply gas reactant with a high uniformity, forced convection and fine
Fig. 6. Various flow fields: (a) new optimized 3D flow field [65], (b) MSI and MSS [74], (c) trapezoid-baffle flow field [68], (d) graphene foam flow field [73], and
(e) the through-plane array [67].
8
Journal of Power Sources 488 (2021) 229434
water management, including the novel 3D flow field [62], baffle flow
field and porous media flow field [63,64], as shown in Fig. 6. Shen et al.
[65] proposed a new optimized 3D flow field, and the corresponding
operation characteristics were evaluated. The end of each straight flow
channel was inclined, which increased the mass transfer ability and the
removal capacity of liquid water. Chen et al. [66] proposed a novel 3D
wave channel to improve mass transfer and current density of PEMFC,
and studied the effects of channel depth and wavelength on current
density, temperature distribution, oxygen distribution, and water satu­
ration through CFD methods. It was pointed out that the periodic
structure of the 3D wave flow channel significantly improved the
transportation of reaction gas and the removal of liquid water in the
porous layer, and the minimum depth and wavelength of the optimal
channel of the 3D wave flow field were 0.45 mm and 2 mm, respectively.
Whiteley et al. [67] proposed a novel flow field—"the through-plane
array” (TPA), which significantly improved the performance of PEMFC
at high current densities. At the same time, the pressure drop and the
distribution of gas along the flow channel could be controlled by
adjusting the size, position and density of hole-arrays along the flow
channel.
Many researchers have found that baffles added to the channel could
effectively facilitate the supply of reactant to CL and thus improve
PEMFC performance [68–70]. In addition, the liquid water and tem­
perature distribution of PEMFC with baffles were found to be more
uniform because of the enhanced gas convection effect [71]. He et al.
[72] designed and processed a series of three-dimensional flow fields
(3DFF) with trapezoidal baffles, and studied the relationship between
transport capacity and tilt angle. The results showed that the flow field
with a smaller inclination had stronger water management capabilities.
Park et al. [73] investigated the effect of using graphene foam as a flow
field on the performance of PEMFC. The compressed graphene foam
provided smaller in-plane pores and large through-plane pores, which
enhanced the mass transport of the reactant and improved the perfor­
mance of the single cell at high current densities. Karthikeyan [74] used
the inline arrangement of porous inserts (MSI) and the staggered
arrangement of porous inserts (MSS) to modify the serpentine flow field
J. Zhao et al. Journal of Power Sources 488 (2021) 229434

at the cathode side, and investigated the effects of porous carbon filler
(PCI) and porous sponge filler (PSI) on water management. It was found
that PSI had better performance than PCI, and increasing the size of the
insert from 2 mm to 4 mm increased the power density of PEMFC.
4.2.3. Enhancing the hydrophobicity of GDL and CL
When the PEMFC is flooded, the pore structure of the GDL and CL is
filled with water, preventing the reactive gas from reaching the catalytic
layer. Therefore, improving the hydrophobicity of the GDL and CL can
effectively alleviate gas starvation caused by water flooding [49]. The
GDL and CL treated with a hydrophobic material, such as PTFE or FEP,
has both hydrophobic and hydrophilic pores that respectively enable the
passage of reactant gases and liquid water, thus, it helps the mainte­
nance of continuous two-phase flow in the cell [75–77]. Bao et al. [78]
used the VOF method to study the effect of GDL surface roughness on the
removal efficiency of liquid water, and found that increasing the
roughness can reduce the droplet separation time and elongation rate,
thereby increasing the discharge rate of liquid water. Therefore, the
surface roughness of GDL is very important for water management in
PEMFCs.
Ferreira et al. [79] used EIS measurements to study the effect of GDL
hydrophobic treatment on cell performance. It was found that GDL hy­
drophobic treatment significantly reduced mass transfer losses, thus
improving the performance of PEMFC. John et al. [80] studied the
impact of multi-stage PTFE treatment on the surface hydrophobicity and
electrochemical durability of GDLs. They found that with the same total
amount of PTFE, the surface hydrophobicity and electrochemical
durability of multi-stage PTFE treated GDLs were better than that of
single-stage PTFE treated GDLs. Joo et al. [81] reported a new and
simple method for preparing superhydrophobic GDLs, that is, the entire
surface of GDL was coating with SiOx-incorporated carbon (Si–C)
without a significant change in GDL porosity. The average contact angle
of the macroporous backbone side of the Si–C-coated GDL changed from
134.7◦ to 150.3◦ . Avcioglu et al. [82] prepared the CL with the ink
containing 0 to 30 wt% PTFE on a dry basis. The 5PTFE_AC (the MEA
that has 5 wt% PTFE on both anode and cathode CLs.) provided
enhanced water management compared to that of conventional CLs.
Therefore, adding a lower amount of PTFE to the catalytic layer can
enhance the water management capability while ensuring the power
density [83]. Wang et al. [84] incorporated Vulcan XC-72@PTFE par­
ticles into the conventional Pt/C catalyst layer to reconstruct the gas
transmission channel in the cathode catalyst layer. The results showed
that when the PTFE content exceeded 10 wt%, the PTFE-treated carbon
powder showed good hydrophobicity, and the hydrophobicity of the
catalytic layer could be effectively enhanced with the increase of the
PTFE content. Therefore, Vulcan XC-72@PTFE particles can be used to
build hydrophobic mass transfer channels in the catalyst layer to
improve the water management capability.
actual area of a rough surface to its projected geometric area, f is the
fraction of the surface on top of the protrusions, θ is the contact angle on
a flat surface. From this equation, one can find that when the contact
angle with the plane is less than 90◦ , the increase in the surface
roughness can reduce the apparent contact angle of the rough surface
and increase the hydrophilicity. However, when the contact angle with
the plane is greater than 90◦ , such as MPL, the increased surface
roughness will result in a high contact angle of the hydrophobic surface.
Latorrata et al. [87] used PFPE, FEP and PFA to manufacture three
different kinds of MPLs to replace traditional PTFE-based MPLs. The
contact angle of FEP-based MPLs was larger than that of PTFE-based
MPLs, resulting in stronger hydrophobicity, which are considered as a
reasonable alternative to PTFE. Öztürk et al. [88] compared the water
management capabilities of different MPLs with PTFE, FEP and PDMS. It
was found that the low MW of PDMS polymer exhibited the best cell
performance, when compared to that of the PTFE and FEP. Afterwards,
they added PS-silica particles to the PDMS polymer to further increase
its hydrophobicity, and the molar mass of PDMS-1 and PDMS-2 were
236.53 g/mol and 117,000 g/mol, respectively. As shown in Table 4, it
was found that the utilization of PDMS-2 together with PS-silica parti­
cles was generally beneficial to improve the hydrophobicity of MPL,
which was nearly opposite for the PDMS-1 [89].
Water management is critical for the commercialization of PEMFCs.
Water flooding will accelerate the oxidation of the carbon support,
which eventually leads to the collapse of the entire porous structure [8].
A study by Young [90] showed that the collapse of the porous structure
would hinder the diffusion of gas to the catalyst, causing additional mass
transport and ohmic loss. Changing operating conditions can alleviate
flooding, such as pressure drop and temperature rise, counter-flow
operation, sub-saturated gas streams, etc. Treatment of the GDL and
CL with hydrophobic materials or adding a microporous layer (MPL)
between the GDL and CL are the fundamental ways for improving the
water management capability of PEMFC. At present, the hydrophobic
treatment of GDL and CL has been widely used in practice, and the main
research direction to alleviate flooding is the development of novel flow
fields. In recent years, the introduction of ultra-thin proton exchange
membranes and 3D flow fields have made breakthroughs in solving
cathode flooding. Future work may focus on optimizing water man­
agement strategies and designing a series of novel three-dimensional
flow fields (3DFF), such as the optimized 3D flow field, baffle flow
field and porous media flow field.
5. Carbon corrosion during long-term operation
The oxidation rate of the carbon support under low-temperature and
low-humidity conditions is very slow, but Pt nanoparticles in PEMFCs
can reduce the onset potential of the carbon corrosion reaction, thereby
accelerating the corrosion of the carbon support [91]. Takeuchi et al.

4.2.4. Micro porous layer (MPL) within the cell

Table 4
The hydrophobic material of MPL and the capillary action of mi­
Contact angle and average surface roughness values of the MPLs (CA: contact
cropores make MPL have good hydrophobic and drainage performance,
angle, SA: average roughness) [89].
thus providing stable gas channels and water channels for reactions, and
Sample PDMS -1 PDMS -1 PDMS -1 PDMS -2 PDMS -2 PDMS-2
conductive carbon black makes MPL have excellent electron channels
(1 wt%) (3 wt%) (5 wt%) (1 wt%) (3 wt%) (5 wt%)
[49]. Adding a microporous layer (MPL) modified with a hydrophobic
material between the GDL and CL will reduce water flooding and CA [◦ ] 122.1◦ 145.7◦ 147.4◦ 118.4◦ 138.3◦ 135.7◦
± 1.1 ± 0.5 ± 5.6 ± 7.0 ± 0.3 ± 1.4
thereby improve cell performance [85,86]. SA 3.97 3.78 4.06 7.99 3.55 3.04
There are two common methods to improve the hydrophobic prop­ (μm)
erties of MPL. The first one is the treatment of hydrophobic materials
Sample PDMS-1 PDMS-1 PDMS -1 PDMS-2 PDMS-2 PDMS -2
and the second one is to increase the roughness of the material surface. (1 wt%) (3 wt%) (5 wt%) (1 wt%) (3 wt%) (5 wt%)
Kosak et al. [85] proposed the relationship between apparent contact PS-silica PS-silica PS-silica PS-silica PS-silica PS-silica
angle and surface roughness: (1 wt%) (1 wt%) (1 wt%) (1 wt%) (1 wt%) (1 wt%)

CA [◦ ] 120.8◦ 122.2◦ 116.7◦ 125.1◦ 142.1◦ 133.4◦

COSθR = r⋅f ⋅COSθ + f − 1 (7)
± 0.9 ± 4.7 ± 1.8 ± 1.3 ± 2.0 ± 6.3
SA 5.61 2.63 3.25 2.98 7.81 4.54
θR is the apparent contact angles on a rough surface, r is the ratio of the (μm)

9
J. Zhao et al.
[92] proposed that the overpotential of carbon oxidation depends on the
overall cell voltage and the solution potential. Under normal operation,
the ORR on the cathode reduces the solution potential in the membrane.
When the overall cell voltage remains unchanged, the overpotential of
carbon oxidation on the cathode is larger, and the carbon corrosion
became significant. Increasing the ORR activity will promote carbon
corrosion under normal operation.
Moreover, the normal operation time of PEMFC is significantly
higher than that of the startup and shutdown processes and water
flooding process. The impact of carbon corrosion caused by the cumu­
lative effect of time on the performance degradation, especially on the
later performance of PEMFC, cannot be ignored. According to the DOE,
the lifetime requirements of automotive PEMFCs are 5000 h with less
than 10% performance loss. As shown in Fig. 7, the FC was operated
uninterruptedly for 5000 h in non-humidified mode, and the degrada­
tion rate of cell performance can reach about 10%/2000 h, which is
about halfway to the target for automobile applications. Moreover, the
loss of ECSA after 5000 h continuous operation was estimated to be
about 20% [93]. Therefore, it is necessary to develop new carbon sup­
port materials to strengthen the bonding force between Pt particles and
the carbon support.
The decay rate of the performance under steady state has reached
10% within 2000 h, and automotive PEMFCs will experience many
complex working conditions, such as dynamic cycle conditions,
continuous low load or idling operation conditions and high-power
variable load conditions. Therefore, the performance degradation after
long-term operation in the automotive application will be more serious,
which is also a major obstacle to commercialization at present.
5.1. Degradation mechanism
Vehicle PEMFCs will experience many complicated working condi­
tions during long-term operation [94]. Therefore, the PEMFC system
must have good dynamic response capabilities. During operation, the
load must be changed to adapt to these conditions, which may cause
performance degradation of PEMFC [26]. In normal operation of the
PEMFC, the average output voltage is generally higher than 0.6 V, and
the carbon support is easily oxidized by water vapor during the
operation.
Anode:2H2→4H++4e− (Hydrogen Oxidation Reaction, HOR);
Cathode:C+2H2O→CO2+4H++4e− and O2+4H++4e− →2H2O (Oxygen
Reduction Reaction, ORR).
Dubau et al. [95] performed a series of physicochemical analysis of
the MEAs after 12,860 h of continuous operation. It was found that the
Fig. 7. Durability test (5000 h of uninterrupted operation under a non-
humidified regime) of an MEA assembled with electrodes prepared from 20
wt% Pt/C and a Pt loading of 0.2 mg cm− 2 [93].
10
Journal of Power Sources 488 (2021) 229434
appearance of membrane large-size pinholes would cause the local
degradation of the carbon support in the cathode catalytic layer adjacent
to the holes. Large-size pores leaded to hydrogen crossover, which in
turn leaded to the formation of radical species. The radical species
participated in the irreversible corrosion of the carbon support adjacent
to the pores and caused the collapse of the porous structure of the cat­
alytic layer, thereby weakening the bonding force between the Pt par­
ticles and the carbon support. The weak bonding force between Pt and
carbon support will cause Pt to dissolve, detach, and agglomerate,
resulting in a decrease in active area. Therefore, the main reason for the
performance decay is the degradation of Pt particles caused by carbon
corrosion, which is a process that continuously occurs during long-term
operation [96]. The result is that the performance of the catalyst con­
tinues to decline with the accumulation of vehicle operation time.
5.2. Mitigation strategies
An ideal catalyst support in PEMFC needs to have the following
characteristics: (1) high conductivity to reduce the internal resistance of
the electrode; (2) high specific surface area to reduce the amount of Pt
loaded; (3) reasonable pore structure and hydrophobicity to meet the
mass transfer requirements; (4) a strong interaction between the support
and the catalyst to improve the catalytic activity of the catalyst; (5) good
chemical and thermal stability in the operating environment of PEMFC.
Pt supported on carbon black is the most widely used catalyst in
PEMFCs. However, the use of carbon black as a support has two major
drawbacks: the first drawback is that the platinum nanoparticles
deposited in the micropores cannot play a catalytic role, resulting in low
platinum utilization; the second drawback is that the carbon corrosion
reaction consumes the amount of carbon used to support Pt, which
causes Pt particles to separate and agglomerate from the surface of
carbon, resulting in a decrease in the surface area [97]. Many studies
have showed that the properties of carbon can also affect its degradation
rate. The higher the graphitization degree of carbon support, the slower
its degradation rate [12,98]. Therefore, the main reason for carbon
support corrosion may be their low degree of graphitization. To solve the
above problems, people have developed a variety of new supports,
including mesoporous carbon, graphene, carbon nanotubes (CNTs),
carbon nanofibers (CNFs), metal oxides, and so on.
5.2.1. Mesoporous carbon
Compared with traditional carbon materials, mesoporous carbon
materials show specific properties including: (1) High specific surface
area and high porosity; (2) The adjustable pore size within 2–50 nm; (3)
High thermal stability through optimizing synthetic conditions. There­
fore, it has potential application value in PEMFC catalyst support.
Liu et al. [99] prepared an efficient and stable ORR catalyst by
anchoring Pt nanoclusters with a diameter of 1–3 nm on ordered mes­
oporous carbon (OMC). It was found that the reduction of electrophi­
licity and coordination of Pt NCs, the provision of more active sites by Pt
NCs and the ordered mesopores of OMC were all helpful to improve the
ORR activity and stability of Pt NCs/OMC. After 1500 potential cycles in
O2-saturated electrolytes, the MA and SA of commercial Pt/C decreased
by 35.8% and 37.2%, respectively, while that of Pt NCs/OMC only
decreased by 2.3% and 2.7%. Varathan et al. [100] synthesized a unique
Pt-based bio-derived catalyst-Pt/N-AVC from natural Aloe Vera plant.
Doping N into AVC can enhance the anchoring effect on Pt NP. After 30,
000 potential cycles, the Pt/N-AVC catalyst had no obvious potential
change (ΔE1/2~5 mV) in the entire area, while the Pt/C catalyst
exhibited a negative shift of E1/2 potential ~ 30 mV in the adsorp­
tion/desorption area. Wang et al. [101] used nitrogen-doped meso­
porous carbon framework (N-MCF) as a support to prepare Pt/N-MCF
catalyst. It was found that the anchoring effect of N-MCF support on Pt
improved their interaction, thereby improving the durability and ORR
activity of Pt/N-MFC. After 2000 ADT cycles, the half-wave potential of
the JM-Pt/C catalyst was decreased by 20 mV, while that of the
J. Zhao et al.
Pt/N-MCF catalyst was only decreased by 8 mV. Jung et al. [102] syn­
thesized nitrogen-doped mesoporous graphitic carbon (NMGC), which
showed a higher degree of graphitization than traditional carbon sup­
ports. They found that the N-doped carbon support suppressed the
coarsening of Pt particles during AST, thereby improving the durability
of the catalyst. After 30,000 potential cycles between 0.6 V and 1.0 V,
the ECSA of Pt/NMGC and commercial Pt/C catalysts were reduced by
69% and 88%, respectively. You et al. [103] used OMC and highly
electrochemically stable SiC materials to prepare a new type of nano­
composite as a durable support for the catalyst. After 1.000 cycle-ADTs,
the ORR current density of Pt/OMC-1350 and commercial Pt/C catalysts
at 0.9 V decreased by 30% and 0.16%, respectively. The authors
attributed it to the unique carbon skeleton structure of the OMC material
and the strong interaction between Pt and Si atoms.
5.2.2. Graphene, CNTs and CNFs
Due to their large specific area, high electrochemical stability and
excellent conductivity, graphene, CNTs and CNFs have been extensively
studied as the support of catalysts [104–111]. Kim et al. [112] studied
the characteristics of Pt nanoparticles (NPs) supported on graphene
oxide (GO), partially reduced graphene oxide (GO-r), and reduced gra­
phene oxide (rGO). It was found that the presence of oxygen containing
functional groups weakened the interaction between the carbon support
and Pt particles, so the Pt/rGO catalyst with the lowest concentration of
oxygen containing functional groups exhibited the highest catalytic
activity and durability. After durability analysis, the charge transfer
resistance of Pt/CB, Pt/GO, Pt/GO-r, and Pt/rGO catalysts were 30,600
Fig. 8. (A) SEM images of (a) CNFs and (b) CNTs. (B) TEM images of Pt deposited on (a) CNFs and (b) CNTs [118].
11
Journal of Power Sources 488 (2021) 229434
Ω, 1323 Ω, 832.9 Ω, and 354.2 Ω, respectively. Lee et al. [113] coated
polymeric graphitic carbon nitride (pg-CN) on amorphous carbon black
(a-CB) to prepare a-CB@pg-CNs catalyst support. The Pt/a-CB@pg-CNs
catalyst not only has better electrochemical performance than the
existing commercial catalyst based on a-CB, but also improves the
corrosion resistance of the catalyst. After 5.000 cycles of 0.6 V–1.2 V
voltage, the ECSA of Pt/a-CB@pg-CNs decreased by 19%, and the
binding energies of Pt1 and Pt13 on a-CB@pg-CNs were 1.80 eV and
2.37 eV higher than that on a-CB. Some studies have found that adding
carbon black to graphene can enhance the catalytic activity of Pt
nanoparticles [114,115]. Bayrakçeken [116] found that a specific rGO:
CB ratio could reduce the interlayer forces between the rGO sheets,
thereby enhancing structural properties and improving the performance
of PEMFC. The ECSA loss rate of rGO: CB ratio from 90:10 to 50:50 was
70%, 50%, 50%, 65% and 67%., respectively.
Kanninen et al. [117] prepared highly active Pt/MWCNT and
Pt/N-MWCNT catalysts by microemulsion technique, and studied the
carbon corrosion behavior of the catalysts under PEMFC conditions by
online mass spectrometry. It was found that they both exhibited a more
stable behavior than that of commercial Pt/Vulcan. The similar carbon
corrosion loss was reached after 70, 60 and 50 cycles of 0.1V–1.6 V
voltage for the Pt/MWCNT, Pt/N-MWCNT and Pt/Vulcan, respectively.
As shown in Fig. 8, Andersen [118] prepared and optimized CNF and
CNT supported Pt catalysts and evaluated their thermal and electro­
chemical stabilities. The researchers found that they both exhibited a
better stability than carbon black during the entire measurements, and
highly crystalline CNFs showed a higher stability than that of CNTs. CNF
J. Zhao et al. Journal of Power Sources 488 (2021) 229434

and CNT support for Pt showed approximately 3.3 and 2.3 times less Pt/C decreased by 76%. Table 5 gives a summary of the representative
dissolution than Vulcan supported catalyst. Li [119] synthesized CNFs electrochemical stability tests of catalyst.
with nitrogen, phosphorus and boron dopants by chemical vapor Under normal operating conditions, the output voltage is consider­
deposition of acetylene on electroless copper-plated foams. Through the ably higher than the corrosion potential of the carbon support, so the
analysis of AST and initial reduction potential, the durability and cata­ carbon support corrosion behavior is unavoidable. Meanwhile, the
lytic activity of Pt/CNF were higher than that of Pt/C-JM. From the complexity of the vehicle operating conditions leads to the accelerated
500th scan to 2,000th scan in the range of 0 V–1.2 V, the ECSA of Pt/CNF degradation of performance. To improve the durability of vehicle
and Pt/C-JM decreased by 17.7% and 38.4%, respectively. Alipour et al. PEMFCs, it is necessary to formulate strategies from the improvement
[120] mixed metal oxides (NbO) and CNTs to prepare NbO/CNTs sup­ and innovation of catalysts support. The current researches mainly focus
ports. The ORR activity and durability of the catalyst were significantly on the modification of carbon support materials or the development of
enhanced through the strong interaction between NbO and Pt nano­ non-carbon support materials. Whether it is the modification of carbon
particles compared with Pt/CNT and Pt/C catalysts as evidenced by load support materials or the innovation of new carbon support materials, the
cycles and start-stop cycles. After 5000 potential cycles between 0.05 V ultimate goal is to improve its oxidation resistance without scarifying
and 1.25 V, the ECSA of Pt/NbO/CNTs, Pt/CNTs and Pt/C decreased by the specific surface area and electronic conductivity. In addition, low
5%, 64.4% and 73.2%, respectively. cost is also an issue that must be considered. Graphite supports show
excellent catalytic activity and durability in PEMFC applications.
5.2.3. Metal oxides Developing various modified and functionalized graphite materials can
Recently, metal oxides (such as tin oxide, titanium oxide, etc.) have further improve their application performance. For carbon-free sup­
been widely used as superior corrosion-resistant support materials, ports, the low electrical conductivity and low specific surface area are
which could improve the catalytic activity and stability of PEMFC cat­ still the main obstacles that hinder their application, but they show good
alysts [121–124]. Rajalakshmi [125] found that the presence of TiO2 in corrosion resistance and are expected to become highly durable catalyst
the Pt matrix made the Pt particles dispersed more uniformly, avoided supports for PEMFC applications. Therefore, the technical challenge of
the agglomeration of Pt particles, and provided higher thermal stability graphitic carbon support is how to improve its oxidation resistance
and oxidation stability. Wei et al. [126] found that TiN support had a without destroying their specific surface area and electrical conductiv­
high conductivity but a poor corrosion resistance and TiO2 support had a ity, and the technical challenge of carbon-free support is how to improve
low conductivity but a good corrosion resistance. Therefore, they con­ its low conductivity and low specific surface area. At present, catalyst
verted part of the TiN into TiO2 through alkali treatment, and the pre­ supports that meet the requirements of performance, stability and cost
pared TiN–TiO2 support had high conductivity and corrosion resistance. are still being explored, and combining metal oxides with CNFs may be
After 800 cycles of − 0.2 V–1.2 V voltage, the ECSA of the Pt/C catalyst the development direction of catalyst support. In recent years, Pt alloy
decreased by 82%, and that of Pt/TiN–TiO2 decreased by 62%. Naik catalysts have shown success in effectively improving the durability of
et al. [127] prepared a no-carbon catalyst support-TiO2-x NSs, and used a catalysts in membrane electrode assembly and stack level, which are
simple Pt reduction method to prepare a Pt/TiO2-x NSs catalyst. It was expected to be the development direction of catalysts [133–135].
found that the strong-metal-support interaction (SMSI) with Pt greatly
improved the durability and ORR activity of the catalyst. After 10,000 Table 5
potential cycles between 0.6 V and 1.0 V, the ECSA loss of the Pt–TiO2-x Representative electrochemical stability tests of catalyst.
NSs and commercial Pt/C were 32% and 59%, respectively. They
Authors Catalyst Measurement Degradation rate of ECSA
explained that the introduction of oxygen vacancies on the TiO2 NSs conditions
promoted the transfer of electrons from the TiO2-x NS support to the Pt
Liu et al. Pt NCs/ 1500 potential cycles in Pt NCs/OMC - ECSA decreases
NPs and increased the ORR activity of the catalyst, which is an effective
OMC O2-saturated 4%, Pt/C- ECSA decreases
way to solve the low conductivity of no-carbon supports. electrolytes 26%.
Many studies have also confirmed that a combination of SnO2 and Jung Pt/NMGC 30,000 potential cycles The ECSA of Pt/NMGC and
carbon makes catalysts become more tolerant to a high potential and a et al. between 0.6 V and 1.0 V commercial Pt/C catalysts
were reduced by 69% and
rich oxygen environment [128,129]. Zhang et al. [130] prepared a novel
88%, respectively.
nanostructural Pt/SnO2/C catalyst by depositing Pt nanoparticles on the You Pt/OMC- 1000 potential cycles The ECSA of Pt/OMC-1350
surface of SnO2/C. The results showed that the catalytic activity and et al. 1350 between 0.6 V and 1.4 V and Pt/C decreased by 62.3%
electrochemical stability of Pt/SnO2/C catalysts were 2.3 times and and 78.3%, respectively.
twice higher than those of conventional Pt/C catalysts. After 8000 cycles Lee et al. Pt/a- 5.000 cycles of 0.6 The ECSA of Pt/a-CB@pg-CNs
CB@pg- V–1.2 V voltage decreased by 19%.
between 0.6 V and 1.1 V, Pt/C catalysts showed a more rapid decay
CNs
(− 51.2%), while Pt/SnO2/C exhibited a smaller ECSA loss of 23.2%, and Li et al. Pt/CNF From the 500th scan to Initial ECSA Pt/CNF and Pt/C-
the ORR current density loss for the Pt/C catalysts reached 42.3%, 2,000th scan in the JM retain 82.3% and 61.6%,
nearly twice that of the Pt/SnO2/C catalyst (− 25.0%). Dou et al. [131] range of 0 V–1.2 V respectively.
prepared the SnO2 nanocluster with parallel nanorods structure by a Reza Pt/NbO/ 5000 potential cycles The ECSA of Pt/NbO/CNTs,
et al. CNTs between 0.05 V and Pt/CNTs and Pt/C decreased
hard template method, and studied their stability as cathode catalysts. 1.25 V by 5%, 64.4% and 73.2%,
The authors found that under potential cycling, the ECSA degradation respectively.
rate of Pt/SnO2 was one order of magnitude lower than that of con­ Naik Pt–TiO2-x 10,000 potential cycles The ECSA loss of the Pt–TiO2-
ventional Pt/C. After 1800 cycles between 0.6 V and 1.2 V, the Pt/C et al. NSs between 0.6 and 1.0 V x NSs and commercial Pt/C
were 32% and 59%,
catalyst only retained 0.4% of the initial ECSA, while the Pt/SnO2
respectively.
catalyst retained 77%. Meanwhile the corrosion current of Pt/SnO2 was Zhang Pt/SnO2/ 8000 potential cycles The ECSA degraded by 23.2%
approximately 0.0031 mA cm− 2, which was 94.7% less than that of et al. C between 0.6 and 1.1 V and 51.2% for Pt/SnO2/C and
Pt/C. Alipour et al. [132] deposited Pt on titanium nanotube suboxide Pt/C, respectively.
support doped with molybdenum (TNTS-Mo) to prepare the Dou Pt/SnO2 1800 potential cycles Pt/C and Pt/SnO2 reserved
et al. between 0.6 and 1.2 V 0.4% and 77% of the initial
Pt/TNTS-Mo catalyst. The strong interaction between metal and support ECSA, respectively.
increased the electron donation from TNTS-Mo to Pt, which in turn Reza Pt/TNTS- 2000 cycles of The Pt/TNTS-Mo
improved ORR activity and corrosion resistance. After 2000 continuous et al. Mo 0.05–1.25 V voltage electrocatalyst maintained a
accelerated potential cycling tests in the range of 0.05 V–1.25 V, The stable trend, and the ECSA of
Pt/C decreased by 76%.
Pt/TNTS-Mo electrocatalyst maintains a stable trend, and the ECSA of

12
J. Zhao et al.
6. Conclusions
Catalytic carbon corrosion is an important issue that affects the
durability and lifetime of PEMFCs. To provide a clear picture for un­
derstanding the carbon corrosion mechanisms and their corresponding
mitigation strategies with respect to the PEMFC for vehicle applications,
this paper divides the operation conditions into three categories: startup
and shutdown processes, water flooding process and long-term opera­
tion, and reviews the corresponding carbon corrosion mechanisms and
mitigation strategies.
The high potential at the cathode, introduced by the hydrogen/air
interface at the anode, is the main reason for performance degradation
in PEMFCs during the startup and shutdown processes. Many control
strategies have been developed to mitigate catalyst degradation, such as
gas purge, auxiliary load and so on. During the water flooding process,
the reactant starvation caused by poor water management will accel­
erate the corrosion of carbon supports. Treatment of the GDL and CL
with hydrophobic materials or adding a microporous layer (MPL) be­
tween the GDL and CL are the fundamental ways for improving the
water management capability of PEMFC. The carbon corrosion caused
by the cumulative effect of time is inevitable during the long-term
operation. Some novel materials have been developed to improve the
catalytic activity and stability, such as graphitized carbon, CNTs, CNFs,
metal oxides, and so on. Meanwhile, the researches on Pt alloy catalysts
have also made exciting progress, which can provide an effective strat­
egy to improve the lifetime of PEMFCs.
In the future, additional work should be carried out on the following
aspects: (1) developing effective strategies without increasing the
complexity and cost of the system, and testing them in vehicle appli­
cations, (2) combining multiple strategies or combining system strate­
gies with novel robust catalyst supports to alleviate the carbon corrosion
during the startup and shutdown processes, (3) designing a series of
novel flow fields and optimizing water management strategies to alle­
viate water flooding, and (4) modifying carbon materials and devel­
oping carbon-free supports such as metal oxides to improve the lifetime
of the catalyst. At the same time, combining metal oxides with CNFs and
developing Pt alloy catalysts may be the development direction of high
ORR activity and stable catalysts in the future. The proposed perfor­
mance degradation mechanisms and their corresponding mitigation
strategies discussed in this paper have a definite significance in both
theory and practice for improving the lifetime of PEMFCs, which are
intended to promote the commercial application of FCEVs.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work is supported by the National Natural Science Foundation
of China (No. 51776144) and the National Key Research and Develop­
ment Program of China (No. 2018YFC0810000).
References
[1] M.K. Debe, Nature 486 (2012) 43–51.
[2] J. Shin, W. Hwang, H. Choi, Technol. Forecast Soc. 143 (2019) 239–248.
[3] G. Morrison, J. Stevens, F. Joseck, Transport. Res. C Emerg. Technol. 87 (2018)
183–196.
[4] Y. Wang, K.S. Chen, J. Mishler, S.C. Cho, X.C. Adroher, Appl. Energy 88 (2011)
981–1007.
[5] Q. Meyer, Y. Zeng, C. Zhao, J. Power Sources 437 (2019) 226922.
[6] SAE-China, Technology Road Map for Energy Saving and New Energy Vehicles,
China Machine Press, 2016.
[7] D. Qiu, L. Peng, X. Lai, M. Ni, W. Lehnert, Renew. Sustain. Energy Rev. 113
(2019) 109289.
13
Journal of Power Sources 488 (2021) 229434
[8] H. Chen, X. Zhao, T. Zhang, P. Pei, Energy Convers. Manag. 182 (2019) 282–298.
[9] X. Yu, S. Ye, J. Power Sources 172 (2007) 145–154.
[10] S. Maass, F. Finsterwalder, G. Frank, R. Hartmann, C. Merten, J. Power Sources
176 (2008) 444–451.
[11] R. Makharia, S. Kocha, P. Yu, M.A. Sweikart, W. Gu, F. Wagner, H.A. Gasteiger,
ECS Trans. 1 (2006) 3–18.
[12] S.R. Dhanushkodi, S. Kundu, M.W. Fowler, M.D. Pritzker, J. Power Sources 267
(2014) 171–181.
[13] D.A. Stevens, J.R. Dahn, Carbon 43 (2005) 179–188.
[14] O.V. Cherstiouk, A.N. Simonov, N.S. Moseva, S.V. Cherepanova, P.A. Simonov, V.
I. Zaikovskii, E.R. Savinova, Electrochim. Acta 55 (2010) 8453–8460.
[15] Y. Park, K. Kakinuma, M. Uchida, D.A. Tryk, T. Kamino, H. Uchida, M. Watanabe,
Electrochim. Acta 91 (2013) 195–207.
[16] P. Pei, Q. Chang, T. Tang, Int. J. Hydrogen Energy 33 (2008) 3829–3836.
[17] R. Lin, X. Cui, J. Shan, L. Técher, F. Xiong, Q. Zhang, Int. J. Hydrogen Energy 40
(2015) 14952–14962.
[18] Y. Ishigami, K. Takada, H. Yano, J. Inukai, M. Uchida, Y. Nagumo, T. Hyakutake,
H. Nishide, M. Watanabe, J. Power Sources 196 (2011) 3003–3008.
[19] C.A. Reiser, L. Bregoli, T.W. Patterson, J.S. Yi, J.D. Yang, M.L. Perry, T.D. Jarvi,
Electrochem. Solid State Lett. 8 (2005) A273.
[20] H. Tang, Z. Qi, M. Ramani, J.F. Elter, J. Power Sources 158 (2006) 1306–1312.
[21] T. Zhang, P. Wang, H. Chen, P. Pei, Appl. Energy 223 (2018) 249–262.
[22] J. Kim, J. Lee, Y. Tak, J. Power Sources 192 (2009) 674–678.
[23] H. Schulenburg, B. Schwanitz, N. Linse, G.G. Scherer, A. Wokaun, J. Krbanjevic,
R. Grothausmann, I. Manke, J. Phys. Chem. C 115 (2011) 14236–14243.
[24] A. Oyarce, E. Zakrisson, M. Ivity, C. Lagergren, A.B. Ofstad, A. Bodén,
G. Lindbergh, J. Power Sources 254 (2014) 232–240.
[25] N. Linse, G.G. Scherer, A. Wokaun, L. Gubler, J. Power Sources 219 (2012)
240–248.
[26] G. Wang, Y. Yu, H. Liu, C. Gong, S. Wen, X. Wang, Z. Tu, Fuel Process. Technol.
179 (2018) 203–228.
[27] N. Linse, G.G. Scherer, A. Wokaun, L. Gubler, J. Power Sources 219 (2012)
240–248.
[28] A. Mokmeli, S. Asghari, Int. J. Hydrogen Energy 35 (2010) 9276–9282.
[29] Q. Zhang, Z. Tong, S. Tong, J. Power Sources 468 (2020) 228388.
[30] Q. Shen, M. Hou, D. Liang, Z. Zhou, X. Li, Z. Shao, B. Yi, J. Power Sources 189
(2009) 1114–1119.
[31] F. Jia, F. Liu, L. Guo, H. Liu, Int. J. Hydrogen Energy 41 (2016) 6469–6475.
[32] Y. Yu, H. Li, H. Wang, X. Yuan, G. Wang, M. Pan, J. Power Sources 205 (2012)
10–23.
[33] H. Kim, S.J. Lim, J.W. Lee, I. Min, S. Lee, E. Cho, I. Oh, J.H. Lee, S. Oh, T. Lim,
T. Lim, J. Power Sources 180 (2008) 814–820.
[34] Y. Yu, X. Yuan, H. Li, E. Gu, H. Wang, G. Wang, M. Pan, Int. J. Hydrogen Energy
37 (2012) 15288–15300.
[35] Y. Yang, W. Li, R. Lin, S. Xia, Z. Jiang, J. Power Sources 404 (2018) 126–134.
[36] Y. Yu, G. Wang, Z. Tu, Z. Zhan, M. Pan, Electrochim. Acta 71 (2012) 181–193.
[37] R. Lin, D. Liu, S. Xia, T. Ma, B. Dutruel, Int. J. Hydrogen Energy 45 (2020)
1030–1044.
[38] Q. Zhang, R. Lin, X. Cui, S.X. Xia, Z. Yang, Y.T. Chang, J. Power Sources 341
(2017) 230–239.
[39] K. Eom, G. Kim, E. Cho, J.H. Jang, H. Kim, S.J. Yoo, S. Kim, B.K. Hong, Int. J.
Hydrogen Energy 37 (2012) 18455–18462.
[40] K. Eom, Y.Y. Jo, E. Cho, T. Lim, J.H. Jang, H. Kim, B.K. Hong, J.H. Lee, J. Power
Sources 198 (2012) 42–50.
[41] F. Jia, L. Guo, H. Liu, Energy Convers. Manag. 139 (2017) 175–181.
[42] W. Tokarz, P. Piela, Int. J. Hydrogen Energy 41 (2016) 15002–15006.
[43] Y. Yu, Z. Tu, H. Zhang, Z. Zhan, M. Pan, J. Power Sources 196 (2011) 5077–5083.
[44] P. Gopalan, S.G. Kandlikar, J. Power Sources 248 (2014) 230–238.
[45] W. Dai, H. Wang, X. Yuan, J.J. Martin, D. Yang, J. Qiao, J. Ma, Int. J. Hydrogen
Energy 34 (2009) 9461–9478.
[46] J. Shen, L. Xu, H. Chang, Z. Tu, S.H. Chan, Energy Convers. Manag. 207 (2020)
112537.
[47] M. Dou, M. Hou, D. Liang, Q. Shen, H. Zhang, W. Lu, Z. Shao, B. Yi, J. Power
Sources 196 (2011) 2759–2762.
[48] X. Yang, Q. Ye, P. Cheng, Int. J. Heat Mass Tran. 55 (2012) 4754–4765.
[49] O.S. Ijaodola, Z. El- Hassan, E. Ogungbemi, F.N. Khatib, T. Wilberforce,
J. Thompson, A.G. Olabi, Energy 179 (2019) 246–267.
[50] M. Kim, N. Jung, K. Eom, S.J. Yoo, J.Y. Kim, J.H. Jang, H. Kim, B.K. Hong, E. Cho,
J. Power Sources 266 (2014) 332–340.
[51] X. Zhang, Y. Yang, L. Guo, H. Liu, Int. J. Hydrogen Energy 42 (2017) 4699–4705.
[52] D.P. Wilkinson, J. St-Pierre, J. Power Sources 113 (2003) 101–108.
[53] W. Schmittinger, A. Vahidi, J. Power Sources 180 (2008) 1–14.
[54] Z. Liu, L. Yang, Z. Mao, W. Zhuge, Y. Zhang, L. Wang, J. Power Sources 157
(2006) 166–176.
[55] T. Wilberforce, Z. El Hassan, E. Ogungbemi, O. Ijaodola, F.N. Khatib, A. Durrant,
J. Thompson, A. Baroutaji, A.G. Olabi, Renew. Sustain. Energy Rev. 111 (2019)
236–260.
[56] Y. Li, P. Pei, Z. Wu, H. Xu, D. Chen, S. Huang, Appl. Energy 190 (2017) 713–724.
[57] Y. Li, P. Pei, Z. Wu, P. Ren, X. Jia, D. Chen, S. Huang, Appl. Energy 224 (2018)
42–51.
[58] K. Hou, C. Lin, M. Ger, S. Shiah, H. Chou, Int. J. Hydrogen Energy 37 (2012)
3890–3896.
[59] R. Anderson, M. Blanco, X. Bi, D.P. Wilkinson, Int. J. Hydrogen Energy 37 (2012)
16093–16103.
[60] S. Tanaka, K. Nagumo, M. Yamamoto, H. Chiba, K. Yoshida, R. Okano,
eTransportation 3 (2020) 100046.
J. Zhao et al.
[61] Z. Bao, Z. Niu, K. Jiao, J. Power Sources 438 (2019) 226995.
[62] X. Yan, C. Guan, Y. Zhang, K. Jiang, G. Wei, X. Cheng, S. Shen, J. Zhang, Appl.
Therm. Eng. 147 (2019) 1107–1114.
[63] J. Kim, G. Luo, C. Wang, J. Power Sources 400 (2018) 284–295.
[64] Z. Bao, Z. Niu, K. Jiao, J. Power Sources 438 (2019) 226995.
[65] J. Shen, Z. Tu, S.H. Chan, Appl. Therm. Eng. 164 (2020) 114464.
[66] H. Chen, B. Liu, T. Zhang, P. Pei, Appl. Energy 255 (2019) 113849.
[67] M. Whiteley, J.I.S. Cho, L. Rasha, T. Neville, J. Millichamp, R. Luca, P.
R. Shearing, D.J.L. Brett, J. Power Sources 442 (2019) 227218.
[68] S. Perng, H. Wu, Appl. Energy 143 (2015) 81–95.
[69] H. Liu, W. Yan, C. Soong, F. Chen, J. Power Sources 142 (2005) 125–133.
[70] S. Perng, H. Wu, T. Jue, K. Cheng, Appl. Energy 86 (2009) 1541–1554.
[71] J. Kuo, T. Yen, C.O. Chen, Energy Convers. Manag. 49 (2008) 2776–2787.
[72] L. He, M. Hou, Y. Gao, D. Fang, P. Wang, B. Lv, Z. Shao, Energy Convers. Manag.
205 (2020) 112335.
[73] J.E. Park, J. Lim, S. Kim, I. Choi, C. Ahn, W. Hwang, M.S. Lim, Y. Cho, Y. Sung,
Electrochim. Acta 265 (2018) 488–496.
[74] M. Karthikeyan, P. Karthikeyan, M. Muthukumar, V. Magesh Kannan,
K. Thanarajan, T. Maiyalagan, C. Hong, V.R. Jothi, Sung-ChulYi, Int. J. Hydrogen
Energy 45 (2020) 7863–7872.
[75] M. Ji, Z. Wei, Energies 2 (2009) 1057–1106.
[76] D.M. Fadzillah, M.I. Rosli, M.Z.M. Talib, S.K. Kamarudin, W.R.W. Daud, Renew.
Sustain. Energy Rev. 77 (2017) 1001–1009.
[77] B. Chi, Y. Ye, X. Lu, S. Jiang, L. Du, J. Zeng, J. Ren, S. Liao, J. Power Sources 443
(2019) 227284.
[78] Y. Bao, Y. Gan, Int. J. Hydrogen Energy 45 (2020) 17869–17881.
[79] R.B. Ferreira, D.S. Falcão, V.B. Oliveira, A.M.F.R. Pinto, Electrochim. Acta 224
(2017) 337–345.
[80] R. John Felix Kumar, V. Radhakrishnan, P. Haridoss, Int. J. Hydrogen Energy 37
(2012) 10830–10835.
[81] J. Joo, M. Choun, K. Kim, S. Uhm, Y.D. Kim, J. Lee, Curr. Appl. Phys. 14 (2014)
1374–1379.
[82] G.S. Avcioglu, B. Ficicilar, I. Eroglu, Int. J. Hydrogen Energy 41 (2016)
10010–10020.
[83] G.S. Avcioglu, B. Ficicilar, I. Eroglu, Int. J. Hydrogen Energy 43 (2018)
18632–18641.
[84] M. Wang, M. Chen, Z. Yang, G. Liu, J. Kee Lee, W. Yang, X. Wang, Energy
Convers. Manag. 191 (2019) 132–140.
[85] C. Kosak Söz, E. Yilgör, I. Yilgör, Polymer 62 (2015) 118–128.
[86] E.H. Majlan, D. Rohendi, W.R.W. Daud, T. Husaini, M.A. Haque, Renew. Sustain.
Energy Rev. 89 (2018) 117–134.
[87] S. Latorrata, P. Gallo Stampino, C. Cristiani, G. Dotelli, Int. J. Hydrogen Energy
39 (2014) 5350–5357.
[88] A. Öztürk, B. Fıçıcılar, 0 Eroğlu, A. Bayrakçeken Yurtcan, Int. J. Hydrogen Energy
42 (2017) 21226–21249.
[89] A. Öztürk, A. Bayrakçeken Yurtcan, Appl. Surf. Sci. 511 (2020) 145415.
[90] A.P. Young, J. Stumper, E. Gyenge, J. Electrochem. Soc. 156 (2009) B913.
[91] N. Linse, L. Gubler, G.G. Scherer, A. Wokaun, Electrochim. Acta 56 (2011)
7541–7549.
[92] N. Takeuchi, T.F. Fuller, J. Electrochem. Soc. 157 (2010) B135.
[93] S. Martin, P.L. Garcia-Ybarra, J.L. Castillo, Appl. Energy 205 (2017) 1012–1020.
[94] P. Pei, H. Chen, Appl. Energy 125 (2014) 60–75.
[95] L. Dubau, L. Castanheira, M. Chatenet, F. Maillard, J. Dillet, G. Maranzana,
S. Abbou, O. Lottin, G. De Moor, A. El Kaddouri, C. Bas, L. Flandin, E. Rossinot,
N. Caqué, Int. J. Hydrogen Energy 39 (2014) 21902–21914.
[96] N. Yousfi-Steiner, P. Moçotéguy, D. Candusso, D. Hissel, J. Power Sources 194
(2009) 130–145.
[97] S. Shahgaldi, J. Hamelin, Carbon 94 (2015) 705–728.
[98] X.X. Wang, J. Sokolowski, H. Liu, G. Wu, Chin. J. Catal. 41 (2020) 739–755.
[99] J. Liu, X. Wu, L. Yang, F. Wang, J. Yin, Electrochim. Acta 297 (2019) 539–544.
[100] P. Varathan, S. Akula, P. Moni, A.K. Sahu, Int. J. Hydrogen Energy 45 (2020)
19267–19279.
14
Journal of Power Sources 488 (2021) 229434
[101] J. Wang, G. Wu, W. Xuan, W. Wang, W. Ding, Z. Wei, Int. J. Hydrogen Energy 45
(2020) 22649–22657.
[102] W.S. Jung, B.N. Popov, Carbon 122 (2017) 746–755.
[103] D.J. You, X. Jin, J.H. Kim, S. Jin, S. Lee, K.H. Choi, W.J. Baek, C. Pak, J.M. Kim,
Int. J. Hydrogen Energy 40 (2015) 12352–12361.
[104] J. Ouyang, Nano Mater. Sci. 1 (2019) 77–90.
[105] M.Z. Iqbal, S. Siddique, A. Khan, S.S. Haider, M. Khalid, Mater. Res. Bull. 122
(2020) 110674.
[106] N. Shaari, S.K. Kamarudin, Renew. Sustain. Energy Rev. 69 (2017) 862–870.
[107] A. Iwan, M. Malinowski, G. Pasciak, Renew. Sustain. Energy Rev. 49 (2015)
954–967.
[108] S. Zhu, J. Zheng, J. Huang, N. Dai, P. Li, J.P. Zheng, J. Power Sources 393 (2018)
19–31.
[109] A. Heydari, H. Gharibi, J. Power Sources 325 (2016) 808–815.
[110] M.J. Leeuwner, A. Patra, D.P. Wilkinson, E.L. Gyenge, J. Power Sources 423
(2019) 192–202.
[111] B. Cha, S. Jun, B. Jeong, M. Ezazi, G. Kwon, D. Kim, D.H. Lee, J. Power Sources
401 (2018) 296–302.
[112] J. Kim, S. Kim, S.G. Jo, N.E. Hong, B. Ye, S. Lee, H.S. Dow, D.H. Lee, J.W. Lee,
Catal. Today 352 (2020) 10–17.
[113] I.H. Lee, J. Cho, K.H. Chae, M.K. Cho, J. Jung, J. Cho, H.J. Lee, H.C. Ham, J.
Y. Kim, Appl. Catal. B Environ. 237 (2018) 318–326.
[114] S. Samad, K.S. Loh, W.Y. Wong, T.K. Lee, J. Sunarso, S.T. Chong, W.R. Wan Daud,
Int. J. Hydrogen Energy 43 (2018) 7823–7854.
[115] A. Marinkas, F. Arena, J. Mitzel, G.M. Prinz, A. Heinzel, V. Peinecke, H. Natter,
Carbon 58 (2013) 139–150.
[116] A. Bayrakçeken Yurtcan, E. Daş, Int. J. Hydrogen Energy 43 (2018) 18691–18701.
[117] P. Kanninen, B. Eriksson, F. Davodi, M.E.M. Buan, O. Sorsa, T. Kallio, R.
W. Lindström, Electrochim. Acta 332 (2020) 135384.
[118] S.M. Andersen, M. Borghei, P. Lund, Y. Elina, A. Pasanen, E. Kauppinen, V. Ruiz,
P. Kauranen, E.M. Skou, Solid State Ionics 231 (2013) 94–101.
[119] M. Li, X. Wu, J. Zeng, Z. Hou, S. Liao, Electrochim. Acta 182 (2015) 351–360.
[120] R. Alipour MoghadamEsfahani, S.K. Vankova, E.B. Easton, I.I. Ebralidze,
S. Specchia, Renew. Energy 154 (2020) 913–924.
[121] Y. Chen, J. Wang, X. Meng, Y. Zhong, R. Li, X. Sun, S. Ye, S. Knights, Int. J.
Hydrogen Energy 36 (2011) 11085–11092.
[122] S. Shahgaldi, J. Hamelin, Fuel 150 (2015) 645–655.
[123] J. Stacy, Y.N. Regmi, B. Leonard, M. Fan, Renew. Sustain. Energy Rev. 69 (2017)
401–414.
[124] D. Banham, S. Ye, K. Pei, J. Ozaki, T. Kishimoto, Y. Imashiro, J. Power Sources
285 (2015) 334–348.
[125] N. Rajalakshmi, N. Lakshmi, K. Dhathathreyan, Int. J. Hydrogen Energy 33 (2008)
7521–7526.
[126] L. Wei, J. Shi, G. Cheng, L. Lu, H. Xu, Y. Li, J. Power Sources 454 (2020) 227934.
[127] K.M. Naik, E. Higuchi, H. Inoue, J. Power Sources 455 (2020) 227972.
[128] S.M. Andersen, C.F. Nørgaard, M.J. Larsen, E. Skou, J. Power Sources 273 (2015)
158–161.
[129] P.K. Mohanta, C. Glökler, A.O. Arenas, L. Jörissen, Int. J. Hydrogen Energy 42
(2017) 27950–27961.
[130] N. Zhang, S. Zhang, C. Du, Z. Wang, Y. Shao, F. Kong, Y. Lin, G. Yin, Electrochim.
Acta 117 (2014) 413–419.
[131] M. Dou, M. Hou, D. Liang, W. Lu, Z. Shao, B. Yi, Electrochim. Acta 92 (2013)
468–473.
[132] R. Alipour Moghadam Esfahani, L.M. Rivera Gavidia, G. García, E. Pastor,
S. Specchia, Renew. Energy 120 (2018) 209–219.
[133] R. Lin, L. Che, D. Shen, X. Cai, Electrochim. Acta 330 (2020) 135251.
[134] X. Tian, X. Zhao, Y. Su, L. Wang, H. Wang, D. Dang, B. Chi, H. Liu, E.J.M. Hensen,
X.W.D. Lou, B.Y. Xia, Science (Am. Assoc. Adv. Sci.) 366 (2019) 850–856.
[135] Y. Liu, L. Chen, T. Cheng, H. Guo, B. Sun, Y. Wang, J. Power Sources 395 (2018)
66–76.