Applied Energy 252 (2019) 113416

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Advances in proton exchange membrane fuel cell with dead-end anode T

operation: A review
⁎
Jundika C. Kurniaa, Agus P. Sasmitob, , Tariq Shamimc
a
Department of Mechanical Engineering, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak Darul Ridzuan, Malaysia
b
Department of Mining and Materials Engineering, McGill University, 3450 University, Frank Dawson Adams Bldg., Montreal, QC H3A2A7, Canada
c
Mechanical Engineering Program, The University of Michigan-Flint, 207 Murchie Science Bld. 303 E. Kearsley Street, Flint, MI 48502, USA

H I GH L IG H T S

• APerformance
comprehensive review of researches on PEMFC operates in dead-end anode.
• Purging strategy
deterioration due to hydrogen starvation, water accumulation and nitrogen crossover.
• Alternatives method
to recover cell and stack performance are evaluated.
• Future research directions
to recover stack performance are analyzed.
• to improve dead-end anode operation are discussed.

A R T I C LE I N FO A B S T R A C T

Keywords: To improve fuel utilization and reduce complexity of polymer electrolyte fuel cell especially for automotive
Dead-end anode application, dead-end anode operation is desirable. In this operating mode, the anode outlet is closed to achieve
PEMFC nearly 100% fuel utilization. Despite its great potential, operating the fuel cell in a dead-end anode mode brings
Nitrogen crossover consequence of nitrogen crossover and liquid water back diffusion which accumulate in the anode, hindering
Hydrogen starvation
contact between hydrogen fuel with the catalyst inducing fuel starvation. This fuel starvation not only dete-
Water accumulation
Purging
riorates fuel cell performance but also degrades the cell integrity by inducing carbon corrosion. To address these
issues and achieve optimum operation conditions for the fuel cell, numerous studies on the performance of the
dead-end anode fuel cell have been conducted, several key parameters have been evaluated and various miti-
gation strategies have been proposed. However, the dead-end anode fuel cell has not reached its mature com-
mercialization stage and more research and development is required. To assist further research and development
of the dead-end anode fuel cell and expedite its mass application, it is imperative to grasp and discuss the main
findings of the previously reported studies. At the moment, no review paper on the dead-end anode fuel cell is
available. Therefore, this paper is presented to comprehensively review the development and advancement of
dead-end anode fuel cells. In addition, the required research and development for further advancements of the
field are also outlined and discussed.

1. Introduction
Driven by the growing interest to reduce dependence on fossil-based
energy resources and their severe impacts on environment, global
community has turning their attention towards sustainable and eco-
friendly energy resources and green technologies. One of the most at-
tractive options is fuel cell which offers relatively high efficiency, low
emission by having water as its only by-product, high fuel energy
density, no moving parts and excellent scalability. Depending on the
electrolyte used, fuel cells are generally classified into five categories
[1]: (i) polymer electrolyte membrane or proton exchange membrane
fuel cells (PEMFCs or PEFCs), (ii) solid oxide fuel cells (SOFCs), (iii)
alkaline fuel cells (AFCs), (iv) phosphoric acid fuel cells (PAFCs), and
(v) molten carbonate fuel cells (MCFCs). In addition, some researchers
have been working on the development of a new fuel cell that utilizes
active microorganism as a biocatalyst in an anaerobic anode which is
referred to as microbial fuel cell [2]. Among these fuel cells, the PEMFC
has attracted considerable attention due to its great potential usage in a

⁎
Corresponding author.
E-mail addresses: jundika.kurnia@utp.edu.my (J.C. Kurnia), agus.sasmito@mcgill.ca (A.P. Sasmito).

https://doi.org/10.1016/j.apenergy.2019.113416
Received 6 November 2018; Received in revised form 8 May 2019; Accepted 30 May 2019
0306-2619/ Crown Copyright © 2019 Published by Elsevier Ltd. All rights reserved.
J.C. Kurnia, et al.
a)
Air or O2 Fuel (H2)
Excess air Fuel cell Excess fuel
stack and liquid
c)
Air or O2 Fuel (H2)
Purging
valve
Excess air Fuel cell
stack
Fig. 1. Simplified schematics of fuel delivery strategies of fuel cell system: (a) flow through anode, (b) recirculation anode, (c) dead-end anode and d) dead-end anode
with recirculation.
variety of applications especially in vehicle propulsion systems. In re-
cent years, there has been a growing interest to combine PEMFC with
energy storage (batteries or capacitors) as the primary power source for
eco-vehicles called fuel cell hybrid vehicles (FCHV) [3]. Fuel cells have
been predicted to eventually replace internal combustion engine in the
future vehicles.
In a PEMFC, fuel (hydrogen) and oxygen (air) are delivered through
a series of channels (typically embedded on an electrically conductive
plate) to an active area where the electrochemical reaction occurs be-
tween fuel and oxygen producing electricity, water and heat. As com-
pared to other fuel cells, PEMFC offers some favourable features such as
high power density, low operating temperature, quick start-up, good
response to load changes, easy scale-up and high efficiency [1,4].
During the operation of PEMFCs, several strategies are commonly
adopted in delivering the fuel to the PEMFC stack [5–8], i.e. flow
through, recirculation, dead-end and recirculation with dead-end.
Simplified schematics of these strategies are illustrated in Fig. 1.
On a flow through (open end) anode PEMFC, unused fuel (hy-
drogen) is directly discharged into the atmosphere together with inert
gases. This leads to wastage of the fuel and H2 emission. To overcome
this issue, recirculation and dead-end anode (DEA) have been proposed.
In the former, the excess fuel and other gasses are passed through se-
parator to isolate the fuel from the impurities. The dry fuel is then re-
humidified before it is re-fuelled to the stack. This leads to additional
complexity and parasitic load to the fuel cell stack to drive the fuel
recirculation system. On the dead-end system, the anode outlet is sealed
off to achieve 100% fuel utilization. The stoichiometric amount of fuel
is supplied. The drawbacks of this approach are the build up of liquid
water in the anode channel, nitrogen crossover and fuel starvation that
severely reduces the cell performance. To recover the cell performance,
purging is conducted by opening the anode outlet and flashing out the
accumulated water and built-up nitrogen in the anode. It should be
noted that, without proper management, purging may defeat the
Applied Energy 252 (2019) 113416
b)
Air or O2 Fuel (H2)
Fuel (H2)
Recirculation
Excess air Fuel cell
stack Liquid drain
d)
Air or O2 Fuel (H2)
Fuel (H2)
Recirculation
Purging
Excess air Fuel cell valve
stack Liquid drain
purpose of achieving high fuel utilization. The last system, recirculation
with a dead-end, is a combination of the two previous methods. This
method is motivated by the fact that in a recirculation method, the
separator can only remove the liquid water but not the nitrogen built
up. Thus, purging is still required to recover the optimum cell perfor-
mance. As compared to the previous three fuel delivery approaches, this
last one is the most complex and requires more components to operate.
For some applications, the DEA is the best option, owing to its
simple set up as compared to other systems while having relatively high
fuel utilization. The DEA-PEMFC is especially promising for vehicular
applications where the amount of fuel is relatively limited due to lim-
ited space available in a vehicle [9]. In addition to vehicular applica-
tions, DEA-PEMFC has also been investigated for stationary applica-
tions [10] and for portable power devices [11]. It is also a preferred
choice to power sensor networks operating in unstructured field en-
vironments [12]. Despite its great potential to supplement or even re-
place conventional fossil fuel based energy systems, DEA-PEMFC has
not reached its mature commercialization stage. The key issues to be
addressed are the fuel cell performance, fuel utilization, component
degradation and cost.
Numerous studies on DEA-PEMFC have been conducted and re-
ported. This information has been scattered, creating difficulties in
extracting the essential information for further development of these
technologies. To assist future studies on DEA-PEMFC and expedite its
mass adoption and commercialization, it is essential to review and ex-
amine the main findings of the previously reported studies. To the best
of our knowledge, no review paper on DEA-PEMFC is available in lit-
erature. Therefore, the objective of this paper is to comprehensively
review the development of DEA-PEMFC and to investigate various key
parameters that can potentially affect future development in the field.
The paper presents an overview of the basic fuel cell mechanisms in-
cluding fuel delivery and application. It analyzes the DEA-PEMFC
performance and elucidates the effects of various factors on the fuel cell
2
J.C. Kurnia, et al.
Table 1
Comparison between flow through (open-end) and dead end anode PEMFC.
Flow through (open-end) anode
- Generally feed with humidified hydrogen fuel
- Offers relatively stable performance over time
- Low fuel utilization: it is supplied with excess hydrogen fuel which is discharged directly to
atmosphere
- Not suitable for an application where space is confined (limited storage for the fuel and
accumulation of discharged excess hydrogen can be dangerous)
- Requires complex recirculation system to increase fuel utilization and additional purging system
to remove nitrogen accumulation when recirculation is implemented
- Uses an inlet mass flow controller
performance. It also discusses the challenges in developing the DEA-
PEMFC technology to its mature commercialization stage. The mitiga-
tion strategies to overcome the challenges and the research and de-
velopment needs for advance development of the field are also pre-
sented.
2. PEMFC dead-end anode operation: Performance and challenges
Increasing the performance, efficiency and fuel utilization have
been the main focus on the development of PEMFC system. DEA-PEMFC
is one of the proposed solutions to overcome the low fuel utilization
experienced by flow through (open-end) anode PEMFC while mini-
mizing the added system complexity and maintaining the high effi-
ciency and performance [13]. DEA-PEMFC, however, has its inherent
problems of liquid water accumulation and nitrogen crossover in the
anode due to the outlet blockage [14,15]. A brief comparison between
the open-end and the dead-end PEMFC is summarized in Table 1.
Due to accumulation of water and nitrogen in the anode side, which
restrict the hydrogen contact with the catalyst layer, the performance of
Fig. 2. Power density of a PEMFC operated with flow through (open-end) and dead-end anode [16]. The lower subplot shows the purging cycle duration for the dead-
end anode for each current density.
3
Applied Energy 252 (2019) 113416
Dead end anode
- Generally feed with dehydrated hydrogen fuel to minimize water
accumulation
- Performance degradation over time due to fuel starvation caused by
water accumulation and nitrogen crossover
- Very high (almost 100%) fuel utilization
- Suitable for applications in confined space
- Requires purging system to recover performance
- Commonly uses an inlet pressure regulator than a mass flow controller
DEA-PEMFC, in term of power density, is generally lower than the flow
through (open-ended) anode PEMFC [16], as presented in Fig. 2. De-
spite the results that higher power density can be achieved with the
higher current density, the performance difference between the open-
end and the dead-end widens as the current density increases. More-
over, this higher power density comes at slower purging cycle duration
(shorter dead-end period), which literally means more purging is re-
quired. This implies that more hydrogen fuel losses are expected, un-
dermining the benefit of having a dead-end anode configuration.
Not only creating performance degradation, insufficient hydrogen
supply, triggered by water and nitrogen accumulation, can also pro-
mote carbon corrosion in the catalyst layer which in turn causes an
irreversible damage to the fuel cell and shortens its life time. To gain
better insight, this section presents basic mechanisms and consequences
of these problems.
2.1. Water accumulation
During operation, the anode of a DEA-PEMFC is fed with
J.C. Kurnia, et al.
Fig. 3. Illustration of species transport in PEMFC operated with dead-end anode.
dehydrated hydrogen at a controlled pressure, while its cathode is
supplied with humidified air in a conventional flow-through conditions
associated with a stoichiometry ratio (SR) greater than one. As a result
of electrochemical reactions, water vapors are produced in the cathode
catalyst layer from oxygen and hydrogen ions. Depending on the op-
erating temperature, produced water inside the fuel cell maybe eva-
porated or condensed [17]. Since a PEMFC is generally operated at low
temperature, the produced water vapor may condense into liquid water
depending upon the partial pressure of the water vapor. Water pro-
duction and accumulation create a water concentration gradient be-
tween the anode and cathode which causes back diffusion that pushes
the water to the anode side. Due to capillary pressure, liquid water
flows from membrane through anode gas diffusion layer to the anode
flow channel. This liquid water is pushed by the pressurized hydrogen
toward the anode outlet and accumulated in the outlet area, as illu-
strated in Fig. 3. This liquid accumulation restricts hydrogen transport
to the catalyst, effectively reducing the active area available for the
electrochemical reaction and degrading the overall performance of the
fuel cell. Due to the importance of water accumulation in the anode side
of DEA-PEMFC, this issue has received considerable attention with
numerous researches have been conducted and reported. Several
methods for investigating water accumulation in PEMFC have also been
proposed and evaluated [18], e.g. neutron imaging or radiography, gas
chromatography, X-ray and infrared ray.
Several studies have highlighted the promising potential of the
neutron imaging technique for water transport visualization and water
management systems evaluation in operating PEM fuel cells [19–22].
The basic mechanism of this visualization technique is the attenuation
of a neutron by hydrogen-containing substrate (e.g. water) and fuel cell
components. This imaging technique can be utilized to identify water in
both in-plane direction (with the membrane oriented parallel to the
beam) and through-plane direction (with the membrane oriented
4
Applied Energy 252 (2019) 113416
perpendicular to the beam), offering the possibility to characterize the
water concentration in the cathode and anode as well as the effect of
fuel cell designs, components, and operating conditions [23]. Conse-
quently, it has been widely adopted to visualize water accumulation in
the anode of DEA-PEMFC.
Siegel et al. [24] investigated liquid water accumulation within the
cell structure of a DEA-PEMFC during operation by utilizing neutron
imaging method, similar to that adopted by Bellows et al. [25]. Al-
though the studied fuel cell was supplied with dry hydrogen, accumu-
lation of liquid water was still observed in the anode gas distribution
channels in majority of the investigated conditions which indicates
water back diffusion occurs from the cathode to the anode. The ob-
served liquid water accumulation on the active area of DEA-PEMFC is
presented in Fig. 4. While liquid water in the cathode channel was
found to have little effect on the voltage, liquid water accumulation in
the anode corresponds to the voltage degradation. It was also found
that water accumulation causes the larger slope voltage degradation
(5–8 mV min−1) while nitrogen crossover is responsible for the small
voltage drop (2 mV min−1). Manokaran et al. [26] studied water
transport and accumulation in a DEA-PEMFC using indirect measure-
ment. The current distribution on the fuel cell active area was measured
by using sensor plates installed on 49 segments across the fuel cell
active area. They investigated the contribution of liquid water accu-
mulation and nitrogen crossover on the reversible drop in fuel cell
performance. They conducted two sets of experiments by setting two
initial current densities of 0.6 A cm−2 and 0.3 A cm−2 using air and
oxygen as an oxidant. Their study found that water accumulation is not
the major contributor of the decrease in the fuel cell performance.
O’Rourke et al. [27] proposed a detection method of a PEM fuel cell
anode flooding by using the existing voltage scan cards. The detection
scheme was based on running the fuel cell at low current densities and
periodically spiking the current load to a value of at least 0.5 A cm−2
J.C. Kurnia, et al.
Fig. 4. Visualization of liquid water accumulation on the fuel cell active area using neutron imaging. The cell operating conditions were 566 mA cm−2, 55 °C, fully
humidified air at a stoichiometry of 200% for cathode and dry hydrogen for anode [24].
during which the differences between the median cell voltage and the
individual cells’ voltages are measured: The cell which has voltage
value significantly different from the median anode is expected to be
flooded. Coz et al. [28] utilized operando neutron imaging to visualize
water patterns on a multiple cells of planar breathing fuel cell made by
using Printed Circuit Board (PCB). Drying was observed at a high cur-
rent density and it was correlated to natural convection and self-
heating. Meanwhile, water accumulation was largely observed at a low
current density on the anode side. They found that water is originated
from water condensation on the cathode side, leading to back-diffusion
and anodic flooding. Meyer et al. [29] utilized electrochemical im-
pedance spectroscopy (EIS) to indirectly measure water accumulation
in a DEA-PEMFC stack. Since anode flooding is a major cause of voltage
drop, it can be indicated by an increase in mass transport losses, as
discernible using EIS. In addition, possible water saturation was ob-
served from the changes of the resistance, which corresponds to a rise of
the conductivity of the membrane.
Lee et al. [30] conducted visualization of the accumulation of water
and the variation of water accumulation with time. The water accu-
mulation at the anode was visualized through a transparent, poly-
carbonate window and recorded by using a charge-coupled device
(CCD) camera. Some of their results are presented in Fig. 5 which shows
water presence at the anode of DEA-PEMFC. An increase in the amount
of reactants triggers acceleration of the voltage drop and increases the
amount of water accumulation at the anode. Similar visualization ap-
proach was taken by Rahimi-Esbo et al. [18] who developed a trans-
parent PEM fuel cell to investigate contact resistance and water man-
agement of a fuel cell during a dead-end mode operation. Transparent
end plates were utilized to visualize water transport, accumulation in
the flow field outlet area, and water removal during the purging. Si-
milar to the finding from other studies, accumulation of water in the
anode channel was found to reduce the cell’s voltage.
5
Applied Energy 252 (2019) 113416
Lee and Sohn [31] visualized water accumulation on the anode and
cathode of a DEA-PEMFC by using a transparent unit cell. The average
voltage output and its dependence on two interrelated conditions,
namely, the supply gas pressure, and the purging valve open time were
investigated. They also analyzed the correlation between the purge
conditions and water flooding. Karst et al. [32] built a transparent
micro-PEMFC to visualize back-diffused water accumulating at the
anode channel. They observed water accumulation in the anode
channel despite supplying it with dry hydrogen, similar to the finding
by Siegel et al. [24]. To eliminate the possibility of carry forward water
during the preparation, the membrane was not hydrated beforehand.
Their study indicated the possibility of decreasing the cell flooding or
drying by varying the cover opening ratio depending upon the current
density and environmental conditions.
A numerical model was developed by Soopee et al. [33] to study the
dynamic movement and deformation of a liquid water droplet rising
from the gas diffusion layer (GDL) into the anode flow channel of a
DEA-PEMFC. The results indicated that water generation and accumu-
lation in the flow channel rise, indicated by fast enlargement of water
droplets, as the PEMFC runs at a high current density. A similar ap-
proach was taken by Mahyari et al. [34] who developed three dimen-
sional (3-D) transient multiphase flow simulations of a DEA-PEMFC.
They found that the water produced in the cathode diffuses to the
anode; no water accumulation was observed in the cathode side. In
addition, it was revealed that the accumulation rate is a strong function
of the current drawn from the cell.
Despite the confirmed close relation between water accumulation
and cell performance degradation, some studies highlighted that water
accumulation may not be the dominant factor that severely degrades
the fuel cell performance. Instead, they suggested that the nitrogen
crossover and accumulation at the anode side is the main factor af-
fecting the degradation of cell performance. Thus, in the following
J.C. Kurnia, et al. Applied Energy 252 (2019) 113416

Fig. 5. Water presence at the anode of DEA-PEMFC with 100% RH: (a) just before the closure of the exit valve; (b) just before the voltage reaches the limit; and (c) an
enlargement of parts of the second photograph [30].

section, we shift our attention towards nitrogen crossover from the cathode stoichiometric ratios and operating pressure. In addition, ni-
cathode to anode side and its accumulation in the anode channel. trogen crossover rate is also largely affected by cathode pressure and
stoichiometric ratio. Karimaki et al. [37] employed an on-line hydrogen
sensor to determine nitrogen crossover in a used PEMFC. The nitrogen
2.2. Nitrogen crossover
concentration was estimated based on the hydrogen concentration by
assuming that all other gases in the gas mixture are accumulated ni-
Due to its porous nature and thin profile, fuel cell membrane allows
trogen. They confirmed the application of the on-line hydrogen con-
for hydrogen, oxygen, and nitrogen to permeate across the membrane.
centration sensor in a slipstream in the measurements of inert gas (ni-
Commonly dubbed as gas crossover, this phenomenon creates a chal-
trogen) in PEMFC. However, they also highlighted that the sensor
lenge in the operation of DEA-PEMFC and needs to be addressed
placement in the slipstream should be optimized to achieve accurate
carefully. Some gases, such as hydrogen and oxygen, during crossing
measurements, taking into consideration the gas replacement time in
the membrane may react, generating heat and water without producing
the slipstream loop.
useful work and thus leading to the fuel wastage. On the other hand,
Widely utilized to visualize water transport and accumulation in
due to its inert nature, nitrogen does not react in the fuel cell mem-
PEMFC, neutron imaging has also been adopted in combination with
brane: it passes through it and accumulates at the outlet area of the
gas chromatography and mathematical modeling to visualize nitrogen
anode flow fields. Similar to the liquid water problem, accumulation of
accumulation in the anode of DEA-PEMFC. This approach was adopted
nitrogen in the PEMFC anode obstructs the contact between hydrogen
by Siegel et al. [38] to quantify local concentration of hydrogen and
and the catalyst layer, reducing the active area available for the elec-
nitrogen in the anode channel of a DEA-PEMFC which was operated
trochemical reaction and in turn deteriorating the fuel cell perfor-
with dry hydrogen intake. In their study, samples extracted from the
mance. To address and overcome this issue, numerous studies on ni-
anode channel were simultaneously measured by using gas chromato-
trogen crossover, blanketing phenomena and its effect on the cell
graphy measurements to quantify the nitrogen content while the neu-
performance have been conducted and reported in literature.
tron imaging was adopted to visualize and evaluate the liquid water
Numerous methods have been proposed to investigate nitrogen
distribution. In addition, a one-dimensional model of nitrogen cross-
crossover and its accumulation in the anode side of DEA-PEMFC. Baik
over and accumulation was developed to describe the dynamic beha-
and Kim [35,36] utilized mass spectroscopy (MS) to measure the
vior of nitrogen blanketing area in the anode channel creating hydrogen
amount of the crossovered nitrogen gas at the anode exit. They reported
starved region. It was found that the nitrogen permeation rate is a
that nitrogen gas cross over is dictated by current density, anode and

6
J.C. Kurnia, et al.
function of membrane water content, and the nitrogen accumulation
rate is determined by both the permeation rate and current density
distribution.
Kocha et al. [39] employed an in-situ electrochemical method to
indirectly investigated nitrogen build up in PEMFC by measuring the
magnitude of the hydrogen crossover in the fuel cell of pertinent fuel
cell. To assist the investigation of nitrogen build up throughout the
anode flow fields, a mathematical model was developed and validated
by comparing the numerical prediction with the corresponding ex-
perimental results. The results indicated that the nitrogen accumulation
occurs at the last 5–10% of the exit location. In addition, it was found
that nitrogen concentration at the outlet increases exponentially with
the decrease of current density. Müller et al. [40] proposed a model to
predict the accumulation of nitrogen in the anode channels of a fuel cell
stack with high hydrogen utilization. To balance the trade-off between
modeling complexity and accuracy, the developed model combined
along-the channel one-dimensional partial differential equation (PDE
model) with calculations of the apparent active channel length and
hence the apparent current density. The model managed to accurately
estimate nitrogen concentration in the anode of PEMFC. Their study
indicated that that the crossover of nitrogen and its accumulation in the
anode may induce a considerable reduction in the stack voltage.
Therefore, it should be taken into consideration when operating a
PEMFC under high hydrogen utilization conditions.
In addition to water accumulation investigation, Meyer [29] utilized
the off-gas analysis to investigate the accumulation of nitrogen cross-
over on the anode occurring during the dead-ended operation. It was
observed that nitrogen detected at the anode increases to 3% after 180 s
and reduces back to 0.25% within 30 s in the flow-through mode. Later,
they evaluated a ‘nitrogen blanketing’ effect due to nitrogen crossover
from the cathode of a DEA-PEMFC by utilizing hydro-electro-thermal
analysis which was developed in their previous study [23,41]. This
method combines current, temperature and water distributions into a
single dataset. The cell initial performance deterioration in dead-ended
anode is attributed to a lower water content, current density and
“Nitrogen blanketing”
Nominal hydrogen flow
“Nitrogen blanketing”
“Nitrogen blanketing”
Air flow
Fig. 6. “Nitrogen blanketing” hypotheses in air-cooled open-end cathode DEA-PEMFC [41].
7
Applied Energy 252 (2019) 113416
temperature at the middle area of the cell, as shown in Fig. 6. This is
most likely due to nitrogen covering the electrode and hydrogen ac-
cessing the electrode at the proximity of the periphery due to a small
gap between the GDL and gasket which provide a bypass for gas to
access the GDL edges.
Besides investigating water accumulation in the anode, Manokaran
et al. [26] evaluated the effect of nitrogen crossover to the cell per-
formance. By investigating both air feed and oxygen feed DEA-PEMFC,
they found that the main factors affecting degradation of cell perfor-
mance in dead-end anode operation is nitrogen crossover and not the
water accumulation. Ahluwalia and Wang [42] studied nitrogen accu-
mulation in the anode side of a PEMFC stack. The results indicated that
nitrogen crossover from cathode to anode is determined by several
parameters, i.e. nitrogen concentration in feed hydrogen (if any), purge
rate, and membrane thickness. Meanwhile, nitrogen accumulation in
the anode channel is dictated by the degree of purge, defined as the
average fraction of the anode exit gas that is vented. Based on their
finding, they suggested that removing nitrogen impurities in the hy-
drogen feed to stringent levels may not be beneficial as the nitrogen can
crossover the membrane and accumulated in the anode.
While there is common understanding that nitrogen crossover is the
primary factor determining the performance of DEA-PEMFC, Jiang
et al. [43] through their study indicated that the overpotentials of both
the anode and cathode concurrently increased or decreased at the same
time. The results suggested that the water content in the membrane
electrode assemblies is critical, as indicated by the increases of over-
potentials which correlate to the increase of the high frequency re-
sistance of the cell (Rhf). Nonetheless, the following hydrogen depletion
tests indicated that accumulation of water may occur at the interface
between the surface of the catalyst and the ultrathin perfluorosulfonic
acid (PFSA) ionomer film and this contradicts the above finding (the
increase in Rhf implies the drying out of the MEAs). As such, further
studies are necessary to elaborate water transport phenomenon in the
DEA-PEMFC.
J.C. Kurnia, et al.
2.3. Hydrogen starvation
Due to liquid water and nitrogen accumulations in the anode, some
parts of the catalyst will not receive the required hydrogen, leading to a
localized fuel starvation. This condition in turn deteriorates the cell
performance. Thus, numerous studies have been conducted to in-
vestigate hydrogen starvation in the DEA-PEMFC.
Baumgartner et al. [44] investigated hydrogen starvation of a fuel
cell by utilizing a laboratory-scale single cell assembly operated at both
dead-end as well as the open-end configurations at hydrogen under-
supply conditions. A non-uniform gas distribution within the cell was
observed, which was a firm indication that some regions of the cell
were operated at undersupply conditions. This cell was found to mar-
ginally contribute to the overall cell output current. In their study,
however, no critical electrode potentials were measured. Rangel et al.
[45] experimentally investigated fuel starvation in the PEM fuel cell
and evaluated its effect on the cell performance and integrity. EIS was
utilized to identify membrane dehydration and fuel cell flooding con-
ditions related to reactant starvation (mass transport limitations) and
decrease in protonic conductivity, respectively. Moreover, cross-sec-
tions of the membrane catalyst and gas diffusion layers were measured
by scanning electron microscopy (SEM) to evaluate electrode thickness
decrease as a consequence of reactions taking place during hydrogen
starvation. The presence of morphological defects associated with the
fuel starvation was observed on the investigated samples.
Ohs et al. [46] formulated a steady state and isothermal 2D-PEM
fuel cell model to investigate the hydrogen starvation. The results re-
vealed that the membrane potential locally drops in areas where hy-
drogen starvation occurs. Abbou et al. [14] investigated the effect of
fuel starvation on the local fuel cell performance by conducting aging
protocols comprising a recurring fuel cell operation arrangement with
the anode exhaust closed and a constant (average) current density.
They utilized a segmented, linear cell equipped with reference elec-
trodes along the gas channels. This system was used to collect local
anode and cathode potentials. Significant local cathode potential ex-
cursions were observed in the proximity of anode outlet. At the region
which experience long-term fuel starvation, the damage was more se-
vere. They concluded that the consideration of the overall fuel cell
performance only may lead to difficulties in identifying the localized
and transient hydrogen starvation. Thus, a detail and localize mea-
surement may be needed.
2.4. Carbon corrosion
Hydrogen starvation due to accumulation of water and nitrogen in
the anode does not only deteriorate fuel cell performance but also
triggers corrosion of the carbon as the catalyst support in the cathode.
Carbon corrosion is one of the primary contributors of PEMFC perfor-
mance degradation [16,47]. It triggers loss of electrochemical surface
area [48]. It also leads to catalyst metal sintering [49], and ultimately, a
structural disintegration of the electrode [50]. Using electron microp-
robe analysis, Pattersson and Darling [51] confirmed the serious da-
mage to the cathode catalyst which is restricted from hydrogen access.
Ishigami et al. [52] introduced a new carbon dioxide visualization
technique using a sensitive dye to detect CO2 production during the
corrosion processes in real time and with spatial resolution. This new
visualization method is intended to assist in minimizing the corrosion of
carbon supports in all types of PEMFCs.
To examine carbon corrosion induced by a local hydrogen fuel
starvation in a PEMFC, Liu et al. [53] carried out post-mortem thickness
and morphology study of a degraded membrane electrode assembly
(MEA) using optical, scanning, and transmission electron microscopy. It
was revealed that hydrogen starvation will initiate corrosion of the
carbon electrocatalyst support. This corrosion resulted in a disintegra-
tion of the electrode’s porous structure, lack of mass transport in the
electrode, and subsequent degradation of fuel cell performance. Liang
8
Applied Energy 252 (2019) 113416
et al. [54] investigated the effect of fuel starvation in a single cell
PEMFC and concluded that the carbon corrosion near the anode outlet
worsened when the fuel starvation becomes aggravated. It was ac-
companied by a larger water electrolysis current and higher local in-
terfacial potential. Yang et al. [55] studied the effect of in-plane
transport on hydrogen depletion and carbon corrosion triggered by
anode flooding in PEMFCs. They concluded that the maximum rate of
carbon corrosion strongly depends on the cell voltage, i.e. at high cell
voltages, it is dictated by oxygen crossover rate while at low voltages, it
is determined by oxygen reduction reaction kinetics.
Another method, in-situ online mass spectrometry, was adopted by
Lim et al. [56] to investigate carbon corrosion in the anode. In com-
bination with monitoring the potential behavior and exhaust gas from
the anode using the hydrogen reference electrode, the precise me-
chanism of performance degradation in PEMFCs under the fuel star-
vation condition can be evaluated. Thus, carbon corrosion, which is
detrimental to the cell performance, can be reduced by extending the
duration of the water electrolysis reaction. Using numerical simulation,
Chen et al. [57] evaluated the spatio-temporal evolution of carbon
corrosion rate induced by the elevated cathode interfacial potential of a
DEA-PEMFC during its operation. On top of the catalyst layer de-
gradation, they reported membrane deformation in DEA-PEMFC, spe-
cifically in the inlet region of the channel which is subjected to the peak
dehydrated conditions.
This finding was later supported by experimental observations by
Matsuura et al. [58] who identified multiple degradation patterns
during the DEA operation of the PEMFC. In their subsequent study,
Matsuura et al. [59] used SEM of post-mortem samples to evaluate the
cathode carbon corrosion in a DEA-PEMFC. Measurement of the cata-
lyst layer and membrane thickness were taken at several locations
throughout the cell active area to identify and outline the degradation
patterns, see Fig. 7 for details. It was confirmed that the cathode carbon
corrosion was strongly related to the anode fuel starvation occurring at
the outlet area where 50–70% loss of thickness was observed following
the degradation test, in all cases. Moreover, full inlet humidification in
Case 1 appears to lighten mechanical stress from the DEA cycling
condition, since the post-mortem membrane was generally uniform
with no localized thinning noticed. The post-mortem analysis shows
that that the membrane cracks and delamination occur in the inlet re-
gion where the lowest membrane water content was identified.
2.5. Performance degradation
Due to the aforementioned problems (water and nitrogen accumu-
lations at the anode), the performance of the DEA-PEMFC degrades over
time. Several studies investigating this issue have been conducted and
reported. Before proceeding further, it is important to recall some basic
principle in the PEMFC operation. In practical applications, PEMFC can
be operated in either galvanostatic mode for which the stack current is
prescribed, and the voltage is measured as the output; or in potentio-
static mode where the voltage is set, and the output current is given by
the system. Sasmito and Mujumdar [60] numerically evaluated the
performance of a DEA-PEMFC in both current and voltage operating
modes. Some results from their study are presented in Fig. 8. Fig. 8a
shows that the overall output voltage drops with time for the galva-
nostatic mode.
A closer inspection discloses that at lower operating current den-
sities, the voltage drop is marginal. As the operating current density is
increased, the voltage drop becomes progressively more pronounced
Local distributions of current densities operated in the galvanostatic
mode at 11,000 A/m2 from inlet to outlet are presented in Fig. 8b.
During the open-end operation, uniform current density distribution is
observed at t = 0 s. With the passage of time, the current drops are
observed starting at the outlet (dead-end) area and propagate over time
to the middle and near inlet area. They found that the galvanostatic
(constant current density) mode results in the average current density
J.C. Kurnia, et al.
Fig. 7. The thickness of MEA component after DEA performance degradation test; operating average current density 0.4 A/cm2, cathode stoichiometry ratio 2.5 for:
(Case 1) Tcell 60C, RHc 100%,; (Case 2) Tcell 60C, RHc 50%; and (Case 3) Tcell 80C, RHc 50% [59].
of 11000 A/m2 which is equal to the applied boundary condition.
Consequently, higher current is observed near the inlet area which is
most likely generated to balance the current reduction at the outlet
area. This condition leads to severe degradation in durability of the cell.
In potentiostatic (constant cell voltage) mode, where the cell voltage is
prescribed, the current density is found to drop over time (Fig. 8c). The
drop was attributed to the current density reduction which is initiated
from the outlet region and progressively propagates towards the inlet
area (Fig. 8d). They also found that this performance degradation for
both operating modes is caused by water and nitrogen accumulations in
the anode region over the time, decreasing the amount of available
hydrogen and thus deteriorating the cell performance. In addition, it
was revealed that the accumulation rate is closely correlated to the
current that is drained from the cell.
Mahyari et al. [34] reported that the water accumulation and ni-
trogen transport across the membrane assembly are two main gov-
erning variables for the operation of DEA-PEMFC operation, which are
closely related to the reduced hydrogen content in the PEMFC anode.
The closure of the anode outlet drives water from the cathode to the
anode with more pronounced water accumulation observed in the
anode side. Gomez et al. [15] evaluated the effect of the operating
parameters – inlet humidification, stoichiometry, and operating current
– on the transient performance of a DEA-PEMFC stack. The performance
deterioration over time was found to strongly depend on the operating
conditions. The cathode and anode inlet conditions were the limiting
variables for the stack performance. They concluded that the inlet hu-
midification and water transport across the membrane dictates liquid
accumulation at the anode, while the cathode stoichiometry determines
the nitrogen crossover.
9
Applied Energy 252 (2019) 113416
Abbou et al. [61] conducted a study on the evaluation of the impact
of both water accumulation and nitrogen crossover on the performance
of a DEA-PEMFC. To isolate the effect of each factor, the DEA-PEMFC
was operated with pure oxygen when assessing the nitrogen crossover
contribution and it was operated with colder or hotter anode plate
when evaluating the effect of water accumulation. They found that the
High temperature at the cathode drives the water towards the colder
anode side. It was observed that the fuel starvation was faster with a
colder anode side, indicating the significance of water flooding at the
anode side. On the other hand, the nitrogen crossover across the
membrane was found to be the main cause for hydrogen starvation
when the anode plate was set at higher temperature which means that
water accumulation in the anode compartment was limited.
Marignetti et al. [62] reported the performance of a DEA-PEMFC
under various air stoichiometries and fuel compositions. The experi-
mental results revealed that the air stoichiometry influences the stack
performance mainly in the pure hydrogen feeding, in which the acti-
vation overvoltage is only due to the cathodic reactions. The effect of
air stoichiometry was found to be less significant when the stack is
supplied with the synthetic gas due to the fact that the activation
overvoltage depends on both anodic and cathodic reactions. At a low
current density, the influence of air stoichiometry is marginal, and the
stack performance is similar for all the air stoichiometry values for both
fuelling condition. From their study on degradation phenomenon in the
DEA-PEMFC, Matsuura et al. [59] concluded that the hydrogen star-
vation induced cathode carbon corrosion results in progressive de-
gradation of cell voltage during the DEA-PEMFC operation, which is
indicated by the increasing charge transfer resistance, the decreasing
the electrochemical surface area (ECSA), and the catalyst layer
J.C. Kurnia, et al.
Fig. 8. (a) Time-dependent performance of DEA-PEMFC at constant current densities; (b) Local current density distribution along the center of cathode catalyst layer;
(c) average current density and (d) local current density distributions of DEA-PEMFC at constant cell voltage [60].
thinning. Müller et al. [40] confirmed a considerable cell performance
decay due to the nitrogen crossover and its accumulation in the anode.
Yang et al. [63] conducted a study to evaluate the local and overall
impacts of a number of operating parameters including cathode hu-
midity, air stoichiometry, hydrogen pressure and operating current
density on the performance of DEA-PEMFC and its local characteristics.
Several important conclusions were inferred from their study. First,
water and nitrogen transfer in DEA-PEMFCs are significantly affected
by the fuel cell operating conditions. Second, different locations have
different local current densities change during impurity accumulations.
Third, impurities accumulation was first observed at the end of the
anode channel and it was found to progressively propagate upstream.
Increase in rates of impurities transfer was observed with the increase
in cathode inlet humidity and operating current density and it was
found to decrease with the increase of hydrogen pressure and air stoi-
chiometry. Yu et al. [64] reported uneven current distribution in DEA-
PEMFC during its operation. The local current reduction was first ob-
served at the anode outlet area, which propagated to the inlet area
along the channels over time. The complete hydrogen starvation at the
anode outlet induced a high local potential and in turn carbon corrosion
on the cathode side, leading to irreversible cell performance dete-
rioration.
Abbou et al. [65] utilized a segmented linear cell with reference
electrodes to simultaneously monitor the local potentials and current
densities during the operation of DEA-PEMFC. Similar to the finding
from previous studies, water transport and nitrogen crossover across
the membrane were found to be the two key parameters governing
hydrogen starvation in DEA-PEMFC. In addition, it was found that the
primary factor affecting the cell performance deterioration is dictated
by the operating temperature of the anode: nitrogen crossover was
more pronounced at high temperatures while water accumulation was
10
Applied Energy 252 (2019) 113416
more dominant at low temperatures.
3. Mitigation strategies
As highlighted in the previous section, water and gas management
are utmost important to achieve optimum operation of DEA-PEMFC.
Water accumulation and nitrogen crossover which lead to hydrogen
starvation and in turn carbon corrosion and degradation of cell per-
formance and integration should be mitigated carefully to ensure suc-
cessful adoption of DEA-PEMFC. Accordingly, several methods and
strategies to address the aforementioned issue have been proposed in-
cluding purging, oscillating inlet or pressure swing and cascade design.
These methods together with several other methods will be described
and discussed in this section.
3.1. Anode purging
The most widely method to overcome water and nitrogen accu-
mulation in the anode of DEA-PEMFC is anode purging. This is per-
formed by opening the valve at the anode outlet to flush water and
nitrogen accumulated at the anode channel. With the removal of water
and nitrogen accumulation from the anode, hydrogen is able to reach
the active catalyst area and sufficiently fuel the cell electrochemical
reaction, recovering the cell performance and minimizing cell de-
gradation due to fuel starvation. Purging, however, poses the problem
of hydrogen fuel being flashed out from the anode which defeats the
purpose of dead-end anode operation to achieve high fuel utilization. As
such, careful consideration should be taken when conducting purging of
DEA-PEMFC. Considering its importance, numerous studies on purging
of DEA-PEMFC have been conducted.
Dumercy et al. [66] investigated the purging frequency of a DEA-
J.C. Kurnia, et al.
PEMFC by using 1 kW stack test bench. Their study suggested that the
purging frequency be adjusted to the current density to obtain the op-
timum balance between the fuel saving and the stack performance.
Nikiforow et al. [67] reported optimization study of purge cycle for the
PEMFC system. They evaluated the effect of humidity levels, purge
times and purge triggering criteria. They concluded that the change in
humidity level affects the optimized purge strategy. In addition, it was
shown that high fuel utilization can be achieved by using the optimized
purge strategy.
Belvedere et al. [68] developed a purge strategy based on the
measured slopes of the voltage decrease of a DEA-PEMFC running at
five different load power levels. With increasing load power, the op-
timum purge period was found to decrease. From the hydrogen flow
measurement during operation, it was found that the higher energy
efficiency can be achieved by using their proposed purge strategy. It
should be noted that the correlation between the slope and operating
conditions is required during fluctuating load operations.
A fractional factorial approach was adopted by Sasmito et al. [69] to
examine the effect of hydrogen purging time period, purging duration
and cathode stoichiometry on the performance of a DEA-PEMFC. The
stack performance was found to be a strong function of the interactions
between the cathode air-stoichiometry and the purging parameters.
They found that the optimum operating condition for their fuel cell
stack is a combination of cathode air-stoichiometry of 200%, purging
period of 3 min, and purging duration of 4 s. Gomez et al. [9] studied
the impact of coolant flow rate, cathode stoichiometry, purging period
and duration on a DEA-PEMFC-powered vehicle subjected to segments
of a European driving cycle (Fig. 9). A low purging duration was found
to eliminate the detrimental deceleration at high currents. Meanwhile,
a high purging period could sustain higher performance over time. They
concluded that a low cathode stoichiometry is desirable to achieve the
balance between the parasitic loads and cell performance. Another
important finding was that the coolant flow rate determines the stack
temperature–time response of the cooling control and the stack per-
formance, particularly at high operating currents. Interestingly, lower
hydrogen consumption was observed when the purging period was
high. Nevertheless, the purging strategy may need refinement and ad-
justment when implemented for a long duration operation of the fuel
cell since larger accumulations of liquid and impurities may occur at
the anode side. This highlights the necessity for a proper balance be-
tween the fuel utilization and the stack performance.
A similar study was reported by Hung et al. [70] who proposed a
purge strategy for a DEA-PEMFC operated under fluctuating-load
Fig. 9. Dead-end PEMFC under driving cycle: (a) current input and (b) power output from the stack for 5 min purging interval and purging duration of 1 s, 3 s and 5 s
[9].
11
Applied Energy 252 (2019) 113416
operations. A specially designed single cell was utilized to capture the
local performance over the active area of DEA-PEMFC during its op-
eration. This single cell was subjected to various purge strategies with
different threshold values under varying-load conditions. The purge
strategy proposed in their study is to open the purge valve when the
ratio of the local current density at the channel end to the cell current
density falls below the threshold value. It was found that, the threshold
value of less than 8 would degrade the cell performance for real prac-
tical applications.
Chen et al. [71] conducted optimization of purge cycle for a DEA-
PEMFC to achieve better efficiency by considering the effect of carbon
corrosion. In their optimization study, a model that can capture the
nitrogen and liquid water accumulations in the anode was developed to
illustrate the progression of corrosion rate and the amount of hydrogen
discharged during the purge. To define the target ranges for the purge
interval, the channel gas composition at the end of the purge cycle
duration was measured and analyzed. The significance of purge interval
and purge cycle duration on carbon corrosion and DEA-PEMFC effi-
ciency was then investigated. It was revealed that higher thermo-
dynamic efficiency can be achieved by implementing shorter purge
cycle durations and longer purge intervals while longer purge cycle
durations and shorter purge intervals leads to a reduction in the amount
of hydrogen loss. The lifetime simulation data at each grid within the
2D target domain for the purge cycle duration and purge interval was
collected and compiled to conduct the optimization. In their study, a
medium purge cycle duration with a short purge interval was found to
be the optimum configuration. Nevertheless, the operating conditions
and the physical specifications of the purging valve may change the
optimum purge interval and purge cycle duration.
In a following study, Chen et al. [72] carried out experiments to
evaluate the performance deprivation and recuperation characteristics
of DEA-PEMFC during gas purging and to obtain the optimal purge time
of a DEA-PEMFC. The main cause of performance degradation during
gas purging was membrane dehydration. Due to gas convection in the
purging process, easy removal of residual water in the membrane
electrode assembly could be achieved. Moreover, performance recovery
after gas purging was found to be mainly dictated by the back diffusion
of water. They concluded that increasing the operating temperature,
current density, and cathode RH reduces the performance recovery time
while the increase of the purging duration and anode pressure extends
the performance recovery time.
Another optimization study on the DEA-PEMFC anode purge was
conducted by Hu et al. [73]. They evaluated the effect of purge design
J.C. Kurnia, et al.
strategies, which was characterized as the ratio between purge interval
and purge time, and valve diameters. Three different cases were eval-
uated for various current densities. Fast data acquisition and advanced
tools, e.g. the fast cell voltage measurement (CVM) system and the mass
spectrum were utilized to monitor the cell performance during the
optimization study. Depending upon the cell operating condition, the
DEA fuel cell stack can achieve the required stability and system effi-
ciency when optimum purge strategy was implemented. Moreover, the
voltage stability was found to be significantly influenced by the dia-
meter of the purge valve due to a different purge volume and pressure
drop when the purge valve was open. Lin and Chen [74] experimentally
studied the DEA-PEMFC energy efficiency and the effect of purge
duration on it. At high operating cell current density, the required
purge duration to achieve optimal energy efficiency decreases due to
complete removal of impurities. It was concluded that the optimal en-
ergy efficiency for a DEA-PEMFC can be achieved by setting the purging
approximately one-fourth of anode gas.
Jian et al. [75] reported a slight periodic oscillation of voltage at a
constant load due to the periodic purge process of a DEA-PEMFC stack.
A valley in pressure appears when the load step-up changes, while a
peak appears when the stack transfers to the open-loop state. In their
following study, Jian et al. [76] experimentally investigated various
purge intervals and time to get the optimum purge strategy and to
achieve more stable voltage output. A step-by-step optimization method
was adopted to determine an optimal purge strategy that yields steady
voltage at various current densities. They indicated that optimum purge
strategy for a PEMFC stack can be achieved by balancing the hydrogen
utilization and voltage stability. They reported a stable voltage output
of the PEMFC stack can be achieved by having different purge strategies
without taking the utilization of hydrogen as the main factor. Moreover,
hydrogen utilization and voltage stability need to be considered artifi-
cially when determining the optimal purge strategy.
To reduce both hydrogen wastage and membrane-electrode as-
sembly deterioration during the operation of DEA-PEMFC, Abbou et al.
[77] proposed and evaluated several purge strategies. To simulta-
neously capture the time evolution of local anode and cathode poten-
tials and the current density distribution along the gas channel, a linear
segmented cell with reference electrodes was adopted. Platinum Electro
Chemical Surface Area (ECSA) and cell performance were closely
monitored to assess membrane-electrode assembly degradation and
damage. For a DEA_PEMFC, maintaining anode plate temperature at
5 °C hotter than the cathode plate was suggested as it confines water
accumulation in the anode side, significantly reducing purge frequency
(consequently lowering hydrogen losses) as well as MEA disintegration.
To minimize the hydrogen starvation due to nitrogen crossover and
accumulation at the anode, a microleakage solution was proposed to
continuously discharge most of the nitrogen accumulating in the anode
side but at the same time maintaining low hydrogen wastage and
minimum ECSA losses provided the right microleakage flow rate.
Manokaran et al. [78] reported the development of a self-supported
DEA-PEMFC equipped with internally humidified cathodic oxidant
flow. Purging was conducted to flush out the accumulated inert species
by using a timer-activated purge valve. The fuel cell stack was devel-
oped with a purge cell where all the inert species accumulate. It offers
reduction in the system complexity. It was confirmed that the in-
troduction of self-humidifying composite membranes in DEA-PEMFC
stacks mitigate the performance issue.
To deliver an optimised fuel cell system, Okedi et al. [79] conducted
an optimization study to determine an optimum combination of the
dead-end interval (when the purge valve is closed) and the purge in-
terval (when the purge valve is open), with regards to current density.
To minimize the number of runs without sacrificing the accuracy of
their result, Okedi et al. adopted the Design of Experiment (DoE) ap-
proach using multi-linear models. It was found that the stack efficiency
reduces as the purge interval increases and it increases when the cur-
rent density and dead-ended interval increase. In addition, a
12
Applied Energy 252 (2019) 113416
combination of high current density and purge duration slightly in-
creases the stack efficiency while the combination of higher current
density and the dead-end time decreases it.
Rahimi-Esbo et al. [18] claimed that they could achieve a higher
efficiency while maintaining the same polarization curve as that of the
open-end mode by designing the purge interval time of 5 s and the
opening purge valve of 1 s. However, when the purge interval is in-
creased, a gradual performance degradation was recorded. Santangelo
and Tartarini [10] imposed 4 electric-load conditions in a long duration
test on a DEA-PEMFC system to evaluate the impact of purges on the
system performance with fluctuating load. The tested purging strategy
imposed hydrogen losses and purge time was dictated by the accumu-
lation of water at the anode outlet. A remarkable similarity was ob-
served between a high applied load and operating at a constant applied
load and varying the cathode-air dew point. Overall, operating within
the linear region of the polarization curve was more desirable than
operating in the activation losses region.
Yang et al. [80] combined purging with recirculation to increase
stack and system efficiencies. High fuel utilization of 99.7% could be
achieved in the fuel cell system by re-circulating the hydrogen and
oxygen with the limited periodic purging. Electric efficiencies of ap-
proximately 60% and 49% can be achieved for the PEMFC stack and
system, respectively, at an operating condition of 1.1 kW electric
output. After a month of daily start-and-stop test, no performance de-
gradation of the PEMFC system was noticed. To examine the impact of
the purge strategy on energy efficiency, Tsai and Chen [81] developed a
model that can predict the fluctuation of gas composition along the
anode channel. The results indicated that the energy efficiency decrease
with a shorter purge durations due to incomplete impurity-removal. On
the other hand, while offering a high energy efficiency, long purge
durations increase the hydrogen losses.
Based on nitrogen concentration in the anode, Chen et al. [82] de-
veloped purging strategy and implemented it into the controller for the
anode gas management. The nitrogen accumulation in the anode was
expressed in term of operating current density and it was programmed
into the controller for the anode purge management. A high variation
cell voltage was recorded when the anode was purged at the nitrogen
molar fraction of 0.15 than at 0.07.
To achieve an optimum purging strategy, some researchers propose
active controller for the purging mechanism. Kuan et al. [83] in-
corporated a programmable system-on-chip to make a fuel cell con-
troller to manage the operating condition of PEMFC. During its op-
eration, the performance of the fuel cell was closely monitored and
related to the operating conditions, such as temperature, and water
management. This information was then used for the purge time in-
terval control. The controller developed in this study did not require
additional external power requirements, using only the power provided
by the fuel cell. A state observer and its associated control was proposed
by Piffard et al. [84] to optimize the anodic purge configuration for a
DEA-PEMFC. The observer command increases the fuel cell system ef-
ficiency and possibly its durability as compared to the other available
purge strategies. Nonetheless, enhancement on the control strategies
can be made by considering the opening time of the purge valve and
approximation of liquid water along the channels. In their following
study [85], an updated sliding mode observer was proposed to enhance
the controller performance. This observer provides the average values
of nitrogen and relative humidity with sufficient precision to be used in
a global real-time control scheme.
Despite the importance of purging in recovering the performance of
a DEA-PEMFC, it has to be applied carefully. Wu et al. [86] found that
water accumulation leads to localized flooding and heating, yielding a
low mechanical strength of the membrane. When purging initiated, the
formation of a pin-hole/membrane crack and a rapid decrease in open
circuit voltage due to gas crossover may occurs due to mechanical strain
on the membrane. Due to bipolar plate coupling and the current density
heterogeneities arising from the pin-hole/membrane crack, the crack
J.C. Kurnia, et al.
will potentially propagate to neighbouring cells if it is not handled
appropriately. Reintroduction of hydrogen after this condition may
cause cell voltage loss spreading from the pin-hole/membrane crack
location due to reactant crossover from the anode to the cathode.
Therefore, purging is not recommended and should be prevented when
flooding occurs to prevent permanent breakup to the stack. A similar
finding was also reported by Chen et al. [87] who observed serious
carbon corrosion in MEA when purging is conducted by setting criteria
on the voltage drop arbitrarily. They suggested conducting gas purging
before water flooding to extend lifespan of PEMFC.
3.2. Oscillating flow or pressure swing
As mentioned earlier, while it is widely adopted to recover fuel cell
performance, poorly designed purging may defeat the original purpose
of achieving high fuel utilization. As such, the pulsating technique at
anode has been proposed. Xiao et al. [88] investigated the performance
of a DEA-PEMFC with pulsation to improve the hydrogen utilization
efficiency. The results indicated that significantly improved perfor-
mance of a PEMFC stack can be achieved when the pulsation hydrogen
flow applied from the anode outlet. Jia et al. [89] adopted a hydrogen
pressure pulsation approach which is named hydrogen pressure pulsa-
tion feed (HPPF) to improve the performance of a DEA-PEMFC. HPPF
technique offers mitigation method to overcome the anode flooding
issue due to water back diffusion from the cathode and thus improves
the fuel cell performance, as shown in Fig. 10a. In addition, HPPF offers
Fig. 10. Performance of DEA-PEMFC with pressure swing: (a) as compared to steady input (b) with different pulsating frequency and (c) different pulsating
amplitude [89].
13
Applied Energy 252 (2019) 113416
the possibility to control the distribution of back diffusion water and
hydrogen partial pressure in the anode channels and enhance hydrogen
mass transfer in the anode flow field and diffusion of hydrogen in the
porous medium (anode diffusion layer). The results also indicate that
the performance of the PEMFC stack is a strong function of the pressure
pulsation amplitude and frequency as well as position applied for HPPF
(inlet or outlet of anode). It was possible to achieve higher performance
of a PEMFC by implementing high frequency or amplitude of pressure
pulsation or both, as can be seen in Fig. 10b and c.
Transient study of gas transport in an anode channel during pressure
swing operation of a DEA-PEMFC was conducted by Ichikawa et al.
[90]. The nitrogen concentration in the anode channel of a DEA-PEMFC
operated under constant pressure condition was different from that
operated under pressure swing supply conditions. Pressure swing
supply applied to the DEA-PEMFC generated oscillatory flow which
periodically swept out nitrogen from the active area. Consequently,
stable power generation can be achieved. Yang et al. [91] experimen-
tally studied pressure swing supply effect on a DEA-PEMFC. From the
polarization curve, pressure swing supply was found to effectively mi-
tigate the cell degradation during DEA operations, as indicated by the
finding of the cyclic voltammetry (CV) and EIS. However, it could not
prevent the cathode catalyst degradation during the DEA operation.
Closer examinations by SEM of the MEA confirmed the significant
changes in membrane degradations: a very large difference in average
thickness of the membranes was found after the degradation tests.
In their following study [92], sharp spikes in cell voltage were
J.C. Kurnia, et al.
recorded and reported. These spikes were particularly large close to the
end of a purge period. More detailed study revealed that the backflow
of liquid water and nitrogen in the anode channel from the outlet tube
was the main reason for the observed periodical spikes of cell voltage
and local current densities. A novel strategy was proposed to eliminate
this spike problem by incorporating an anode exit reservoir which was
found to be very effective in dampening the spikes of cell voltage and
local current densities. Another study was conducted to further elim-
inate water and nitrogen accumulation problems [93]. Three different
anode flow fields (parallel, serpentine and interdigitated) were eval-
uated under two operating modes. The most stable cell performance
under both constant pressure and pressure swing supply modes was
observed for the interdigitated flow field. For parallel and serpentine
anode flow fields, it was found that the anode pressure swing supply
mode provide more stable cell performance than the anode constant
pressure supply mode. It should be noted, however, that both flow
fields experience severe non-uniform local current distributions under
the constant pressure supply mode and severe fluctuations and spikes in
local current densities under the pressure swing supply mode.
3.3. Cascade design
In addition to purging and oscillating flow, cascade design has been
widely proposed and adopted to get higher performance of a DEA-
PEMFC. The basic mechanism of this design is that the PEMFC stack is
divided into several stages where outlet gas from each stage is treated in
a separator before inflowing the next stage.
Adopting cascade design approach, Han et al. [6] developed several
segments of anodic cells in a stack by inserting section between the
cells, building a multistage anode with a single-stage cathode in a single
stack. This design is expected to offer higher fuel utilization while
maintaining the simplicity of the system since it does not require hy-
drogen recirculation devices such as hydrogen pumps or ejectors and
control system which not only become parasitic power but also add
complexity to the system. By using this approach, it is possible to
maintain a higher gaseous flow rate at the outlet of the anodic cells,
even when operating the PEMFC under dead-end conditions. As a re-
sult, a reduction of purge-gas emissions can be achieved by hindering
the accumulation of liquid water and nitrogen in the anodic cells. The
experimental results showed that fuel utilization of more than 99.6%
can be achieved, represented by significantly lower purge gas. In ad-
dition, less fluctuation on output voltage of the stack was achieved as
compared to conventional fuel cells as a result of the multistage anode
design. Barzegari et al. [94–96] developed a mathematical model to
analyze and evaluate the performance of a dead-end cascade H2/O2
PEMFC stack. They indicated the capability of their model in closely
predicting the performance of a real cascade DEA-PEMFC. They later
developed a nonlinear dynamic model and model predictive control
(MPC) of a cascade-type PEMFC stack to track the desired voltage tra-
jectory of the dead-end cascade-type PEMFC stack.
Alizadeh et al. [97,98] proposed a novel cascade type design with
internal manifold for a DEA-PEMFC stack to maximize the fuel utili-
zation whilst maintaining the simple configuration of the PEMFC
system. In their design, they proposed a multistage anode and cathode
system where the cells of a stack were divided into a number of stages
by directing the outlet gas of each stage to a separator and injecting it
into the next stage (please refer to Fig. 11a). With this novel design, a
higher gaseous flow rate at the cell outlet can be maintained even under
dead-end conditions, resulting in a reduced purge-gas emission and thus
avoiding the accumulation of liquid water in the cells. This approach
offers better management of flooding issue in the DEA-PEMFC. A si-
milar polarization curve as that of the open-end mode can be achieved
by this design despite it was operated by dead-end anode mode, see
Fig. 11b.
Chen et al. [99] proposed mitigation method for carbon corrosion
by optimizing the opening size of the cathode outlet in a DEA-PEMFC.
14
Applied Energy 252 (2019) 113416
They concluded that larger opening size at the cathode outlet offers the
opportunity to reduce the electrode flooding due to a lower resistance
of water removal from the cathode outlet. As a result, less severe de-
terioration of cell performance and the corrosion of carbon support
were observed.
3.4. Other methods
Another strategy to overcome cell performance degradation due to
carbon corrosion induced by hydrogen starvation is by integrating hy-
drogen spillover materials which behave as a temporary hydrogen
storage as proposed by Halalay et al. [100]. This temporary hydrogen
storage can compensate for any temporary proton deficit caused by
local flooding of the anode channels. Several composite electrodes
made of TiO2, WSi2, and WO3, were tested and their performances were
compared to that of commercial Pt/Vulcan XC-72 carbon (Pt/Vu) which
was chosen as benchmark catalysts. Upon the pause of hydrogen
supply, both WSi2 and WO3 could postpone the voltage excursion of the
gas-diffusion electrode into the oxygen evolution region. Electrodes
with WO3 offer the most superior performance, with a hydrogen storage
charge 6 times higher than that of the Pt/Vu benchmark. A similar
approach was proposed by Lim et al. [56] by suggesting the introduc-
tions of the graphitized carbon support and water electrolysis catalyst
to anode are effective in alleviating the damage due to fuel starvation
by rendering the dominant alternative reaction to continue the water
electrolysis.
Himanen et al. [101] proposed an increased hydrogen pressure to
minimize the detrimental effect of water accumulation in the anode. A
higher hydrogen pressure increases water transport from the anode to
the cathode due to hydraulic permeation. At higher hydrogen pressure,
there was no significant decrease in the cell voltage observed sup-
porting the conclusion of changed water balance caused by an increased
hydraulic permeation. It should be noted, however, that the overall
performance was slightly decreased with the increased hydrogen pres-
sure which most likely attributed to the changed water balance which
in this case led to cathode flooding. Despite its potential in practical
power source application of free-breathing PEMFCs, for long-standing
operation, the cell shall be equipped with a purging system to ensure
the removal of surplus water in case of flooding.
Jang et al. [102] suggested fine-tuning the opening ratio of the
cathode opening geometry to achieve the proper mass and water
management of an air breathing PEMFC in the dead-end mode. Their
study indicated higher cell performance increases with a higher
opening ratio of the air flow field. In addition, by introducing mesoscale
channels on the flow fields surface of the cathode, the formation of the
gas diffusion layer was minimized considerably which was expected to
reduce liquid water back diffusion and accumulation in the anode. Bona
et al. [103] used a stack shunt in PEMFC stack to alleviate corrosion of
the catalyst support carbon. The proposed shunt protocol was claimed
to be very cost effective and required minimal changes in the system.
Thus, this method was suggested as a feasible method to reduce the
catalyst support carbon corrosion rate and lengthen the operating
lifespan of the PEMFC stack. Bussayajarn et al. [104] proposed and
evaluated three different cathode designs with the same opening ratio
for the DEA-PEMFC. The investigated designs were circular open, par-
allel slit, and oblique slit. Under the self-breathing condition, circular
opening design offers the best performance and the highest limiting
current density. Nevertheless, all three designs exhibited significant
improvements in performance and limiting current when the fuel cell
operated under forced convection condition. The stability of AB-PEMFC
can be maintained by introducing the periodic anode purging and water
removal mechanism.
In summary, despite various novel strategies proposed to maintain
or recover performance of DEA-PEMFC, purging mechanism is still
suggested to assist in recovering the cell/stack performance, especially
when the fuel cell is operated for long standing period.
J.C. Kurnia, et al.
Fig. 11. Cascade design (a) schematic and (b) its performance [97].
4. Future direction
To this point, we have presented and discussed a vast number of
reported studies on the DEA-PEMFC. Most of these studies were focused
on the water accumulations and nitrogen crossover and their con-
sequences to the cell performance and integration. Now, it is important
to forecast the direction of research and development in the DEA-
PEMFC. In this section, prediction on the future direction of DEA-
PEMFC will be presented and discussed.
As mentioned earlier, several researches have confirmed that the
nitrogen crossover from the cathode to anode is one main reason of the
cell performance degradation over time. This gas crossover leads to
nitrogen blanketing at the anode and reduces the available hydrogen
fuel for electrochemical reaction. Proper understanding of these phe-
nomena is therefore needed in future research to reduce performance
degradation. Possible mechanism of nitrogen crossover could be due to
(i) porous membrane structure and pressure gradient between anode
and cathode that leads to convective flux of nitrogen; (ii) nitrogen
15
Applied Energy 252 (2019) 113416
diffusion flux due to concentration gradient between anode and
cathode; and (iii) nitrogen solubility in polymeric water phase in
membrane that is dragged due to electroosmotic force. Future research
should focus into experimental and modeling studies to quantify the
above mechanisms in a controlled laboratory environment. Correlating
nitrogen flux and accumulation with overpotential, mass transport
limitation and reduction in activation energy of reactions could also be
carried out. Research in materials science and engineering could also
help improving membrane performance to reduce convective, diffusive
and nitrogen solubility in the polymeric water membrane as well as
electroosmotic drag force that leads to nitrogen crossover.
Understanding liquid water transport in PEMFC with DEA operation
is also crucial to mitigate the cell performance deterioration. It is a
complex process that involves coupled flow in plain and porous media,
phase change (evaporation-condensation), sorption-desorption of water
in polymeric phase, capillary force in saturated and/or unsaturated
porous media, and droplet dynamics in gas diffusion layer and flow
channel. The phenomena can be more complicated when DEA is used in
J.C. Kurnia, et al.
automotive applications in cold weather where water can be frozen and
become solid (ice). Future research should focus on both experimental
and modeling studies to quantify such phenomena, by understanding
the macroscopic aspect as well as pore-scale behavior from funda-
mental and applied aspect of the knowledge. All these processes are in
conjunction with mass transfer of all species involved in the PEMFC,
electrochemical reaction, ionic and electronic transport, and heat
transfer. Optimization on flow channel design for such a DEA operation
may be needed to enhance water removal and droplet dynamics during
purging.
For successful application of DEA-PEMFC, especially in automotive
applications, further research and development works have to be con-
ducted in future to optimize the design and operating conditions.
Optimization of the purging system is one of the crucial aspects. So far,
most of purging studies were conducted in a single cell or a stack
comprising several cells. In automotive applications, however, the fuel
cell stack can comprise hundreds of single cells, thus water manage-
ment and purging become more complex. Purging frequency and
duration coupled with dynamic operation in a driving cycle in large
stacks add complexity to the already complex system. To achieve the
optimum purging condition, understanding the DEA phenomena in
both cell and stack levels and developing advanced control and in-
strumentation system are crucial. Other approaches to eliminate pur-
ging have also become promising alternative to simplify the design.
Oscillating pressure has been proven to produce better performance.
However, for large scale stack and long-term used under dynamic
driving conditions, further evaluations are necessary. Cascade design
shows potential, albeit the dynamic performance and quantification of
nitrogen and water build-up still need extended investigations.
5. Conclusion
The performance of a proton exchange membrane fuel cell with
dead-end anode operation has been reviewed at various operating
conditions. Performance degradation over time is observed in both
galvanostatic and potentiostatic modes. Low operating current yields
more stable performance, while high operating current leads to faster
deterioration. It is also worth mentioning that performance degradation
starts from an area close to the outlet and propagates close to the inlet
area. This is due to reduced available hydrogen fuel from nitrogen
blanketing and water accumulation, which may lead to catalyst poi-
soning and reduced durability. These have been proven both experi-
mentally and from modeling studies. To remove impurities and recover
stack performance, purging is the common method employed. Several
authors have evaluated the effect of purging and optimized it for better
performance. Several alternatives have also been proposed such as
pressure oscillation in anode, cascade design and interdigitated flow
channels to eliminate purging while maintaining stack performance
over time.
Dead-end anode operation has great potential for applications in
automotive industry. It can also be coupled with an open-cathode de-
sign and edge-cooling technology to further reduce the complexity, size,
weight and cost. For successful implementation, however, additional
research is needed from fundamental and applied aspects. The former
concerns on understanding transport phenomena and development of
novel membrane and catalyst material to sustain dead-end anode op-
eration, while the later should focus on integration of applied research,
design and optimization as well as laboratory and in-field testing of the
dead-end anode application.
References
[1] Wang Y, Chen KS, Mishler J, Cho SC, Adroher XC. A review of polymer electrolyte
membrane fuel cells: Technology, applications, and needs on fundamental re-
search. Appl Energy 2011;88:981–1007. https://doi.org/10.1016/j.apenergy.
2010.09.030.
16
Applied Energy 252 (2019) 113416
[2] Rahimnejad M, Adhami A, Darvari S, Zirepour A, Oh S-E. Microbial fuel cell as new
technology for bioelectricity generation: A review. Alexandria Eng J
2015;54:745–56. https://doi.org/10.1016/j.aej.2015.03.031.
[3] Roda V, Carroquino J, Valiño L, Lozano A, Barreras F. Remodeling of a commercial
plug-in battery electric vehicle to a hybrid configuration with a PEM fuel cell. Int J
Hydrogen Energy 2018;43:16959–70. https://doi.org/10.1016/j.ijhydene.2017.
12.171.
[4] Kurnia JC, Sasmito AP, Shamim T. Performance evaluation of a PEM fuel cell stack
with variable inlet flows under simulated driving cycle conditions. Appl Energy
2017;206:751–64. https://doi.org/10.1016/j.apenergy.2017.08.224.
[5] Koski P, Pérez LC, Ihonen J. Comparing anode gas recirculation with hydrogen
purge and bleed in a novel PEMFC laboratory test cell configuration. Fuel Cells
2015;15:494–504. https://doi.org/10.1002/fuce.201400102.
[6] Han I-S, Jeong J, Shin HK. PEM fuel-cell stack design for improved fuel utilization.
Int J Hydrogen Energy 2013;38:11996–2006. https://doi.org/10.1016/j.ijhydene.
2013.06.136.
[7] Hwang J-J. Effect of hydrogen delivery schemes on fuel cell efficiency. J Power
Sources 2013;239:54–63. https://doi.org/10.1016/j.jpowsour.2013.03.090.
[8] Lee H-Y, Su H-C, Chen Y-S. A gas management strategy for anode recirculation in a
proton exchange membrane fuel cell. Int J Hydrogen Energy 2018;43:3803–8.
https://doi.org/10.1016/j.ijhydene.2018.01.026.
[9] Gomez A, Sasmito AP, Shamim T. Investigation of the purging effect on a dead-end
anode PEM fuel cell-powered vehicle during segments of a European driving cycle.
Energy Convers Manage 2015;106:951–7. https://doi.org/10.1016/j.enconman.
2015.10.025.
[10] Santangelo PE, Tartarini P. Effects of load variation and purge cycles on the effi-
ciency of polymer electrolyte membrane fuel cells for stationary applications.
014301 J Rene Sustain Energy 2018;10. https://doi.org/10.1063/1.5000936.
[11] Inman K, Ahmad Z, Shi Z, Wang X. Design of a proton exchange membrane por-
table fuel cell system for the 1st international association for hydrogen energy
design competition. Int J Hydrogen Energy 2011;36:13868–74. https://doi.org/
10.1016/j.ijhydene.2011.04.213.
[12] Thangavelautham J, Strawser DD, Dubowsky S. The design of long-life, high-ef-
ficiency PEM fuel cell power supplies for low power sensor networks. Int J
Hydrogen Energy 2017;42:20277–96. https://doi.org/10.1016/j.ijhydene.2017.
05.206.
[13] Hikita S, Nakatani F, Yamane K, Takagi Y. Power-generation characteristics of
hydrogen fuel cell with dead-end system. JSAE Rev 2002;23:177–82. https://doi.
org/10.1016/S0389-4304(02)00161-3.
[14] Abbou S, Dillet J, Spernjak D, Mukundan R, Borup RL, Maranzana G, et al. High
potential excursions during pem fuel cell operation with dead-ended anode. J
Electrochem Soc 2015;162:F1212–20. https://doi.org/10.1149/2.0511510jes.
[15] Gomez A, Raj A, Sasmito AP, Shamim T. Effect of operating parameters on the
transient performance of a polymer electrolyte membrane fuel cell stack with a
dead-end anode. Appl Energy 2014;130:692–701. https://doi.org/10.1016/j.
apenergy.2013.12.030.
[16] Chen J. Degradation, efficiency, and equilibrium of a dead-ended anode fuel cell.
PhD Thesis. The University of Michigan; 2013.
[17] Perez Page M, Perez-Herranz V. Effect of the operation and humidification tem-
peratures on the performance of a PEM fuel cell stack. Int J Electrochem Sci
2009;25. https://doi.org/10.1149/1.3210625.
[18] Rahimi-Esbo M, Ramiar A, Ranjbar AA, Alizadeh E. Design, manufacturing, as-
sembling and testing of a transparent PEM fuel cell for investigation of water
management and contact resistance at dead-end mode. Int J Hydrogen Energy
2017;42:11673–88. https://doi.org/10.1016/j.ijhydene.2017.02.030.
[19] Satija R, Jacobson DL, Arif M, Werner SA. In situ neutron imaging technique for
evaluation of water management systems in operating PEM fuel cells. J Power
Sources 2004;129:238–45. https://doi.org/10.1016/j.jpowsour.2003.11.068.
[20] Chen Y-S, Peng H, Hussey DS, Jacobson DL, Tran DT, Abdel-Baset T, et al. Water
distribution measurement for a PEMFC through neutron radiography. J Power
Sources 2007;170:376–86. https://doi.org/10.1016/j.jpowsour.2007.03.076.
[21] Trabold TA, Owejan JP, Gagliardo JJ, Jacobson DL, Hussey DS, Arif M. Use of
neutron imaging for proton exchange membrane fuel cell (PEMFC) performance
analysis and design. In: Vielstich W, Lamm A, Gasteiger HA, Yokokawa H, editors.
Handbook of fuel cells Chichester, UK: John Wiley & Sons, Ltd; 2010. https://doi.
org/10.1002/9780470974001.f500047.
[22] Manke I, Markötter H, Arlt T, Tötzke Ch, Klages M, Haußmann J, et al. Fuel cell
research with neutron imaging at helmholtz centre Berlin. Phys Proc
2015;69:619–27. https://doi.org/10.1016/j.phpro.2015.07.088.
[23] Meyer Q, Ashton S, Jervis R, Finegan DP, Boillat P, Cochet M, et al. The hydro-
electro-thermal performance of air-cooled, open-cathode polymer electrolyte fuel
cells: combined localised current density. Temp Water Mapping. Electrochim Acta
2015;180:307–15. https://doi.org/10.1016/j.electacta.2015.08.106.
[24] Siegel JB, McKay DA, Stefanopoulou AG, Hussey DS, Jacobson DL. Measurement of
liquid water accumulation in a PEMFC with dead-ended anode. J Electrochem Soc
2008;155:B1168–78. https://doi.org/10.1149/1.2976356.
[25] Bellows RJ, Lin MY, Arif M, Thompson AK, Jacobson D. Neutron imaging tech-
nique for in situ measurement of water transport gradients within nafion in
polymer electrolyte fuel cells. J Electrochem Soc 1999;146:1099–103. https://doi.
org/10.1149/1.1391727.
[26] Manokaran A, Pushpavanam S, Sridhar P, Pitchumani S. Experimental analysis of
spatio-temporal behavior of anodic dead-end mode operated polymer electrolyte
fuel cell. J Power Sources 2011;196:9931–8. https://doi.org/10.1016/j.jpowsour.
2011.06.103.
[27] O’Rourke J, Ramani M, Arcak M. In situ detection of anode flooding of a PEM fuel
cell. Int J Hydrogen Energy 2009;34:6765–70. https://doi.org/10.1016/j.
J.C. Kurnia, et al.
ijhydene.2009.06.029.
[28] Coz E, Théry J, Boillat P, Faucheux V, Alincant D, Capron P, et al. Water man-
agement in a planar air-breathing fuel cell array using operando neutron imaging.
J Power Sources 2016;331:535–43. https://doi.org/10.1016/j.jpowsour.2016.09.
041.
[29] Meyer Q, Ashton S, Curnick O, Reisch T, Adcock P, Ronaszegi K, et al. Dead-ended
anode polymer electrolyte fuel cell stack operation investigated using electro-
chemical impedance spectroscopy, off-gas analysis and thermal imaging. J Power
Sources 2014;254:1–9. https://doi.org/10.1016/j.jpowsour.2013.11.125.
[30] Lee Y, Kim B, Kim Y. An experimental study on water transport through the
membrane of a PEFC operating in the dead-end mode. Int J Hydrogen Energy
2009;34:7768–79. https://doi.org/10.1016/j.ijhydene.2009.07.010.
[31] Lee B, Sohn Y-J. Experimental analysis for optimization of PEM fuel cell dead-end
operation. Trans Korean Hydrogen New Energy Soc 2015;26:136–47. https://doi.
org/10.7316/KHNES.2015.26.2.136.
[32] Karst N, Faucheux V, Martinent A, Bouillon P, Laurent J-Y, Druart F, et al.
Innovative water management in micro air-breathing polymer electrolyte mem-
brane fuel cells. J Power Sources 2010;195:1156–62. https://doi.org/10.1016/j.
jpowsour.2009.08.068.
[33] Soopee A, Sasmito AP, Shamim T. Water dynamics in the flow channel of a dead-
end anode polymer electrolyte membrane fuel cell. Energy Proced
2017;105:1877–82. https://doi.org/10.1016/j.egypro.2017.03.550.
[34] Mahyari H, Afrouzi HH, Shams M. Three dimensional transient multiphase flow
simulation in a dead end anode polymer electrolyte fuel cell. J Mol Liq
2017;225:391–405. https://doi.org/10.1016/j.molliq.2016.11.063.
[35] Baik KD, Kim MS. Characterization of nitrogen gas crossover in PEM fuel cell
stacks. Trans Korean Soc Mech Eng - B 2009;33:207–14.
[36] Baik KD, Kim MS. Characterization of nitrogen gas crossover through the mem-
brane in proton-exchange membrane fuel cells. Int J Hydrogen Energy
2011;36:732–9. https://doi.org/10.1016/j.ijhydene.2010.09.046.
[37] Karimäki H, Pérez LC, Nikiforow K, Keränen TM, Viitakangas J, Ihonen J. The use
of on-line hydrogen sensor for studying inert gas effects and nitrogen crossover in
PEMFC system. Int J Hydrogen Energy 2011;36:10179–87. https://doi.org/10.
1016/j.ijhydene.2011.04.230.
[38] Siegel JB, Bohac SV, Stefanopoulou AG, Yesilyurt S. Nitrogen front evolution in
purged polymer electrolyte membrane fuel cell with dead-ended anode. J
Electrochem Soc 2010;157:B1081–93. https://doi.org/10.1149/1.3425743.
[39] Kocha SS, Yang JD, Yi JS. Characterization of gas crossover and its implications in
PEM fuel cells. AIChE J 2006;52:1916–25. https://doi.org/10.1002/aic.10780.
[40] Müller EA, Kolb F, Guzzella L, Stefanopoulou AG, McKay DA. Correlating nitrogen
accumulation with temporal fuel cell performance. J Fuel Cell Sci Technol 2010;7.
https://doi.org/10.1115/1.3177447. 021013–021013–11.
[41] Meyer Q, Ashton S, Torija S, Gurney C, Boillat P, Cochet M, et al. Nitrogen blan-
keting and hydrogen starvation in dead-ended-anode polymer electrolyte fuel cells
revealed by hydro-electro-thermal analysis. Electrochim Acta 2016;203:198–205.
https://doi.org/10.1016/j.electacta.2016.04.018.
[42] Ahluwalia RK, Wang X. Buildup of nitrogen in direct hydrogen polymer-electrolyte
fuel cell stacks. J Power Sources 2007;171:63–71. https://doi.org/10.1016/j.
jpowsour.2007.01.032.
[43] Jiang D, Zeng R, Wang S, Jiang L, Varcoe JR. Paradox phenomena of proton ex-
change membrane fuel cells operating under dead-end anode mode. J Power
Sources 2014;265:45–9. https://doi.org/10.1016/j.jpowsour.2014.04.086.
[44] Baumgartner WR, Parz P, Fraser SD, Wallnöfer E, Hacker V. Polarization study of a
PEMFC with four reference electrodes at hydrogen starvation conditions. J Power
Sources 2008;182:413–21. https://doi.org/10.1016/j.jpowsour.2008.01.001.
[45] Rangel C, Silva R, Travassos MA, Paiva T, Fernandes VR. Fuel starvation: irre-
versible degradation mechanisms in PEM fuel cells. In: Stolten D, Grube T, editors.
Proceedings of the WHEC. Essen: Forschungszentrum Julich GmbH; 2010. p. 31–6.
[46] Ohs JH, Sauter U, Maass S, Stolten D. Modeling hydrogen starvation conditions in
proton-exchange membrane fuel cells. J Power Sources 2011;196:255–63. https://
doi.org/10.1016/j.jpowsour.2010.06.038.
[47] Borup R, Meyers J, Pivovar B, Kim YS, Mukundan R, Garland N, et al. Scientific
aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev
2007;107:3904–51. https://doi.org/10.1021/cr050182l.
[48] Yousfi-Steiner N, Moçotéguy Ph, Candusso D, Hissel D. A review on polymer
electrolyte membrane fuel cell catalyst degradation and starvation issues: Causes,
consequences and diagnostic for mitigation. J Power Sources 2009;194:130–45.
https://doi.org/10.1016/j.jpowsour.2009.03.060.
[49] Mathias MF, Makharia R, Gasteiger HA, Conley JJ, Fuller TJ, Gittleman CJ, et al.
Two fuel cell cars in every garage? Electrochem Soc Interface 2005;14:24–35.
[50] Wu J, Yuan XZ, Martin JJ, Wang H, Zhang J, Shen J, et al. A review of PEM fuel
cell durability: Degradation mechanisms and mitigation strategies. J Power
Sources 2008;184:104–19. https://doi.org/10.1016/j.jpowsour.2008.06.006.
[51] Patterson TW, Darling RM. Damage to the cathode catalyst of a PEM fuel cell
caused by localized fuel starvation. Electrochem Solid-State Lett 2006;9. https://
doi.org/10.1149/1.2167930. A183 A185.
[52] Ishigami Y, Maeda I, Takada K, Hyakutake T, Suga T, Inukai J, et al. Real-time
visualization of CO2 generated by corrosion of the carbon support in a PEFC
cathode. Electrochem Solid-State Lett 2012;15. https://doi.org/10.1149/2.
018204esl. B51 B53.
[53] Liu ZY, Brady BK, Carter RN, Litteer B, Budinski M, Hyun JK, et al.
Characterization of carbon corrosion-induced structural damage of PEM fuel cell
cathode electrodes caused by local fuel starvation. J Electrochem Soc
2008;155:B979–84. https://doi.org/10.1149/1.2956198.
[54] Liang D, Shen Q, Hou M, Shao Z, Yi B. Study of the cell reversal process of large
area proton exchange membrane fuel cells under fuel starvation. J Power Sources
17
Applied Energy 252 (2019) 113416
2009;194:847–53. https://doi.org/10.1016/j.jpowsour.2009.06.059.
[55] Yang X-G, Ye Q, Cheng P. In-plane transport effects on hydrogen depletion and
carbon corrosion induced by anode flooding in proton exchange membrane fuel
cells. Int J Heat Mass Transfer 2012;55:4754–65. https://doi.org/10.1016/j.
ijheatmasstransfer.2012.04.040.
[56] Lim KH, Lee WH, Jeong Y, Kim H. Analysis of carbon corrosion in anode under fuel
starvation using on-line mass spectrometry in polymer electrolyte membrane fuel
cells. J Electrochem Soc 2017;164. https://doi.org/10.1149/2.0731714jes. F1580
F1586.
[57] Chen J, Siegel JB, Matsuura T, Stefanopoulou AG. Carbon corrosion in PEM fuel
cell dead-ended anode operations. J Electrochem Soc 2011;158. https://doi.org/
10.1149/1.3609770. B1164 B1174.
[58] Matsuura T, Siegel JB, Chen J, Stefanopoulou AG. Multiple degradation phe-
nomena in polymer electrolyte fuel cell operation with dead-ended anode.
Washington, DC, USA: ASME; 2011. p. 127–35. https://doi.org/10.1115/
FuelCell2011-54344.
[59] Matsuura T, Chen J, Siegel JB, Stefanopoulou AG. Degradation phenomena in PEM
fuel cell with dead-ended anode. Int J Hydrogen Energy 2013;38:11346–56.
https://doi.org/10.1016/j.ijhydene.2013.06.096.
[60] Sasmito AP, Mujumdar AS. Performance evaluation of a polymer electrolyte fuel
cell with a dead-end anode: A computational fluid dynamic study. Int J Hydrogen
Energy 2011;36:10917–33. https://doi.org/10.1016/j.ijhydene.2011.05.171.
[61] Abbou S, Dillet J, Maranzana G, Didierjean S, Lottin O. Local potential evolutions
during proton exchange membrane fuel cell operation with dead-ended anode –
Part I: Impact of water diffusion and nitrogen crossover. J Power Sources
2017;340:337–46. https://doi.org/10.1016/j.jpowsour.2016.11.079.
[62] Marignetti F, Minutillo M, Perna A, Jannelli E. Assessment of fuel cell performance
under different air stoichiometries and fuel composition. IEEE T Ind Electron
2011;58:2420–6. https://doi.org/10.1109/TIE.2010.2069073.
[63] Yang Y, Zhang X, Guo L, Liu H. Overall and local effects of operating conditions in
PEM fuel cells with dead-ended anode. Int J Hydrogen Energy 2017;42:4690–8.
https://doi.org/10.1016/j.ijhydene.2016.08.091.
[64] Yu J, Jiang Z, Hou M, Liang D, Xiao Y, Dou M, et al. Analysis of the behavior and
degradation in proton exchange membrane fuel cells with a dead-ended anode. J
Power Sources 2014;246:90–4. https://doi.org/10.1016/j.jpowsour.2013.06.163.
[65] Abbou S, Dillet J, Maranzana G, Didierjean S, Lottin O. Impact of water man-
agement on local potential evolutions during PEM fuel cell operation with dead-
ended anode. ECS Trans 2015;69:1267–76. https://doi.org/10.1149/06917.
1267ecst.
[66] Dumercy L, Péra M-C, Glises R, Hissel D, Hamandi S, Badin F, et al. PEFC stack
operating in anodic dead end mode. Fuel Cells 2004;4:352–7. https://doi.org/10.
1002/fuce.200400053.
[67] Nikiforow K, Karimäki H, Keränen TM, Ihonen J. Optimization study of purge
cycle in proton exchange membrane fuel cell system. J Power Sources
2013;238:336–44. https://doi.org/10.1016/j.jpowsour.2012.11.153.
[68] Belvedere B, Bianchi M, Borghetti A, De Pascale A, Paolone M, Vecci R.
Experimental analysis of a PEM fuel cell performance at variable load with anodic
exhaust management optimization. Int J Hydrogen Energy 2013;38:385–93.
https://doi.org/10.1016/j.ijhydene.2012.09.147.
[69] Sasmito AP, Ali MI, Shamim T. A factorial study to investigate the purging effect
on the performance of a dead-end anode PEM fuel cell stack. Fuel Cells
2015;15:160–9. https://doi.org/10.1002/fuce.201300069.
[70] Hung C-Y, Huang H-S, Tsai S-W, Chen Y-S. A purge strategy for proton exchange
membrane fuel cells under varying-load operations. Int J Hydrogen Energy
2016;41:12369–76. https://doi.org/10.1016/j.ijhydene.2016.05.132.
[71] Chen J, Siegel JB, Stefanopoulou AG, Waldecker JR. Optimization of purge cycle
for dead-ended anode fuel cell operation. Int J Hydrogen Energy
2013;38:5092–105. https://doi.org/10.1016/j.ijhydene.2013.02.022.
[72] Chen B, Tu Z, Chan SH. Performance degradation and recovery characteristics
during gas purging in a proton exchange membrane fuel cell with a dead-ended
anode. Appl Therm Eng 2018;129:968–78. https://doi.org/10.1016/j.
applthermaleng.2017.10.102.
[73] Hu Z, Yu Y, Wang G, Chen X, Chen P, Chen J, et al. Anode purge strategy opti-
mization of the polymer electrode membrane fuel cell system under the dead-end
anode operation. J Power Sources 2016;320:68–77. https://doi.org/10.1016/j.
jpowsour.2016.04.023.
[74] Lin Y-F, Chen Y-S. Experimental study on the optimal purge duration of a proton
exchange membrane fuel cell with a dead-ended anode. J Power Sources
2017;340:176–82. https://doi.org/10.1016/j.jpowsour.2016.11.039.
[75] Jian Q, Zhao Y, Wang H. An experimental study of the dynamic behavior of a 2 kW
proton exchange membrane fuel cell stack under various loading conditions.
Energy 2015;80:740–5. https://doi.org/10.1016/j.energy.2014.12.032.
[76] Jian Q, Luo L, Huang B, Zhao J, Cao S, Huang Z. Experimental study on the purge
process of a proton exchange membrane fuel cell stack with a dead-end anode.
Appl Therm Eng 2018;142:203–14. https://doi.org/10.1016/j.applthermaleng.
2018.07.001.
[77] Abbou S, Dillet J, Maranzana G, Didierjean S, Lottin O. Local potential evolutions
during proton exchange membrane fuel cell operation with dead-ended anode –
Part II: Aging mitigation strategies based on water management and nitrogen
crossover. J Power Sources 2017;340:419–27. https://doi.org/10.1016/j.
jpowsour.2016.10.045.
[78] Manokaran A, Jalajakshi A, Sahu AK, Sridhar P, Pitchumani S, Shukla AK. Design
and development of a self-supported polymer electrolyte fuel cell system with
anodic dead-end operation. P I Mech Eng A-J Pow 2011;225:175–82. https://doi.
org/10.1177/2041296710394262.
[79] Okedi TI, Meyer Q, Hunter HMA, Shearing PR, Brett DJL. Development of a
J.C. Kurnia, et al.
polymer electrolyte fuel cell dead-ended anode purge strategy for use with a ni-
trogen-containing hydrogen gas supply. Int J Hydrogen Energy 2017;42:13850–9.
https://doi.org/10.1016/j.ijhydene.2016.11.081.
[80] Yang C, Moon S, Kim Y. A self-operated polymer electrolyte fuel cell system op-
erating at dead-end conditions using pure hydrogen and oxygen gases. J Mech Sci
Technol 2015;29:3541–7. https://doi.org/10.1007/s12206-015-0751-4.
[81] Tsai S-W, Chen Y-S. A mathematical model to study the energy efficiency of a
proton exchange membrane fuel cell with a dead-ended anode. Appl Energy
2017;188:151–9. https://doi.org/10.1016/j.apenergy.2016.11.128.
[82] Chen Y-S, Yang C-W, Lee J-Y. Implementation and evaluation for anode purging of
a fuel cell based on nitrogen concentration. Appl Energy 2014;113:1519–24.
https://doi.org/10.1016/j.apenergy.2013.09.028.
[83] Kuan Y-D, Chang J-Y, Ku H-T. Proton exchange membrane fuel cell purge and fan
control using a microcontroller. Int J Green Energy 2017;14:86–91. https://doi.
org/10.1080/15435075.2016.1206011.
[84] Piffard M, Gerard M, Bideaux E, Fonseca RD, Massioni P. Control by state observer
of PEMFC anodic purges in dead-end operating mode. IFAC-PapersOnLine.
Columbus, Ohio, USA: Elsevier; 2015. p. 237–43. https://doi.org/10.1016/j.ifacol.
2015.10.034.
[85] Piffard M, Gerard M, Fonseca RD, Massioni P, Bideaux E. Sliding mode observer for
proton exchange membrane fuel cell: automotive application. J Power Sources
2018;388:71–7. https://doi.org/10.1016/j.jpowsour.2018.03.057.
[86] Wu B, Parkes MA, de Benedetti L, Marquis AJ, Offer GJ, Brandon NP. Real-time
monitoring of proton exchange membrane fuel cell stack failure. J Appl
Electrochem 2016;46:1157–62. https://doi.org/10.1007/s10800-016-0995-4.
[87] Chen B, Wang J, Yang T, Cai Y, Zhang C, Chan SH, et al. Carbon corrosion and
performance degradation mechanism in a proton exchange membrane fuel cell
with dead-ended anode and cathode. Energy 2016;106:54–62. https://doi.org/10.
1016/j.energy.2016.03.045.
[88] Xiao Y, Jia QH, Li C, Chang YJ. Performance analysis of PEM fuel cell using pul-
sation approach. Appl Mech Mater 2014;644–650:5188–92. https://doi.org/10.
4028/www.scientific.net/AMM.644-650.5188.
[89] Jia Q, Zhang C, Deng B, Han M. Performance improvement for proton exchange
membrane fuel cell using hydrogen pressure pulsation approach. J Fuel Cell Sci
Technol 2015;12. https://doi.org/10.1115/1.4031525. 041008–041008–6.
[90] Ichikawa Y, Oshima N, Tabuchi Y, Ikezoe K. Transient analysis of gas transport in
anode channel of a polymer electrolyte membrane fuel cell with dead-ended anode
under pressure swing operation. J Power Sources 2014;272:743–52. https://doi.
org/10.1016/j.jpowsour.2014.09.023.
[91] Yang Y, Zhang X, Guo L, Liu H. Degradation mitigation effects of pressure swing in
proton exchange membrane fuel cells with dead-ended anode. Int J Hydrogen
Energy 2017;42:24435–47. https://doi.org/10.1016/j.ijhydene.2017.07.223.
[92] Yang Y, Zhang X, Guo L, Liu H. Mechanisms of voltage spikes and mitigation
strategies for proton exchange membrane fuel cells with dead-ended anode under
pressure swing operation. Int J Hydrogen Energy 2017;42:28578–87. https://doi.
18
Applied Energy 252 (2019) 113416
org/10.1016/j.ijhydene.2017.09.103.
[93] Yang Y, Zhang X, Guo L, Liu H. Different flow fields, operation modes and designs
for proton exchange membrane fuel cells with dead-ended anode. Int J Hydrogen
Energy 2018;43:1769–80. https://doi.org/10.1016/j.ijhydene.2017.10.137.
[94] Barzegari MM, Dardel M, Alizadeh E, Ramiar A. Dynamic modeling and validation
studies of dead-end cascade H2/O2 PEM fuel cell stack with integrated humidifier
and separator. Appl Energy 2016;177:298–308. https://doi.org/10.1016/j.
apenergy.2016.05.132.
[95] Barzegari MM, Dardel M, Ramiar A, Alizadeh E. An investigation of temperature
effect on performance of dead-end cascade H2/O2 PEMFC stack with integrated
humidifier and separator. Int J Hydrogen Energy 2016;41:3136–46. https://doi.
org/10.1016/j.ijhydene.2015.12.082.
[96] Barzegari MM, Alizadeh E, Khorshidian M, Rahgoshay SM, Saadat SHM. Nonlinear
grey-box modeling and model predictive control for cascade-type PEM fuel cell
stack. IEEE Vehicle Power and Propulsion Conference (VPPC) 2017;2017:1–5.
https://doi.org/10.1109/VPPC.2017.8330979.
[97] Alizadeh E, Khorshidian M, Saadat SHM, Rahgoshay SM, Rahimi-Esbo M. The
experimental analysis of a dead-end H2/O2 PEM fuel cell stack with cascade type
design. Int J Hydrogen Energy 2017;42:11662–72. https://doi.org/10.1016/j.
ijhydene.2017.03.094.
[98] Alizadeh E, Khorshidian M, Saadat SHM, Rahgoshay SM, Rahimi-Esbo M.
Experimental study on a 1000W dead-end H2/O2 PEM fuel cell stack with cascade
type for improving fuel utilization. Iranian J Hydrogen Fuel Cell 2016. https://doi.
org/10.22104/ijhfc.2017.421.
[99] Chen B, Wang J, Yang T, Cai Y, Pan M, Tu Z, et al. Mitigation studies of carbon
corrosion by optimizing the opening size of the cathode outlet in a proton ex-
change membrane fuel cell with dead-ended anode. Energy Convers Manage
2016;119:60–6. https://doi.org/10.1016/j.enconman.2016.04.043.
[100] Halalay IC, Swathirajan S, Merzougui B, Balogh MP, Garabedian GC, Carpenter
MK. Anode materials for mitigating hydrogen starvation effects in PEM fuel cells. J
Electrochem Soc 2011;158:B313–21. https://doi.org/10.1149/1.3530796.
[101] Himanen O, Hottinen T, Tuurala S. Operation of a planar free-breathing PEMFC in
a dead-end mode. Electrochem Commun 2007;9:891–4. https://doi.org/10.1016/
j.elecom.2006.12.002.
[102] Jang WK, Choi J, Seo YH, Kim BH. Effect of cathode flow field configuration on
air-breathing proton exchange membrane fuel cell. Int J Precis Eng Manuf
2015;16:1129–34. https://doi.org/10.1007/s12541-015-0146-6.
[103] Bona D, Curtin DE, Pedrazzo F, Tresso EM. Using a stack shunt to mitigate catalyst
support carbon corrosion in polymer electrolyte membrane fuel cell stacks during
start-stop cycling. J Fuel Cell Sci Technol 2013;11. https://doi.org/10.1115/1.
4025535. 011010–011010–7.
[104] Bussayajarn N, Ming H, Hoong KK, Ming Stephen WY, Hwa CS. Planar air
breathing PEMFC with self-humidifying MEA and open cathode geometry design
for portable applications. Int J Hydrogen Energy 2009;34:7761–7. https://doi.
org/10.1016/j.ijhydene.2009.07.077.