i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8

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Review

A review of unitized regenerative fuel cell stack:

Material, design and research achievements

Mohamed Gabbasa a,b, Kamaruzzaman Sopian a, Ahmad Fudholi a,

Nilofar Asim a,*
a
Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
b
Department of Chemical and Process Engineering, Zawia Higher Institute of Polytechnics, Al-Zawia, Tripoli, Libya

article info abstract

Article history: The stack design of a unitized regenerative fuel cell (URFC) can modify the structure of cells
Received 20 May 2014 that can be used as storage and energy regenerator aside from cells that use other sources
Received in revised form such as solar or wind energy. A reversible unitized polymer electrolyte membrane fuel cell
21 August 2014 (PEMFC) contains a dual-functional single cell that is less expensive and has enhanced
Accepted 23 August 2014 performance. The use of URFCs on hydrogen and oxygen is preferred because it is highly
Available online 17 September 2014 efficient, environmentally friendly, and uses power generators. The stack, then, must be
made affordable or accessible. The expenses of URFC stack must be reduced by improving
Keywords: its design, materials, and performance. This study referred to recent studies on developing
Regenerative fuel cell a method to cut the expenses of the URFC stack. The study also aims to determine its main
Polymer electrolyte membrane constituents and to look further into its design by observing its performance and electro-
Electrolyser chemical behaviors. It also presents the issues that are currently encountered in this field.
Stack Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Performance reserved.
Platinum

[1,2]. Recent studies have focused on fuel cell technology

Introduction
World development now calls for the minimal use of natural
gas and pure oil as main sources of energy. The search is on
for alternative or substitute sources as a response to climate
change [1]. The concentration of the industrial countries in
upcoming years will be on finding the cheaper and more
accessible energy sources. The priorities in replacement of
the conventional energy source are based on new source
abundance, renewability and its impact on the environment
because of its effectiveness and low effect on pollution [3].
These cells have been classified based on its electrolyte and
its electrochemical element that directly converts stored
chemical energy into electrical energy. Fuel cells are poten-
tial substitute energy sources that can reduce dependence on
inner ignition engines. Attempts to make it commercially
available can be successful by developing a hydrogen-based
economy for reducing petroleum dependency, thereby
reducing environmental damage [4]. The conventional bat-
tery that works by only hydrogen energy has been used in

* Corresponding author. Tel.: þ60 3 89118576; fax: þ60 3 89118574.

E-mail addresses: asimnilofar@gmail.com, nilofarasim@ukm.edu.my (N. Asim).
http://dx.doi.org/10.1016/j.ijhydene.2014.08.121
0360-3199/Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
17766 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
Fig. 1 e A schematic design of the MEA in URFC stack.
PEM fuel cell, and therefore, its low energy concentration is
not capable of meeting the current demand. Moreover, the
conventional batteries that have been used in this cell for
these purposes have produced low energy density
(<200 Wh kg1). This amount cannot meet the practical re-
quires [5,6]. Regenerative-type fuel cells are a good alterna-
tive because they can function both as H2/O2 fuel cells. They
can also electrolyse water with only an operation unit. Thus,
the concentration of the feasible energy of URFC is capable of
generating 400 Wh kg1e800 Wh kg1 [6,7]. URFC is a
reversible electrochemical tool that can function as H2/O2
fuel cells to generate electricity and heat, which is the so-
called fuel cell mode (FC), and can electrolyse water to pro-
duce hydrogen and oxygen, which is the so-called water
electrolysis mode (WE) [8,9]. Primary efforts to use URFCs in
the proton exchange membrane technology have been done
at the end of the 1960s. At that time, its mechanism and
methods resulted in low electrochemical performance
because of problems involving the membrane and electro-
catalysts [10,11]. The General Electric Company (GEC) found
more encouraging outcomes in the 1970s [12]. At the outset
of the 1990s, researchers of the Lawrence Livermore National
Laboratory (LLNL) developed a typical URFC stack that had a
particular kind of power concentration of 500 Wh kg1
[12,13].
Over the past few decades, all-inclusive fundamental
experimental actualizations of single cell PEM-URFC perfor-
mance have been conducted, but stack inquiry did not get
much attention [13]. At first, URFC cell research concentrated
on its material and the transport behavior phenomena, which
include membrane electrode assembly (MEA) materials, bipolar
plate design, MEA durability and degradation, and water and
heat thermal management, as shown in Fig. 1. URFC stack level
research has been primarily focused its performance and
durability and aimed to characterize stack manner [14]. Tech-
nological developments should use the matching concept of
the so-called “hydrogen and oxygen electrodes,” such as H2
produced in WE or consumed FC modes in the same cell
cubicle, as well as O2 produced in both WE or consumed FC
modes in the other cell cubicle. This process requires the
development of “reversible bifunctional electrodes,” a task not
commonly performed especially on oxygen electrodes when
the H2O/O2 redox system is significantly irreversible at a tem-
perature range of 80  Ce100  C in the PEM technology. This
process has advantages such as simpler management of gases,
but it also has its disadvantages [15]. The problems involved in
this process include material stability, corrosion of carbon-
based materials (carbon used as catalyst carrier, gas diffusion
layer, and bipolar plate) at the anode during water electrolysis.
Thus, performance is significantly reduced [15,16].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
Fig. 2 e Electrochemical reactions in unitized regenerative fuel cell.
This study presents an overview of the latest de-
velopments in PEM-URFC stack design, materials, and the cost
reduction of its constituents. It reviews the latest specifica-
tions on the progress of stack constitutions and the status on
its cost reduction. Furthermore, it attempts to investigate the
performance and electrochemical behaviors of the stack
design and to illustrate the issues that may be encountered in
this mechanism with regards to its performance.
Unitized regenerative fuel cell stack system
Two methods are used for reversible PEMFCs. The first is
URFC, and the second is the discrete regenerative fuel cell
(DRFC) [17]. The first method involves the use of an electro-
chemical cell that can function as a fuel cell and a water
electrolyser in a single cell in various statuses. The advantage
of the URFC mechanism is its ability to unite fuel cell oper-
ations and electrolysis in stack hardware and membrane
[18,19]. Regenerative fuel cells can perform in a reversible
mode as an electrolyser. Thereafter, electricity is utilized to
form water back into oxygen and hydrogen [20]. This dual-
function mechanism can be regarded as a convertible fuel
cell. Moreover, through a convertible electrochemical proce-
dure, URFC can store and generate energy. In electrolysis (EL)
mode, water is divided into oxygen and hydrogen via elec-
tricity. However, hydrogen and oxygen combine in water
when electricity is generated in FC mode [21]. The sketch in
Fig. 2 shows the electrochemical reaction that occurs in
URFC. However, both designs differ based on their
application.
17767
URFCs are designed to utilize polymer electrolyte mem-
branes (PEM) (notably Nafion), and are known as proton con-
ductors based on platinum materials [22]. These phenomena
in PEM fuel cell performance seem to be complicated because
they are involved in heat transfer, charge transport, and
electrochemical reactions. This multi-physics phenomenon in
fuel cell performance and its relation to material features is
significant in figuring out two main issues, namely: perma-
nence and expense (i.e., durability and cost). Furthermore,
there are many different consistent and sophisticated phe-
nomena which rule fuel cell process, namely electrochemical
reactions, ionic/electronic transport and mass/heat transfer.
For fuel cell commercialization, additional scientific studies
are needed to solve the obstacles associated with durability
and cost. These scientific studies should include material
development, fundamental knowledge, and improvement of
experimental tools and analytical models [7,22]. These pro-
cesses take place in different constituents, such as in mem-
brane electrodes composed of elements similar to the gas
diffusion layer, catalyst layer in the gas flow channel, and the
bipolar plate [21,22]. For a fuel cell assembly, various parts are
combined to produce cells and for the reactions to occur [23].
The equation below shows the reactions that occur in the
anode and cathode in the fuel cell system:
Anode: 2H2 / 4Hþ þ 4e
Cathode: O2 þ 4Hþ þ 4e / 2H2O
Overall Reaction: 2H2 þ O2 / 2H2O
17768 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8

Fig. 3 e Scheme of PEM fuel cell stack hardware [55].

In Fig. 3 the sketch shows the structure of a PEM URFC for a functional groups. Furthermore, there are some other per-
single cell. The arrangement of a URFC with PEM commonly fluorinated polymer materials including Neosepta-F™
uses conventional PEMFC composed of proton exchange (Tokuyama), Asiplex™ (Asahi Chemical Industry) that can be
membrane, catalyst layer, gas diffusion layer, gasket, bipolar used in PEM fuel cells. Besides, membrane materials which
plate or flow filed plate, and current collector plate [24]. may run at high temperatures (100e200Co) are chosen for
high temperature PEM fuel cell that include some benefits of
better catalyst and cooling strategy for fuel cell [22,27]. The
The basic structure of URFC stack system
complex synthesis process for the Nafion®112 based mem-
branes made them expensive membranes [22,25]. Investiga-
The main constituents of URFC are as follows:
tion to find high performance electrolyte materials,
considering their cost effectiveness, is an active research area
Membrane layer
in fuel cell. Some of recent researches focused on developing
The membrane can be identified as a chain of polytetra-
of Hyflon® ion ionomers, also popular as short side chain (SSC)
fluoroethylene (PTFE) along with side chains that terminate in
ionomer that present a better durability and performance
an SO3H group. The hydrogen on the sulfonate group is
than Nafion® in many cases. It is improved originally by Dow
separated from the polymer when it gets wet and is then
Chemicals Company [22] The main drawback for this mem-
released as a proton in the solution. Moreover, the fixation of
brane material is its severe degradation [22,25,26]. Phosphoric
the anion in the electrolyte is regarded as an advantage for
acid-doped Polybenzimidazole (PBI) membrane is considered
polymer acids. The Nafion membrane, which is a popularly
as a promising material for high temperature membrane
known PEM, is a polymer produced by DuPont. In the chlor-
application. This membrane exhibits high proton conductivity
alkali industry, this polymer has been utilized as a divider,
at temperatures up to 200Co and low methanol permeability
among many other usages, by several electrochemical in-
that make it favorable for high temperature application. On
dustries [25]. Indeed, producing PEM with sizes up to 50 mm is
the other hand, there are some worries on low solubility of
possible, which is similar to thickly compressed stacks.
oxygen as well as evaluation of stack elements such as seals
Moreover, high power concentrations can also be achieved.
An encouraging element for the URFC can be another proton
exchange membrane [25,26]. As shown in Fig. 4 the membrane
layer for Nafion®117 has a thin layer of electrolyte
(20 mme80 mm) that conducts protons from the anode to the
cathode. The membrane materials with high ionic conduc-
tivity that prevent electron transport and the crossover of
hydrogen fuel from the anode and oxygen reactant from the
cathode have more priority. Most of the existing membrane
materials are on the basis of the perfluorosulfonic acid. Some
of the best membranes like Nafion, Nafion® owe their physical
strength to their backbone structure of (PTFE), familiar as the
trade name (Teflon). The proton transports in Nafion® take
place by using charge sites provided by sulfonic acid Fig. 4 e Membranes structure of Nafion®117 [89].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
and coolant, bipolar plates, and thermal and water manage-
ment and low proton conductivity at low temperature (sig-
nificant for cold start). PolyFuel is investigated on
hydrocarbon-based membranes for fuel cell application
[22,28]. Due to these discussion above, the Nafion®117 is
commonly used as a commercially accessible membrane for
technologies such as PEMFC [29,30]. Nafion®112 is used in
URFC implementations and has more ionic ability to resist in
the cells, in spite of the popularity of Nafion®117 as a mem-
brane for URFCs [28].
Catalyst layer
The catalyst layer (CL) which normally consists of platinum
supported carbon black 10% Pt/C and 30 wt% Teflon is
considered as a very important part in URFC-PEM fuel cell. For
preparation of it, 10 wt% platinum supported carbon black and
30 wt% Teflon should be mixed in isopropyl alcohol as solvent
to make a homogenous suspension [31]. Based on Fig. 5 the
catalyst layer is directly related to the membrane and layers of
the gas diffusion layer. Moreover, the appointed layer can be
directly applied to gas diffusion layer or on the membrane so
that the catalyst is closer to PEM. Thus, for URFCs, a catalyst
layer is significant to develop an effective regenerative cell
[32,33]. Studies have used black platinum (Pt) as the only
catalyst, whereas others have used other proper catalysts
such as iridium and rhodium. Other researchers have also
considered reducing the high Pt density in URFC catalyst
layers (usually 3e5 mg/cm2), whereas others considered a
catalyst loading of 0.4 mg/cm2, which can be achieved using a
supported bifunctional catalyst [34]. The oxygen reduction
reaction (ORR) or hydrogen oxidation reaction (HOR) occurs in
catalyst layer (CL) with very small thickness (about 10 mm).
The electrochemical reaction could take place in different
phases in a CL, namely: (1) carbon support with Pt catalyst
particles dispersed on its surface, (2) ionomer, and (3) void
space. The reaction activation barrier could reduce using
catalyst. The oxidation of hydrogen takes place in the anode
whereas the oxygen reduction reaction occurs in the cathode.
CL is responsible for major share of fuel cell cost since it has
Platinum or platinum alloy in its composition. Pt and some of
its alloys (PteCo, PteNi, PteFe, and PteCr) present good cata-
lyst kinetics [22]. The Pt loading is a significant parameter in
Fig. 5 e A cross-sections of catalyst layers via scanning
electron microscopy [90].
17769
the development of CL. Besides, the CL thickness reduction is
vital to improve its performance because of mass transport
limitation. For thickness optimization, a CL model can be
employed to consider all transport phenomena and the ORR or
HOR reaction at the three-phase interface.
This model clarifies the influence of catalyst layer reduc-
tion on URFC-PEMFC performance. In addition, Catalyst with
thinner layers (about 1 mm) led to lower catalyst loading and
therefore reduction in the CL cost. More investigation in this
area is vital [22].
Micro-porous layer (MPL)
Micro-porous and gas diffusion layers (GDL) are both known
as diffusion media (DM). These layers have multiple functions
as follows: (a) electronic link between the bipolar plate and the
electrode, (b) provides reactant transport, (c) mechanical
support for membrane electrode assembly, and (4) protects
the catalyst layer against oxidation and abrasion brought by
flows [35,36]. The porous gas diffusion layer assures an equal
distribution and the elimination of reactants from the elec-
trode zone. Furthermore, it seems to function as an electrical
conductor that assures the transfer of electrons to and from
the catalyst layer [26]. Moreover, GDL has a significant func-
tion on PEM hydration. It is also necessary to promote a
porous gas diffusion layer so that the reactants are equally
distributed and eliminated from the whole electrode zone.
Thus, continuous electrical relation between the electrodes
and the collector is assured. Yao et al. [6] has investigated the
preparation of gas diffusion electrodes, and presented a
sandwich structure with pure Ti as a current collector be-
tween the catalyst layer and the gas diffusion layer. For the
preparation of the deposited catalyst layer, Pt/IrO2 composite
powder was mixed with 15 wt% highly hydrophobic PTFE and
an appropriate amount of isopropyl alcohol was used as the
dispersion agent. A highly dispersed mixture was obtained via
ultrasound method, and the resulting dough was rolled to the
desired size [6,19]. In Fig. 6 the model of the two-stage channel
flow was promoted based on the two-stage mixture scheme.
The channel design has three issues as follows: water con-
struction, channel incongruity, and lack of equal distribution.
Basu et al. [37] has suggested a two-stage design to consider
the lack of equal distribution in the channels of fuel cells.
Furthermore, Wang et al. [22] has also suggested the idea of
porous media channels and investigated the features of
reactant stream, heat transfer, species transport, and two-
phase transport. The liquid profile along the channel (Lx/Lz),
whereas (Lx) is the length of the electrode and (Lz) is the length
of the channel, were analytically obtained using a two-fluid
flow model (Ug/UL), where (Ug) is the flow-filled gas and (UL)
is the flow-filled liquid in the cell.
Flow field plate (FFP)
The vital constituents of URFC are flow field plate, which is
also called the bipolar plate (BP), and gas flow channels (GFCs)
that can spread hydrogen fuel and oxygen reactant and can
also eliminate byproduct water. These elements that are
placed in the bipolar plates have a cross-section size of about
1.25 mm. Shortage of reactants can result in the starvation of
hydrogen/oxygen, which decreases cell performance and
durability. Bipolar plates mechanically support DMs and
17770 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
Fig. 6 e Scheme of the internal two-phase flow and the porous media channel [22].
provide conductive ways for heat and electron transfer [38,39].
Manufacturing BPs along with GFCs can be significant in
reducing the cost of fuel cells. BPs degradation such as metal
plate oxidation might occur and decrease the lifetime of fuel
cells. GFCs are easily changed into a bipolar plate, which re-
sults in high and consistent electronic and thermal conduc-
tivities in a particular chemical area in fuel cells [22].
Each bipolar plate of a fuel cell stack provides support for
two adjoining cells. It has also been considered for its four
particular performances as follows: (a) distributes fuel and cell
corrosion, (b) facilitates water/heat administration in the cells
(c) separates individual cell within the stack (d) transports
currents from the cells [40]. Fig. 7 shows the pattern of the flow
field plate in the URFC stack.
URFC stack
The URFC stack includes several cells containing a bipolar
plate, a cathode, an anode, and an electrolyte matrix. The bi-
polar plate connects the cells in sequence, and also supplies
gas for the cathode and anode. The URFC stack approximately
contains about 20 cells to generate a utilizable voltage [41].
Fig. 8 shows a sample of URFC stack localization and the size
that should be improved to distribute water homogeneously
throughout the whole surface of the cells in the stack. In a
proper design, water is homogeneously distributed in every
cell, which results in a decrease in pressure in the stack [42]. In
a single cell of the URFC stack, the following issues can be
resolved: (a) stack system optimization (b) procedures of fuel
subsystems such as reformer, fuel management, and steam
generator (c) power subsystem and (d) ancillary subsystem.
Creating a URFC stack model entails preparing a strong in-
strument to optimize the stack design. In addition, the models
require a complete connection of the reactant stream to the
GFC and its manifolds, and the transport of fuel cells in
connection to electrochemical reactions.
Characterization of design for unitized regenerative fuel cells
The regenerative fuel cell can function as an electrolyser that
divides water into oxygen and hydrogen via electrical energy.
This cell is the same as a fuel cell that supplies electric power
obtained from oxygen and hydrogen. URFCs provide a way to
store energy for a long period of time [43]. The possible
mechanism of storage for the exchange of electrical energy
includes a unit of hydrogen, a means of storage, and a unit
that helps converts the chemical stored energy in the
hydrogen to electrical energy with the help of oxygen. This
kind of mechanism is related to an energy source, such as
solar or biomass energies that are renewable and can be used
as an electrolyser cell that provides sufficient energy to divide
water into oxygen and hydrogen [41,43,44]. An electrolyser
uses power supply to split water into hydrogen and oxygen.
Employing an electrolyser to generate gases that consume
later to create power via the fuel cell makes a hydrogen sys-
tem self-dependent energy source. Depend on various appli-
cations, particular weight (power per unit weight) must be
considered significantly. The studies achieve success in
acquiring one cell to function as electrolyser and fuel cell in
one cell at distinct modes [15,43]. At first step the URFC works
as an electrolyser to produce hydrogen and perform like a
battery as a self-independent power source. Unlike the battery
system, the URFC is not affected by the cycle duration length
or the discharge depth. The power and energy are not related
in the URFC system. For example, while the cell is sized for
power, the storage tank is sized for energy [15]. Thus, the gases
can be stored or utilized in a fuel cell where an opposite re-
action towards electrolysis occurs. Thus, oxygen and
hydrogen combine to generate water and electricity [19,45].
Fig. 7 e Etched Metal Fuel Cell Flow Plates used in URFC
stack [91].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
Fig. 8 e A 100-W class regenerative fuel cell stack [44].
Such a mechanism is characteristic of a regenerative fuel cell
(RFC). Fig. 9 shows a more compressed unit in which the
electrolysers and the fuel cells are united in a single unit and
just one of the two modes can operate at the same time in the
same system. The electrolyser first generates oxygen and
hydrogen, which are then converted to the same unit when
the cell should function as a fuel cell system [45,46].
The preparation of active electrocatalyst on the oxygen
electrode where oxygen redox reaction take place is very
important for URFC development. Carbon black as the most
used catalyst support in fuel cells is not appropriate for URFC
application because in water electrolysis mode with high
voltage, carbon black is subjected to corrosion. The low ac-
tivity and high loading in URFC resulted from the unsupported
bifunctional oxygen electrode electrocatalysts [7,15,19]. Some
scholars [7,15] provided supported bifunctional electro-
catalysts to address this problem. For preparation, Pt or oxide
is used as support and the two forms of catalysts are deposited
on each other respectively. Since Pt or IrO2 are not good sup-
port like carbon black to obtain highly dispersed particles with
Fig. 9 e A sketch for the unitized regenerative fuel cell mechanism system.
17771
Fig. 10 e SEM micrograph for the cross-section of a
reversible fuel cell [88].
high loading, the methods mentioned above could not make
important developments of the electrocatalyst activity for
both OER and ORR. Furthermore, the Pt supported activity on
IrO2 (40 wt% Pt) bifunctional catalyst for ORR was less than
that of the IrO2 catalyst and mixed Pt black [7,44,45].
In the latest preparation of a URFC stack design, Grigoriev
et al. [47] prepared the stack via a specified technique [48].
Nafion1135 (88 mm thickness) has been used as PEM. For the
cathode, platinum nanoparticles that are coated on Vulcan
XC-72 (Pt40/Vulcan) and mixed with 10 wt% of PTFE were used
as electrocatalysts to promote hydrogen evolution reaction
(HER) in the electrolysis mode and to promote oxygen reduc-
tion reaction (ORR) in the fuel cell mode [13,48]. Typically,
loadings of 0.75 mg Pt cm2 were used. For the anode, mix-
tures (50:50 wt%) of iridium and platinum powders were used
as electrocatalysts to promote oxygen evolution reaction
(OER) in the electrolysis mode and to promote hydrogen
oxidation reaction (HOR) in the fuel cell mode. Iridium and
platinum catalyst layers were separately deposited [48e50]. A
first layer of iridium black was directly deposited on the stack,
followed by a second layer of Pt powder on top of the first
layer. Typical metal loadings of 1.10 mg cm2 were used for
17772 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
each metal. The catalytic structures (Pt40/Vulcan XC-72 on the
cathodic sides and PteIr black powders on the anodic sides)
were mixed with 15 (cathodes) or 7 (anodes) wt% of the ion-
exchange polymer (wt% values are expressed with respect to
the weight of catalyst). Porous titanium sheets (256 cm2 sur-
face area and 0.90:0.20 mm thick) were used at the anode as a
gas diffusion layer and a current collector [48,49].
Polymer electrolyte membrane for unitized regenerative fuel
cell
The PEM in URFC is usually a perfluorosulfonic acid polymer.
The PEM can perform as an electrolyzser that splits water into
oxygen and hydrogen by utilizing electric power [50,51]. In
Fig. 10 depicts an SEM micrograph that illustrates the cross-
section of reversible fuel cells. URFCs that include a hydrogen
unit of storage is the system of choice for its ability to store
energy for a long period of time along with its supporting
power [52]. In 1968, a PEM electrolyser was used for the first
time by GEC in space discoveries [53]. In comparison with
alkaline electrolyser, PEM has other benefits such as safety,
less maintenance, easy mechanism, higher energy effective-
ness, and particular capacity of production. Several obstacles
were raised in designing electrodes for the PEM-URFC mecha-
nism, and highly hydrophobitized carbon papers are mostly
used as electrode materials or as the gas diffusion layer [54,55].
Therefore, they are not utilized as the gas diffusion layer of a
URFC because carbon materials can corrode the oxygen elec-
trode side during water electrolysis. The GDLs must also have a
proper balance between the hydrophilic and hydrophobic
properties during water electrolysis and fuel cell operation.
Membrane electrode assembly for unitized regenerative fuel
cell
The membrane electrode assembly is at the center of a URFC
electrolyser. It is also the core part in the cell. However, the
Fig. 11 e The SEM micrograph of (a) platinum black (b) iridium oxide [34].
electrochemical reaction just occurs in “triple phase bound-
aries” in which reaction materials, electrically conducted
catalysts, and electrolyte are combined. Thus, the connection
between catalyst layers and PEM must be maximum and their
contact resistance must be minimum [56]. The current fabri-
cation procedures of membrane electrode assembly for URFC
electrolysis involve chemical plating [57,58]. MEAs have been
produced via the chemical plating approach. MEAs include
catalysts with large diameters, low surface area, and high
catalyst loading. Thus, they have lower performance. Etching
and sand blasting of the utilized membrane surface increase
membrane roughness and also extend the reaction between
the electrode and PEM [57,59]. However, surface roughening
resulted in a decrease in the mechanical power of the mem-
brane and also shortened the lifetime of MEA [60]. The prob-
lem involved in the oxidation of conventional fuel cells is not
as significant as that in URFC because the cells function solely
as fuel cells. However, comprehensive studies were conducted
to increase the capacity and power of the membrane to
generate the necessary chemical reactions. Towne et al. [61]
considered a new approach to fabricate MEAs for PEM-URFC
by utilizing an inkjet printer tool to set down the Pt/C cata-
lyst layers. Fortunately, the catalyst loading of the cell was
10% less compared with that of commercial membranes, and
almost had the same performance with a catalyst loading that
is 35% less compared with that of 0.25 mg/cm2 of platinum
[62].
Electrodes materials
Platinum
Platinum (Pt) is an expensive metal and has different uses
because of its special features such as high resistance, high
temperature, and good conductivity. Pt is utilized as an elec-
trocatalyst for URFCs, and is highly active for H2 corrosion and
O2 diminution at very low temperatures. However, Pt is also
used to reduce catalyst loading in the electrodes [63]. The
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
expense of electrode fuel cells were significantly decreased
because pure Pt was substituted via Pt-supported carbon black
(Pt/C), and Pt ions were reduced to metallic Pt by adding liquid
[64]. Moreover, iridium and Pt black were employed as
bifunctional hydrogen catalysts. In addition, the conventional
Pt catalyst for oxygen reduction reaction is combined with
oxide catalysts of Ru or Ir for oxygen evolution reaction to be
employed as the bifunctional electrocatalyst [7,63,64]. Nor-
mally, Pt black was created by using HCHO to reduce H2PtCI6
[34,64]. Thus, Pt crystals and iridium oxides were utilized in
electrode preparation. These processes are shown in Fig. 11a
and b. Pt particles have diameters of about 20 mm, whereas
iridium oxides have a particle of about 40 mm. The recent re-
searchers have discovered the surface modification effects on
the titanium bipolar plate. Two distinct surface modification
materials, platinum iridium and oxide (IrO2) were examined
and their performance is discovered to be the same as the
graphite plate [7,15].
Carbon black
As a critical substance in fuel cells, especially those that
contain phosphoric acid, carbon black (C) is a nonmetallic
material that has a broad scope of crystalline and amorphous
patterns [63]. These features give the electrode a nonmetallic
pattern. Carbon black largely supports heterogeneous elec-
trocatalysts because of its high surface zone, porosity, con-
sistency in deferent liquid medium, and good conductivity. In
fuel cell applications for oxygen reduction and methanol
oxidation, the catalytic activity of high surface area carbon
was maximum. Drazic & Adzic [65] observed that HC1-treated
carbon blacks can promote Pt catalyst performance in acid
solutions. Moreover, Antonucci et al. [66] proved that for Pt
attracted to carbon blacks, oxygen-including groups are raised
on carbon surfaces, whereas Pt surface zones are reduced. The
electronic essence of Pt was influenced by functional groups
on the carbon black support [64].
Teflon
Teflon, as a Nafion membrane, contains an arrangement of
copolymers of flouoro 3, 6-dioxo 4, 6-octane sulfonic acid,
similar to PTFE. Therefore, the Teflon spine of this arrange-
ment results in hydrophobicity of the membrane. Hydrophilic
sulfonic acid groups (HSO3) are also chemically implanted into
the spine [40]. Nafion in compound patterns can be impreg-
nated into an inert Teflon-like matrix. Nafion is commercially
accessible in as Nafion112, 115, 117, 900, 1100, 1200, or
equivalent weights. However, Nafion1100 with thicknesses of
2, 5, 7, and 10 mil (1.0 mil is equal to 25.4 mm), is the only
accessible Nafion today [26]. The content of Nafion in the
electrode influences fuel cell and water electrolysis perfor-
mance. The electrode, which contains 8e10 wt% Nafion so-
lution, indicates an excellent performance. Furthermore,
adding a tiny percentage of iridium catalyst to the oxygen
electrode layer could remarkably improve URFC performance
[15,26].
Gaskets
URFC stack uses gasket in each cell to remain the reactant
gases (oxygen and hydrogen) within their respective areas.
The gaskets are exposed to hydrogen, humid air and acidic
17773
environment, and also exposed to mechanical compressive
load. The gasket materials could lose its elasticity and seal
functionality because of material aging. In this case which led
to gasket degradation, there is a possibility of leaking and
mixing of the reactant gases during operation, and this cause
the stack performance decrease and safety concern both
[67,68]. Gaskets are generally considered to have two sealing
features, namely, overboard and crossover leaks [69]. The first
feature can be observed when the gas is released to the
environment from the anode or the cathode. The gasket ele-
ments consist of physical, mechanical, and chemical traits
that are appropriate for PEMFC operative conditions. Thermal
stability occurs at a range of 50  C to 180  C, and gas sealing
was performed at 10 bars. More significant traits of the sili-
cone gaskets include water repulsion, fire-extinguishing
properties, and electric insulation, among others [70]. Gas-
kets in URFCs have always been utilized to insulate anodic and
cathodic areas. A pattern is generally designed around MEA in
the inactive field of the flow area. Given that the cell plates are
compressed, the thickness of the gasket may affect cell per-
formance. All constituents are completely joined together by
using clamping plates by applying torque power on fastening
screws. Thus, the clamping force is pivotal in fabricating a
stack. Various elements and materials were utilized as gaskets
in the hardware of the cells [71,72]. These materials are
described in Table 1.
Electrodes design and stack performance
Proton exchange membrane performance of URFC is very
crucial to the water management in the fuel cell system. The
conditions of low humidity operating display a sophisticated
interaction between water transport and dynamic behavior
due to time scale difference of water transport mechanism
happened in transient process [73,74]. URFC electrodes effi-
ciency was assessed when the fuel cells were operated. Ob-
servations show that the URFC performed at 80  C with H2/O2
at a pressure of 0.2 MPa. Pure oxygen and hydrogen were
highly humidified before they were placed in the cell via
bubbling through water at 80  C and 90  C [73]. Deionized
water was pumped into the membrane electrode assembly
from the water supplies at 85  C and within atmospheric
pressure. The performance of the URFC electrodes was
examined at a concentration of 200 mA cm2 in the water
electrolysis and fuel cell modes. The water electrolysis mode
was observed as a zero-gap cell [73,75]. Moreover, the half-cell
was composed of a gas collector, bipolar plate, MEA, and a
porous current collector. The internal performances of the cell
and the stack were related to its effectiveness. Thus, an equal
Table 1 e Utilized gasket materials.
Gasket Material Provider Thickness Pressure
modules (MPa)
PTFE-040 PTFE DIFLON 0.40 mm 440e600
PTFE-035 PTFE DIFLON 0.35 mm 440e600
PTFE-020 PTFE DIFLON 0.20 mm 410e550
PTFE-015 PTFE DIFLON 0.15 mm 410e550
Exp-PTFE PTFE GORETEX 0.50 mm 10e100
17774 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
repartition of present lines and porous current collectors were
fabricated out of sintered titanium powders [47]. The use of
titanium particles with a size of about 500 mm was sufficient to
assure an equal distribution of the present connections, even
at high current densities [42]. The performance of the elec-
trodes was dependent on several factors such as: (1) kind of
support and its features; (2) kind of catalyst, such as Pt alone
or Pt with another material, macro cycles, Pt amount, Pt par-
ticle size, (3) thermal treatment, (4) catalyst layer and diffu-
sion thickness, and (5) manufacturing procedure. The
manufacturing procedure for diffusion as well as for the
catalyst layer could be done by utilizing various methods such
as spraying techniques, filtering, and screen-printing [42,63].
In testing the URFC performance, Ioroi et al. [43] studied the
relation between PTFE coating amount on gas diffusion
backing. The PTFE coating on the GDB of the H2 electrode did
not affect cell performance [62]. The PTFE concentration in the
supporting layer was varied while the loading of the sup-
porting layer was fixed at 3.5 mg cm2. The ieV curves for a
family of cells, each having a different PTFE concentration, are
shown in Fig. 12. The results show that the optimal concen-
tration of PTFE in the supporting layer is 30 wt%. The ieV
performance of the cell composed of electrodes with a 40 wt%
layer is similar to that of the 10 wt% layer [76]. The perfor-
mance of a reversible cell can be very close to those of the
reference cells (state-of-the-art water electrolysis and fuel
cells), but significant decrease in performance was observed
after several hundred cycles of operation. In terms of per-
spectives, finding new (low-cost) electrocatalysts is needed to
improve performances in cycling conditions. Moreover, the
development of the system (ancillary equipment, monitoring
software, process management when shifting from electrol-
ysis to fuel cell mode) still requires more observations [42,77].
URFC stack technology: applications and current
status
Owing to worldwide comprehensive researches and rapid
development, URFC PEMs have recently partly reached the
commercialization stage. However, several years need to be
overcome the remaining challenges before full commerciali-
zation [78].
Fig. 12 e The ieV curves of the cell incorporating electrodes
with the supporting layer containing various PTFE
concentrations: (1) 10 wt%; (2) 20 wt%; (3) 30 wt%; (4) 40 wt%
[76].
Lifetime & cost reduction of the URFC stack
Low operating temperature, fast start ups, sustainable oper-
ation at a high current density, potential for low volume and
cost, long stack life, low weight of the stack and suitability for
discontinuous operation are considered as the main URFC
stack advantages. These characteristics make URFC PEMs the
most attractive and promising candidate for a wide range of
power applications differing from micro or/and portable
transportation and power to stationary power system in large
scale normally used for distributed generations and building
[78,79]. The URFC is starting to become a commercially avail-
able. Thus far, the necessary lifetime for a commercial fuel
cell seems to be more than 5000 h of operations for lightweight
operations and more than 40,000 h for static power genera-
tion, which include approximately 10% performance decay
[80e82]. The Department of Energy (DOE) reported stack cells
with a lifetime of 30,000 h at the end of 2011, which have 40%
effectiveness for represented power and 60% effectiveness for
transport by 2015 [83,84]. Although fuel cell expense remains
almost the same from $75/kW in 2004 to $73/kW in 2008,
furthermore the cost of the stack has doubled compared with
internal combustion engine mechanisms. In 2009, the
expense further decreased to $62/kW ($34/kW for balance of
plant, which include assembly and testing, and $28/kW for the
stack) and was even reduced by 35% at the later part of 2011
[85].
A main factor for the fuel cell stack expense is the MEA that
contains a catalyst layer and a Nafion membrane. Therefore,
The DOE defined several goals from 2010 to 2015 to reduce the
cost of these contains only from $45/kW to $30/kW for
transport use and from $61/kW to $30/kW for power genera-
tion use [83,86,87]. Fig. 13 indicates the decrease in URFC stack
cost. Although many achievements have been realized in this
area, the expense and lifetime for present automotive internal
combustion engine power plants seem to be $25e$35/kW
respectively, which are in agreement with the DOE goals by
2015. Therefore, the expense of the whole URFC stack almost
now go beyond $1800/kW to $2000/kW, and manufacturers
seem to be sure enough to decrease the expenses to $150/kW
for transport. However, the expense of URFC must be less than
$100/kW. Promoted models and substances and more power
concentrations are needed. The means of transportation i.e.
mobile applications with high annual mileage show niche
markets where fuel cell can compete at expenses of
$145e$200/kW because high effectiveness makes up for
increased vehicle expenses [86,87]. Low temperature, low
pollution and high power density and specified characteristics
of a URFC PEM fuel cell make it attractive for both mobile and
stationary applications. However, the high material cost is
considered as a major drawback for URFC PEM worldwide
application. To address this issue many researchers are
working to develop the electrodes with low platinum loading
for fuel cells [31,78]. The electrodes are currently influenced by
URFC expenses, and they are manually produced. Electrode
expense can decrease from $1500/m2 and $2000/m2 to $250/m2
and $300/m2 via mass production and newly invented tech-
nologies that need less Pt amount. Current mechanisms need
0.6e0.8 mg Pt/cm2, which result in a performance of about
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8 17775

Fig. 13 e Breakdown of URFC stack cost [22].

1.0 g/kW. The target is to obtain a performance of 0.2 mg/kW. determined by the improvement of social and industrial
Supposing Pt costs $20e$40/g, the Pt price could be $4e$6/kW structure, various full cells applications have been the sig-
[86,87]. Although this price is not seen as a dominant one for nificant focus. URFC-PEMs are considered as the main prom-
current URFCs, decreasing URFC price under $100/kW is might ising system regarding compactness and energy efficiency
crucial. Universal accessibility of Pt would be crucial as well. among different fuel cell types. This make URFC-PEMs tech-
Supposing 0.2 g Pt/kW (20 g/vehicle), 100 million fuel cell ve- nology and application more attractive research subject
hicles (FCVs) would need 2000 tons of Pt each year. Thus, it is worldwide [78].
ten times per year of production. Pt fabrication results reveal The storage and conversion energy applications with a
that the demand for more production and a system of recy- high efficiency, particularly a high specific energy, will be a
cling would increase. However, lower Pt amount and the use significant parameter in following space activities along with
of new catalysts have great significance [83,88]. The cost in terrestrial applications. Quite easy possibility to store oxy-
specifications are displayed in Table 2. gen and hydrogen with high specific energy mixed with high
energy conversion efficiency in fuel cells and electrolyser
displays a significant opportunity for the regenerative fuel cell
Commercialization and future opportunities of URFC stack
systems employment as energy storage devices [34]. A URFC-
PEM fuel cell is considered as efficient and emission-free
A stable hydrogen source with high purity is necessary for
power source and these features make it popular technol-
URFC-PEM system to be fully commercialized. On the other
ogy. The operation is the same as the operation of a battery
hand, this is not available nowadays; plus, this challenge has
but the only difference is that one of the reluctant or both of
been debated for a long time. The economical and/or tech-
them are not kept permanently in electrochemical cells. But
nological point and the social are the issues that related to this
rather, they are fed from external sources once power is
problem [74,78,79]. Fundamentally, fuel cells have been
desired. The electrode materials of the fuel cells are catalyst
examined as an innovative system that may be combined
and same as every catalyst, they are inert and do not
with conventional electrical power plants or to provide elec-
consume. They only increase the rate of electro-oxidation of
tricity as on-site power generators [74,78]. Nevertheless, as
the fuel and the electro-reduction of the oxidant in fuel cell.
Nowadays surging of attention on resulted environmental
pollution because of using fossil fuels in transportation ap-
Table 2 e The Expense Projections for URFC stack.
plications is considered as the key factor for fuel cell devel-
URFC stack Prototype Mass Target opment. Despite the significant development in the field of
production
fuel cell, the main drawback for its commercialization is its
$/kW % $/kW % $/kW % cost [79]. Besides, the durability issue is another barrier for
Membrane 250 14 14 16 13 25 URFC-PEM fuel cells commercialization. To date, the opera-
Electrodes 710 39 50 49 25 48 tional lifetime for real life application does not meet the re-
Flow field plate 825 45 28 29 9 17 quirements for the art technologies state, such as 40,000 h for
Pt catalyst 25 2 3 3 2 4
stationary applications, 20,000 h for buses, and 5000 h for cars.
Subordinate units 7 0 1 1 1 2
The fundamental knowledge on failure modes for each
Assembly 8 0 2 2 2 4
Total 1825 100% 98 100% 51 100% component and corresponding mitigation strategies are vital
17776 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 7 6 5 e1 7 7 7 8
to enhance the lifetime of URFC-PEM fuel cell. Many re-
searchers have investigated the degradation issues of URFC-
PEM fuel cells. Their finding revealed that PEM thinning,
catalyst layer degradation because of carbon support corro-
sion or platinum sintering and gas diffusion layer degradation
are the factors that could influence the URFC-PEM fuel cell
durability. The Catalyst layer degradation is considered as a
key factor among others. There are many experimental re-
sults which reveal the severe catalyst degradation in both
stationary and automotive application. Regarding to this
issue, the enhancement of CL durability as a key factor in
increasing the URFC-PEM fuel cell durability has received re-
searcher's attention a lot [67,79]. Despite many efforts to
develop the URFC-PEM fuel cell technology in past decades, its
major barriers including durability and cost for commerciali-
zation purpose have not been solved [22,67,78].
Conclusion
This paper presented the recent developments on URFC stack.
It also discussed its mechanisms and the status of cost
reduction of the newest stack models and substances. More
cutbacks on stack cost and durability are required, and can be
achieved by improving the structure and the performance of
the membrane electrode assembly of the URFC stack. The
conclusions of this study are as follows:
1. The selection of elements and substances for the elec-
trodes catalyst layer via carbon mutual supportive actions
and changing carbon chemistry could benefit Pt electro-
catalysts performance.
2. The stack could perform better with fewer connections
between the electrode and the electrolyte. Thus, the power
concentration is reduced at a higher current density in the
URFC stack.
3. The PTFE electrode performance of the cell is improved by
increasing the force in the water concentration in the
electrode assembly and by increasing the platinum active
area.
4. The electrical relation between electrodes and plates is
improved by increasing the clamping force of the gasket.
However, a lower cell resistance does not indicate better
cell performance.
5. The essential criterion for achieving higher energy effec-
tiveness and higher power densities in the URFC stack is by
utilizing the electrocatalyst with a high current density for
hydrogen oxidation.
6. Suggestions for future studies include more practical data
to confirm that the cell will also be useful for the progress
of forecasting URFC stack optimization designs.
Acknowledgment
The authors would like to acknowledge the financial support
of the work by the Universiti Kebangsaan Malaysia for funding
this project under research grant: Dana Impak Perdana (DLP-
2013-015) and the Solar Energy Research Institute (SERI), Na-
tional University of Malaysia for their providing invaluable
assistance to accomplish this research.
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