Journal of Power Sources Advances 3 (2020) 100012

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Journal of Power Sources Advances

journal homepage: www.journals.elsevier.com/journal-of-power-sources-advances

Cathode starvation as an accelerated conditioning procedure for

perfluorosulfonic acid ionomer fuel cells
Emmanuel Balogun a, Alejandro Oyarce Barnett b, c, Steven Holdcroft a, *
a
Holdcroft Research Group, Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada
b
SINTEF Industry, New Energy Solutions, Sem Sælands Vei 12, Trondheim, 7034, Norway
c
Department of Energy and Process Engineering, Norwegian University of Science and Technology, NO-7491, Trondheim, Norway

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

Keywords: Freshly assembled proton exchange fuel cells (PEMFC) require conditioning to reach maximum power density.
PEMFC This process may last up to tens of hours and adds to the cost of commercial fuel cell technology. We present an
Fuel cell conditioning accelerated conditioning procedure involving starving the cathode of oxidant. In single cells, this procedure
Perfluorosulfonic acid ionomer
conditions a membrane electrode assembly (MEA) within 40 min, without compromising durability. The per-
Accelerated degradation
formance and durability of MEAs conditioned using this technique are compared with US Department of Energy
(DOE) and European Union (EU) harmonized protocols, and to an amperometric conditioning protocol. The time
to reach peak power density using cathode starvation conditioning is <10% of the time required for DOE, EU, and
amperometric protocols. Conditioned MEAs were subjected to accelerated degradation by cycling the cell voltage
between 0.6 V and open-circuit voltage under low relative humidity. Degradation was found to be caused by loss
of electrochemical surface area of the cathode, which in turn increases the charge transfer resistance of the MEA.
MEAs conditioned using cathode starvation experienced only a 15% loss in performance; in contrast to 19, 17 and
17% losses in performance caused by the DOE, EU, and amperometric protocols, respectively.

1. Introduction to several hours or even days, and requires lengthy deployment of

Fuel cell technology has great potential in the portable, transportation
and stationary sectors. Of these, polymer electrolyte membrane fuel cells
(PEMFC) have proven potential as zero-emission energy conversion de-
vices due to their rapid refueling, compactness, low noise, and scalability
[1]. However, the technology could benefit from improvements in
durability and a reduction in materials cost [2]. While improvements in
the overall PEMFC performance have been realized, there is still a need to
implement other cost mitigating strategies to be able to meet the US
Department of Energy (DOE) target of $30/kW by 2030 [2,3].
There is a need to condition the fuel cell prior to its intended use
(referred to as initial conditioning, activation or break-in). Conditioning
hydrates the membrane and catalyst layers of the membrane-electrode-
assembly (MEA) that may dry out during manufacturing [4]. The phys-
ical processes behind conditioning are not fully understood, but it is
assumed that during the conditioning process the number of active
catalyst sites is increased, the polymer membrane and ionomer in the
catalyst layer are humidified, improving protonic pathways through the
MEA [5–7]. The initial conditioning procedure can be lengthy, taking up
expensive test benches and consumption of hydrogen fuel. Conditioning
increases the cost of PEMFC technology and bottlenecks in their mass
manufacture and deployment. One way to reduce PEMFC manufacturing
cost is to establish new and efficient conditioning procedures to minimize
the time required for activation of MEAs without compromising
maximum power density and fuel cell durability.
Several reports present ex-situ and in-situ techniques to maximize
power density of the PEMFC within the shortest time possible. Off-line
conditioning procedures generally involve taking steps to activate the
cell before operation. Qi et al. [6], and Anderson et al. [8] report a
conditioning procedure that entails the steam treatment of the MEA.
Palanichamy et al. [9], proposed a method that involves physically dis-
engaging impurities from the electrode surface through a process of
electrochemical treatment. In-situ conditioning procedures typically
entail the use of current control [10–12], voltage control [13,14] or both
[13], and are by far the most commonly applied conditioning protocols.
Other in-situ conditioning protocols include short-circuiting [15], CO
stripping [16], temperature control [17], air braking [18], and thermal
cycling (for Pt/NSTF catalyst layers [19,20]. Kato et al. [21] proposed

* Corresponding author.
E-mail address: holdcrof@sfu.ca (S. Holdcroft).

https://doi.org/10.1016/j.powera.2020.100012
Received 3 April 2020; Received in revised form 7 May 2020; Accepted 12 May 2020
2666-2485/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
E. Balogun et al.
methods of activating single cells and stacks using series of cyclic po-
tential sweeps. Similarly, Choo et al. [22] put forward a method of
accelerated activation for fuel cell stacks by applying high current for a
designated time. Although, there is no standard measurement to verify
the effectiveness of a particular PEMFC conditioning protocol, there are
recommendations on ways to compare conditioning efficiencies using
maximum output power and polarization curve performance [23]. Much
information on conditioning commercial fuel cells is often proprietary,
inaccessible to the public, and specific to each fuel cell company tech-
nology platform.
In an attempt to standardize and accelerate the conditioning process,
the US Department of Energy (DOE) proposed a method of conditioning
which entails applying a cyclic potential between the OCV and 0.55 V
[24]. Similarly, the European Union (EU) fuel cell community proposed a
harmonized test protocol that involves a series of relative humidity-,
stepwise current-, and potential-cycles [25]. These standardized pro-
tocols helped uniformity of MEA performance but require in excess of 7 h
and 11 h, respectively. There have emerged other accelerated condi-
tioning procedures that reportedly activate MEAs in less than 1 h. One
such protocol involves a short-circuiting procedure [15], which yields
good I–V performance but durability is compromised due to increased
degradation rates caused by corrosion of the catalyst carbon support [26,
27]. A steam-treatment conditioning protocol [6,8] is reported to acti-
vate MEAs within 1 h but MEA performance and durability are
compromised compared to other protocols [26]. In a recent report by
Taghiabadi et al. [28], an accelerated stress test (AST) was introduced to
investigate the effect of different current- and potential-based condi-
tioning procedures on PEMFC durability. It was shown that a constant
current conditioning protocol may require a longer time to activate the
MEA and causes rapid degradation of the catalyst layer.
In addition to considerations of FC conditioning, the mitigation and/
or recovery of reversible (transient) degradation of PEMFCs to ensure
their prolonged durability are important areas of research. Several
methods of recovering transient degradation have been proposed,
ranging from overnight rest, various shutdown procedures, and contin-
uous in-situ testing. In a recent report on FC shutdown procedures, Pivac
and Barbir [29] illustrated that a shorter soak time following the shut-
down of a PEMFC results in higher performance when the FC is rejuve-
nated. Oyarce et al. [30], compared the effects of different shutdown
procedures on PEMFC degradation and found two methods, (i) H2 purge
of the cathode, and (ii) O2 consumption under load were most effective,
resulting in the least amount of degradation. Holmstr€ om et al. [31],
subsequently applied it as a start-up procedure. There have been studies
on the impact of reactant starvation on PEMFC performance. Gerad et al.
[32] had earlier studied the effect of oxygen starvation on PEMFC
durability, Colbow et al. [33] proposed a technique of PEMFC operation
using periodic reactant starvation. Reiser et al. [34] and Gould et al. [35]
introduced methods of cyclic oxidant starvation for PEMFC performance
recovery.
The accelerated conditioning protocol used in this study is modified
from an approach by Eickes et al. [18] to condition DMFCs. In this study,
we report for the first time an in-depth analysis of an accelerated cathode
starvation conditioning procedure for PFSA-based MEAs, contrasting its
performance and durability to established state-of-the-art conditioning
procedures. The cathode starvation protocol involves starving the cath-
ode of oxidant while allowing H2 to diffuse from the anode to cathode.
MEAs conditioned using this cathodic starvation protocol are favorably
compared with MEAs conditioned using the standardized DOE, EU and
an in-house amperometric protocol which is similar to those conditioning
procedures reported by Bi et al. [11] and Shan et al. [12]. The time for
conditioning is determined by observing the time taken to reach peak
power density, and the current density of the cell at 0.6 V, as recom-
mended by Murphy et al. [36] The durability of MEAs is investigated by
comparing the peak power density, polarization curves, ionic resistances
of the membrane and catalyst layer, the charge transfer resistance, and
electrochemical surface area before and after 9000 aging cycles, as
2
Journal of Power Sources Advances 3 (2020) 100012
recommended by Taghiabadi et al. [28].
2. Experimental
2.1. MEA preparation and fuel cell operation
Catalyst ink consisting of a homogeneous mixture of Pt/C catalyst
powder (TEC10E50E, lot 109–0111, 46.4% Pt), Nafion PFSA polymer
dispersion D520 (Ion Power Inc., lot SGA-12-02CS) and methanol (re-
agent grade, Fischer Scientific) was spray-coated onto Nafion NR-N211
membrane (DuPont, TE143904) using a spray coater (Sono-tak Exacta-
Coat). The Pt loading on both anode and cathode electrodes was
0.4 mg Pt/cm2. The catalyst coated membrane (CCM) was sandwiched
between two 5 cm2 (2.24
2.24 cm) PTFE treated gas diffusion layers
(Sigracet 29BC, FuelCellStore) and compressed in fuel cell hardware
(AHNS Co.) using a torque wrench, with fuel cell compression deter-
mined by pressure-sensitive paper (5.7 Nm).
The cell hardware was connected to a fuel cell test station (Scribner
890CL). MEAs were conditioned using our novel cathode starvation
procedure and compared to the standardized DOE conditioning proced-
ure, EU harmonized conditioning procedure, and an amperometric pro-
cedure. The fuel cell temperature was set at 80  C and 100% relative
humidity (RH) at both electrodes. The inlet gas flows were 0.5 slpm
hydrogen at the anode and 1.0 slpm oxygen at the cathode.
12 MEAs samples were prepared under identical conditions and
divided into four sets of 3 for evaluation using 4 different conditioning
procedures. Each of the conditioning procedures described below was
repeated three times on individually prepared MEAs. For each of the
three tests carried out using the same conditioning procedure, the per-
formance and degradation profile obtained were found reproducible,
showing the same trend. Further information on how the accuracy of
comparison is ensured is included in the SI (Fig. S1- S6, Table S5).
2.2. Conditioning procedures
The conditioning procedures investigated in this study are listed
below:
(a) Cathode starvation conditioning protocol. The cell is operated
under H2/O2 configuration and the backpressure is increased from
ambient to 1.5 bar. The current is held constant as the cathode gas
feed is switched off, then turned back on as the voltage reaches
0.2 V. This process is repeated in cycles until the difference be-
tween the last two cycles is < 5 mV.
(b) Standardized DOE conditioning procedure: The voltage is
switched between OCV (held for 1 s) and 0.55 V (held for 1 h)
until the difference in current (recorded immediately after
returning to 0.55 V) between 2 successive cycles is < 50 mA
(10 mA/cm2).
(c) Standardized EU conditioning protocol: (i) The power density
response is monitored as the current density is ramped from 0.5 A
(100 mA/cm2) to 4A (800 mA/cm2) and allowed to stabilize for
6 h. (ii) The voltage response is monitored at a constant current of
5 A (1000 mA/cm2) for 2 h at 50% RH. (iii) The voltage is sub-
sequently cycled between 0.75 V and 0.45 V until the difference in
the current response between the last 2 steps is < 5 mA (1 mA/
cm2).
(d) In-house, amperometric conditioning protocol. The current is
linearly increased from 2 A (400 mA/cm2) to 15 A (3000 mA/cm2)
over an 18 h period. The procedure is repeated until attaining
optimal power density performance (i.e., the difference between
the last 2 current scans is < 50 mA (10 mA/cm2)).
2.3. Electrochemical characterization
The electrochemical characteristics of the MEAs were investigated
E. Balogun et al.
using polarization data, EIS and cyclic voltammetry (CV). Polarization
data were recorded from OCV to a shutoff potential of 0.3 V in 200 mA
steps, measuring 5 min⋅point1. Higher resolution in the kinetic region
was attained using a current scan from 0.00 to 0.20 A (40 mA/cm2) in
0.01 A steps at 1 min⋅point1. Similarly, the Ohmic region of the I–V
curves was evaluated from 0.50 A (100 mA/cm2) to 1.50 A (300 mA/
cm2), in 0.50 A (100 mA/cm2) steps of 5 min⋅point1. The latter region of
the polarization curve was obtained by scanning through 2A (400 mA/
cm2) to 15A (3000 mA/cm2) using 1 A (200 mA/cm2) steps at
5 min⋅point1.
A VersaStat 4 Potentiostat/Frequency Response Analyzer (FRA) was
used for electrochemical characterizations. Cyclic voltammograms (CV)
were measured by sweeping the potential between 0.04 V and 0.80 V vs.
RHE at a scan rate of 50 mV/s, after an initial potential hold at 0.4 V vs.
RHE for 45 sec. Measurement conditions were 80  C and 100% RH, with
inlet gas flows of 0.5 slpm H2 at the anode and 1.0 slpm O2 (0.5 slpm N2
for CL investigation) at the cathode.
The electrochemical surface area associated with hydrogen adsorp-
tion was estimated using the following relation:
Q
ECSA ¼ (1)
L * μPt
where ECSA is the electrochemically active surface area, Q is the charge
density of the atomic hydrogen adsorption, L is the Pt loading (0.4 mg Pt/
cm2) and μpt is the charge required to reduce a monolayer of protons on a
polycrystalline Pt surface of 1 cm2 (210 mC cm2 Pt).
EIS analysis was performed on cells equilibrated under 0.5 slpm H2 at
the anode and 0.5 slpm N2 at the cathode, once a stable potential of
<0.15 V was achieved. Under these conditions, an AC voltage amplitude
of 10 mV (RMS) was applied, and frequency scans were performed from
100 kHz to 100 mHz. EIS characterization was performed potentiostati-
cally at 0.8 V. A Randle's equivalent circuit model was used to extract
meaningful information by modeling the different regions of the fuel cell
as an electrical circuit having ideal resistors, capacitors, and inductors
[37–39]. The corresponding impedance data were plotted in a Nyquist
plot, and fitted in Zview software using a simple Randles circuit [40].
To determine the ionic resistance of the catalyst layer, a double par-
allel resistive rail was used, as detailed by Qi et al. [41], and Lefebvre
et al. [42]. One of the parallel resistive rails represents the electron
transport through the conducting carbon support, and the other repre-
sents ion transport through the inter-particle regions corresponding to
ion migration through the catalyst layer [41,42]. The low-frequency
resistance (LFR) is represented by an upward curve in the impedance
plot, to a limiting capacitive response (vertical) which corresponds to the
total capacitance and resistance of the catalyst layer. The ionic resistance,
Rionic, was obtained from the length of the Warburg-like region projected
onto the real impedance (Z') axis (Rionic/3) [40–43]. The membrane's
ionic resistance was obtained from the high-frequency intercept (HFR)
with the x-axis on the Nyquist plot [27].
L MEAs did not meet the assigned metric for conditioning until 8 condi-
σm ¼ (2)
A * Rionic
Similarly, from the electrode's ionic resistance was calculated using
the equation below [31],
REionic
LFR ¼
3
and,
LE 3 * LE
σE ¼ ¼ (3)
A * REionic A * LFR
where σm and σE are the membrane and electrode's conductivity
respectively. Rionic and RE-ionic represent the membrane and electrode's
ionic resistance. A is the active cell area, and L and LE are the membrane
3
Journal of Power Sources Advances 3 (2020) 100012
and electrode thickness, respectively, while LFR is the low-frequency
resistance.
2.4. Accelerated degradation
The accelerated degradation protocol is described in Ref. [28].
Briefly, at 80  C, and 100% RH and 30% RH at the anode and cathode,
respectively, the aging process is accelerated via the following steps: (i)
maintain the cell at OCV for 8 sec; (ii) perform a voltage scan in the range
OCV → 0.6 V → OCV, at a scan rate of 50 mV/s. Steps i and ii are repeated
for up to 9000 cycles. The cell performance was characterized after 3000
cycle intervals.
3. Results and discussion
Cathode Starvation Conditioning Procedure. The approach used
here is similar to the proton-pump configuration. This protocol focuses
not just on the hydration of the MEA but also on reclaiming dehydrated
and blocked catalyst sites in the cathode. This is achieved by allowing
crossover of hydrogen gas from the anode to the cathode, lowering the
cathode potential and thereby promoting reducing conditions at the
cathode. The proposed cathode starvation procedure entails a series of
steps. First, the backpressure on the anode is increased from ambient to
1.5 bar to aid the crossover of H2 from anode to the cathode. Thereafter,
the current is increased in steps until the cell voltage is 0.3 V. The cell is
maintained at this voltage for 2–5 min in order for the current response to
stabilize. The current is then reduced to 1 A (200 mA/cm2). The supply of
cathode gas is stopped while maintaining the current at 1 A. The voltage
of the cell is observed to drop since there is no supply of oxygen to the
cathode. At the point where the voltage reaches 0.2 V, the cathode gas
flow is quickly re-supplied. The process is repeated. A more rapid drop
voltage is observed overtime when the cathode gas is shut off. At the end
of the conditioning procedure, the backpressure at both electrodes is
returned to ambient. This protocol is illustrated in Fig. 1a and the
resultant maximum power density obtained as a function of these cycles
is listed in Table S1. The MEA is considered conditioned when the dif-
ference between the last two cycles is < 5 mV. Full conditioning is
attained in <40 min. Moreover, > 90% of the maximum current (density)
is achieved after one conditioning cycle (12 min). The reproducibility of
the polarization curves using three individual MEAs is illustrated in
Fig. S1, which shows overlaid I–V and power density plots immediately
after their conditioning.
DOE Conditioning Procedure. The DOE conditioning procedure
entails applying multiple cycles of potential [24]. In this protocol, as
illustrated in Fig. 1d, the fuel cell is switched between its open-circuit
voltage and 0.55 V repeatedly every hour until the last two measured
current values are < 50 mA (10 mA/cm2). The MEA is expected to reach
its peak performance after 6 h [20]. The current response to the condi-
tioning cycles is illustrated in Fig. 1b and the current and current den-
sities after each conditioning cycle is listed in Table S2, which shows
tioning cycles had been carried out, i.e., the equivalent of 8 h condi-
tioning time. It is noted that >90% of the maximum current (density) is
achieved after one conditioning cycle (1 h). The reproducibility of the
polarization curves using three individual MEAs is demonstrated in
Fig. S2, which shows overlaid I–V and power density plots immediately
after their conditioning.
EU Harmonized Conditioning Procedure. The EU procedure in-
volves relative humidity cycling, together with stepwise current and
potential cycling [25]. As illustrated in Fig. 1c, the current density is
increased in steps of 100 mA/cm2 up to 800 mA/cm2 while keeping the
cell voltage >400 mV. The cell is allowed to stabilize for 6 h (region i).
The relative humidity of the reactants is then reduced to 50% RH while
increasing the current and keeping the cell voltage >400 mV, up to 1
A/cm2. The current is maintained under this condition for 2 h (region ii).
Following this, potential cycling is carried out between 0.75 V and
E. Balogun et al. Journal of Power Sources Advances 3 (2020) 100012

Fig. 1. Plots showing the current and

power density response as a function of
conditioning time with current (black
dotted line) and power density (red)
response for MEAs consisting of Nafion®
NR-211, Nafion® D520 ionomer in the
catalyst layer and Pt loadings of
0.4 mg Pt/cm2 for cathode and anode:
(a) Cathode starvation conditioning (b)
DOE conditioning, (c) EU conditioning,
(d) amperometric conditioning. (For
interpretation of the references to colour
in this figure legend, the reader is
referred to the Web version of this
article.)

0.45 V, and the cell is allowed to stabilize for 30 min at 0.45 V. This cycle maintained a maximum power density of 1230 mW/cm2 (15% drop), the
is repeated until the cell current becomes stable. The recommended EU-conditioned MEA yielded 1190 mW/cm2 (17% drop), and the
stability criterion is based on the cell voltage fluctuation and is consid- amperometric conditioned-MEA yielded 1180 mW/cm2 (17% drop) as
ered fulfilled when lower than 5 mA (1 mA/cm2) in the final 2 steps depicted in Fig. 4. Table 1 shows the values of the maximum power
(region iii) [21]. The current (density) after successive conditioning density and current density at 0.6 V for the MEAs conditioned by the
potential cycles are listed in Table S3. MEAs are considered fully condi- different conditioning procedures. The reproducibility of the polarization
tioned after 11 h. Overlaid I–V curves for three individual MEAs imme- curves using three individual MEAs for each of the four condition pro-
diately after their conditioning are shown in Fig. S3 to demonstrate tocols are illustrated in Figs. S1–S4, which shows overlaid I–V and power
experimental reproducibility. density plots immediately after 9000 degradation cycles.
Amperometric Conditioning. This is a common conditioning pro- To further characterize MEAs, impedance spectra were analyzed
cedure and one we had adopted for several years in our laboratory. As using EIS and the corresponding frequency response plotted as Nyquist
illustrated in Fig. 1d, the entire conditioning process involves linear plots (shown in Figs. S7 and S8). Data for unconditioned MEAs are shown
sweeps of current ranging from 2A (400 mA/cm2 initial point) to 15 A for comparison and to exemplify the importance of conditioning
(3.0 A/cm2 final point) at 5 min.point1 and 0.25 A (50 mA/cm2) steps
per point. The procedure was repeated four times before attaining
optimal power density performance (i.e., the difference between the last
2 current scans is < 50 mA (10 mA/cm2)). The current (density)
response as a function of the current cycle is illustrated in Fig. 1c and the
resultant maximum power density obtained as a function of these cycles
is listed in Table S3. From these data, MEA is considered fully condi-
tioned after 18 h. Overlaid I–V curves for three individual MEAs condi-
tioned amperometrically are shown in Fig. S4.
Fig. 2 shows graphically the time taken to attain optimum condi-
tioning when each of the conditioning procedure is used. As observed
from the polarization and power density curve shown in Fig. 3a, the DOE
conditioning protocol yields the highest initial performance immediately
after conditioning with a maximum power density of 1530  20 mW/
cm2. This is followed by MEAs conditioned with the cathode starvation
protocol with 1450  10 mW/cm2; followed by the EU protocol, with
1430  6 mW/cm2; and the amperometric conditioning protocol, with
1420  6 mW/cm2 (see Table 1).
After 9000 degradation cycles, the DOE-conditioned MEA yields a Fig. 2. Time for the fuel cell to reach maximum power density using various
power density of 1245 mW/cm2 representing a 19% drop in performance conditioning protocols. Error bars represent the upper and lower boundaries of
from its initial value. The cathode starvation conditioned-MEA three separate measurements.

4
E. Balogun et al. Journal of Power Sources Advances 3 (2020) 100012

Fig. 3. Polarization (black) and power density plots (red) of MEAs subjected to the four conditioning procedures: (a) immediately following conditioning, (b) after
9000 degradation cycles. FC polarization data were obtained at 80  C, H2 anode and O2 cathode, 100% RH, 1 atm pressure. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

Table 1
Maximum power density, and current density at 0.6 V, for MEAs conditioned under different procedures and after accelerated degradation cycles. Std. Devs. provided in
Table S5.
Conditioning Maximum power density (mA/cm2) Current density at 0.6 V (A/cm2)
Procedure
After conditioning (0 After 3000 After 6000 After 9000 After conditioning (0 After 3000 After 6000 After 9000
cycles) cycles cycles cycles cycles) cycles cycles cycles

Cathode Starvation 1450 1380 1310 1230 2000 1650 1450 1330
DOE 1530 1420 1360 1245 2100 1750 1650 1450
EU 1430 1390 1290 1190 1800 1650 1430 1280
Amperometric 1420 1320 1240 1180 1800 1600 1430 1230

30% increase and a 23% decrease in membrane resistances (Rmea before

Fig. 4. Degradation data comparing the performance loss observed as a function
of percentage loss in maximum power density after various accelerated degra-
dation cycles for MEAs conditioned by the different procedures.
(Fig. S7). The data extracted from Nyquist plots of unconditioned MEAs
are shown in Table S5. Unconditioned MEAs are observed to possess a
relatively large membrane resistance (Rmea) of 99.5 mΩ cm2 which is
almost double that of conditioned cells, as can be observed from the
extracted resistance data presented in Table 2. The cathode starvation
procedure is observed to yield MEAs with the lowest membrane resis-
tance immediately after conditioning. The highest Rmea value is found for
the amperometric procedure. After 9000 cycles, there were no significant
changes in membrane resistances before and after degradation for MEAs
conditioned by the DOE and cathode starvation procedures. However, a
and after degradation) were observed for MEAs conditioned using the EU
and amperometric protocols, respectively. This is an indication that for
MEAs conditioned by the DOE and cathode starvation protocols, the
membrane is well hydrated and that there is no significant degradation of
the membrane occurring even after 9000 degradation cycles. For the EU
conditioning protocol, a significant increase in membrane resistance is an
indication of accelerated degradation of the membrane. Similarly, the
reduction in membrane resistance observed in the amperometric pro-
cedure after 9000 cycles indicate that the membrane was not fully
conditioned initially. This is interesting to note considering that the
amperometric protocol required the longest time to attain its peak
performance.
Similarly, the charge transfer resistance (Rct) recorded for uncondi-
tioned MEAs is observed (Fig. S7, Table 2) to be > 485 mΩ cm2, this is
more than double the Rct values for conditioned cells (Table 2) irre-
spective of the conditioning procedure. Rct values recorded immediately
after conditioning and after 9000 degradation cycles are observed to
almost double, as listed in Table 2. This implies that the degradation of
the MEA is prominent in the catalyst layer. It is observed that the cathode
starvation conditioning protocol yields MEAs with the lowest Rct
immediately after conditioning while the DOE protocol yields the largest
charge transfer resistance. This suggests that the cathode starvation
protocol promotes the rate of ORR and by extension leads to the reduc-
tion in the activation polarization and improvement in overall MEA
performance. Noting that Pt oxides and hydroxides may exist on the
catalyst surface, formed in the presence of humidified O2, and that the
rate of the O2 reduction reaction is higher on Pt than on PtO or Pt(OH)4
[44], we speculate that the cathode starvation protocol, which is asso-
ciated with the H2 fuel being consumed at the anode and produced at the
cathode produces sufficiently strong reducing conditions at the cathode

5
E. Balogun et al. Journal of Power Sources Advances 3 (2020) 100012

Table 2
MEA resistance data immediately after conditioning and after 9000 degradation cycles for MEAs conditioned using different procedures.
Conditioning procedure Unconditoned MEA Cathode starvation DOE EU Amperometric
2
After conditioning (0 cycles) Rmea (mΩ cm ) 99.5  10.1 37.3  3.78 41.8  4.24 39.3  3.99 51.5  4.85
Rct (mΩ cm2) 488  5.22 193  6.52 242  5.01 210  4.02 209  8.04
After 9000 cylces Rmea (mΩ cm2) – 37.4  3.24 42.4  2.19 56  4.62 39.6  3.23
Rct (mΩ cm2) – 428  5.84 355  3.22 465  5.20 489  6.08

CL Ionic resistance after conditioning Rionic/3(mΩ cm2) 143  4.98 41.6  2.32 51.5  3.24 55.5  1.08 58.5  3.06
Rionic (mΩ cm2) 429  10.1 125  6.96 155  9.72 166  3.24 175  9.18
CL Ionic resistance 9000 cylces Rionic/3(mΩ cm2) – 40.8  2.24 55  3.92 46.4  2.98 47.5  4.02
Rionic (mΩ cm2) – 123  6.72 166  11.8 139  8.94 143  12.1

electrode to reduce Pt oxides and hydroxide to bare Pt.

To determine the ionic resistance of the CL, a transmission line
Randles equivalent electric circuit model was used to model the Nyquist
plot as shown in Fig. S9 and Fig. S10. The ionic resistance of an uncon-
ditioned catalyst layer in an MEA is found to be 428 mΩ cm2 (Fig. S8,
Table S5). Upon conditioning, this resistance drops by 200%. The
reduced CL ionic resistance observed in the CL after conditioning is
believed to be associated with hydration and improved alignment of
hydrophilic domains leading to well-connected protonic pathways
within the CL.
Comparing the various conditioning protocols, from Table 2, it is
observed that CL ionic resistance is lowest for the cathode starvation
protocol both immediately after conditioning (Cathode starvation,
125 mΩ cm2; Amperometic, 175 mΩ cm2; DOE, 155 mΩ cm2; EU,
166 mΩ cm2) and after 9000 degradation cycles (Cathode starvation,
122 mΩ cm2; Amperometric, 142 mΩ cm2; DOE: 166 mΩ cm2; EU:
139 mΩ cm2). The reduction in Rionic observed after degradation is
corroborated by an earlier report by Farhana et al. [45], which is an
indication that potential cycling does not lead to ionomer degradation
under these aging conditions. From the values of proton resistance within
the CL, it is observed that for the cathode starvation protocol, there is
little difference between the ionic resistance of the CL immediately after
activation and after 9000 degradation cycles. It shows that the cathode
starvation conditioning procedure yields an MEA that is well hydrated
and maintains its performance over a longer period. Hydration within the
CL is key to proton conductivity and reduced resistance [45,46], the
cathode starvation protocol promotes the hydration of the CL, which is
necessary for efficient proton transfer within the CL, and between the CL
to the membrane.
The CV-determined electrochemical surface area (ECSA) of the Fig. 5. Plot showing (a) Electrochemical Surface Area (ECSA) for MEA cathodes
cathode for MEAs conditioned using different procedures are shown in conditioned with different procedures and subjected to increasing accelerated
Fig. 5a. The ECSA recorded for each MEA after conditioning was similar degradation cycles. (b) An inverse relationship between the ECSA (m2/g pt) and
to values reported in earlier studies for MEAs with similar configurations the MEA charge transfer resistance (mΩ cm2) for MEAs conditioned using four
different conditioning procedures. (A) Data obtained immediately after condi-
[45,47,48]. MEAs conditioned using the cathode starvation protocol
tioning, (B) after 3000 degradation cycles, (C) after 6000 degradation cycles,
yielded the highest ECSA values after conditioning and throughout the
and (D) after 9000 degradation cycles. Conditions for ECSA measurement:
degradation process. Similarly, contrasting the ECSA lost after 9000 cy- 80  C, H2 anode and N2 cathode, 100% RH, 1 atm pressure.
cles, MEAs conditioned by cathode starvation, the amperometric pro-
cedure, the DOE procedure, and the EU procedure lost 40%, 42%, 40%,
hydrophilic phase, it is clear from the higher double-layer capacitance
and 42% of their value, respectively. The reduction in ECSA observed
observed that the conditioning procedure increases the total electroni-
after degradation is believed the result of carbon substrate corrosion,
cally conductive surface area, which is consistent with the observed in-
dissolution of the Pt catalyst and/or washing away of the catalyst as a
crease in ECSA [45,47]. Similarly, from Fig. S11, the cathode starvation
result of excess water formation at the electrode [26].
conditioning procedure also showed the highest Cdl value, which is
The catalyst layer was also analyzed for double-layer capacitance
indicative of a larger ECSA as observed from Fig. 5a. Furthermore, it is
formation using a plot of 1/-Im Z*ω vs Re Z as shown in Fig. S11. The
observed that an inverse relationship between the charge transfer resis-
slope of the plot for the MEA prior to conditioning was relatively low,
tance (Rct) of the MEA and the ECSA exists, as illustrated in Fig. 5b. As the
indicating that the catalyst layer possessed a higher resistivity [47]. The
ECSA decreases, the charge transfer resistance (Rct) of the MEA increases.
MEA conditioned by the cathode starvation procedure was observed to
Scanning electron micrographs (SEM) of cross-sections the different
yield the steepest slope (lowest resistivity), followed by the DOE,
MEAs are shown in Fig. S12. It is observed that the thickness of the
amperometric and EU procedures, respectively. Furthermore, it is
membranes of the MEAs after undergoing accelerated degradation is
observed from Fig. 5a and Fig. S11, that the double layer capacitance
relatively unchanged, with the membrane thickness ranging between
increases with increasing ECSA. Since the charge double capacitance
24.7 and 25.7 μm regardless of the conditioning procedure used. How-
(Cdl) reports on the total electronically conductive surface area (catalyst
ever, differences in catalyst layer thicknesses were observed based on the
þ conductive support) in the catalyst layer that is in contact with the

6
E. Balogun et al.
conditioning procedure employed. Membranes conditioned using the
cathode starvation and DOE procedures showed a similar cathode cata-
lyst thickness of 9.9–10.2 μm and similar anode thickness of
11.2–11.7 μm. MEAs conditioned using the EU protocol showed a thinner
electrode thickness of 9.84–9.88 μm for the cathode and 10.1–10.9 μm
for the anode. MEAs conditioned using the amperometric procedure
showed the thinnest electrode thicknesses, with 9.54–9.56 μm for the
cathode and 9.80–9.84 μm for the anode. According to Oyarce et al. [30],
changes in electrode thickness during degradation may be attributed to
the loss of carbon support as a result of carbon corrosion at high oxidative
potentials. It is observed that both the cathode starvation and the DOE
protocol provides superior protection to the electrode against such losses
compared to the other two activation protocols.
4. Conclusion
The performance and durability of MEAs subjected to a new accel-
erated conditioning procedure, involving cathode starvation, was
investigated and compared with the standardized DOE and EU harmo-
nized conditioning procedures and against an in-house-adapted amper-
ometric procedure. The time required to condition MEAs using the
cathode starvation procedure, as determined by the time to reach peak
power density is 40 min. Greater than 90% of the maximum current
(density) is achieved after 12 min. However, unlike other accelerated
conditioning procedures reported in the literature that are purported to
condition MEAs in under an hour, our cathode starvation procedure was
found to lead to MEAs that were more durable under an accelerated
degradation test. The cathode starvation procedure results in a significant
reduction in ionic resistance of the catalyst layer, increased ECSA and
decreased charge transfer resistance. This is attributed to the low cathode
potential and H2 crossover from anode to cathode during the condi-
tioning that promotes proton transport within the CL and provides
reducing conditions at the cathode to promote sufficiently strong
reducing conditions at the cathode electrode to reduce Pt oxides and
hydroxide to bare Pt. Future work should be undertaken to address the
validity of these processes.
For the MEAs conditioned by cathode starvation, the smallest per-
centage change in CL ionic resistance and ECSA was found during
accelerated degradation, with no significant difference in ionic resistance
and smallest percentage loss of active sites before and after degradation,
compared to the other conditioning procedures examined. It can be
concluded that the new cathode starvation conditioning procedure has
proven to yield MEAs exhibiting high performance and durability while
taking 90% less amount of time compared to other standardized condi-
tioning protocols. The positive attributes of this conditioning protocol
warrant further investigation to determine if the same attributes apply to
larger MEAs, fuel cell stacks, and state-of-the-art MEAs used in the in-
dustry which operate with stabilized materials, thinner membranes, anti-
oxidant additives, lower Pt loadings, and. multi-component catalysts.
Acknowledgments
This work was supported by the Natural Sciences and Engineering
Research Council of Canada (NSERC) and made use of facilities in 4D
LABS, SFU.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https
://doi.org/10.1016/j.powera.2020.100012.
References
[1] R. Souzy, B. Ameduri, Functional fluoropolymers for fuel cell membranes,
Fluorinated Mater. Energy Convers. (2005) 469–511, https://doi.org/10.1016/
B978-008044472-7/50049-7.
7
Journal of Power Sources Advances 3 (2020) 100012
[2] J. Peron, Z. Shi, S. Holdcroft, Hydrocarbon Proton Conducting Polymers for Fuel
Cell Catalyst Layers, 2011, https://doi.org/10.1039/c0ee00638f.
[3] D. Papageorgopoulos, Fuel cell R&D overview, in: Annu. Merit Rev. Peer Eval.
Meet., 2019 (2019) 33.
[4] T.W. Lim, S.H. Kim, S.Y. Ahn, B.K. Hong, B.K. Ahn, (12) United States Patent, 2013,
US 2010/0129689 A.
[5] J. Peron, A. Mani, X. Zhao, D. Edwards, M. Adachi, T. Soboleva, Z. Shi, Z. Xie,
T. Navessin, S. Holdcroft, Properties of Nafion® NR-211 membranes for PEMFCs,
J. Membr. Sci. 356 (2010) 44–51, https://doi.org/10.1016/j.memsci.2010.03.025.
[6] Z. Qi, A. Kaufman, Quick and effective activation of proton-exchange membrane
fuel cells, J. Power Sources 114 (2003) 21–31, https://doi.org/10.1016/S0378-
7753(02)00587-6.
[7] D. Bezmalinovic, J. Radosevic, F. Barbir, Initial conditioning of polymer electrolyte
membrane fuel cell by temperature and potential cycling, Acta Chim. Slov. 62
(2015) 83–87, https://doi.org/10.17344/acsi.2014.730.
[8] M. Bradley P. Anderson, Andover, United States Patent 12 (2009). US7608118B2.
[9] K. Palanichamy, A.K. Prasad, S.G. Advani, 214th ECS meeting, abstract #1739,
Electrochem. Soc. 410 (2008) 1739.
[10] Z. Xie, X. Zhao, M. Adachi, Z. Shi, T. Mashio, A. Ohma, K. Shinohara, S. Holdcroft,
T. Navessin, Fuel cell cathode catalyst layers from “green” catalyst inks, Energy
Environ. Sci. 1 (2008) 184–193, https://doi.org/10.1039/b808613n.
[11] W. Bi, G.E. Gray, T.F. Fuller, PEM fuel cell PtC dissolution and deposition in Nafion
electrolyte, Electrochem. Solid State Lett. 10 (2007) 101–104, https://doi.org/
10.1149/1.2712796.
[12] J. Shan, X. Yan, X. Sun, Z. Hou, P. Qi, P. Ming, Chinese Patent 2010, CN
10010014.3.
[13] USFCC single cell test protocol, Available from: http://www.fchea.org/core/impor
t/PDFs/TechnicalResources/MatCompSingleCellTestProtocol05-014RevB.207130
6.pdf. (Accessed 10 December 2019).
[14] L.N.( US, Ryan, Hallum, (12) United States Patent, 2003. US 6576356 B1.
[15] C.O. Seung, E.Y. Seung, H.K. Myong, H.L. Jong, J.K. Jun, J.I. Son, Chinese Patent
2009, CN 101340004A.
[16] Z. Xu, Z. Qi, A. Kaufman, Activation of proton-exchange membrane fuel cells via CO
oxidative stripping, J. Power Sources 156 (2006) 281–283, https://doi.org/
10.1016/j.jpowsour.2005.02.094.
[17] K. Fumio, M.Naoya, S. Ryoichi, European patent, 2005, EU05004688.7.
[18] C. Eickes, P. Piela, J. Davey, P. Zelenay, Recoverable cathode performance loss in
direct methanol fuel cells, J. Electrochem. Soc. 153 (2006) A171, https://doi.org/
10.1149/1.2136073.
[19] M.K. Debe, Tutorial on the fundamental characteristics and practical properties of
nanostructured thin film (NSTF) catalysts, J. Electrochem. Soc. 160 (2013)
F522–F534, https://doi.org/10.1149/2.049306jes.
[20] A. Goleman, D. Richard, M. Perdana, J. Chem. Inf. Model. 53 (2018) 1689–1699,
https://doi.org/10.1017/CBO9781107415324.004.
[21] B.Gould, K. Lyons, O. Baturina, United States Patent, 2011, US 20110008686A1.
[22] T. Kato, H. Tsuge, T. Yamada, United States Patent, 2013, US2013171529A1.
[23] X.Z. Yuan, S. Zhang, J.C. Sun, H. Wang, A review of accelerated conditioning for a
polymer electrolyte membrane fuel cell, J. Power Sources 196 (2011) 9097–9106,
https://doi.org/10.1016/j.jpowsour.2011.06.098.
[24] U.S. Department of Energy, DoE Procedures for Performing PEM Single Cell Testing,
2009, p. 47. # DE-FC36-06GO16028 April 8.
[25] G. Tsotridis, A. Pilenga, G. De Marco, T. Malkow, EU Harmonised Test Protocols for
PEMFC MEA Testing in Single Cell Configuration for Automotive Applications, JRC
Science for Policy report, 2015, https://doi.org/10.2790/54653.
[26] X.Z. Yuan, J.C. Sun, H. Wang, H. Li, Accelerated conditioning for a proton exchange
membrane fuel cell, J. Power Sources 205 (2012) 340–344, https://doi.org/
10.1016/j.jpowsour.2012.01.039.
[27] T. Mittermeier, A. Weiß, F. Hasche, G. Hübner, H.A. Gasteiger, PEM fuel cell start-
up/shut-down losses vs temperature for non-graphitized and graphitized cathode
carbon supports, J. Electrochem. Soc. 164 (2017) F127–F137, https://doi.org/
10.1149/2.1061702jes.
[28] M.M. Taghiabadi, M. Zhiani, V. Silva, Effect of MEA activation method on the long-
term performance of PEM fuel cell, Appl. Energy 242 (2019) 602–611, https://
doi.org/10.1016/j.apenergy.2019.03.157.
[29] I. Pivac, Barbir, Rejuvenation Techniques for Automotive Fuel Cells, 2019, p. 20. htt
ps://www.semanticscholar.org/paper/Rejuvenation-techniques-for-automotive-fue
l-cells-Pivac-Barbir/50a7ea5eef9dcd906c93ef199f4478da9aea19d9.
[30] A. Oyarce, E. Zakrisson, M. Ivity, C. Lagergren, A.B. Ofstad, A. Boden, G. Lindbergh,
Comparing shut-down strategies for proton exchange membrane fuel cells, J. Power
Sources 254 (2014) 232–240, https://doi.org/10.1016/j.jpowsour.2013.12.058.
[31] N. Holmstr€ om, K. Wiezell, G. Lindbergh, Studying low-humidity effects in PEFCs
using EIS, J. Electrochem. Soc. 159 (2012) F369–F378, https://doi.org/10.1149/
2.005208jes.
[32] M. Gerard, J. Poirot-Crouvezier, D. Hissel, M. Pera, Oxygen starvation effects on
pemfc durability, in: Proceedings of the ASME 2010 Eighth International Fuel Cell
Science, Engineering and Technology Conference, 2010, pp. 1–8.
[33] K. Colbow, M. Van der Geest, C. Longley, J. Muller, J. Roberts, J. St[HYPHEN]
Pierre, P. Urba, R. Wezel and D. Wilkinson, J. Zhang. US 6,472,090 B1. Oct, 29,
2002.
[34] C. Reiser, R. Balliet, United States Patent, 2003, US 2003224228A1.
[35] Hyundai Motor Company, United States Patent, US 20170271693A1, 2017.
[36] W.H. Zhu, R.U. Payne, B.J. Tatarchuk, PEM stack test and analysis in a power
system at operational load via ac impedance, J. Power Sources 168 (2007)
211–217, https://doi.org/10.1016/j.jpowsour.2007.02.071.
[37] A. Baricci, R. Mereu, M. Messaggi, M. Zago, F. Inzoli, A. Casalegno, Application of
computational fluid dynamics to the analysis of geometrical features in PEM fuel
E. Balogun et al.
cells flow fields with the aid of impedance spectroscopy, Appl. Energy 205 (2017)
670–682, https://doi.org/10.1016/j.apenergy.2017.08.017.
[38] Scribner Associates Inc, Electrochemical impedance spectroscopy ( EIS ): a powerful
and cost- effective tool for fuel cell diagnostics, electrochem. Impedance spectrosc.
A powerful cost- eff, Tool Fuel Cell Diagnostics 35 (2014) 1–5, https://doi.org/
10.1016/0013-4686(90)80007-B.
[39] Z. Qi, P.G. Pickup, High performance conducting polymer supported oxygen
reduction catalysts, Chem. Commun. (1998) 2299–2300, https://doi.org/10.1039/
a805322g.
[40] M.C. Lefebvre, R.B. Martin, P.G. Pickup, Characterization of ionic conductivity
profiles within proton exchange membrane fuel cell gas diffusion electrodes by
impedance spectroscopy, Electrochem. Solid State Lett. 2 (1999) 259–261, https://
doi.org/10.1149/1.1390804.
[41] S. Touhami, J. Mainka, J. Dillet, S.A.H. Taleb, O. Lottin, Transmission line
impedance models considering oxygen transport limitations in polymer electrolyte
membrane fuel cells, J. Electrochem. Soc. 166 (2019) F1209–F1217, https://
doi.org/10.1149/2.0891915jes.
[42] I.C. Yu, R. Chen, J.J. Li, J.J. Li, M. Drahansky, M. Paridah, A. Moradbak,
A. Mohamed, H. abdulwahab taiwo Owolabi, FolaLi, M. Asniza, S.H. Abdul Khalid,
T. Sharma, N. Dohare, M. Kumari, U.K. Singh, A.B. Khan, M.S. Borse, R. Patel,
A. Paez, A. Howe, D. Goldschmidt, C. Corporation, J. Coates, F. Reading, We Are
Journal of Power Sources Advances 3 (2020) 100012
IntechOpen , the World ’ S Leading Publisher of Open Access Books Built by
Scientists , for Scientists TOP 1 %, 2012, p. 13, https://doi.org/10.1016/
j.colsurfa.2011.12.014. Intech. i.
[43] F.S. Saleh, E.B. Easton, Diagnosing degradation within PEM fuel cell catalyst layers
using electrochemical impedance spectroscopy, J. Electrochem. Soc. 159 (2012)
B546–B553, https://doi.org/10.1149/2.098205jes.
[44] S. Holdcroft, Fuel cell catalyst layers: a polymer science perspective, Chem. Mater.
26 (2014) 381–393, https://doi.org/10.1021/cm401445h.
[45] O'Rian O. Reid, Farhana S. Saleh, E. Bradley Easton, Application of the transmission
line EIS model to fuel cell catalyst layer durability, ECS Transactions 457 (2014)
356–359, https://doi.org/10.7868/s0869565214210269.
[46] R. Alipour Moghadam Esfahani, E.B. Easton, Exceptionally durable Pt/TOMS
catalysts for fuel cells, Appl. Catal. B Environ. 268 (2020) 118743, https://doi.org/
10.1016/j.apcatb.2020.118743.
[47] E.B. Easton, P.G. Pickup, An electrochemical impedance spectroscopy study of fuel
cell electrodes, Electrochim. Acta 50 (2005) 2469–2474, https://doi.org/10.1016/
j.electacta.2004.10.074.
[48] A.J. Steinbach, M.K. Debe, J.L. Wong, M.J. Kurkowski, A.T. Haug, D.M. Peppin,
S.K. Deppe, S.M. Hendricks, E.M. Fischer, A new paradigm for PEMFC ultra-thin
electrode water management at low temperatures, E.C.S. Transactions 33 (2010)
1179–1188.