international journal of hydrogen energy 35 (2010) 3147–3151

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Analysis on the PEM fuel cells after accelerated

life experiment

Pucheng Pei*, Xing Yuan, Pengxiang Chao, Xizhong Wang

The State Key Lab. of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China

article info abstract

Article history: After 500 h accelerated lifetime test on an automotive PEM (proton exchange membrane)
Received 10 June 2009 fuel cell stack, the performance of the cells at the stack’s foreside is the worst. The elec-
Received in revised form trochemical surface area, internal resistance, particle size and hydrophobic nature of
6 July 2009 catalyst are measured based on the electrochemical methods, electronic-lens and dropped
Accepted 22 September 2009 water test. The results show that the internal resistance increases to double and the
Available online 25 October 2009 average particle diameter increases to 3 times when electrochemically active area surface
coefficient decreases to one-fifth. The open circle voltage of the worst cell is 0.7 V and its
Keywords: maximum current density is 200 mA/cm2. Especially, the performance of part at air-outlet
PEM Fuel cell is the worst, followed by the part at air-inlet, hydrogen-outlet, and hydrogen-inlet. The
Performance degradation phenomenon mentioned above at the inlet of stack is the most serious among all the cells
Electrochemical in the stack.
Test ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
Life

1. Introduction 2. Experimental

The automotive fuel cell’s lifetime is only around 2000 h at
present. There is a wide gap to the minimum requirement
of 5000 hours for the automotive commercial purpose [1].
Performance degradation of fuel cell is closely related to
catalyst agglomeration, loss on membrane electrode
assembly (MEA) [2–5], catalyst poisoning [6,7] and MEA
contaminated [6–8]. The start-stop process, idling and
frequent load changing are the most important reasons
affecting the performance of PEMFC. Starvation of gas and
water flooding occur frequently in PEMFC used in vehicle
[9–15]. Considering the different location on flow field in
a cell and in different cells, electrochemical methods, TEM
(transmission electron microscopy) and drop water method
are used to test and analyze performance degradation of
different fuel cells and different flow field positions.
2.1. Performance degradation in the stack
After 500 hours accelerated lifetime test on an automotive
PEM fuel cell stack with conditions of idling cycle, load
changing cycle, high power cycle, and start-stop cycle, the
performance is deteriorate obviously. As shown in Fig. 1, the
average cell voltage curve of every cell from No.1 to No.14 cell
is lower than that of No.15 to No.100 cell.
2.2. Preparation of MEA for experiment
MEAs from No.1 to No.14 cell have been taken out of the 100
cells stack. Three representative cells, No.1 cell, No.4 cell and
No.8 cell, are chosen for destructive test. As shown in Fig. 2,
five small sections have been taken out from each MEA for

* Corresponding author. Tel./fax: þ86 10 62788558.

E-mail addresses: pchpei@tsinghua.edu.cn (P. Pei), yuanx@mails.tsinghua.edu.cn (X. Yuan), cpx07@mails.tsinghua.edu.cn (P. Chao),
morning_bell@263.net.cn (X. Wang).
0360-3199/$ – see front matter ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.09.103
3148 international journal of hydrogen energy 35 (2010) 3147–3151
Fig. 1 – (a) Polarization curve characteristics of No.1–14 cells
and No.15–100 cells in a stack. (b) Cell voltages of stack
after 500 h working comparing with new stack on the
same load.
Fig. 2 – Five small sections have been taken from stack
MEA: hydrogen-inlet part, hydrogen-outlet part, air-inlet
part, air-outlet part and the middle part.
different positions performance tests. The five parts are
hydrogen-inlet part, hydrogen-outlet part, air-inlet part, air-
outlet part and the middle part. The small sections are
around 5 cm2of each. At the same time, five small sections
have been taken from the same position of a new MEA for
comparison.
The selected small parts from MEA are assembled to
new small cells with the same type bipolar plate, com-
pacting force and other assembling factors. The small cells
are taken to test on a normal PEMFC testing platform under
the same temperature, gas pressure, and humidity
value etc.
2.3. Descriptions of some experiments
Cyclic voltammograms are taken in the small cells (assembled
of 5 cm2 MEA) tests both on the anode and cathode to calculate
and compare the electrochemically active surface areas. The
experiments are performed on the PEMFC test platform using
the CHI-600B electrochemically test and measurement
equipment. The temperature of small cell is 60  C, and the
absolute pressure of gas is 0.05 MPa. A two-electrode poten-
tiostatic measurement circuit is used for in cyclic voltamme-
try. Fully hydrated nitrogen with the flow rate of 200 mL/min
passes through the working electrode, which is fuel cell
cathode if electrochemically active surface area of cathode is
received, and in the other side there is fuel cell anode. Fully
hydrated hydrogen with the flow rate of 10 mL/min passes
through the counter electrode, which is fuel cell anode if
electrochemically active surface area of cathode is received,
and in the other side there is fuel cell cathode. The voltage is
changed at a scan rate 20 mV/s, and within the scope from
0.05 to 0.9 V vs. SHE.
A small piece of catalyst is removed from the air-inlet part
of cell MEA to prepare TEM sample, and of which carbon paper
is peeled from both sides. Samples for the TEM observations
are taken into some proper alcohol solution for ultrasonic
dispersion for half an hour, and then directly supported on
a copper mesh which is 3 mm in diameter with a carbon micro
grid. The TEM observation is performed using a Tecnai G2
Spirit transmission electron microscope at an accelerating
voltage of 120 kV and magnification of 400,000 times. The
particle size distribution measurements are performed on
digital images using the image-analysis software Image-Pro.
More than 250 catalytic particles are selected for diameter
statistic analysis. Samples of other parts such as the air-outlet
part of cell MEA for TEM are performed in the same way.
Sessile drop method is adopted to test hydrophobic nature
of MEA surface. Water drops on surface of MEA sample for test
directly, the figure of which is recorded by camera instantly to
avoid water evaporation. Contact angle is calculated by
computer. Droplet diameter is less than 1 mm to decrease the
influence of gravity [16]. This reference [16] also shows that
the dropped water picture and the contact angle.
The fuel cell performance is evaluated by measuring the
polarization characteristics on PEMFC testing platform. The
impedance is measured using impedance testing instrument
(KFM2030) for PEMFC. For the evaluation of fuel cell perfor-
mance, hydrogen and air are fully humidified, and fed to each
 international journal of hydrogen energy 35 (2010) 3147–3151 3149

Fig. 3 – Polarization curve of small cells in different part of primary stack cells. (a) No.1 cell. (b) No.4 cell. (c) No.8 cell.

electrode at a cell temperature of 60  C and gas pressure of (Fig. 3 (c)) is better than the new cell. The open circuit potentials
1.05 MPa. Impedance of new MEA cell is about 120 mU cm2. is more than 0.85 V. The polarization curves of them drop gently
in the ohmic potential loss area. Their maximum current
density is more than 1000 mA/cm2, which is the highest of all.
Some open circuit potentials of small cells are lower than
3. Results and discussion 0.75 V, and membranes of which may have been damaged
after working more than 500 hours.
3.1. Polarization curve

The small cells tests are performed on the PEMFC testing 3.2. Electrochemically active surface area, particle size,
platform, the temperature of which is 60  C, and the absolute hydrophobic nature and impedance
pressure of fully hydrated hydrogen and air is 1.05 MPa with
the flow rate of 10 mL/min passed through anode and 200 mL/ Electrochemically active surface area coefficient is defined as:
min passed through cathode in cell. The Fig. 3 expresses the Z Z
1 SIV
polarization curve of small cells of different parts taken from Qh ¼ Idt ¼ IdV ¼ (1)
m m
different primary cells.
As shown in the Fig. 3, the small cells taken from air-outlet
Qh SIV
parts of primary cells have the worst performance of all parts. Ac ¼ ¼ (2)
Qm Ageometric mQm Ageometric
They also have lowest open circuit potentials of all. The polari-
zation curves of them drop fast in the ohmic potential loss area, Qh (/C) stands for total quantity of electricity in the adsorbed
and the maximum current density is less than 300 mA/cm2. process, SIV (/W) is given from Cyclic voltammograms curve,
The small cells taken from hydrogen-outlet parts of primary m (mV/s) stands for voltage scan rate, Qm (/C/cm2) stands for
cells are also performed poorly, sometimes even worse than the atomic electric charge adsorbed smooth catalyzer’s surface,
air-outlet part such as that in No.4 cell (Fig. 3 (b)). The small cells Ageometric (/cm2) stands for the geometric area of a MEA.
taken from air-inlet, middle parts of primary have the average Fig. 4 (a) shows the electrochemically active surface area
performance of all. coefficients of different parts in every cell. Electrochemically
The small cells taken from hydrogen-inlet parts of primary active surface area coefficients of hydrogen-inlet parts are the
cells have the best performance, especially which of No.8 cell biggest of all parts, which shows that the catalyzers in these
3150 international journal of hydrogen energy 35 (2010) 3147–3151

Fig. 4 – Results comparison of all parts in every cell. (a) Electrochemically active surface area coefficient. (b) Average particle
diameter values. (c) Contact angle values. (d) Impedance values.

areas are the most active of all after working long time. At the Fig. 4 (b) compares the particle diameter size among different
same time, electrochemically active surface area coefficients position of three representative foreside cells MEA in the 100
of hydrogen-outlet, especially and hydrogen-outlet parts are cells stack, which worked more than 500 hours. As shown in this
low, catalyzers on some parts have little activity. Primary figure, after working more than 500 hours, the cathode particles
characters are acquired by coefficient analysis and compare are highly agglomerated compared with that of new. Average
for this method has a commonly exactitude. Along air flowing particle diameter and standard deviation of particle diameter
from inlet to outlet in an actual single cell, the electrochemi- are defined to describe the degree of particle agglomeration and
cally active areas decrease gradually, which certainly much distribution extension on diameter values as:
less than that of a new cell. Along air flowing in primary Pn
Si X
m
distributive channel from No.1 cell to No.8 cell in an actual S¼ i¼1
¼ Pi Si (3)
stack, the electrochemically active areas increase gradually n i¼1

contrary to that in a cell. Currents of double electrode layer

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
capacitance of air-outlet parts and some middle parts are Pn 2 X m
i¼1 ðSi  SÞ
inconspicuous, as show in Fig. 3, the open circuit potentials of s¼ ¼ Pi ðSi  SÞ2 (4)
n i¼1
those are also low, for possibility of MEA leaking after more
than 500 hours working. Table 1 shows the standard deviation of particle diameter of
all parts in any cell. As shown in Fig. 4 (b), the average particle
diameter of air-outlet part is the biggest of all in every cell. The
Table 1 – Standard deviations of average particle hydrogen-inlet part has the smallest average particle diameter,
diameter. and the air-inlet, hydrogen –outlet and middle parts have the
medium diameter level. Viewed from different cells, particles
s/nm Air-inlet Air-outlet H2-inlet H2-outlet Middle
of No.1 cell are agglomerated more obviously than ones of No.4
No.1 cell 5.13 10.77 3.87 3.77 3.23 and No.8 cell in air parts, and almost had less difference in
No.4 cell 4.08 6.76 3.02 5.56 4.34
hydrogen parts. Particles of air-inlet part distribute more board
No.8 cell 3.60 8.13 3.11 5.75 6.31
extension on diameter value than new MEA, some primary
new 1.66 1.66 1.66 1.66 1.66
particle diameter value proportion of which are more
 international journal of hydrogen energy 35 (2010) 3147–3151
centralized. At the same time, the more board extension those
of air-outlet part distribute, the more proportions assemble on
big diameter values. As shown in Table 1, standard deviations
of particle diameter of air-outlet part are bigger than air-inlet,
and of course are bigger than which of new MEA.
Contact angle is gained in the experiments referred
before. If the contact angle is bigger than 90 degree, MEA
surface is hydrophobic, and in other case, MEA surface is
hydrophilic. O. Chapuis, M. Prat’s studies show that, the
hydrophobic nature of MEA surface has no difference when
the Contact angle is from 120 to 140 degree [17]. As shown in
Fig. 4 (c), the contact angles in different parts of every cell
are from 124 to 130 degree, which makes clear that the
hydrophobic nature of any part in MEA surface has no
obvious change after working for more than 500 hours. The
drainage nature of cell is steady, which shows that proba-
bility of flooding in the flow channel of old cell is almost the
same compared with new cell.
As shown in Fig. 4 (d), the impedances of air-outlet and
hydrogen-outlet part are biggest of all parts in every cell,
which of hydrogen-inlet part is the smallest of all, but all of
them are bigger than that of the new MEA (120 mU cm2). The
impedances of No.1 cell are biggest of all cells, and which of
No.8 are smallest of all.
4. Conclusions
After an accelerated lifetime test, catalyzes on the MEA
agglomerate to some degree. The average particle diameter
grows bigger and internal resistance increases while hydro-
phobic nature remains the same. In addition, the catalyzes
electrochemically active surface area coefficient increases,
oppositely the maximum of loading current decreases.
There are enormous differences on performance degrada-
tion among different flow field positions and among different
cells. Open circuit potential of the worst position is 0.7 V while
the best one is 0.96 V. Maximum of current density of the
worst position is 200 mA/cm2, which is one-sixth of the best
one. Electrochemically active surface area coefficient of the
worst position is 25, which is less than one-fifth of the best
one. Average particle diameter of the worst position is 21 nm,
which is 2 times bigger than the best one. Impedance of the
worst position is 250 mU cm2, which is twice of the best one.
But contact angle of the worst position and the best one does
not differ by more than 10%.
The best performance of fuel cell is the hydrogen-inlet
part, while the worst part is air-outlet part. This may be
caused by frequent air starvation or flooding in the air-outlet.
The performance of first cell is the worst and that of eighth cell
is the best. The probable reason is Non-uniform gas intake and
water distribution.
3151
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