Energy 270 (2023) 126937

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Energy
journal homepage: www.elsevier.com/locate/energy

Experimental study of the performance degradation of proton exchange

membrane fuel cell based on a multi-module stack under selected load
profiles by clustering algorithm
Weifeng Huang a, 1, Tong Niu a, 1, Caizhi Zhang a, *, Zuhang Fu a, Yuqi Zhang a, Weijiang Zhou b,
Zehua Pan c, Kaiqing Zhang d, **
a
College of Mechanical and Vehicle Engineering; The State Key Laboratory of Mechanical Transmissions; Chongqing Automotive Collaborative Innovation Center,
Chongqing University, Chongqing, 400044, China
b
Sinocat Environmental Technology Co., Ltd, Chengdu Hi-tech Industrial Development Zone, Chengdu, 611731, China
c
School of Science, Harbin Institute of Technology, Shenzhen, Guangdong, 518055, China
d
Chongqing Key Laboratory of Industrial and Information Technology of Electric Vehicle Safety Evaluation; China Merchants Testing Vehicle Technology Research
Institute Co., Ltd, 400050, China

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

Keywords:
Multi-module PEMFC. Durability testing.
clustering. performance degradation. load cycle
In order to investigate the impact of actual vehicle conditions on the durability of fuel cell, the hierarchical
clustering algorithm is used to select two representative driving cycles, which are urban driving cycle and
expressway driving cycle. Then a durability test is performed under two dynamic conditions and one steady-state
condition. This study chooses a newly designed fuel cell with four modules which can be applied different
loading conditions simultaneously. It ensures operating conditions of each module are consistent during the
experiment. Eventually, the polarization curve, electrochemical impedance spectroscopy and voltage are
measured as health assessment indexes. The degradation of different modules can be compared more precisely by
above methods. The results show that the fuel cells have the fastest performance degradation under urban
driving cycle, followed by expressway driving cycle, finally steady-state condition. There is a certain time
threshold, ohmic and activation resistance has a significant increase and fuel cell has a significant performance
degradation after it, the severe driving conditions cause it to be advanced. Otherwise, the voltage degrades faster
at high currents by extracting the voltage at different currents. The voltage degradation percentages of module 1
and 2 at 40A both exceed the threshold of 10%.

1. Introduction durability of cell performance to achieve commercialization.

In recent years, energy scarcity and climate change, which are
caused by the use of fossil fuels and the related carbon dioxide emis­
sions, have become inevitable global problem [1,2]. In response to the
energy crisis and environmental pollution, hydrogen energy has been
paid more attention [3,4]. The hydrogen-based PEMFC (Proton Ex­
change Membrane Fuel Cell) is the most representative and widely used
in NEVs (New Energy Vehicles) [5] due to the advantages of high power
density, low operating temperature, rapid start-up and environmentally
benign technology. However, PEMFC is still in the stage of research and
development, and it is necessary to overcome the key issue [6,7]-low
Most of the researches have begun to focus on the lifespan of fuel cell
[8,9], which explores the impact of different test conditions on fuel cell
performance, and quickly tests the distribution curve of degradation
processes. The lifespan test of fuel cells is divided into two types: static
test and dynamic test [10]. Initially, the lifetime test was carried out in a
steady state (constant voltage or constant current), and the various pa­
rameters of the fuel cell remained relatively unchanged during the test
[11,12]. However, it is generally impractical and costly to operate a fuel
cell under normal conditions for several thousand hours [13]. Therefore
accelerated stress test (AST) methods [14,15] are preferred to facilitate
rapid learning about key durability issues. The US Department of Energy

* Corresponding author.
** Corresponding author.
E-mail addresses: czzhang@cqu.edu.cn (C. Zhang), zhangkaiqing@cmhk.com (K. Zhang).
1
equal contribution.

https://doi.org/10.1016/j.energy.2023.126937
Received 17 October 2022; Received in revised form 26 December 2022; Accepted 10 February 2023
Available online 11 February 2023
0360-5442/© 2023 Elsevier Ltd. All rights reserved.
W. Huang et al.
(DOE) [16] and US Fuel Cell Council (USFCC) [17] have developed AST
protocols, which commonly embraced by the community. And they put
forward that targeted degradation percentage should be less than 10%
loss in the efficiency of the fuel cell by the end of life(EoL), and a
commonly acceptable degradation rate is 2–10 μV/h for most applica­
tions at present.
Another reason for the widespread adoption of AST is that the
measured results can reflect the real lifespan of fuel cell under the
vehicle condition. During the actual operation of the vehicle, the fuel
cell often operates at variable load conditions involving start-stop [18],
idling [19], cold start [20], load changing [21] and high power [22], etc.
Changes in conditions have caused physical and chemical damage to the
internal catalyst, proton exchange membrane, gas diffusion layer and
other components of the fuel cell, and some of them are even irrevers­
ible. It must be lead to faster degradation rate [23,24]. Therefore, it is of
great significance to study the dynamic response characteristics of
PEMFC in actual operation to extend the durability and reliability of
vehicle fuel cell systems [25,26]. For this reason, a large number of
literatures have been performed by researchers about the durability of
PEMFCs under different load conditions in recent years. Liu et al. [22]
applied five stressors (i.e., high temperature, thermal cycling, open
circuit voltage, high load cycling, and low load cycling) to identical
HT-PEMFCs. They found the highest amount of Pt agglomeration occurs
in the cells held at open circuit voltage and cycled at low loads. How­
ever, this study only focused on the impact of single stressor on dura­
bility, and did not combine these stressors to develop driving cycles
protocols that were closer to real road conditions. Chu et al. [27] applied
the dynamic load cycles in durability tests that were developed based on
NEDC. After 1000 h, the mean cell voltage degradation percentage
under two different current density were 5.90% and 5.67%. But the
NEDC cycle, which is now out of use for being too ideal, has been
replaced by other cycles, such as WLTP cycle. Zlatina et al. [28] tried to
use WLTP cycle to study the state change of the cell in the simulation
platform with four stacks of different power. Whereas it was difficult to
make a distinction on the influence of different load conditions.
Nevertheless, there are the following problems that need to be solved
urgently: (1)There is no research attempting to explore and contrast the
degradation of fuel cell under several of the most representative actual
vehicle conditions at the same time. Therefore, the representative actual
vehicle conditions need to be screened out and the corresponding
driving protocols need to be developed. Then carrying out a comparative
experiment. (2) Beyond that, it is difficult to ensure the consistency of
experimental conditions on multiple stacks, such as time synchroniza­
tion, consistent humidity and pressure. It has been proposed in recent
years that several stacks connect in series [29] maybe lead to costs
increasing and make it more complicated to set up experimental
platforms.
This work tries to put forward a solution to the above-mentioned
problems. This work primarily investigates the impact of real vehicle
load cycles on the durability of fuel cells. Two dynamic driving cycles
protocols are selected and developed by hierarchical clustering algo­
rithm, and a steady-state test (constant current) is set up to compare
with them. A durability test is performed for 200 h on a four-module fuel
cell stack under these three protocols. By analyzing the polarization
curve, electrochemical impedance spectroscopy (EIS) and voltage at
different times, the aging degradation of the fuel cell under three driving
cycles can be intuitively detected. The novel contributions of this study
are following:
(1) Using a newly developed multi-module fuel cell to guarantee
uniformity of operating conditions and carry out more accurate
and comprehensive aging experiments. The new stacks have been
developed to cope with these deficiencies well and carry out more
accurate and comprehensive aging experiments.
(2) The clustering analysis can well classify the typical driving con­
ditions, as one of the most commonly used and effective
2
Energy 270 (2023) 126937
unsupervised learning methods, clustering analysis [32] can well
classify the typical driving conditions at home and abroad.
(3) According to the clustering results, the corresponding driving
cycle protocols are designed and loaded into the stack for ex­
periments. The degradation of the fuel cell under the urban
driving cycle, the expressway driving cycle can be explored and
compared in detail.
2. The driving cycles selection based on clustering algorithm
In different driving cycles, the driving state of the vehicle, such as
acceleration, speed and other characteristic parameters are significantly
different, the fuel cell installed in the vehicle needs to respond to
different situations in time, thus durability must be affected. The driving
cycles are classified by clustering algorithm in this section. Then two
types of driving cycles that are eventually selected and loaded into the
fuel cell for experiments. Firstly, 35 standard driving cycles are derived
from the ADVISOR, and the 23 characteristics parameters are selected
according to Refs. [30,31]. After the original data is standardized, 2
typical driving cycles are screened out in combination with hierarchical
clustering, namely the urban driving cycle and the expressway driving
cycle, and the hierarchical diagram is obtained.
2.1. Hierarchical clustering
First, a hierarchical nested clustering tree is created by calculating
the similarity between different categories of data points. In the clus­
tering tree, the original data points for different categories are at the
bottom layer of the tree and a root node of a cluster is at the top layer of
the tree. Hierarchical clustering attempts to divide the sample data sets
on different “hierarchies”, then clustering is performed on each of these
hierarchies [32]. The steps are as follows:
1. Select the analysis variables of the sample and determine the raw
dataset.
If the dataset contains n samples, and each sample information can
be represented by m variables. The dataset can be represented as a data
matrix of n×m.
⎡
x11 ⋯ x1m
⎤
Xn×m = ⋮ ⋱ ⋮ ⎦
⎣ (1)
xn1 ⋯ xnm
2. Standardize raw data.
The different data dimensions maybe affect the results of the cluster
analysis, so it need to standardize raw data before clustering. In this
paper, the Min-max normalization method (deviation normalization)
[33] is selected to standardize the data. The original data is transformed
linearly, and setting the values to [0,1]. The specific formula for stan­
dardization is as follows:
{ }
xij − min xkj
yij = { 1≤k≤n
} { } (i = 1, 2, 3⋯n; j = 1, 2, 3⋯m) (2)
max xkj − min xkj
1≤k≤n 1≤k≤n
Where yij ∈ [0, 1]. Therefore, the data matrix through normalization is:
⎡ ⎤
y11 ⋯ y1m
⎣
Yn×m = ⋮ ⋱ ⋮ ⎦ (3)
yn1 ⋯ ynm
3. Calculate the distance between samples.
Clustering algorithms usually use distance to measure the similarity
W. Huang et al. Energy 270 (2023) 126937

between samples. The higher the similarity, the shorter the distance. Table 1
Common methods for calculating the distance between samples are 35 standard operating conditions commonly used at home and abroad.
Euclidean distance, Chebyshev distance, Manhattan distance and cosine Number Driving cycles Number Driving cycles
similarity, etc. This paper selects Euclidean distance.
1 CYC_ARB02 19 CYC_REP05
Euclidean distance [34] can be simply described as the geometric 2 CYC_ARTERIAL 20 CYC_SC03
distance between any two points in multi-dimensional space. Usually, 3 CYC_BUSRTE 21 CYC_UDDS
original data is used instead of normalized data. In this way, the original 4 CYC_COMMUTER 22 CYC_UDDSHDV
meaning of Euclidean distance is eliminated, so the advantage is that a 5 CYC_CSHVR_Vehicle 23 CYC_UKBUS6
6 CYC_ECE 24 CYC_UNIF01
new object does not affect the distance between any two objects. This 7 CYC_EUDC 25 CYC_US06
distance is defined as follows: 8 CYC_HL07 26 CYC_US06_HWY
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ 9 CYC_HWFET 27 CYC_WVUINTER
∑ n
( )2 10 CYC_IM240 28 CYC_WVUSUB
deuc = xik − xjk (4) 11 CYC_INDIA_HWY_SAMPLE 29 CYC_FTP75
12 CYC_INDIA_URBAN_SAMPLE 30 CYC_NEDC
k=1

13 CYC_LA92 31 CYC_JC08
14 CYC_MANHATTAN 32 CYC_Japanese10-15mode
4. Calculate the inter-cluster distance. 15 CYC_NurembergR36 33 CYC_CBD
16 CYC_NYCC 34 CYC_CSC
Hierarchical clustering algorithms need to calculate not only the 17 CYC_NYCCOMP 35 CYC_New York Bus Cycle
distance between samples, but also the distance between different 18 CYC_NYGTC
clusters. There are 7 commonly used methods for calculating the inter-
cluster distance, Between-groups linkage, Within-groups linkage,
Centroid clustering, Median clustering, Nearest neighbor, Furthest Table 2
neighbor, and Ward’s method. In this paper, the Ward’s method [35] is The operating condition characteristic parameters.
selected to judge the inter-cluster distance. The sum of the squares of Number Characteristic parameters Symbol
deviations of the same classes is small, and the sum of the squares of
1 Mean velocity（km/h） v_avg
deviations of the different classes is large, and the Ward’s method is 2 Maximum speed（km/h） v_max
always allowed to minimize the sum of squares of deviations increments 3 The deviation of speed（km/h） v_std
caused by clustering. 4 Percentage of speed ranging from 0 to 30 km/h v_0_30
Assuming that n samples have been divided into k clusters, denoted 5 Percentage of speed ranging from 30 to 70 km/h v_30_70
t 6 Percentage of speed ranging from 70 to 120 km/h v_70_120
as G1, G2, …, Gk, nt represents the number of samples of Gt, X indicates 7 Percentage of speed in excess of 120 km/h v_120
the centroid of Gt, and Xit represents the ith sample in Gt, then the sum of 8 Average acceleration（m/s2） a_avg
the squares of deviations of the samples in Gt is obtained: 9 Maximum acceleration（m/s2） a_max
10 Acceleration standard deviation（m/s2） a_std
∑
nt
( t)
′ ( t)
11 Percentage of acceleration ranging from 0 to 1.0 m/s2 a_0_10
Wt = Xit − X Xit − X (5) 12 Percentage of acceleration ranging from 1.0 to 2.5 m/ a_10_25
i=1 s2
13 Percentage of speed in excess of 2.5 m/s2 a_25
The total sum of the squares deviations is: 14 Average deceleration（m/s2） d_avg
15 Maximum deceleration（m/s2） d_max
∑
k k ∑
∑ nt
( t) ( t) Deceleration standard deviation（m/s2）
′
W= Wt = Xit − X Xit − X (6) 16 d_std
t t i=1 17 Percentage of deceleration ranging from 0 to 1.0 m/s2 d_10_0
18 Percentage of deceleration ranging from 1.0 to 2.5 m/ d_25_10
s2
5. According to the principle of closest inter-cluster distance and closest 19 Percentage of deceleration in excess of 2.5 m/s2 d_25
20 Driving distance（km） range
intra-cluster distance, the n clusters continue to merge into the n-1
21 The number of stops n_total
clusters. 22 The number of stops per kilometer n_per_kilometer
6. Above steps are repeated until all samples are categorized into one 23 The ratio of idle time r_idel
cluster.

influence of the characteristic parameter dimensions on clustering, the

2.2. Classification of typical driving cycles
Due to the complex and changeable road conditions and various
emergencies encountered during driving process, there are a large
number of driving cycles. The clustering algorithm can divide them
according to characteristics such as speed and acceleration, and obtain
high accuracy in the presence of a lots of features. So, before clustering,
it is needed to selecting the original data of standard driving cycles and
the characteristic parameters representing the driving cycles informa­
tion for clustering analysis. This paper collects 35 standard driving cy­
cles commonly used at home and abroad as the original analysis data,
these include typical driving cycles in different regions and different
real-time road conditions. as shown in Table 1. The 23 characteristic
parameters for describing the driving cycles information in Table 2, all
the parameters that can best reflect the characteristics of the driving
process are included, which can make the clustering have more refer­
ence information in the distance calculation and make the results more
reliable. The specific clustering process and results are as follows:
The above data constitutes a 35 × 23 matrix, in order to eliminate the
Min-max normalization method is selected to standardize the data. The
whole clustering analysis is realized by using Python programing lan­
guage. Fig. 1 is a hierarchical diagram showing the results of the clus­
tering of 35 driving cycles, where the horizontal axis represents 35
driving cycles, the vertical axis represents the distance between them.
The farther the Euclidean distance indicates the greater the difference
between driving cycles. According to Fig. 1, it can be seen that the 35
standard driving cycles are divided into two categories, the types of
urban driving cycle and the expressway driving cycle.
Urban driving cycle: This kind of driving cycle is mainly composed of
the driving data on the town, outskirts of the town or the urban area.
Sometimes there may be traffic jams, lots of traffic lights, etc. Vehicles
often are in a state of start-stop, low power, idling, acceleration and
deceleration. When the traffic is in a good condition, the distance be­
tween cars is greater, there are less start-stop process and faster speed.
Expressway driving cycle: This kind of driving cycle is mainly
composed of the driving data of the car on the expressway. The fre­
quency of acceleration and deceleration is low, and the speed often in

3
W. Huang et al. Energy 270 (2023) 126937

Fig. 1. The hierarchical diagram of driving conditions.

exceed of 100 km/h. There are few stopping, idling states and higher 3.2. Driving cycles
speed, higher demand power.
Based on the results shown in Fig. 1 and in order to facilitate the
3. Experiments input of simulation driving cycles by electronic load, the clustered urban
driving cycle and expressway driving cycle are converted into docu­
3.1. Experimental setup ments with current-time characteristic, as shown in Fig. 3, and named
profile 1 and profile 2, respectively. For profile 1, the load changes
The experimental equipment includes: Fuel cell with ex-factory rated quickly, with open-circuit voltage operation accounting for 20% of the
power of 900 W, three electronic loads (Kikusui PLZ664, Kikusui driving cycle protocol, while the overload state accounting for only
PLZ100, IT8514C), three DC power supplies, one Gamry electrochemical 13.3%, and most of the remaining moments are at idling condition. For
workstation, one digital thermometer, six temperature sensors, one profile 2, the load changes slowly, there is few idling conditions, and fuel
digital flowmeter, one data acquisition card (DAQ), one solenoid valve, cell needs to output a high power in most of the time. According to
one relay, one computer. The fuel cell used in the experiment is a Ref. [36–38], it is known that the degradation rate is faster for cells near
customized air-cooled fuel cell stack, the parameters of this stack are in the inlet end, so module 4 near the inlet end is not used. Profile 3 is
Table 3.The stack is composed of 48 cells with an effective reaction area defined as a constant current mode of 15A. Profile 1, profile 2 and profile
of 54 cm2, each stack contains a pair of end plates, five pieces of col­ 3 are applied to modules 1, 2, and 3 respectively through the electronic
lecting plates. The stack is composed with four modules and each load.
module contains 12 cells. They are supplied air and cooled by the same
set of fans. The internal parameters such as the internal compression 3.3. Data monitoring
pressure and internal gas supply of the four modules are consistent, they
can be used for different loading conditions simultaneously. The above- After passing through two pressure relief values, the high-pressure
mentioned devices were connected to build the experimental bench hydrogen was fed into the stack and the intake pressure was recorded
herein, as shown in Fig. 2. in real time by a digital flowmeter. The digital thermometer recorded
the temperature of the four modules, the inlet and outlet respectively. If
Table 3
the operating temperature exceeded 55 ◦ C, it would be alarmed. A
The parameters of customized air-cooled fuel cell stack. voltage acquisition card (DAQ) was used to record the voltage of the
three modules in real time, the DAQ sampling frequency was 10 Hz. A
Parameters Value
total of 200 h aging test has been performed, and a certain time of
Rated power 900 W experiment has been carried out for about 6–12 h every day. The Gamry
Rated current 30A
electrochemical workstation was used to measure the EIS and polari­
Rated voltage 30 V
The range of voltage 24–48 V zation curves once per week (around every 50 h), with the “Nyquist”
Open-circuit voltage 46 V–48 V plot of the fuel cell stack measured at the current of 15A and a current
The number of cells 48 disturbance (20% of the cell load) and a frequency range between 50
Effective reaction area 54 cm2 mHz and 10 kHz. Finally, five sets of data were obtained. A LabVIEW-
The pressure of hydrogen 0.5–0.7Bar
The efficiency of electricity generating ≥50%
based purge control program has been designed. The exhaust cycle
Hydrogen consumption 11.5L/min(Rated power) time was set to 30s for 1s each time, taking into account the stack
Environmental temperature − 5◦ C-40 ◦ C operating state and the cost of hydrogen.
Environment humidity 10%–95%
The temperature of stack 25◦ C–55 ◦ C

4
W. Huang et al.
Fig. 2. The flow chart of experimental bench design.
Fig. 3. Two driving cycle protocols: (a)urban driving cycle; (b)expressway driving cycle.
4. Results and discussion
4.1. Results of initial states
The polarization curve mainly describes the static characteristics of
the fuel cell, while the EIS can reflect the dynamic characteristics of the
fuel cell at different times. They are the most used methods for char­
acterizing the state of fuel cells [39]. The polarization curves and
Nyquist curves of modules 1, 2 and 3 were tested when T = 0 h
respectively, as shown in Fig. 4. The Nyquist curve in Fig. 4(a) of the fuel
cell consists of four irregular arcs. The two intersections with the real
axis in the figure are ohmic resistance and activation resistance, and the
marked arcs correspond to wire or peripheral inductance, cathode
activation semicircle, diffusion semicircle and inductive loop respec­
tively [39]. It is found that the initial ohmic resistances of these three
modules are 0.061 mΩ, 0.057 mΩ and 0.054 mΩ, and the activation
resistances are 0.33 mΩ, 0.34 mΩ and 0.328 mΩ, respectively. The
5
Energy 270 (2023) 126937
polarization curve in Fig. 4(b) of a PEM fuel cell can be categorized into
three distinct regions based on the causes of potential loss: activation,
ohmic and concentration [42]. Although the OCV of module 3 is
significantly smaller than module 1 and 2, the OCV value remains almost
constant during the normal aging of the stack, it maybe not affect the
experimental results. So it can be considered that the initial performance
of the three modules is almost the same, and the experimental results of
different modules are comparable mutually.
4.2. The results after experiment
4.2.1. Nyquist curves and polarization curves
The experiment was completed after 200 h. Compared with initial
result, the polarization curves and Nyquist curves corresponding to the
three modules are significantly different. Nyquist curves provide more
microscopic information about the fuel cell system. The high-frequency
resistance (HFR) represents the total ohmic resistance of the stack. It is
W. Huang et al.
Fig. 4. (a) Nyquist curves and (b) polarization curves of modules 1, 2 and 3 when T = 0 h
expressed as the sum of the contributions from contact resistances be­
tween components and ohmic resistances of the cell components,
including the membrane, catalyst layer, gas diffusion layer, and bipolar
plates. From Fig. 5(a), it is obvious that the semicircles radius of modules
1 is largest in low-frequency region. As the internal polarization loss of
the fuel cell gradually increases during the aging process, the ohmic
resistance and the total activation resistance increase. After the 200 h
aging test, the ohmic resistances of these three modules are 0.074 mΩ,
0.072 mΩ and 0.061 mΩ, and the activation resistances are 0.384 mΩ,
0.374 mΩ and 0.354 mΩ, respectively. On the other hand, the growth in
the diameter of the semicircle loop of module 1 and module 2 was
obviously greater than that of module 3.
There are various potential losses during the use of the stack, such as
activation loss, ohmic loss and concentration loss. The drop rate of po­
larization curve can also be used as an important basis for judging the
aging degree of fuel cells. The larger the drop rate, the more severe the
aging degree. As can be seen from Fig. 5(b), the downward slopes of the
three curves are − 0.138, − 0.137 and − 0.128, respectively. Especially
when the current is high, the voltage of module 3 is significantly higher,
indicating the concentration losses of modules 1 and 2 are greater. The
Fig. 5. (a) Nyquist curves and (b) polarization curves of modules 1, 2 and 3 when T = 200 h
6
Energy 270 (2023) 126937
ratio of ohmic polarization and concentration polarization to the total
polarization increased gradually at high current density. Changes in the
ohmic polarization occurred over time at low current densities. Overall,
due to the effect of various accelerated stressors, module 1 and 2 of fuel
cell have greater total voltage loss and faster performance degradation.
In order to understand more about the degradation process of stack
at different moments in experiments, the polarization curves and
Nyquist curves of modules 1, module 2 and module 3 at 0 h, 44 h, 91 h,
147 h, 200 h are plotted respectively in Fig. 6. And the corresponding
ohmic resistance and activation resistance of the three modules at these
five moments are given in Fig. 7. With the aging test of fuel cell, it can be
seen from Fig. 6(a-c) that the Nyquist curves shows a trend of expansion.
Both intersections show a right shift trend, the ohmic resistance in­
creases slightly, while the total activation resistance has a significant
increase. Ohmic resistance is used to describe obstacles to mass transfer
processes, and total activation resistance describes obstacles to charge
transfer and diffusion processes. The EIS experimental results are listed
in Table 4: For module 1 to module 3, the ohmic resistance increase by
0.0128 mΩ, 0.0145 mΩ and 0.0059 mΩ, and the activation resistance
increase by 0.0508 mΩ, 0.0375 mΩ and 0.0261 mΩ, respectively. The
W. Huang et al. Energy 270 (2023) 126937

Fig. 6. (a)–(c) Nyquist curves of modules 1, 2 and 3; (d)–(f) Polarization curves of modules 1, 2 and 3.

Fig. 7. The activation resistance and the ohmic resistance of the stack (a) ohmic resistance, (b) activation resistance.

Table 4
The EIS experimental results.
Time(h) Ohmic resistance(Ω) Activation resistance(Ω)

Module 1 2 3 1 2 3

0 0.061232 0.057159 0.055000 0.33313 0.33600 0.32802

44 0.061491 0.060465 0.055107 0.33406 0.33372 0.32825
91 0.068445 0.060774 0.055791 0.35299 0.33817 0.32323
147 0.071181 0.063543 0.057957 0.36119 0.35549 0.34216
200 0.074031 0.071637 0.060921 0.38389 0.37350 0.35413
Increment 0.0128 0.0145 0.00590 0.0508 0.0375 0.0261

7
W. Huang et al.
higher value of activation resistance means the more sluggish speed of
oxygen reduction reaction, and signifies an activity area loss process
happened during the high voltage condition of PEMFC, where Pt on
surface of catalyst is easily oxidized to PtO or other oxides. In particular,
it runs under the urban driving cycle in module 1, the internal structure
of the fuel cell maybe subject to greater irreversible damage due to rapid
load changing.
In addition, other phenomena can also be found: With the use of fuel
cells, the proton exchange membrane becomes thinner, the electro­
chemical surface area (ECSA) reduces, and the hydrophobicity of the gas
diffusion layer becomes worse, when these events continue to occur to a
certain time threshold, the internal resistance has a significant increase,
fuel cell has a significant performance degradation, and before time
threshold that the internal resistance is almost unchanged. It is not
difficult to see from Fig. 7 that the time threshold of module 1 and
module 2 is about 50 h, while module 3 is at 100 h, the severe driving
conditions cause this time threshold to be advanced.
As test time increases, the polarization curve shows a downward
trend. But the OCV remains almost constant, which means that the de­
gree of gas permeability and charge permeability remain almost un­
changed throughout the aging test. Thus, it can be determined that the
proton exchange membrane of the fuel cell does not encounter signifi­
cant chemical degradation and mechanical damage. It is also found from
Fig. 6(d-f) that the performance degradation of fuel cell is faster at high
current. That is because the rate of water generation increases at cathode
electrode and causes flooding when fuel cell is operated at high current
density (i.e., low voltages). A large amount of liquid water accumulates
in the gas diffusion layer and the catalyst layer, thereby the pores of the
electrode are blocked with water that hinders the flow of oxidants into
the catalyst layer, and causes oxygen starvation and corrosion of the
electrode carbon. In the dynamic conditions, stack is more affected by
the above phenomena, compared to module 3, the degree of degradation
Fig. 8. The voltage degradation: (a) module 1; (b)module 2; (c)module 3; (d) module 1 under 10A, 20A and 40A; (e) module 2 under 10A, 20A and 40A;
8
Energy 270 (2023) 126937
of module 1 and module 2 is more serious. However, the difference
between module 1 and module 2 is not obvious, and it will be quanti­
tatively analyzed by voltage curve later.
In summary, it can be seen that the aging severity is sorted from
highest to lowest as module 1, module 2, module 3. The reliability of this
conclusion is further enhanced by voltage degradation.
4.2.2. Voltage curve
Cell voltage is among the cheapest and easiest ways to evaluate aging
condition of fuel cell. It is also one of the quickest approaches to monitor
a fuel cell, as voltage measurements do not require specialized sensors.
Most of the fault modes of the fuel cell cause a voltage drop. The voltage
data usually measured are corresponding to the time one by one, and the
straight line fitted by these two parameters is generally regarded as the
trend of stack performance degradation. The slope of this straight line is
equal to the voltage degradation rate, which can directly reflect the
aging degree of the stack. As shown in Fig. 8(a-c), the voltage data for
three modules are linearly fitted with error, and the Pearson Correlation
Coefficient is used as the evaluation index. It can evaluate whether the
parameters used for line fitting have a strong linear relationship,
otherwise other polynomial curve fitting need to be used.
∑ ∑ ∑
N xi yi − xi yi
R = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅√ ̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (7)
∑ 2 ∑
N xi − (xi ) N y2i − (yi )2
2
where x, y are independent variable and dependent variable. The closer
to ±1 R approaches, the higher relevance is. The closer to 0 R ap­
proaches, the weaker correlation is.
The voltage-time curve is similar to the polarization curve and re­
flects the degree of voltage loss. As the aging of fuel cell, the voltage at a
specific current gradually decreases. When it drops to a certain defined
value, the stack must be discontinued. The voltage degradation rates of
W. Huang et al.
the three modules are 2.84 mV/h, 3.07 mV/h and 1.9 mV/h, respec­
tively. It can be seen that in the process of dynamic conditions, materials
and internal structures change more drastically, which affect the elec­
trochemical reaction of fuel cells and the dynamic process of heat and
mass transfer, and have a significant acceleration effect on voltage loss
and performance degradation. Besides this, it can be seen from Fig. 8(c)
that the degradations are mixed with transient phenomena when time
scales in hours are considered. It highlights that these punctual char­
acterizations disturb the voltage and create transient stages. The reasons
for the voltage recovery phenomenon are: (1) The water content in the
electrode is reduced when the fuel cell in stopping operation, so the
concentration polarization loss is alleviated to a certain extent. (2) The
polarization curve test process maybe oxidizes CO and reduce platinum
oxides, which plays a certain activation role in fuel cells. Very often,
these events appear as recoveries in the voltage signal and they should
be taken with caution, or even removed, for prognostics.
In addition, according to the voltage degradation rate, it can be seen
that module 2 degrades faster than module 1(3.07 mV/h vs 2.84 mV/h).
However, since the fluctuations of voltage values are easy to cause a
large margin of error in the linear fitting, which can be seen clearly
through the Pearson Correlation Coefficient. Especially for module 1 and
module 2, because the current circulates in a short time to fluctuate
more than 30A, resulting in voltage in 200 h also fluctuating more than
4 V, so the linear relationship between voltage and time is greatly
affected. If the linear fitting method is adopted, there must be a large
error in the accuracy of voltage degradation rate. Module 3 keep the
constant current 15A unchanged, only occasional, slow fluctuations due
to voltage recovery phenomenon, so the error is small. For module1 to
module 3, the Pearson Correlation Coefficients are − 0.10, − 0.22 and
− 0.72, respectively. When Pearson correlation coefficient is less than
0.4, the two variables are almost uncorrelated. So, in order to compare
module 1 and module 2 in detail, the voltage-time curves under different
currents are drawn in Fig. 8(d-e). At this point, the Pearson Correlation
Coefficients for the corresponding voltage curves at three currents in
Module 1 are − 0.85, − 0.87 and − 0.92, respectively. And the R values
for module 2 are − 0.78, − 0.90 and − 0.89 respectively. It shows that the
linear fitting effect is wonderful at this situation.
From the voltage curves of the three sets of different currents fitted
in Fig. 8(d–e), it is possible to clearly compare the effects of the two
different driving cycles used on the voltage degradation rate. In the
initial stage of the experiment, the fresh catalyst has a rapid aging
process, resulting in rapid degradation of stack performance; After a
long period of operation, the reason why the stack performance de­
grades seriously became the severe gas penetration of membrane elec­
trode assembly (MEA). The voltage experimental results are listed in
Table 5: The voltage degradation rates of module 1 at these three current
levels are faster than module 2, especially in high voltage level. The
voltage degradation percentage of module 1 at 40A even reaches
14.61%, module 2 is 13.69%, both exceed the EoL threshold of 10%. At
high currents, the stack is no longer able to meet normal usage stan­
dards. But at 10A, the voltage degradation percentage are 6.38% and
4.75%, and the voltage degradation percentage of module 3 reaches
4.76% at 15A. With all that in mind, the fuel cells have the fastest aging
rate under urban driving cycle, and the slowest aging rate under steady-
state tests. The main reason for this result is as follows: open-circuit/
idling condition and frequent load changing condition are the main
Table 5
The voltage experimental results.
Current(A) Voltage degradation rate (mV/h) Voltage degradation percentage (%)
Module 1 2 3 1
All 2.84 3.07 1.90 6.38
10 2.74 1.92 / 6.38
20 3.12 2.76 / 8.26
40 4.25 4.03 / 14.61
9
Energy 270 (2023) 126937
factors causing the rapid performance degradation of module 1. As for
module 2, the performance degradation rate is affected by high power
condition and load changing condition. Rapid load changing is the
harshest condition for the durability of PEMFC. Following changes in the
load, the fuel cell goes through a transient fluctuation process, affecting
the inbound fuel cell parameters. Eventually, this radically accelerates
catalyst aging and mechanical degradation of other components. With
the change of cell voltage, the dissolution and precipitation processes of
Pt particles in the catalyst are alternated with each other. In this process,
the Pt particles are lost or grow from the support surface, and the Pt
active surface area is inevitably decreased, resulting in the PEMFC
performance degradation.
5. Conclusion
In this work, a four-module fuel cell is chosen and tested with two
dynamic driving cycles protocols selected by hierarchical clustering al­
gorithm, and a steady-state protocol. By analyzing the polarization
curve, EIS and voltage, the aging degradation under different driving
cycles can be directly detected. From the results, following qualitative
conclusions can be made: (1)The urban driving cycle is more likely to
cause performance degradation of fuel cell than expressway driving
cycle due to frequent load changing. The resistance increasing of module
1 is most prominent. And there is a certain time threshold, after this the
internal resistance has a significant increase, fuel cell has a significant
performance degradation. And the severe driving conditions cause this
time threshold to be advanced. (2) For the latter two, module 1 has a
faster voltage degradation rate than module 2, especially in high current
level. The voltage degradation percentage even reaches 14.6% for
module 1, 13.7% for module 2 at 40A, but the voltage degradation
percentage are 6.38% and 4.75% at 10A. And module 3 reaches 4.76%
at 15A. At high currents, the stack is no longer able to meet normal usage
standards.
The experiment offers valuable insights about the field of fuel cell
lifespan and degradation. It can learn about durability of fuel cells with
the voltage of different current and other factors. To extend fuel cell
lifespan, it is necessary to combat the negative impacts of frequent load
changing, improve the existing power distribution strategy, and provide
early warning or backup power solutions when the high-power demand
cannot be met, especially when the fuel cell reaches the EoL.
There are still a lot of room for improvement and research in this
paper. It only tried to analyze of the external characteristics of the fuel
cell, and did not conduct the microscopic observation and evaluation of
the internal structure through three-dimensional scanning electron mi­
croscopy(SEM). In addition, a prognostics and health management
(PHM) system can be designed to predict the remaining life to further
restore the performance of the fuel cell. In-depth research on these
contents will be carried out in the future.
Credit author statement
Weifeng Huang: Conceptualization, Methodology, Investigation,
Formal analysis, Project administration, Writing – original draft. Tong
Niu: Methodology, Software, Formal analysis, Writing – original draft.
Caizhi Zhang: Conceptualization, Validation, Supervision, Writing –
original draft, Writing – review & editing. Zuhang Fu: Investigation,
Pearson Correlation Coefficient
2 3 1 2 3
4.75 4.76 − 0.10 − 0.22 − 0.72
4.34 / − 0.85 − 0.78 /
7.08 / − 0.87 − 0.90 /
13.69 / − 0.92 − 0.89 /
W. Huang et al.
Resources, Methodology. Yuqi Zhang: Investigation, Data curation.
Weijiang Zhou: Validation, Writing – review & editing. Zehua Pan:
Writing – review & editing. Kaiqing Zhang: Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The data that has been used is confidential.
Acknowledgements
This paper is supported by funding (No.: 21AKC26) from Chongqing
Key Laboratory of Industrial and Information Technology of Electric
Vehicle Safety Evaluation; China Merchants Testing Vehicle Technology
Research Institute Co., Ltd.
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