Energy Conversion and Management 45 (2004) 1949–1961

www.elsevier.com/locate/enconman

Exergy analysis of a PEM fuel cell at variable

operating conditions
Ayoub Kazim *

Department of Mechanical Engineering, Faculty of Engineering, United Arab Emirates University,

P.O. Box 17555, Al-Ain, United Arab Emirates
Received 18 September 2002; received in revised form 24 June 2003; accepted 27 September 2003

Abstract
This paper presents a comprehensive exergy analysis of a 10 kW PEM fuel cell at variable operating
temperatures, pressures, cell voltages and air stoichiometrics. The calculations of the physical and chemical
exergies, mass flow rates and exergetic efficiency are performed at temperature ratios ðT =T0 Þ and pressure
ratios ðP =P0 Þ ranging from 1 to 1.25 and 1 to 3, respectively. In addition, the analysis is conducted on fuel
cell operating voltages of 0.5 and 0.6 V and at air stoichiometrics of 2, 3 and 4 in order to determine their
effects on the efficiency of the fuel cell. The calculated results illustrate the significance of the operating
temperature, pressure, cell voltage and air stoichiometry on the exergetic efficiency of the fuel cell. How-
ever, it is recommended that the fuel cell should operate at stoichiometric ratios less than 4 in order to
maintain the relative humidity level in the product air and to avoid the membrane drying out at high
operating temperatures.
Ó 2003 Elsevier Ltd. All rights reserved.

Keywords: PEM fuel cell; Exergetic efficiency; Chemical exergy; Physical exergy

1. Introduction

Determination of an effective utilization of a proton exchange membrane (PEM) fuel cell and
measuring its true performance based on thermodynamic laws are considered to be extremely
essential. Theoretically, the efficiency of a PEM fuel cell based on the first law of thermody-
namics makes no reference to the best possible performance of the fuel cell, and thus, it could be

*
Tel.: +971-3-705-1435; fax: +971-3-762-3158.
E-mail address: akazim@uaeu.ac.ae (A. Kazim).

0196-8904/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2003.09.030
1950 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

Nomenclature

e total exergy per unit mass, kJ/kg

E_ total exergy rate, kW
m_ mass flow rate, kg/s
W_ electrical energy output rate, kW
h enthalpy, kJ/kg
h0 specific enthalpy at standard conditions, kJ/kg
s entropy, kJ/kg K
s0 specific entropy at standard conditions, kJ/kg K
Cp average specific heat, kJ/kg K
T temperature, K
T0 standard temperature, 298.15 K
P pressure, atm
P0 standard pressure, 1 atm
k specific heat ratio
V cell voltage, V
R universal gas constant, 8.314 kJ/kmol K
x mole fraction
Greek letters
e exergetic efficiency
k stoichiometry of air
Subscript
air air
H2 hydrogen
H2 O water
R reactant
P product
Superscript
CH chemical
PH physical

misleading. On the other hand, the second law efficiency or exergetic efficiency of a PEM fuel cell,
which is the ratio of the electrical output over the maximum possible work output, could give a
true measure of the PEM fuel cellÕs performance. Energy analysis performed on a system based on
the second law of thermodynamics is known as exergy analysis (availability analysis). Unlike
energy, which deals merely with the quantity of energy, exergy deals with both the quantity as well
as the quality of energy [1]. The total exergy consists of physical exergy, which is associated with
the temperature and pressure of the matter, and chemical exergy, which is associated with the
departure of the chemical composition of a system from that of the environment [2].
 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961 1951

Extensive and detailed studies have been conducted on energy and exergy analysis on various
types of fuel cells and have demonstrated the significance of the second law efficiency to hydrogen
and the fuel cell system processes [3–6]. Other studies analyzed the efficiency of a PEM fuel cell, its
economics at various loads [7–9] and its potential applications, especially in transportation
[10,11]. Others performed energy and exergy analyses of PEM fuel cell systems with varying
degrees of cogeneration in order to seek and develop fuel cell systems with better economic and
energy saving characteristics than the conventional systems of power generating plants [12–14].
It should be noted that the above studies were performed without conducting a complete exergy
analysis of the fuel cell efficiency taking into consideration all the variations of the fuel cellÕs
operational conditions, such as operating pressure and temperature, cell voltages and stoi-
chiometric ratio of air in the electrochemical process. Furthermore, these analyses did not discuss
the details of the physical and chemical exergies of the reactants, which are air and hydrogen, and
the products, which are water and air, except the works of Oosterkamp et al. [3] and Dincer [5],
even though they did not demonstrate the trends of the physical exergies of the reactants and the
products against the variable operating temperature and pressure of the fuel cell. Therefore, there
is a strong need for conducting an exergy analysis that takes into account all the operational
aspects of a fuel cell as well as the trends of the physical exergy of each reacting and producing
element in the electrochemical process.
The objective of the current study is to perform a comprehensive exergy analysis on a 10 kW
PEM fuel developed by Energy Partners Inc. [15]. The analysis will consider both the physical and
chemical exergies of all the reactants and the products of the electrochemical process in the fuel
cell at variable operating conditions, which are the fuel cell operating temperature and pressure,
cell voltage and fuel cell inlet air stoichiometry. Moreover, the overall exergetic efficiency of the
electrochemical process of the fuel cell will be determined at variable operating conditions.

2. Mathematical model

Exergetic efficiency, which is defined as the second law efficiency, gives the true value of the
performance of an energy system from the thermodynamic viewpoint [1–3]. The exergetic effi-
ciency of a fuel cell system, shown in Fig. 1, is the ratio of the power output W_ , over the dif-
ferences between the exergy of the reactants (air + hydrogen) and the exergy of the products
(air + water), which can be determined by the following formula:

Fig. 1. Schematic diagram of fuel cell system.

1952 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

ElectricalOutput
e¼
ðExergyÞR
ðExergyÞP
ð1Þ
W_
e¼
ðE_ air;R þ E_ H2 ;R Þ
ðE_ air;P þ E_ H2 O;P Þ
where E_ air;R , E_ H2 ;R , E_ air;P and E_ H2 O;P are the total exergies of the reactants, air and fuel (hydrogen),
and the products air and water, respectively. Assuming negligible potential and kinetic energy
effects on the fuel cell electrochemical process, the total exergy transfer per unit mass of each
reactant and product consists of the combination of both physical and chemical exergies [2]:
e ¼ eCH þ ePH ð2Þ

2.1. Physical exergy

Physical exergy is associated with the temperature and pressure of the reactants and the
products in the fuel cell system. The physical exergy is expressed in terms of the differences of
enthalpy from those and entropy from those at standard conditions of temperature and pressure
of T0 ¼ 298 K and P0 ¼ 1 atm, respectively. The general expression of the physical exergy can be
described as:
ePH ¼ ðh
h0 Þ
T0 ðs
s0 Þ ð3Þ
where h0 and s0 denote the specific enthalpy and entropy evaluated at standard conditions,
respectively. The physical exergy of an ideal gas with constant specific heat Cp and specific heat
ratio k can be written as:
"

k
1 #
T T P k
ePH ¼ Cp T0
1
ln þ ln ð4Þ
T0 T0 P0

2.2. Chemical exergy

The chemical exergy is associated with the departure of the chemical composition of a system
from that of the environment. For the sake of simplicity, the chemical exergy considered in the
analysis is rather a standard chemical exergy that is based on the standard values of the envi-
ronmental temperature of T0 ¼ 298 K and pressure of P0 ¼ 1 atm. Generally, these values are in
good agreement with the calculated chemical exergy relative to alternative specifications of the
environment [2]. Values of the chemical exergies for both the reactants and products are taken
from published literature and presented in Table 2. However, the chemical exergy of air produced
from the electrochemical reaction should be calculated in terms of the mole fraction of each
component in the mixture x using the following equation:
X X
eCH ¼ xn eCH
n þ RT 0 xn ln xn ð5Þ

The main reason for using the above chemical exergy equation for the product air is that the mole
fractions of mixtures in air would be different than those at the standard condition, especially the
 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961 1953

mole fraction of oxygen that will be reduced as a result of the combination with hydrogen to form
water.

2.3. Mass flow rates of the products and the reactants in the fuel cell

Depending on the power output W_ and a fuel cell voltage V , and the stoichiometry of air k, the
mass flow rates of the reactants and the products in the fuel cell can be easily evaluated from the
equations used by Larminie and Dicks [16]. The mass flow rates of the inlet air and fuel, hydrogen,
can be evaluated through the following equations:
!

7 kW_
m_ air;R ¼ 3:57  10 ð6Þ
V
!
W_
m_ H2 ;R ¼ 1:05  10
8 ð7Þ
V
The mass flow rate of the product, air, can be defined as the difference between the amount of
oxygen in the electrochemical reaction and the amount of oxygen consumed by reacting with
hydrogen to produce water:
! !
k _
W _
W
m_ air;P ¼ 3:57  10
7
8:29  10
8 ð8Þ
V V
The amount of water produced by the fuel cell can be calculated by the following equation:
!
_
W
m_ H2 O;P ¼ 9:34  10
8 ð9Þ
V
Subsequently, the total exergy of the reactants and the products can be determined through the
following equations:
E_ H2 ;R ¼ m_ H2 ;R eH2 ;R ¼ m_ H2 ;R ðeCH þ ePH ÞH2 ;R ð10Þ

E_ air;R ¼ m_ air;R eair;R ¼ m_ air;R ðeCH þ ePH Þair;R ð11Þ

E_ H2 O;P ¼ m_ H2 O;P eH2 O;P ¼ m_ H2 O;P ðeCH þ ePH ÞH2 O;P ð12Þ

E_ air;P ¼ m_ air;P eair;P ¼ m_ air;P ðeCH þ ePH Þair;P ð13Þ

At standard atmospheric conditions, the air molal analysis (%) would be: 77.48 N2 , 20.59 O2 , 0.03
CO2 and 1.9 H2 O (g). The calculations of the physical and chemical exergies, mass flow rates and
efficiency will be performed at temperature ratios ðT =T0 Þ and pressure ratios ðP =P0 Þ ranging from
1 to 1.25 and 1 to 3, respectively. These ranges of the operating temperature and pressure are
specifically to be typical for PEM fuel cells. In addition, the analysis will be conducted on 2 cases,
namely at cell voltages of 0.5 and 0.6 V. Moreover, exergetic efficiency calculations will be pe-
formed at air stoichiometries of 2, 3 and 4 and at a cell voltage of 0.5V. The properties of the PEM
1954 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

Table 1
Properties at the standard condition [1,2,15]
Property Value
Standard temperature, T0 298 K
Standard pressure, P0 1 atm
Average specific heat of air, Cp 1.005 kJ/kg K
Average specific heat of hydrogen, Cp 14.3 kJ/kg K
Specific heat ratio for air and hydrogen, k 1.4
Enthalpy of water at standard condition, h0 104.88 kJ/kg
Entropy of water at standard condition, s0 0.3674 kJ/kg K
Enthalpy of product air at standard condition, h0 )21,120.0 kJ/kmol
Entropy of product air at standard condition, s0 129.17 kJ/kmol K
Electrical energy output, W_ 10 KW
Stoichiometry of air, k 3

Table 2
Chemical exergy and the calculated mass flow rates of the reactants and the products of a PEM fuel cell at cell voltages
of 0.5 and 0.6 V [2,16]
Reactant/product Chemical exergy, Mass flow rate at V ¼ 0:5 V, Mass flow rate at V ¼ 0:6 V,
eCH (kJ/kg) m_ (kg/s) m_ (kg/s)
Reactant––Air 0 0.02142 0.01785
Reactant–– 159,138 0.00021 0.000175
Hydrogen
Product––Water 2.5 0.001868 0.001557
Product––Air 8.58 0.019762 0.01647

fuel cell with the specified operating conditions are presented in Table 1. The analysis will be
performed on an experimentally tested 10 kW PEM fuel stack developed by Energy Partners Inc.
[15]. The fuel cell consists of 40 cells with an active cell area of 780 cm2 , capable of generating 10
kW DC power output at 40% efficiency at 300 kPa and 65 °C [7].

3. Results and discussions

The physical exergy of air entering the fuel cell, shown in Fig. 2, ranges from zero at the
respective temperature and pressure of 298 K ðT =T0 ¼ 1Þ and 1 atm ðP =P0 ¼ 1Þ to 95 kJ/kg at the
respective temperature and pressure of 298 K ðT =T0 ¼ 1Þ and 3 atm ðP =P0 ¼ 3Þ. Furthermore, a
15% increase in the physical exergy of the air can be achieved if the operating temperature is
increased from 298 K ðT =T0 ¼ 1Þ to 373 K ðT =T0 ¼ 1:25Þ. In the analysis, air was treated as an
ideal gas and Eq. (4) was used to determine its physical exergy. The first two dimensionless terms
of the equation represent the thermal and mechanical components of the exergy associated with
air, but generally, the physical exergy cannot be represented by these two components. By the
same token, the physical exergy of the fuel, hydrogen, entering the fuel cell, shown in Fig. 3,
ranges from zero at the respective temperature and pressure ratios of T =T0 ¼ 1 and P =P0 ¼ 1 to
1.350 kJ/kg at T =T0 ¼ 1 and P =P0 ¼ 3. Again, hydrogen was treated as an ideal gas and Eq. (4)
 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961 1955

Fig. 2. Physical exergy of inlet air.

Fig. 3. Physical exergy of inlet hydrogen.

was used to determine its physical exergy. The trends of both reactant gases are similar with the
exception of their magnitude, which is higher in the case of hydrogen than in the case of air due to
the higher average specific heat of hydrogen Cp than that of air.
In the current analysis, the chemical exergy of reactant air is taken to be zero, since the
composition of air at the reference environment is considered as being negligibly different from the
actual environment. However, the value of the chemical exergy of hydrogen was estimated to be
159,138 kJ/kg, which is considered the highest of all the reactants and products. These values are
consistent with those of Model I, which was illustrated by Bejan [2]. This model represents the
standard chemical exergy based on the environmental temperature T0 and pressure P0 , namely at
1956 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

298.15 K and 1 atm. The model attempts to satisfy the equilibrium requirement of thermody-
namic theory, and the chemical composition of the gas phase is acceptably approximated to the
composition of the natural atmosphere.
The physical exergy of the product water leaving the fuel cell ranges from zero at the respective
temperature and pressure ratios of T =T0 ¼ 1 and P =P0 ¼ 1 to 160 kJ/kg at T =T0 ¼ 1 and P =P0 ¼ 3,
as depicted in Fig. 4. Depending on the pressure ratio, an increase in the physical exergy of water
of at least 3 fold can be achieved if the operating temperature is increased from the standard
temperature of 298 K (T =T0 ¼ 1) to 373 K (T =T0 ¼ 1:25). Eq. (3) was used to determine the
physical exergy of water, with values of enthalpy and entropy taken from available steam and

Fig. 4. Physical exergy of product water.

Fig. 5. Physical exergy of product air.

 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961 1957

saturated water tables [1]. With the exception of air, the chemical exergy of the product water is
the least among the reactants and products according to Model I (eCH ¼ 2:5 kJ/kg), and it could
be neglected in the analysis with a minor percentage of error.
The physical exergy of product air leaving the fuel cell, presented in Fig. 5, ranges from 320 kJ/
kg at the respective temperature and pressure ratios of T =T0 ¼ 1 and P =P0 ¼ 1 to 420 kJ/kg at
T =T0 ¼ 1 and P =P0 ¼ 3. In addition, a slight increase in the physical exergy of air, of approxi-
mately 2%, could take place if the operating temperature is increased from the standard operating
temperature of 298 K (T =T0 ¼ 1) to 373 K (T =T0 ¼ 1:25). Similar to the product water, Eq. (3) was
used to determine the physical exergy of the air. However, the physical exergy of each element
contained in the product air mixture (N2 , O2 , CO2 and H2 O (V)) was calculated individually and
added later according to their mole fractions in the air mixture. The values of enthalpy and en-
tropy were taken from available properties of ideal gas tables [1]. Similarly, the chemical exergy of
air was calculated to be 8.58 kJ/kg, which was determined through summation of the chemical
exergies of all the elements in the product air mixture and represented in terms of standard
chemical exergy and mole fraction of each element as illustrated in Eq. (5).
The differences in exergetic efficiency of a PEM fuel cell tend to be prominent at variable
operating pressures and temperatures, as depicted in Fig. 6. This is mainly attributed to the in-
crease in the cell voltage, which is a strong function of the system pressure, in an equation
commonly called the ÔNernstÕ equation, which is a function of the Gibbs free energy, the partial
pressures of hydrogen and oxygen and the operating temperature, leading to an increase in the
system efficiency. For instance, a 2% increase in the exergetic efficiency can be obtained if the
operating pressure of the system is increased from P =P0 ¼ 1 to P =P0 ¼ 3. Similarly, a maximum
increase in the exergetic efficiency of 2.5% can be achieved if the fuel cell operating temperature is
increased from the standard temperature of 298 K (T =T0 ¼ 1) to 373 K (T =T0 ¼ 1:25). However, it
should be emphasized that it is always recommended to operate PEM fuel cells at lower inlet

Fig. 6. Exergetic efficiency of a PEM cell at variable operating pressure and temperature and at cell voltage of
V ¼ 0:5 V.
1958 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

hydrogen pressure in the anode than the inlet air pressure in the cathode in order to enhance the
electro-osmotic drag that occurs between the cathode and the anode, resulting in a better fuel cell
efficiency. This observation was verified theoretically and experimentally [17].
Variable PEM fuel cell voltages plays a significant role in the exergetic efficiency of the cell
operation as depicted in Fig. 7. The lower the cell voltage, the greater is the mass flow rates re-
quired for the reactants and the products to operate the fuel cell in order to produce a power
output of 10 kW. This will result in a higher magnitude of the difference between the total exergies
of the reactants and the products, leading to lower exergetic efficiency. For example, a 7% increase
in the efficiency could be acquired if the fuel cell operates at a cell voltage of 0.6 V rather than 0.5
V. Furthermore, the efficiency of a PEM fuel cell can be increased through increasing its operating
temperature in spite of its small and low operating temperature range, as opposed to other types
of fuel cells that operate at high temperatures, such as solid oxide fuel cells and molten carbonate
fuel cells [18]. For instance, a maximum increase in the exergetic efficiency of 2.5% can be achieved
if the fuel cell operating temperature is increased from a standard temperature of 298 K
(T =T0 ¼ 1) to 373 K (T =T0 ¼ 1:25).
The calculations of the mass flow rates of the reactants and the products in the electrochemical
reaction are performed based on Eqs. (6)–(9) and are presented in Table 2. The difference between
the flow rates of the inlet and outlet air represents the amount of oxygen being consumed by
combining with hydrogen. The oxygen usage of a PEM fuel cell operating at voltages of V ¼ 0:5
and V ¼ 0:6 V are calculated to be 0.00166 kg/s and 0.00138 kg/s, respectively.
Depending on the stoichiometry of air k the efficiency of the fuel cell can be greatly improved if
the air stoichiometry is increased because the reactant mass flow rate of air is a strong function of
its stoichiometry. In order to demonstrate the relation between the air stoichiometry and the fuel
cell exergetic efficiency, an exergy analysis is performed at air stoichiometries of 2 and 4 and at an
operating fuel cell voltage of V ¼ 0:5 V and compared against the calculated results at an air
stoichiometry of 3 as shown in Fig. 8. Without any doubt, a fuel cell with higher air stoichiometry

Fig. 7. Exergetic efficiency at operating fuel cell voltage V ¼ 0:5 and 0.6 V and ðP =P0 Þ ¼ 1.
 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961 1959

Fig. 8. Exergetic efficiency at variable air stoichiometry and at operating fuel cell voltage of V ¼ 0:5 V and ðP =P0 Þ ¼ 1.

has better exergetic efficiency as opposed to lower air stoichiometry. For instance, a 7%
improvement in the fuel cell efficiency could be achieved if the air stoichiometry in the fuel cell is
switched from 2 to 4. However, one should be extremely careful in setting up the air stoichiometry
greater than the recommended range, which is between 2 and 4. This is because, at high fuel cell
operating temperature and air stoichiometry, the relative humidity of the exit air will be lowered,
leading to a higher risk for the cells to dry out and a sharp decrease in the efficiency of the fuel cell
could take place [16,19].
A general remark can be made regarding the limited and small range of variation in the ex-
ergetic efficiency of the fuel cell with respect to variations in the fuel cell operating conditions. This
limited range of variation is mainly attributed to the consistency of the physical exergies of the
products and reactants that follow similar trends with increasing or decreasing the fuel cell
operating conditions, even though they differ in magnitudes. Hence, a minor difference of the total
exergy between the reactants and the products occurs, resulting in a minor variation in the ex-
ergetic efficiency. Nevertheless, it should be emphasized that the general calculated results at
various fuel cell operating conditions are consistent with the theoretical and experimental results
demonstrated in published works. For instance, a higher cell voltage can be attained as a result of
a higher operating temperature or pressure as demonstrated by Bernardi and Verbrugge [17] and
Kazim et al. [20], leading to a higher power output. Consequently, a greater fuel cell exergetic
efficiency is achieved, since the cell efficiency is directly proportional to the cell power output as
illustrated in Eq. (1). Furthermore, greater cell voltage and exergetic efficiency are achieved
through a higher stoichiometric ratio, which is also demonstrated by Buchi and Srinivasan [19].

4. Conclusion

Exergy analysis of a proton exchange membrane fuel cell (PEM) is conducted at variable
operating temperatures, pressures, cell voltages and air stoichiometry. In the analysis, the exergetic
1960 A. Kazim / Energy Conversion and Management 45 (2004) 1949–1961

efficiency of a fuel cell system is determined in terms of the ratio of the power output of the fuel
cell over the differences between the total exergies of the reactants and products of the fuel cell
electrochemical process. The total exergy of the reactants and the products consist of both
physical and chemical exergies, which are calculated for each element in the electrochemical
process.
From the current results, a general conclusion could be drawn concerning the fuel cell exergetic
efficiency, which can be improved significantly by adopting any or a combination of the four
operational measures. Firstly, the exergetic efficiency of a PEM fuel cell can be improved by
having a higher operating pressure. However, a high pressure difference between the cathode and
the anode is recommended in order to enhance the electro-osmotic drag phenomena between the
two electrodes. Secondly, the efficiency of the fuel cell can be increased through increasing the fuel
cell operating temperature in spite of the small and low temperature range of a PEM fuel cell as
opposed to other types of fuel cells that operate at high temperatures. Thirdly, higher exergetic
efficiency could be attained if the fuel cell operates at relatively higher cell voltages that would
require less mass flow rates for the reactants and the products to achieve a high electrical output.
Fourthly, by having a high air stoichiometry, a significant increase in the efficiency of the fuel cell
can be achieved, although it would be recommended to have an air stoichiometry in the range
between 2 and 4 in order to maintain the relative humidity level in the product air and avoid the
fuel cell membrane drying out at high operating temperatures.

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