Factors Affecting the Performance of a

Polymer Electrolyte Fuel Cell

Presented to: Shadi Taghavi

Group BB
Laboratory Projects II
Department of Chemical Engineering
Queens University

January 30, 2015

We do hereby verify that this written report is our own individual work and contains our own
original ideas, concepts and designs. No portion of this report has been copied in whole or in
part from another source, with the possible exception of properly referenced material.
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1.0 Introduction
This experiment analyzes the factors affecting the performance of a polymer electrolyte
membrane (PEM) fuel cell by varying the cell operating conditions. A fuel cell converts chemical
energy into electrical energy.

1.1 Principles of Polymer Electrolyte Fuel Cells

Fuel cells consists of three main components: an anode, an electrolyte membrane and a cathode
as seen in Figure 1.

Figure 1: Schematic of a polymer electrolyte membrane fuel cell (PerkinElmer Inc., 2010).
In this experiment hydrogen gas is used as a fuel and is fed to the anode, while oxygen is used as
the oxidant and is fed to the cathode. Equation 1 is the reaction that occurs in PEM fuel cell
power generation:

2 H 2 +O2 2 H 2 O

(1)

At the anode, dihydrogen dissociates into hydrogen ions and electrons as seen in equation 2.

+ +4 e
(2)
2 H2 4 H

The hydrogen ions can then move through the electrolyte membrane towards the cathode and the
electrons are forced outside the cell to produce an electric current. At the cathode, hydrogen and
oxygen react to form water as seen in Equation 3 (U.S. Department of Energy, 2000).
2 H 2 O
++ O2+ 4 e (3)
4 H

1.2 Fuel Source and Oxidant

Hydrogen gas is used as the fuel source because of its reactivity towards an appropriate catalyst,
the convenience of production via hydrocarbons and its ability to be cryogenically stored while
maintaining an increased energy density allowing for easy storage. Oxygen is chosen as an
oxidant since it is easily obtained from air and, like hydrogen gas, is easily stored (U.S.
Department of Energy, 2000).

1.3 Electrolytic Membrane

The electrolyte is located between the two electrodes and is responsible for the transfer of
protons. PEM fuel cells require a solid polymer electrolyte (SPE) membrane that meets the
following criteria: high conductivity of protons, low loses from resistance, no electric
conductivity, minimal fuel and oxygen transport, durable material and cost-efficient. There are
several types of SPE membranes, such as perfluorinated isomers, partially fluorinated polymers
and non-fluorinated membranes with aromatic backbone (Smitha, Sridhar, & Khan, 2005).
This type of cell has only one liquid source resulting in minimized corrosion of equipment. Water
produced at the cathode is evaporated based on a calculated humidifier temperature. The
temperature is chosen such that water does not evaporate too quickly so that the membrane
remains hydrated. Water traps are also included in the system to prevent flooding, as seen in
Figure 2 (U.S. Department of Energy, 2000).

Figure 2: Schematic of the ProFC-XU series stacks (H2 Economy, 2008).

1.4 Performance Graph of a Typical Fuel Cell

The equilibrium potential ( EOCV ) of a PEM fuel cell is calculated via the following equation:

EOCV =
Where

G
nF

(4)

is the change in Gibbs free energy calculated by the half-cell reactions at the

anode and cathode (assuming an ideal system). The number of electrons is denoted by
Faradays constant by

and

F . If this were an ideal process, open circuit voltage (OCV) could be

used to determine the potential of the fuel cell by measuring the potential difference between the
anode and cathode with no current. Since there are losses associated with real fuel cells this
approach is inaccurate. To account for these losses the following equation is used to calculate the
operational potential ( V op ):

V op=EOCV V act V ohmV trans (5)

Where

V act

accounts for the activation losses,

V act

accounts for the ohmic losses and

V trans accounts for the mass transport losses. A general performance graph for a fuel cell can
be seen in Figure 3 (Department of Chemical Engineering, 2015).

Figure 3: Performance graph for a fuel cell (U.S. Department of Energy, 2000).

1.5 Sources of Losses

Activation polarization is a result of energy barriers preventing electron flow and is determined
by the rate at which electrochemical reactions are occurring. By increasing the temperature and
surface area of the catalyst the effects of activation polarization are minimized. This can be seen
at low current densities on the performance graph in Figure 3 (U.S. Department of Energy,
2000).
Ohmic polarization is caused by the resistance of ions through the electrolyte membrane as well
as the resistance of electrons in the electrode. The effects of ohmic polarization can be minimized
by decreasing the separation between the anode and cathode as well as increasing the conductive
capabilities of the electrolyte. The severity of ohmic losses occurs as current density increases, as
seen in Figure 3 (U.S. Department of Energy, 2000).

Concentration polarization occurs as a result of a concentration gradient which prevents the

transport of hydrogen to the cathode. Losses can be reduced by increasing the output humidity to
remove excess water, increasing the rate at which hydrogen enters the system and using porous
electrodes. Concentration polarization occurs at high current density, as seen in Figure 3, due to
blocked reaction sites by excess water and humidification (U.S. Department of Energy, 2000).

1.6 Advancements in Fuel Cell Technology

Currently, the leading source of energy used in the production of electricity is fossil fuels. Fossil
fuels are transformed into a useful energy via combustion reactions. However, 50% of the energy
produced in this process is lost as heat and pollutant gasses are produced. The conversion of
chemical energy directly into electrical energy is thus an active area of study. PEM fuel cells are
of interest since hydrogen as a fuel is obtained from a sustainable source, the energy produced
per unit volume of gas is high and the process does not require combustion. Fuel cells can
operate at 60% efficiency and can reach up to 80% in systems that involve cogeneration (Calay
& Mustafa, 2013).
In the past 10 years fuel cells have been introduced as a potential alternative to internal
combustion engines in vehicles. Honda released the first fuel cell car commercially in 2008. Fuel
cell applications in public transportation have also received government funding in hopes of
reducing the production of pollutants. The first fuel cell buses were released in 1994. The
application of fuel cell technology has also been seen in vehicles used for material handling such
as forklifts (Calay & Mustafa, 2013).
Platinum catalysts are most commonly used in PEM fuel cells, such as in this experiment.
However, there have been recent efforts to implement a more cost-efficient alternative, such as

an iron catalyst. Iron catalysts are less expensive but have lower power density. They possess
weaker mass-transport properties (Proietti, et al., 2011). To increase the efficiency catalytic and
conductive electrodes are required. The rate at which reactions occur is increased by the use of
porous electrodes that have a greater surface area (U.S. Department of Energy, 2000).
1.6 Limitations of Fuel Cell Technology

In order to overcome commercial barriers associated with fuel cells the technology would have
to become as reliable as the internal combustion engine. Fueling stations as well as qualified
mechanics would also be required in order for the fuel cell technology to be successful. In order
for the fuel cell to compete with the current combustion engine the cost of the system must be
decreased by a factor of two and the life time of the system increased by a factor of two. The
predicted fuel cell cost in transport applications is $49 per kilowatt. This cost must be reduced to
at least $39 per kilowatt to be in competition with the combustion engine. Reducing costs
requires a cut back on materials (such as platinum), power density enhancement, and increase in
durability of the system (Calay & Mustafa, 2013).

2.0 Experimental
2.1 Equipment Used
The experiment was conducted using an H 2 ECOnomy ProFC series fuel cell. This model has 3
cells in the stack, and an N-112 perfluorosulfonic acid polymer membrane (H2 Economy, 2008).
In order to control the water content of the air entering the cell, a (insert name/model of
humidifier used) was used at a temperature of 40C. The selection of this temperature is
explained in Appendix B. To ensure temperature control throughout the duration of the
experiment, a (insert model of oven) was used.

2.2 Safety Hazards

Wear gloves, lab coat and goggles

Hydrogen and oxygen gas are explosive and self-igniting
Pressurized gas canisters must be secured and handled properly

2.3 Procedure
Following is a description of the procedure used for each trial of the experiment. The
gas flows were adjusted to investigate cell performance in multiple flow ratios, both varying

the amount of gas as well as the hydrogen:oxygen ratio. The flowrates tested may be found in
Table 1.
Table 1: Gas flowrates used in the performance investigation.
Flowrates of Hydrogen:Oxygen (mL/min)
100 : 50
150 : 75
200 : 100
50 : 100
100 : 200
100 : 100

1. It was ensured that the gas lines were attached to the large 3-cell PEM fuel cell.
2. The hydrogen and oxygen gas tanks were turned on with one full turn and then the
pressures were adjusted with the regulator.
3. The mass flow controllers were adjusted to produce the desired gas flowrates.
4. The oven was turned on to 50C, and it was ensured that it remained near this operating
temperature throughout the experiment. If the temperature fluctuated while measurements
were taken it was noted.
5. The humidifier was set to an operating temperature of 40C.
6. The ammeter and voltmeter were turned on. It was ensured that the ammeter was
connected in series and the voltmeter connected in a parallel circuit.

7. The temperature was noted. The resistance was applied to the cell in increments of 0.1 ,
slowly moving up in larger increments. All 0.1 increments were recorded followed by
5 measurements in the 1 range, 3 or 4 in the 10 range and 2 at a time in the 100
range.
8. With each resistance level the voltage and current were recorded.
9. Steps 1-8 were repeated with various flow rates of hydrogen and oxygen.
10. After completion of the experiment the main valve on the hydrogen and oxygen tanks
were turned off first followed by the pressure gauge.

Figure 4: Schematic of experimental setup.

3.0 Results and Discussion

3.1 Cell Performance Curves
Figure 5 summarizes the cell performance at each flowrate and stoichiometry analyzed. It is clear
from the plot that the cell shows highly non-ideal performance characteristics. The figure also
shows that the cell operates most predictably when the hydrogen:oxygen ratio is 2:1. As can be
seen in Appendix B, this is what would be expected. Each mole of oxygen reduced requires 4
electrons, while each mole of hydrogen oxidized only provides 2. It is clear from Figure 5 that

operating in a reverse stoichiometric ratio of 1:2 hydrogen:oxygen highly impacts the cells
functionality. Almost no voltage is provided when current is drawn from the cell. This is likely
because this gas mixture leaves the cell starved for fuel.

3000

2500

2000
250H:125O

Voltage, V (mV)

100H:50O

1500

150H:75O
200H:100O
100H:200O

1000

100H:100O

500

0.01

0.01

0.01

0.01

Current Density (A/cm^2)

Figure 5: Cell Performance at various flowrates and stoichiometries.

3.2 Cell Power Output

While previously discussed results make it clear that the fuel cell functions best when gas is fed
in stoichiometric ratios, further analysis is needed to examine how varying flowrate impacts the
overall power output of the cell. Cell power at the 100:50, 150:75, and 200:100 flowrates was
calculated, and is summarized in Figure 6.

300
250
200

Power (mW)

150

100/50
150/75

100

200/100

50
0
0

0.01

0.01

0.01

0.01

Current Density (Amp/cm2)

Figure 6: Power Output for the 2:1 ratio flowrates.

3.3 Linear fit of the region of Ohmic Polarization (Resistance Loss).

Table 2 Summary of the lines of best fit applied to the data recorded. All the plots can be found in the
appendix in figures XXX to XXX.

H2 Flowrate
ml/min
100
150
200
250
100
100
50

O2 flowrate
ml/min
50
75
100
125
100
200
100

Slope of linear section

mV/A
-3878.2
-3383.0
-3275.0
-3151.8
-5024.3
-9404.9
-607.18

Y-Intercept
mV
1904.6
1884.1
1591.9
1403
2342.3
1195.2
21.5

R2 Value
0.9953
0.9994
0.9920
09788
0.9687
0.7888
0.0833

As it can be observed from the table above, a linear trend line was found to be a
very good fit for the region of Ohmic polarization for stoichiometric ratio of
2(H2):1(O2) as the R2 values are above 99% for the first 3 data sets and nearly
98% for the fourth data set. Furthermore, it was also found that the higher the
total flow rate at this stoichiometric ratio, the better the cell performs in this
region of the graph as the slope of the linear portion becomes less steep. This
indicates that the difference between the ideal and actual voltage decreased
meaning that it would be recommended to operate the cell at higher flow rates.
Furthermore, the higher the current is the greater the performance difference is.
In the case of the data resulting from the 1:1 H 2 to O2 ratio experiment, it was possible to fit a
straight line that resulted in a R2 value of 96% by avoiding a couple of point which would have
caused the deviation to increase greatly. Consequently, a linear relationship could be established
in a considerable portion of the graph (see fig. XX). As expected, the cell does not perform as
well as with a 2:1 ratio. The slope was nearly 33% higher than the one of corresponding to the
100 (H2): 50 (O2) data set which suggests that an oversupply of oxygen causes a significant drop
in cell performance.
For the data sets corresponding to the experiments performed with a reverse stoichiometric ratio
(1(H2): 2 (O2)) it was impossible to find a good linear fit. As it can be seen on table XX. the R 2
value corresponding to the trend line was 8.33% which is too low and implies that there is
practically no linear relationship between the voltage and the current.
Overall, this table not only confirms that the stoichiometric ratio of 2:1 results in the best
performance but also suggests that a higher flowrate results in improved performance. However,

it is important to note that increasing the flowrate increases the costs as the exhaust gases are not
recycled.
3.4 Error propagation and main sources of error.
The major source of error came from the voltmeter readings. In general, the greater the resistance
was, the greater the error. For the 2:1 stoichiometric readings, the voltmeters values oscillated
around +-1 mV at the beginning with a total resistance of less than 1 ohm but ended varying in
almost 20mV when the total resistancce was increased to 1000 ohms. The ampeter vas fairly
constant and only varied very slightly giving a maximum absolute error of +-0.01A. These errors
are relatively small as the maximum relative error for the voltage readings is
The flow meters seemed to be very constant throughout the experiment and an absolute error of
+-0.5 ml/min was assumed. This translates into a maxmum relative error of 1% for our lowest
flow rate (50 mL/min) and 0.25% for our highest flow rate (200 mL/min).
The humidifier settings were not touched and it was assumed that it was correctly calibrated and
maintained a humidity level of 40%.
In our pre-lab calculations, it was determined that temperature was not a major factor in the
performance of the cell if the cell was to operate ideally. This is because the EOCV was nearly
identical at 50 C than at 25 C. To avoid increasing our total error, the oven was opened when the
temperature surpassed 51.0 C and was closed as soon as the temperature dropped to 50 C.

4.0 Conclusions

5.0 References
Calay, R. K., & Mustafa, M. Y. (2013). Challenges facing hydrogen fuel cell
technology to replace combustion. Advanced Materials Research.
Department of Chemical Engineering. (2015). Factors Affecting The Performance of
a Polymer Electrolyte Fuel Cell. Queen's University.
H2 Economy. (2008). PEM Fuel Cell Stacks ProFC-XU. Armenia.
Larminie, J., & Dicks, A. (2003). Fuel Cell Systems Explained. England: John Wiley &
Sons Ltd.
PerkinElmer Inc. (2010). (PerkinElmer) Retrieved January 18, 2015, from Quality
Control of Polymer Electrolyte Membrane Fuel Cells by Thermogravimetric
Analysis: www.perkinelemer.com
Proietti, E., Jaouen, F., Lefevre, M., Larouche, N., Tian, J., Herranz, J., & Dodelet, J.-P.
(2011). Iron-based cathode catalyst with enhanced power density in polymer
electrolyte membrane fuel cells. Nature Communications.
doi:10.1038/ncomms1427
Smitha, B., Sridhar, S., & Khan, A. A. (2005). Solid polymer electrolyte membranes
for fuel cell applications-a review. Journal of Membrane Science, 12-15.
U.S. Department of Energy. (2000). Fuel Cell Handbook (Fifth Edition). West Virginia:
Natinal Energy Technology Laboratory.

Appendix A: Raw Data

I)

Data for Calculating Equilibrium Potential

The following data from Fuel Cell Systems Explained is used to determine Gibbs free energy for
the calculation of the equilibrium potential, EOCV (Larminie & Dicks, 2003).

Table 3: Gibb's free energy of liquid water at different temperatures

Gibbs Free

Form of
Temperature
Water
[C]

Energy, G

Product

II)

[kJ/mol]
Liquid
25
-237.2
Liquid
80
-228.2
Physical Properties of Anode and Cathode Reagents

The table below summarizes some of the physical properties of oxygen and hydrogen, used in
deriving the expressions for oxygen and hydrogen usage (Larminie & Dicks, 2003):
Table 4: Physical properties of gases
Molecular
Type of Gas

Weight

Density [g/cm3]

O2
H2

[g/mol]
32
2

0.0013 @ 25C and 1 atm

0.0001 @ 0C and 1 atm

Appendix B: Sample Calculations

I)

Calculating the Energy of Open Circuit Voltage

The equilibrium potential is given by the following expression:

G
EOCV =
nF
Where:
EOCV is the energy of the open circuit voltage [V] = [J/C]
G is the Gibbs free energy released [kJ/mol]

F is Faradays constant [96485 C/mol]

n is the number of transferred electrons [mol]
An approximate value for Gibbs free energy for the reaction at 50C is calculated assuming a
linear relationship between Gibbs free energy and temperature. The linear interpolation was
performed based on tabulated values (see Appendix A, Section I) and resulted in the following:
G ( T =50 C )=233.1kJ
Now, the energy of the open circuit voltage can be determined:
(233.1 kJ )
EOCV =
C
(2 mol)(96485
)
mol

(233100 J )
C
(2 mol)(96485
)
mol
EOCV =1.21 V

II)

Finding the Humidifier Operating Temperature

For a cell operating at 50C with a relative humidity of 60%, this corresponds to a partial
pressure of water in the gas of 7.54 kPa. This is found using the definition of relative humidity
and data from steam tables.

relative humidity=
0.60=

pressure of water
saturation pressure of water

Pw
Pw
=
sat
12.35 kPa
P

Rearranging gives a required Pw of 7.41 kPa. Referring to the steam tables, the saturation
temperature at this pressure is 40C. This is the desired temperature for the humidifier.

III)

Derivation of Oxygen and Hydrogen Flowrates

The usage of anode and cathode reactants can be calculated based on Faraday's Law (Larminie &
Dicks, 2003).
Gasusage =

I
F

Where
F is Faradays constant [96485 C/mol]
I is current [C/s]
is the electron stoichiometric coefficient [mol]

Equation (1) depicts that four electrons are transferred for every mole of oxygen. Equation (2)
depicts that 2 moles of electrons are transferred for every mole of hydrogen. Therefore, the flowrate of oxygen and hydrogen can be expressed as:

[ ]
[ ]

O2 usage=

I mol
4F s

H 2 usage =

I mol
2F s

For a stack of n fuel cells, the reactant usages become:

mol
O2 usage=
4F s

[ ]
[ ]

mol
H 2 usage =
2F s

Typically, the units of mol/s is not practical. In order to write the usages in mL/min, one must
use the molecular weight and density of the gas at the given temperature. These values are
located in Appendix A, section II. Assuming that the density of the gases remain relatively
constant with temperature, the usage expressions can be written in terms of mL/min as follows:
3
mol
32 g
60 s
cm
O2 usage=

4F s
1 mol O2
1 min
0.0013 g

[ ](

)( )(

[ ]

O2 usage=3.74

mL
min

mol
2g
60 s
cm3
H 2 usage =

2F s
1mol O2
1 min
0.0001 g

[ ](

H 2 usage

)( )(
mL
=6.22 [
min ]