Fuel Cell Prac - Mpfnor001 - Group b2

C H E 3 0 4 9 W - H y d r o g e n F u e l C e l l P a g e | 1
2013 Norman Mpofu (MPFNOR001)

Synopsis
This report thoroughly describes the functioning of a Proton-Electron-Membrane hydrogen
fuel cell in the context of the departments HP600 Fuel cell system. Industrial equipment and
instrument manufacturers face unprecedented demands from their customers for greater
value in the products and services they provide. Ideally, all industrial equipment comes with
manufacturers specifications, of which in our case, the power, current and voltage rating is
pertinent in establishing whether or not the fuel cell is functioning properly. The performance
of the hydrogen fuel cell against the manufacturers specification sheet was investigated by
the means of mass balance on the hydrogen stream entering the system, an energy balance
over the coolant recycle and by systematically inquiring into the rate law of the hydrogen fuel
cell stack using the Butler-Volmer equation.

Mass balance results show that the fuel cell is working properly, but under the yoke of design
and technological constraints due to what happens at the three phase boundary.
Since the minimum potential of the hydrogen fuel stack is constant, it was deduced that it is
current that is directly related to the power output. The current is generated by the
electrochemical reaction occurring at the active catalyst sites in the fuel cell. Therefore fuel
cell performance is highly dependent on integrity of this catalyst layer. This report proposes
that in order to ascertain the extent of compromise of active catalyst sites, current mass
balance data must be compared to hydrogen consumption data as at factory setting dates.
The power density curve revealed that the fuel cell was programmed to shut down before
entering the high current density, mass transfer region of fuel cell operation. As a result,
power output does not reach a maximum and the fuel cell was found to be performing at a
reduced power rating of 374W. It is clear that the hydrogen fuel cell is not operating at
optimal performance. The problem though is not so much a faulty hydrogen fuel cell, but
rather internal design and technological constraints affecting the fuel cell.



Contents
Synopsis ................................................................................................................................................ 1
Contents ................................................................................................................................................2
List of Figures ........................................................................................................................................ 4
List of Tables.......................................................................................................................................... 4
Nomenclature .......................................................................................................................................4
Glossary ................................................................................................................................................5
1. Introduction...................................................................................................................................... 6
1.1 Subject of Report6
1.2 Background to Report.6
1.3 Objectives...6
1.4 Scope and Limitations....7
1.5 Plan of Development7
2. Literature Review............................................................................................................................. 7
2.1 Practical Background.....7
2.2 Electrode kinetics.....7
2.3 Reaction kinetics......8
2.4 Polarization and power curves...................................................................................................... 10
3. Experimental... ....11
3.1 Experimental Development ...11
3.2 Apparatus......12
3.3 Procedure .................................................................................................................................... 12
3.4 Start-up of HP600 Fuel Cell system ..12
3.5 External current variation and recording data for mass and energy balance...12
3.6 Rate law data capturing.12
3.7 Risk Assessment..12
4. Results.....13
4.1 Hydrogen mass balance.13
4.2 Energy balance over cooling system.14
4.3 Rate law: Polarisation and Power density curves...14
4.4 Error analysis....16
5. Discussion of results...17
5.1 Mass balance analysis....17
5.2 Energy balance analysis..17


5.3 Polarisation curves..17
5.4 Power curve..18
6. Conclusion19
7. References...20
8. Appendix.21
8.1 Raw data21
8.2 Sample calculations21



List of Figures
Figure 1: Polarization and power curves illustration.
Figure 2: Block flow diagram of PEM hydrogen fuel cell system.
Figure 3: Bar graph comparing experimental and theoretical hydrogen consumption.
Figure 4: Bar graph comparing experimental and theoretical heat quantity.
Figure 5: Theoretical and experimental polarization curves.
Figure 6: Theoretical and experimental polarization curves with power density plotted on
secondary axis.
List of Tables
Table 1: Percentage difference between experimental and theoretical hydrogen consumption.
Table 2: Percentage difference between experimental and theoretical heat quantity.
Table 3: External and internal current settings comparison.
Table 4: Standard deviation for theoretical and experimental data collected.

Nomenclature
= transfer coefficient
C
OX
= surface concentration of reacting species (mol/cm
2
)
C
RD
= surface concentration of reacting species (mol/cm
2
)
E
r
= reversible potential (V)
(E- E
r
) = over potential (V)
F = Faradays constant (C/mol)
i = net current density (A/cm)
i
0
= exchange current density (A/cm)
k
f
= forward reaction (reduction) rate coefficient (s
-1
)
k
b
= backward reaction (oxidation) rate coefficient (s
-1
)
nF = charge transferred (Coulombs/mol)
n = number of electrons per molecule (H
2
= 2 electrons)
R= 8.314 J/mol.K
T= temperature measured in Kelvins



Glossary
Anode: Positive fuel cell electrode.
Cathode: Negative fuel cell electrode.
Current density: The quantity of current per unit area (1 fuel cell has an area of 130 cm
2
).
Exchange current density: In electrochemical reactions it is analogous to the rate constant
in chemical reactions, unlike rate constants, it is concentration dependent.
Fuel cell stack: (In this case study) 24 fuel cells connected together in order to acquire an
amplified amount of useful power.
Over potential: The difference between the electrode potential and the reversible potential
that is required to produce current.
PEM: Proton Exchange Membrane, a fuel cell that depends on a semi permeable membrane
to allow mass transport of protons through it.
Power density: The quantity of power per unit area (Each fuel cell has an area of 130 cm
2
).
Polarisation Curve: Plot of cell voltage against current density. Used to illustrate how
voltage losses affect the performance of a fuel cell or the deviation of fuel cell performance
from ideality.



1. Introduction
1.1. Subject of Report
This report gives a comprehensive account on how a hydrogen fuel cell functions and
through a thorough investigation by means of mass , energy and rate law findings; sets out
to compare the specifications claimed by the manufacturer of the Chemical Engineering
departments HP600 hydrogen fuel cell and empirical data from the experiment.
Furthermore, the challenge posed is to delve into the hydrogen fuel cell stacks kinetics by
Obtaining the rate law of the fuel cell through the derivation of the Butler- Vollmer equation

1.2. Background to Report

Hydrogen fuel cell technology is a more expensive source of energy than the mature oil and
electricity commodities. The fuel cell economy is high-priced because it is a highly
specialized industry that requires proficiency and technology at every step. Also, hydrogen
is not readily available as a fuel; it must be obtained through means like steam reforming of
natural gas or electrolysis. For the hydrogen fuel cell to penetrate the world energy market,
it must start with technologies that have niche markets, like hydrogen powered vehicles.
South Africa is the worlds leading producer of platinum group metals. The aforementioned
metals are used as catalysts in the hydrogen fuel cell. In the long term, South Africa seems
well positioned to dominate the hydrogen fuel cell economy which heavily utilises platinum
metals. At this, the South African government has heavily invested in this green
technology. It has embraced this technology by funding many research institutions
(including HySA Catalysis at the University of Cape Town) to develop of a safe, clean and
reliable energy source that will not only wean the world of its dependence on fossil fuels,
but have the world depend on South Africa for its hydrogen fuel cells, catalysts or platinum.
By this, South Africa will be able to transform itself through job creation, increasing Gross
Domestic Product and knowledge based economy through research and development. This
report has been prepared for the Department of Environmental affairs as proof of on-going
work in green technology.

1.3. Objectives
In this report we endeavour to:
- Display an understanding of how the hydrogen fuel cell works by means of a block
flow diagram.
- Determine whether the fuel cell is operating correctly using fundamental concepts in
chemical engineering like mass and energy balances and obtaining the rate law
through the derivation of the Butler-Vollmer equation.
- Prove that the fuel cell stack is operating according to manufacturer specifications
Vis--vis the aforementioned mass and energy balances and rate law findings
obtained empirically.
The manufacturers specifications state that the fuel cell is rated as follows:
Power rating: 600W; Voltage rating: 14.4V; Current Rating: 45A.
As for Fuel cell kinetics, the Butler-Volmer equation is used as a model to discern the


relationship between current density and cell potential.
1.4. Scope and Limitations
There was ample time to ascertain the functionality of the HP600 hydrogen fuel cell system
as at the date the practical was performed. However it would have been interesting to
compare the empirical data collected on the day of the practical with the empirical data
from the first time the fuel cell was operated in our departments laboratory. This would give
us an insight into other factors that might be affecting the fuel cell like the degradation of
the carbon support (electrodes) and perhaps the extent of competing reactions like the
oxidation of platinum metal. Such a comparison would not only exonerate the manufacturer
but could also enlighten us on how we could account for depreciation of equipment. This is
important because depreciation is a tax allowed deduction that not only lower income tax
but provides for the recovery of capital that has been invested in physical property or
assets. This might not be of interest to the faculty because it is sponsored by the
government and mining companies but to a small business owner it would really make a
difference.

1.5. Plan of Development
This report begins with an abbreviated account on how a Proton-Exchange-Membrane fuel
cell operates. The theory and detailed account of how the fuel cell works is substantiated by
peer reviewed journals and other credible sources of literature. A brief account of the
experimental procedure and equipment used comes after. Then, in the context of an HP600
fuel cell system, the performance of the fuel cell against manufacturers specifications is
determined using mass balances, energy balances and rate law findings over the fuel cell
stack. The linearization of the Butler-Volmer equation will then be tackled step by step, so
as to understand the chemical kinetics within the fuel cell. As for the random error in the
measurement the appropriate statistical tools will be used to account for it, only then can
conclusions and recommendations be made about the reliability of the manufacturers
specifications and appropriateness of the Butler-Volmer equation as a model for fuel cell
kinetics.

2. Literature Review
2.1. Practical Background

Miansari et al (2009: 356) state that: the Proton Exchange Membrane fuel cell is an
electrochemical energy conversion device, which converts the energy conversion of hydrogen
and oxygen directly and efficiently into electrical energy, with waste heat and liquid water as
by-products. The rudimentary structure of the PEM fuel cell can be described as two
platinum coated electrodes which are the anode and cathode of the fuel cell. The electrodes
are separated by a solid membrane acting as the electrolyte (Al-Baghdadi, 2005: 1587).In the
context of the HP600 fuel cell system, hydrogen and oxygen enter the fuel cell stack.
Hydrogen flows through a system of channels to the positive electrode- the anode, whilst the
oxygen in air diffuses to the negative electrode-the cathode. At the anode the hydrogen
dissociates into protons and electrons. The electrons flow through an external circuit to the
cathode, whereas the protons then flow through the solid membrane to the cathode, where
they combine with the oxygen and electrons from the external circuit to form water. The
excess water and inerts are expelled from the system via the purge stream.



2.2. Electrode Kinetics

Gases are involved in fuel cell electro-chemical reactions. Therefore the electrodes are porous,
and this allows gases to arrive to the reaction sites, as well as products to leave the reaction
sites.

Anode reaction (Oxidation):
(Equation 1)

Cathode reaction (Reduction):
(Equation 2)

Overall reaction:
. (Equation 3)
The above reactions occur concurrently on an interface between the solid, ionically conductive
electrolyte and the electrically conductive platinum on carbon electrodes. In order for the reaction to
occur, a catalyst is needed to reduce the height of the activation barrier. Therefore the hydrogen and
the oxygen molecules must diffuse through the pores of the metal catalyst and adsorb. In order for the
reaction to occur the protons, platinum catalyst and carbon (from the electrode) need to be in contact
at the same time. This is referred to in literature as the Three phase boundary problem.
2.3. Reaction Kinetics

The Butler-Vollmer equation describes the current density at an electrode in terms of over potential.
By linearizing this equation we want to determine the unknown activity coefficient and the exchange
current density. The main idea behind the derivation is that the net current generated is the difference
between electrons released at the anode and electrons consumed at the cathode. Furthermore, the
mathematics is simplified by the fact that the over potential at the cathode is greater than that at the
anode. Consequently the cathode reaction is regarded as the rate determining step.
The aforementioned outline on the linearization of the Butler-Volmer equation is
mathematically expressed as follows:
According to (Barbir, 2005: 33), as previously mentioned, the net current generated is the
difference between the electrons released and consumed:
( )
f OX b RD
i nF k C k C =
(Equation 5)

Net current density is determined as follows:
0, 0,
exp exp
OX RD
f OX b RD
FE FE
i nF k C k C
RT RT
o o ( (
=
`
( (
)
(Equation 6)



Taking into account that at equilibrium, the potential is E
r,
and net current is equal to zero:

0 0, 0,
exp exp
OX RD
f OX b RD
FE FE
i nFk C nFk C
RT RT
o o ( (
= =
( (

(Equation 7)

Exchange current density is the rate at which these reactions proceed at equilibrium.
Dividing i/i
o
:

(Equation 8)
This yields equation 9:
i/i
0
=exp [(-
RD
F (E-E
R)
/ RT] exp [(
ox
F(E-E
R)
/RT] (Equation 9)
And finally the relationship between current density and potential:
0
( ) ( )
exp exp
OX r RD r
F E E F E E
i i
RT RT
o o ( (
=
`
( (
)
(Equation 10)
Equation 10 is known as the Butler-Vollmer equation that relates current density and
potential. The E
R
term is known as the reversible or equilibrium potential. According to
literature the reversible or equilibrium potential at standard temperature and pressure is 0V at
the anode and 1.229V at the cathode and this does not vary with temperature and pressure.
As aforementioned at the beginning of this section, the over potential on the cathode side is
greater than the anode over potential. Therefore the cell potential current is given by
(approximately):

, ,
0,
( )
exp
RD c c r c
c c
F E E
i i
RT
o (
=
(

(Equation 11)
Taking Equation 11 and linearizing it through the following steps:
)
(Equation 12)
(
)
(Equation 13)
(
)
(Equation 14)
Thus the linearized Butler-Volmer equation is the means by which the activity coefficient
(
RD
)

and the exchange current density (i
o
) can be determined:
i/i
0
=exp[(-
RD
FE/RT)/(-
RD
FE
R
)/RT]-exp[([(-
ox
FE/RT)/( -
ox
FE
R
/RT)]


0
( ) ln( ) ln( )
r
RD RD
RT RT
E E i i
F F o o
= +
(Equation 15)

2.4. Polarisation and Power Curves
The hydrogen fuel cells cell potential is limited by energy losses due to the kinetics. These loses are
often illustrated in polarization curves. A polarization curve is a plot of cell voltage against the cell
current density (Figure 1). Current density represents the pace at which the reaction is taking place.
At low current densities, in the activation potential region, voltage losses are caused by
electrochemical drive to overcome the activation energy that leads to the dissociation of the oxygen
and hydrogen molecules. From Srinivasan et al (1993), it is understood that the hydrogen and oxygen
molecules must diffuse through the pores of the platinum catalyst and adsorb. In literature this is
termed the three phase boundary problem, where hydrogen, platinum metal catalyst and carbon must
all be in contact. The role of the platinum catalyst is to reduce the activation energy barrier.

As current density increases, there is a gradual and continuous drop in cell potential. This is due to
what is termed as Ohmic losses in the conduction of ions through the electrolyte membrane.

At high current densities, mass transfer processes become the limiting factor as the supply of
hydrogen and oxygen to electrodes becomes sluggish. The HP600 fuel cell system used in the
experiment was programmed to shut down before entering this region of high current densities.
Figure 1 also shows power density as a function of current density. The power curve peaks at high
current density, which is the mass transfer region as mentioned earlier.

Figure 1: Polarisation curves at different temperatures (from Cell Voltage axes sloping downwards) and Power curves at
different temperatures (from origin sloping upwards), Song et al (2007: 2552-2561).



3. Experimental

3.1. Experimental Development

Start-up of the HP600 fuel cell system entails switching on the fuel cell and opening the gas tap from
the hydrogen container. Turning the fuel cell on, initiates the blowing of air (oxygen source) into the
fuel stack. The fuel cells relative humidity and set-point temperature are then set. This particular
fuel cell is automated, and so it runs output data like temperature, pressure, hydrogen flow rate,
current and voltage onto a computer. This data is usually represented graphically. Steady state is
reached when the graphs depict constant temperature, hydrogen flow rate and current. Different
external current settings are selected and the fuel cell can be made to run recording data on an Excel
spread sheet.

3.2. Apparatus

Hydrogen Fuel Cell
Computer System
Electronic Load
Purge
Coolant
System
Air (Oxygen source)
Hydrogen
Figure 2: Block flow Diagram of the PEM Hydrogen Fuel Cell System in the context of the HP600 System

3.3. Procedure
The first part of this practical entails adjusting the external current settings over the widest
range permissible, in order to run recording data onto a spread sheet. The data is then used to
perform mass and energy balances over the hydrogen fuel stack. The second part to this
experiment involves the increasing of current from 0A, incrementally, and continuously after
a specified amount of time. The data gleaned from the latter exercise will be necessary to
model the rate law of the electro-chemical reaction within the fuel cell stack.



3.4. Start-up of HP600 Fuel cell System
- Turn on HP600 Fuel cell system at the mains (air blower starts).
- Open the hydrogen tap to allow flow from pressurized tank to fuel cell
- Adjust set point temperature to 30C and relative humidity to 80%
- Once Temperature, hydrogen flow rate and current are constant, record data onto the
Excel spread sheet.

3.5. External Current Variation and Recording Data for Mass and Energy Balances
The HP600 fuel cell was fine-tuned by the department to shut down if it voltage goes below
14.4V.This was done as a precaution or prudent measure to ensure that the operator of the
fuel cell does not go below the critical voltage specified by the manufacturer: 13.3V. Based
on this information, the practical was carried out with the 14.4V threshold in mind. The
external current output on the electronic load was varied in steps of 5A, 10A, 15A, 20A and
25A (internally this was 7.6A, 13.07A, 18.44A, 23.91A and 28.99A). The fine dial was used
for currents up to 6A and above this the course dial played its part. Each interval was allowed
to run for 2 minutes. The data was captured onto a spread sheet on a per second basis.
3.6. Rate Law Data Capturing
The external current was set to 0A, and then the system was allowed to reach steady state.
Data was recorded with external current settings changing every 40 seconds in increments of
0.3, 0.6, 1.0, 5.0 between 0A and 3A, 3A and 6A, 6A and 10A, 10A and 25A respectively.
3.7. Health and Safety using Anglo Risk Matrix rating
- Risk of electric Shock: 8 (M).
- Purge stream produces enough water to cause some someone to slip and fall:
5 (L).
- Hydrogen gas leak caused by faulty connections and piping: 12 (M).



4. Results
4.1. Hydrogen Mass Balance

Figure3: Experimental hydrogen consumption within the fuel cell compared to theoretical hydrogen consumption.

Average Stack Current (A) % Difference between Experimental & Theoretical H2 Consumption
7.66 7.1
13.34 4.6
18.68 5.9
23.92 5.2
28.93 4.5
Table 1: Percentage difference between experimental and theoretical hydrogen consumption data.

0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.7 13.3 18.7 23.9 28.9
H
y
d
r
o
g
e
n

C
o
n
s
u
m
p
t
i
o
n

(
L
/
M
i
n
)

Average Stack Current (A)
Hydrogen Mass Balance
Experimental Hydrogen
Consumption (L/Min)
Theoretical Hydrogen
Consumption (L/min)


4.2. Energy balance

Figure 4: Experimental average heat quantity compared to the theoretical average heat quantity.
Average Stack Current (A) % Difference between Experimental & Theoretical Heat Quantity
7.7 8.6
13.3 2.1
18.7 1.4
23.9 0.8
28.9 0.7
Table 2: Percentage difference between the experimental heat quantity and theoretical heat quantity.
4.3. Rate law: Polarisation and Power density curves
Given the transfer coefficient from literature as:
Rd
= 1
And exchange current density as:

= 3.70E-7 A/cm
2

The theoretical cell voltage was calculated using (Equation 14):
(
)
The experimental cell voltage was calculated by dividing the average stack voltage by the number of
fuel cell stacks, that is 24. The current density in the following graphs represents the speed of the
reaction. It is the number of electrons per second, divided by the facial surface area of the
solid hydrogen fuel cell electrolyte.
0
100
200
300
400
500
600
7.7 13.3 18.7 23.9 28.9
A
v
e
r
a
g
e

H
e
a
t

[
W
]

Average Stack Current (A)
Energy Balance over Cooling System
Experimental Average Heat
[W]
Theoretical Average Heat
[W]


Figure 5: Graph comparing theoretical and experimental polarisation curves.
Current density values in Figure 5 do not start at 0A. Table 3 give us an insight into the reasons why
this is the case:
External Current Setting (A) Average Internal Stack Current (A) Experimental Cell Voltage [V] Theoretical Cell Voltage [V]
0.00 2.23 0.78 0.95
Table 3: External current settings and internal current settings.
Notice that Figure 5 plots cell voltage against a current density which was computed from internal
stack current data. This is the reason why the graph does not start at the expected zero current density.
Table 3 shows that when the external current is set a 0A, the fuel cell has its own internal current
reading since the system is switched on. Figure 5 and Table 3 point to a later discussion on open
circuit potential.

Figure 6: Polarisation curves with Power density plotted on secondary axis
5.00E-01
6.00E-01
7.00E-01
8.00E-01
9.00E-01
1.00E+00
0.0200 0.0600 0.1000 0.1400 0.1800 0.2200
C
e
l
l

V
o
l
t
a
g
e

(
V
)

Current Density (A/cm2)
Comparing Theoretical and Experimental Polarisation Curves
Theoretical
Polarisation
Curve
Experimental
Polarisation
Curve
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
1.00E-01
1.10E+00
2.10E+00
3.10E+00
0.0190 0.0690 0.1190 0.1690 0.2190 0.2690
P
o
w
e
r

D
e
n
s
i
t
y

(
W
/
c
m
2
)

C
e
l
l

V
o
l
t
a
g
e

(
V
)

Current Density (A/cm2)
Power Density Curve and Polarisation Curves
Theoretical Polarisation Curve Experimental Polarisation Curve Power Curve


The power generated by one fuel cell is calculated as follows:
P = IV (Equation 16)
4.4. Error Analysis
Literature states that absolute steady state can never be attained because of what happens at the three
phase boundary. The three phase boundary is responsible for random error in experimental data, and
this is accounted for using error bars Srinivasan et al (1999). At low current density, what happens at
the three phase boundary is responsible for the initial sharp decline of the slope of the polarisation
curves. Close to zero current density the polarization curves depicted in Figure 5 illustrate this.
The standard deviation for the experimental and theoretical hydrogen consumption curve is very small
due to the fact all data recorded was done by the sensors connected to the computer system. Therefore
the error associated with this is random and deviation from the mean is very small. Standard deviation
values for theoretical heat quantity data are conspicuously larger than the rest (Table 4). This is
because of the propagation of error due to different instrumentation used to measure flow-rate of
water in the cooling system, inlet and outlet temperatures.
Table 4: Standard deviation with respect to theoretical and experimental hydrogen consumption and heat quantity

Average Stack Current (A) Experimental H2 Consumption (L/min) Standard Deviation
7.66 1.20 0.78
13.34 2.13 0.09
18.68 2.95 0.74
23.92 3.81 0.73
28.93 4.64 0.66
Average Stack Current (A) Theoretical H2 Consumption (L/min) Standard Deviation
7.66 1.28 0.04
13.3 2.23 0.04
18.7 3.13 0.02
23.9 4.01 0.01
28.9 4.84 0.01
Average Stack Current (A) Experimental Average Heat (W) Standard Deviation
7.66 40 0.77
13.3 193 2.3
18.7 274 2.4
23.9 366 2.3
28.9 453 1.7
Current Output (A) Theoretical Average Heat (W) Standard Deviation
7.66 43 8.3
13.3 197 7.9
18.7 278 7.4
23.9 369 7.0
28.9 456 7.3


5. Discussion of Results
5.1. Mass balance analysis
The mass balance performed over the fuel stack shows a small discrepancy between experimental and
calculated hydrogen consumption data, of which calculated values are greater than empirical values.
This difference is at least 4.5% at high average stack current and at most 7.1% at low average stack
current. One of the advantages of a PEM hydrogen fuel cell is a quick start up. The data in Table 1
suggests that given enough time the difference between experimental and calculated hydrogen
consumption decreases. This trend leads to an interesting question: how quickly does the fuel cell
respond to abrupt changes in external current settings?
Figure 3 illustrates that one hundred per cent conversion of hydrogen was a huge assumption.
According to (Barbir, 2005), this is a three phase boundary problem, since protons, platinum
catalyst metal and carbon all have to be in contact for a reaction to occur. This notion is also highly
supported by Zhan et al (2007) who emphasize the importance of the internal mechanisms of the fuel
stack with regard to performance.
It is clear that the performance of the fuel cell is highly affected by the delivery of hydrogen to the
stack via controls such as the flow meter. However, instead of focusing on the instrument itself (flow
meter) and any of its intrinsic errors, it is more engaging to think about the effect of increasing the
partial pressure of hydrogen and oxygen on fuel cell performance. Song et al (2007: 2552-2561) show
in their study that the higher the pressure the higher the performance of the fuel cell.
Another reason for the difference between theoretical and experimental hydrogen consumption are
competing reactions that occur at the oxygen electrode: oxidation of the platinum, corrosion of
carbon support, and oxidation of organic impurities on the electrode Srinivasan et al (1993: 39).
5.2. Energy balance analysis
Figure 4 shows that theoretical heat quantity is slightly greater than experimental heat quantity. The
graph also depicts an almost dismissible difference between the theoretical and experimental heat
quantity values as stack current increases. Table 2 illustrates the extent and rapidity at which
experimental heat quantity approaches theoretical heat quantity. The difference between the compared
quantities drops from 8.6% to a very low 0.7% as average stack current increases. According to a
formidable case study by Song et al (2007: 2552-2561), the fuel cell performance in low current
density increases with increasing temperature from 23C to 80C.
5.3. Polarization Curves
Figure 5 shows that within low current density range, the Butler-Volmer equation models the
electro-chemical kinetics of the hydrogen fuel cell appreciably. Comparing the shape of the
two polarisation curves plotted in Figure 5, with the polarisation curve at room temperature in
Figure 1, shows that the trend is correct.
The theoretical polarisation curve intersects the cell potential axes at 0.95V, which is the
potential per cell at a zero current density reading. The empirical polarisation curve intersects
the cell potential axes at 0.78V. The theoretical zero current reading per stack is 22.8V,
whilst the experimental zero current reading per stack is 18.7V.


The potential per cell at zero current density is called the open circuit potential. In practice
the experimental open cell potential is significantly lower than the theoretical potential
because there are some voltage losses in the fuel cell even when no external current is
generated. Under closed circuit conditions with a load, the potential is expected to drop even
further as a function of current being generated due to voltage losses caused by activation and
Ohmic over potentials (Fuel cell basics).This is the reason why the empirical data curve is
below the theoretical data curve.
The experiment was conducted in the range of low to medium current density, so the
degradation of the three dimensional phase boundary and the oxidation of some platinum
catalyst sites may be the reason for the voltage losses. These problems at the reaction sites
lead to higher activation energies for the reactions within the fuel cell (Sepa et al, 1984:
1169).
5.4. Power Curve
In the HP600 fuel cell system, 24 fuel cells are stacked to multiply the power.
The minimum potential for the HP600s hydrogen fuel cell stack is constant; therefore it is current
that directly affects the power output. The power curve peaks at high current density. The peak is not
depicted in the graph above because the departments fuel cell is programmed to shut down before the
mass transfer region is entered. Shut down occurs below 0.6V per fuel cell, which means the stack is
operating at 14.4V at 26A. Figure 1 shows that the fuel cell, unrestrained, has a power density curve
that peaks at high current density values.



6. Conclusion
The results from the mass balance reveal that the hydrogen fuel cell does not have a hundred per cent
conversion of hydrogen into protons and electrons. This is not only the case for old fuel cell
equipment but this also applies to newly manufactured fuel cells. As aforementioned, literature states
that absolute steady state can never be reached as a consequence of sluggish electrode kinetics or the
three phase boundary problem. Therefore, in order to measure the performance of the fuel cell by
using a mass balance we need to compare the current mass balance data with hydrogen consumption
data as at factory settings. Only then will we be able to ascertain to what extent the electrode and
catalyst sites have deteriorated. It is not a plausible argument to make the conclusion that the fuel cell
is not operating properly purely on the basis that there is a small difference (less than 8%, see Table 1)
between theoretical and experimental hydrogen consumption. Therefore, instead of saying that the
mass balance reveals that the hydrogen fuel cell is not working according to manufacturers
specifications, it is more prudent to make the assertion that the fuel cell is working properly but
subject to constraints that are a function of the intrinsic property and state of the internal fuel cell
equipment.
The energy balance shows empirical data approaching theoretical data as time increases (see Table 2).
The fuel cell set-point temperature at the beginning of the experiment was set to 30C, however, the
computer showed that the fuel cell temperature was slowly and gradually increasing with time. By the
end of the experiment the temperature was above 35C. The increase in temperature was due to
intrinsic and extrinsic factors affecting the fuel cell. From the time of fuel cell start-up, as operation
time increases, the fuel cell stack starts to heat up due to the co-generation of current and heat.
Internal resistances increase as current density increases; these Ohmic resistances also generate heat.
Extrinsically, an increase in the temperature of the surroundings could also take its toll, but to a very
small extent. As earlier mentioned in the discussion, increasing temperature improves fuel cell
performance. This is the reason why the experimental data approached theoretical data as close as
0.7% at the highest current density (see Table 2). The water-cooling system was designed to keep the
fuel cell set-point temperature constant. The cooling system may be faulty or failing to keep up. The
former, being highly improbable since a faulty cooling system would lead to run-away temperatures.
A refrigerant based cooling system can be recommended for the latter case.
The Butler-Volmer equation models the electro-chemical processes within the fuel well. Polarisation
curves plotted (Figure 5) are similar to those found in literature (Figure 1) for low to medium current
density values. As predicted by theory, the empirical curve is below the theoretical curve because of
voltage losses in the fuel cell even when no current is running and furthermore, losses due to
activation and Ohmic over potentials as current density increases. A good look at the chemistry shows
that these loses is unavoidable. There are irreversible losses in energy conversion due to entropy
generation, mass transfer of reactants into catalytic pores and internal resistances.
The power density curve in Figure 6 is expected to have a maximum but because the fuel cell is
programmed to shut down below 0.6V (per cell); the curve is truncated as it approaches its peak. The
power output of the HP600 hydrogen fuel cell is therefore 374V instead of 600V.
It is clear that the hydrogen fuel cell is not operating at optimal performance. The problem though is
not so much a faulty hydrogen fuel cell, but rather internal design and technological constraints
affecting the fuel cell.



7. References

1. Barbir, F., 2005, PEM Fuel Cells, 1
st
ed. Elsevier Academic Press, San Diego, pp. 17-
25, pp. 33-38.
2. Miansari, Me., Sedighi, K., Amidpour, M., Alizadeh, E., & Miansari, Mo., 2009,
Experimental and thermodynamic approach on proton exchange membrane fuel cell
performance, Journal of Power Sources, 190(2), pp. 356-361.
3. Song, C., Tang, Y., Lu, J., Zhang, J., Wang, H., and Shen, J., 2007, PEM fuel cell
reaction kinetics in the temperature range of 23120
o
C, High Temperature, 52, pp.
2552-2561.
4. Srinivasan, S., Mosdale, R., Stevens, P., Yang, C., 1999, Fuel Cells: Reaching the Era
of Clean and Efficient Power Generation in the Twenty-First Century, Annual Review
of Energy and the Environment, 24, pp. 227-281.



8. Appendix
8.1. Raw Data
The raw data in this experiment is too bulky to summarize, as a result, electronic copies for group B2
are available on request.
8.2. Sample Calculations
Table from which data for Figure 3, Figure 4, Figure 5, and Figure 6 is derived.
Average
Stack Current
(A)
Average
Stack
Voltage (V)
Current
Density
(A/cm^2)
E-Er
(Per
Cell) V
Experimental
Cell Voltage
[V]
Theoretical
Cell Voltage
[V]
Power
[W]
2.23 18.76 0.0172 0.447 0.78 9.49E-01 0.32
2.27 18.70 0.0174 0.450 0.78 9.49E-01 0.33
2.57 18.56 0.0198 0.456 0.77 9.46E-01 0.37
3.36 18.19 0.0258 0.471 0.76 9.39E-01 0.47
3.68 18.08 0.0283 0.476 0.75 9.36E-01 0.51
4.01 17.95 0.0309 0.481 0.75 9.34E-01 0.55
4.43 17.80 0.0341 0.487 0.74 9.31E-01 0.61
4.56 17.75 0.0350 0.489 0.74 9.31E-01 0.62
4.84 17.65 0.0373 0.494 0.74 9.29E-01 0.66
5.30 17.51 0.0407 0.499 0.73 9.27E-01 0.71
5.91 17.33 0.0455 0.507 0.72 9.24E-01 0.79
6.66 17.12 0.0513 0.516 0.71 9.21E-01 0.88
7.41 16.93 0.0570 0.523 0.71 9.18E-01 0.97
7.95 16.80 0.0611 0.529 0.70 9.16E-01 1.03
8.45 16.69 0.0650 0.533 0.70 9.15E-01 1.08
9.66 16.43 0.0743 0.544 0.68 9.11E-01 1.22
10.69 16.23 0.0822 0.553 0.68 9.08E-01 1.33
11.99 15.97 0.0922 0.564 0.67 9.05E-01 1.47
13.16 15.78 0.1012 0.572 0.66 9.03E-01 1.60
18.10 14.97 0.1393 0.605 0.62 8.95E-01 2.08
23.09 14.29 0.1776 0.634 0.60 8.88E-01 2.54
27.91 13.73 0.2147 0.657 0.57 8.83E-01 2.95
Excel computations were as follows:
- Current density = Average stack current/ 130cm
2

- E
R
-E= 1.229-(Average Stack Voltage/24 cells)
- Experimental cell voltage (V) = Average stack Voltage/24 cells
- Theoretical cell voltage: E
cell
= E
R
[((RT)/f)*LN(i/i
o
)] where E
R
=1.23V
- P= (Average stack current * Average stack voltage)/130cm
2

The table below contains extra information used in the aforementioned excel computations:


Below is an abbreviated table showing calculation of standard deviation values for theoretical heat
values etc.:

Standard deviation for 5A current output, for example:

Table used in the calculation for experimental and theoretical hydrogen consumption:

Sample calculations for theoretical hydrogen consumption:
Theoretical hydrogen consumption= (Average stack current/Avogadros number/Electron Charge/2)*22.4*24*60.
Average Stack Current (A) Experimental H2 Consumption (L/min) Standard Deviation Theoretical H2 Consumption (L/min) Standard Deviation
7.66 1.20 0.78 1.28 0.04
13.34 2.13 0.09 2.23 0.04
18.68 2.95 0.74 3.13 0.02
23.92 3.81 0.73 4.01 0.01
28.93 4.64 0.66 4.84 0.01
Extra information
Avogadro's Number 6.02E+23
Electron Charge 1.60E-19
STP gas 22.4
Extra Information Value units
R 8.314 j/mol.k
T 303.15 k
F 96485.34 s.A/mol
Io,c 3.70E-07 A/cm2
1.00 dimensionless
Max Theoretical Voltage 1.23 V
5Amperes Theoretical Heat Deviation Deviation
2

43.65 0.27 0.07
51.27 7.89 62.23
30.34 -13.04 170.01
36.38 -7.00 49.07
51.96 8.57 73.48
44.83 1.44 2.08
58.70 15.32 234.64
38.42 -4.96 24.61
Average 43.38
sum 8266.32
N-1 119.00
SD 8.33


Energy Balance calculations:

Theoretical average heat = [Cold water flow rate (l/min) / 60]*4185.5* [Tout - Tin]

Current Output (A) Average Heat Experimental (W) Standard Deviation Average Heat Theoretical (W) Standard Deviation
7.66 40 0.77 43 8.3
13.34 193 2.3 197 7.9
18.68 274 2.4 278 7.4
23.92 366 2.3 369 7.0
28.93 453 1.7 456 7.3

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2013 Norman Mpofu (MPFNOR001)

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