Test Module P-05:

Fuel/Oxidant Composition

Objective and Scope Test Output Parameters (TOPs)

Determine the sensitivity of a PEM fuel cell stack to fuel TOPs Type
and oxidant concentrations as well as included impurities at Uav,cell calculated
Ustack measured
varying electrical load.
Ucell i measured
Test Input Parameters (TIPs) Pstack calculated

The stack can operate under nominal conditions given by - Stabilisation time and analysis time depend on the test
manufacturer or conditions of interest for the application. objective. Recommended minimum values:
The variable TIPs are the parameters under test, namely the o Stabilisation time: 40 minutes
reactant and impurity concentration and the electrical load. o Analysis time: 20 minutes
The accuracy and stability of the determined concentration - The data received is evaluated in tabular and/or
values have to be assured during the entire procedure. graphical way including mean value, standard deviation,
Variable TIPs and min. and max. deviation of variable TIPs and TOPs.
Static TIPs
Parameter Direction of Change
Variable TIPs
pfuel, pox x fuel, x ox high to low Test
Conc.Si.A.CO [ppm]
Test
I.S [A]
mean standard min. max. mean standard min. max.
DPfuel, DPox x imp point point
value deviation deviation deviation value deviation deviation deviation
low to high
lfuel, lox I 1
2
1
2
Tstack 3 3
… …

Test Procedure TOPs

U.S.AveCell [V]
Test
mean standard min. max.
The test procedure has to be adapted to the test object and point
value deviation deviation deviation
1
the test objective. The procedures regarding reactant and 2
impurity concentration slightly vary: 3
…
- If the effect of the reactant concentration is examined,
the concentration should be stepwise decreased and Data Post Processing
the electrical load should be varied at constant It is recommended to present the test profile as well as the
concentration levels. test results in figures as shown below.
- If the effect of impurity concentration is examined, the
concentration should be stepwise increased and the
concentration should be varied at constant load levels.
Additionally, the use of the reference stack voltage and
recovery phases between the test phases with
impurities is strongly recommended to assure
comparable results.

Critical Parameters and Parameter Controls

- Accuracy and stability of the investigated concentration
values have to be assured (sensors recommended).
- Dwell time and stability criterion are very sensitive
parameters for impurity studies due to a slow and
continuous poisoning effect.
- Combinations of high reactant concentration, low
stoichiometry, high dew point and/or high electrical
load are critical regarding electrode flooding.
- The concentration ranges for reactants and impurities
specified by stack manufacturer have to be considered.

Contact Stack-Test: The research leading to these results has received funding from the European
Stacktest.zsw-bw.de Union Seventh Framework Programme (FP7/2007-2013) for the Fuel Cells and
Hydrogen Joint Technology Initiative under grant n° 303445.
 Project no. 303445

Development of PEM Fuel Cell Stack Reference Test

Procedures for Industry

Test Module P-05: Fuel/Oxidant Composition

Final revised document

Version 6.0 (August 21, 2015)

Authors:
Jens Mitzel (DLR)
Piotr Piela (ICRI)
Alberto Pilenga, Thomas Malkow (JRC)
TM P-05 Fuel/Oxidant Composition

Table of Contents

1. Objective and Scope .............................................................................................................................2

2. List of Quantities...................................................................................................................................2

3. Test Equipment and Setup ...................................................................................................................3

4. Test Input Parameters (TIPs) ................................................................................................................3

5. Test Output Parameters (TOPs)............................................................................................................4

6. Test Procedure .....................................................................................................................................4

6.1. Critical Parameters and Parameter Controls.................................................................................4

6.2. Preconditioning of the Fuel Cell Stack ...........................................................................................5

6.3. Test Procedure ..............................................................................................................................5

6.3.1. Test Procedure for Reactant Concentration ......................................................................... 6

6.3.2. Test Procedure for Impurity Concentration .......................................................................... 7
7. Data Post Processing ............................................................................................................................8

8. Appendix............................................................................................................................................ 11

8.1. Procedure Adaption for Single Cell Measurements ................................................................... 11

8.2. Recommended Ranges for Test Parameters .............................................................................. 11

8.3. Linkage to Endurance Testing..................................................................................................... 12

8.4. Efficiency Calculation.................................................................................................................. 12

8.5. Differences to Existing Procedures............................................................................................. 12

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TM P-05 Fuel/Oxidant Composition

1. Objective and Scope

The Test Module P-05 entitled “Fuel/Oxidant Composition” is a testing procedure to characterise the
influence of the reactant composition on the single cell voltages, the stack voltage, and the electrical
stack power output at different electrical load levels. The reactant composition includes fuel and
oxidant as well as impurity concentrations. The target of this Test Module is to measure the influence
of reactant and impurity concentration on the stack performance.

2. List of Quantities

Symbol Sensor/actuator nomenclature Unit Parameter name

pfuel Fuel pressure stack outlet anode kPaabs p.So.A
pox Oxidant pressure stack outlet cathode kPaabs p.So.C
lfuel Fuel stoichiometry stack anode - Stoic.S.A
lox Oxidant stoichiometry stack cathode - Stoic.S.C
Tstack Stack temperature defined by temperature stack inlet °C T.Si.CL
coolant liquid
DPfuel Fuel dew point temperature stack inlet anode °C DPT.Si.A
DPox Oxidant dew point temperature stack inlet cathode °C DPT.Si.C
RHfuel Fuel relative humidity stack inlet anode % RH.Si.A
RHox Oxidant relative humidity stack inlet cathode % RH.Si.C
I Electrical stack load A I.S
i Stack current density A cm-2 Idens.S
xfuel Hydrogen concentration stack inlet anode Vol.-% Conc.Si.A.H2
xox Oxygen concentration stack inlet cathode Vol.-% Conc.Si.C.O2
ximp,a Impurity concentration stack inlet anode (i.e. CO) ppm Conc.Si.A.CO
ximp,c Impurity concentration stack inlet cathode (i.e. CO) ppm Conc.Si.C.CO
Ustack Stack voltage V U.S
Ucell i Single cell voltage of cell i V CVM.x
Uav,cell Average cell voltage V U.S.AveCell
Pstack Electrical stack output power W P.S.el
A Active geometric area of the electrode cm²

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TM P-05 Fuel/Oxidant Composition

3. Test Equipment and Setup

The required test bench equipment for parameter control and data recording is defined in the Stack-
Test Master Document (TM P-00).
Additionally, the gas concentrations have to assured for the reactants as well as the impurities. There
are two possibilities to provide the required gas feeds. On the one hand, premixed gas cylinders can
be used to avoid unsteady fuel, oxidant and impurity concentrations during the test. On the other
hand, a gas mixing unit using mass flow controllers attached to the test bench can be used. For both,
the use of concentration sensors for the reactants and the investigated impurities near to the stack
inlet is recommended.
The methanol concentration for DMFC studies can also be varied by two methods. Two tanks with
separate fluid pumps can be used. One tank shall be filled with purified water and the second with an
aqueous methanol solution in the highest concentration used for the test. Both liquids can be mixed
as desired by controlling the pumps. Alternatively, stock methanol solutions of different
concentrations can be prepared using proper analytics and fed to the stack using a precision pump.

4. Test Input Parameters (TIPs)

The static TIPs do not vary during the entire test duration and depend on the used fuel cell stack. The
stack can be operated at nominal conditions given by the manufacturer or evaluated with other
Stack-Test test procedures as well as conditions of interest for the application.
The variable TIPs are the parameters under test, namely the fuel, oxidant, and impurity
concentration as well as the electrical load.
Recommended parameter ranges, measurements uncertainties, and sampling rates for the
parameters of the test operating conditions (TOCs) are summarised in the Stack-Test Master
Document (TM P-00). The characteristics for the reactants and impurity concentrations are
summarised in the Appendix.
To achieve reproducible results, it is mandatory to vary the investigated concentrations as well as the
electrical load in a consistent manner starting with the most stable conditions. For studies regarding
the reactant concentration the test should be realised from high to low concentrations and for
studies regarding impurity concentration vice versa. The TIPs are summarised in Table 1 and
visualised in Figure 1. Static TIPs are marked in grey, variable TIPs in yellow. The white marked
parameters vary depending on other parameters (e.g. gas flow and electrical load).

Table 1: test input parameters

Variable TIPs
Static TIPs
Parameter Direction of Change
pfuel, pox x fuel, x ox high to low
DPfuel, DPox x imp
low to high
lfuel, lox I
Tstack

3
TM P-05 Fuel/Oxidant Composition

Figure 1: test input parameter positions on a PEMFC stack

5. Test Output Parameters (TOPs)

The TOPs of this test are the stack voltage and the single cell voltages (marked in black in Figure 1).
The outputs have to be recorded at the different test steps. Based on these parameters, the average
cell voltage and the electrical stack output power can be calculated. The TOPs are summarised in
Table 2.

Table 2: test output parameters

TOPs Type
Uav,cell calculated
Ustack measured
Ucell i measured
Pstack calculated

Additionally, impedance measurements can be helpful to evaluate the effect of impurities and
reactant concentration on the stack performance (see TM P-10c).

6. Test Procedure
6.1. Critical Parameters and Parameter Controls

The accuracy and stability of the investigated concentration values at the stack inlet have to be
assured and should be monitored during the test procedure. Therefore, the use of concentration
sensors is recommended. Especially, the accuracy and stability of impurities in the ppm range
prepared with the use of the gas mixing unit can be challenging and should be monitored.
The dwell time is a very sensitive parameter for studies regarding the effect of impurities due to slow
and continuous poisoning effects. Therefore, the use of a reasonable stability criterion is necessary
for these measurements.

4
TM P-05 Fuel/Oxidant Composition

The water management on both electrode sides is influenced by the reactant concentration. This has
to be taken into account for the tests. Even though the dew point at the stack inlet is constant, the
water removal capacity varies. E.g., this capacity decreases with increasing oxygen concentration
when the stoichiometry and the dew point are constant. Due to the lower resulting gas flow on the
cathode side, the risk of electrode flooding is increased.
In general, the combination of high reactant concentration, low stoichiometry, high dew point and/or
high electrical load has to be handled with care to avoid electrode flooding. Furthermore, parameter
variations with high risk of reactant starvation (low reactant concentration, fuel in particular) have to
be handled with care.
The concentration ranges for reactants and impurities specified by the stack manufacturer have to be
considered to avoid stack damage.

6.2. Preconditioning of the Fuel Cell Stack

The preconditioning of the fuel cell stack is specified in the Stack-Test Master Document (TM P-00)
and should be realised under nominal conditions given by the stack manufacturer. The
preconditioning has to be carried out considering the limits of fuel or oxidant concentration ranges
recommended by the stack manufacturer and without the use of impurities to assure a well-
conditioned stack prior to the test.

6.3. Test Procedure

The ranges for the concentration and the electrical load as well as the individual set points and the
TOCs have to be defined before the test. The set points can be chosen in a constant interval or at
special operating points. The used conditions have to be chosen considering the limit of fuel or
oxidant concentration ranges specified by the stack manufacturer. Based on these parameters the
Test Point Matrix can be prepared.
The dwell time (stabilisation time plus analysis time) for each test point is defined by the stability
criterion for the TOPs. Stabilisation time and analysis time will depend on the test objective. The
following minimum time scale is recommended, but can be adjusted to the test objective to decrease
the overall test duration:
- Stabilisation time: 40 minutes
- Analysis time: 20 minutes
- Resulting dwell time: 60 minutes
The dwell time is a very sensitive parameter for studies regarding the effect of impurities. The
impurities can cause a lowering of stack voltage that appears continuous and the dwell time can
mainly influence the results. Therefore, the voltage stability has to be monitored carefully and a
reasonable stability criterion should be adopted.
A minimum cell voltage should be defined to avoid stack damage. A value of 0.3 V is recommended
for hydrogen fed stacks and 0.2 V for DMFC stacks. This minimum cell voltage is used as an additional
end-of-step criterion.

5
TM P-05 Fuel/Oxidant Composition

6.3.1. Test Procedure for Reactant Concentration

The procedure for reactant concentration can be used to validate the influence of fuel and oxidant
dilution as well as the effect of oxygen-enriched air on the PEMFC stack performance. Thereby, the
fuel and oxidant concentration should be reduced by dilution with nitrogen and the oxygen
enrichment can be realised using mixtures of pure oxygen and air.
For example, this Test Module can be used to determine the behaviour of a stack when the hydrogen
concentration used as fuel is stepwise decreased (100, 75, 50 vol-%). Simultaneously, the load is
varied (50 and 100% of the range) to study the effect at half and full load. It is recommended to start
with the highest fuel concentration and realise additional tests with the highest concentration at the
end of the test. The resulting Test Point Matrix consists of 8 test points and is presented in Table 3.

Table 3: example Test Point Matrix for the variation of the reactant concentration

The example variation of the variable TIPs is presented in Figure 2.

Figure 2: example variation of variable test input parameters for the variation of the reactant concentration

It is recommended to vary the stack current on each concentration level rather than change the
concentration at one constant load level due to faster attainment of stack equilibrium. Thereby, the
required stabilisation time and the overall testing duration are decreased.

6
TM P-05 Fuel/Oxidant Composition

6.3.2. Test Procedure for Impurity Concentration

The procedure for reactant impurities has to start with a phase under TOCs in the absence of
impurities to determine a reference stack voltage. In the following, the different steps with
increasing impurity concentration will be realised. After each test step with impurities in the reactant
feed, a recovery step without impurities should be realised and the electrical load should be ramped
to the highest level to remove residual impurities. If needed, these steps can be prolonged after test
points using high impurity concentrations. In general, it is recommended to define a recovery
criterion. E.g., 95 % of the initial stack voltage should be recovered before the next test step is
started.
In contrast to section 6.3.1., it is recommended to vary the impurity concentration first on the lowest
load level and then increase the electrical load to continue the procedure due to the high effect of
the load level on the performance using reactants with impurities.
Finally, an additional phase under TOCs in the absence of impurities has to be used to reveal the
nature of the effect of the investigated impurity (reversible or irreversible). The voltage in this phase
will be compared with the reference stack voltage for the different load levels.

For example, this Test Module can be used to determine the behaviour of a stack when the CO level
in the fuel is varied (0, 1, 2 and 3 ppm). Simultaneously, the load is varied (50 and 100 % of the range)
to study the CO effect at half and full load. The resulting Test Point Matrix, including recovery test
points (marked by asterisk), consists of 14 test points and is presented in Table 4.

Table 4: example Test Point Matrix

The example variation of the variable TIPs is presented in Figure 3.

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TM P-05 Fuel/Oxidant Composition

Figure 3: example variation of variable test input parameters for CO tolerance tests

7. Data Post Processing

The main TIPs and TOPs should be determined from the average during the analysis time after
sufficient parameter stabilisation (stabilisation time). The stability criterion is based on the TOPs
(stack or single cell voltage) and is defined in the Stack-Test Master Document (TM P-00). It can be
adapted for studies regarding reactant impurities if needed.
The data received can be evaluated in a tabular or a graphical way. The tabular form should include
the mean value, the standard deviation as well as the minimum and maximum deviation of the main
TIPs and TOPs as shown in Table 5 for the above mentioned study regarding the CO tolerance.

Table 5: recommended tabular presentation of the test input and test output parameters
Variable TIPs
Conc.Si.A.CO [ppm] I.S [A]
Test Test
mean standard min. max. mean standard min. max.
point point
value deviation deviation deviation value deviation deviation deviation
1 1
2 2
3 3
… …

TOPs
U.S.AveCell [V]
Test
mean standard min. max.
point
value deviation deviation deviation
1
2
3
…

For the graphical evaluation, it is recommended to present the test profile as well as the test results.
Thereby, the test profile has to include the variable TIPs and the TOPs. Additionally, static TIPs with
high influence on the stack performance can be added. An example test profile for a CO tolerance
study using the recommended visualisation is shown in Figure 4.

8
TM P-05 Fuel/Oxidant Composition

Figure 4: recommended test profile visualisation

The test results should be presented as shown in Figure 5. The use of the average cell voltage is
recommended for better comparability of the results when stacks with various numbers of single
cells are used.
Regarding the use of error bars, it is recommended to insert two different types. The standard
deviation represents the variation of the average cell voltage over the analysis time and is, therefore,
an indication for the TOP stability. The min/max deviation represents the deviation between the
average cell voltage and the minimum and the maximum single cell voltage ever recorded during the
entire analysis time of a test point. It is an indicator for the stack homogeneity over the stack length
and identifies the voltage deviation of the single cells with the best and the worst performance. For a
comparative study of different stacks the plot can be too confusing when both error bars are
included. In such case, the use of standard deviation is optional, but the use of min/max deviation is
strongly recommended.

9
TM P-05 Fuel/Oxidant Composition

Figure 5: scheme of test result presentation including error bars for standard deviation (grey) as well as min/max deviation
(black)

Additional results from EIS measurements can be presented in a similar figure for a more detailed
evaluation of the concentration effect.

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TM P-05 Fuel/Oxidant Composition

8. Appendix

8.1. Procedure Adaption for Single Cell Measurements

In contrast to stacks, single cells can be assumed to be isothermal and the parameter variation from
cell inlet to cell outlet is negligible. Therefore, the scheme regarding the TIP positioning (see Figure 1)
can be simplified as shown in Figure 6.

Figure 6: test input parameter positions on a PEMFC single cell

Furthermore, the setup can be simplified by the use of an electrical heating. Due to the low thermal
output of a single cell, the required cell cooling at high load can be realised by air cooling. The use of
a liquid coolant is here optional.
It should be mentioned, that the ratio between test stand volume and reactant flow is here higher
and parameter changes (e.g. pressure variation) can require a longer stabilisation time. The use of a
pilot control for parameter changes can be necessary to avoid cell damage.

8.2. Recommended Ranges for Test Parameters

Recommended parameter ranges, measurements uncertainties, and sampling rates for the
parameters of the test operating conditions (TOCs) are summarised in the Stack-Test Master
Document (TM P-00). The recommended characteristics for the reactant and impurity concentration
are given in Table 6, including the electrode side that can be influenced by the parameter.

11
TM P-05 Fuel/Oxidant Composition

Table 6: recommended concentration ranges

Parameter Recommended Range of interest for
Hydrogen concentration 30 - 100 vol-% fuel
Methanol concentration 0.5 - 2.0 mol/L fuel
Oxygen concentration 10 - 100 vol-% oxidant
CO impurity 0 ppm - 2 vol-% fuel
NH3 concentration 0 - 50 ppm fuel / oxidant
NO2 concentration 0 - 5 ppm oxidant
SO2 concentration 0 - 5 ppm oxidant
Toluene concentration 0 - 100 ppm oxidant

The range of the CO concentration spans over a few orders of magnitude and depends on the
application as well as the test objective. Low ppm values are typical for fuel gas quality studies using
electrodes with pure Pt catalysts. High ppm up to % values are typical for reformate studies using
electrodes with CO tolerant catalysts such as PtRu.

8.3. Linkage to Endurance Testing

The use of impurities in the reactants can cause a continuous lowering of stack voltage and electrical
power output. Therefore, it is reasonable to calculate a “degradation rate” to determine the effect of
impurities on the stack performance as described in the Stack-Test Master Document (TM P-00).
Additional information given in the Test Module “TM D-01 Constant Load Durability” should be
considered.

8.4. Efficiency Calculation

The fuel cell efficiency for each parameter set point can be calculated according to the Stack-Test
Master Document (TM P-00). These calculated values can be used as additional TOPs.

8.5. Differences to Existing Procedures

SAE J2617 has defined two different test procedures for the measurement using diluted hydrogen
(6.2.3) or diluted oxygen (6.2.2), respectively. Both procedures are defined by polarisation curves
under TOCs using diluted fuel or oxidant. Thereby, the diluted oxygen is defined as a mixture of 10%
oxygen and 90% nitrogen. The hydrogen concentration in the fuel feed is varied between defined
values of 80% and 50% in nitrogen in the order of decreasing hydrogen concentration. The use of CO2
sensors is recommended to monitor the CO2 level at the cathode outlet and to avoid stack damage.
Procedures for the impact of different impurities are not defined and critical parameters are not
identified. Additionally, the summarised procedures by the SAE Fuel Cell Standards Committee only
focus on automotive applications.

12
TM P-05 Fuel/Oxidant Composition

The reactant concentration in the Stack-Test procedure is also varied in the order of decreasing
concentration. But the concentration set points are not defined by absolute values. This approach
enables the use of one document for all applications (stationary, automotive and portable).
Nevertheless, reference conditions are recommended for the different applications in the Stack-Test
Master Document (TM P-00) to assure comparable measurements by different testing facilities. In
both procedures, SAE and Stack-Test, the load is varied at constant concentration levels to assure
fast equilibration.
In contrast to the SAE procedures, Stack-Test only defines one procedure for the variation of both
reactants concentrations and impurity concentrations are also included. Furthermore, the
simultaneous variation of the load is realised by different set points and not by polarisation curves.
Due to the possibility of continuous, prolonged catalyst poisoning in the presence of impurities, this
approach enables faster measurements to minimise this effect. Nevertheless, a Test Program can be
defined using the load set points in accordance with a polarisation curve load profile (see TM P-08)
and stepwise variation of the reactant concentrations.
The critical parameters, the parameter controls and the reversibility are also pointed out in the
Stack-Test document to assure reliable measurements and to avoid stack damage.

JIS C 8832 has defined separate procedures for every impurity of interest in fuel and oxidant,
resulting in 6 procedures. They are addressed to CO (Annex E) and NH3 (Annex F) in the fuel as well as
NO2 (Annex G), SO2 (Annex H), NH3 (Annex J) and toluene (Annex K) in the oxidant. The procedures
are the same except for the different impurity concentrations. Thereby, the ranges are
recommended but the individual set points can be chosen prior to the test. Measurements with
increasing impurity concentrations are defined without simultaneous variation of the electrical load.
Furthermore, the nature of the impurity effect, reversible or irreversible, is not pointed out. There
are no procedures available for the variation of the reactant concentration and critical parameters
are not identified. In contrast to the SAE procedures, the procedure defined by the JIS committee is
focused on stationary applications.

JIS has defined different procedures for different impurities in the fuel as well as in the oxidant but
none for the reactant concentrations. In general, the procedures are identical, only the concentration
ranges vary for the different impurities. Therefore, Stack-Test has defined only one procedure and
the concentration range has to be adjusted depending on the investigated impurity, the test object,
and the test objective. Using this approach, the impact of impurities as well as reactant
concentration can be covered by one test procedure. The Stack-Test procedure also added the
possibility to vary the load simultaneously during the procedure to determine the concentration
effect at different load levels. Furthermore, the critical parameter, the parameter controls and the
reversibility are pointed out in the Stack-Test document.

13