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Different Approaches for the Determination of

Degradation Rates in PEMFC Durability Tests

P. Gazdzicki, M. Schulze, K.A. Friedrich

German Aerospace Center, Institute of Engineering Thermodynamics,

Pfaffenwaldring 38-40, 70569 Stuttgart, Germany

European Fuel Cell Technology & Applications

Conference - Piero Lunghi Conference
December 16-18, 2015, Naples, Italy
www.DLR.de • Chart 2 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Contents

• IMPACT project
• Motivation
• Durability test for automotive applications
• Voltage recovery
• Determination of irreversible degradation
• Summary
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IMPACT Project
Main Objectives:

Increased PEFC life time (>5000 h) for: Target conditions:

- dynamic conditions - power density: >1 W/cm2 @ 670 mV
- ultra low Pt-loadings (<0.2 mgPt/cm2) - reduced degradation rate (<10 μV/h)

Starting date: November 1st, 2012

End date: October 30th, 2016
Status: 38 months /48 months
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IMPACT Project
Performance achievements:

Target

Current status

0.25 mgPt/cm2

~0.60 mgPt/cm2

o Status: Increased power density at reduced loading

 improved thinner PFSA membrane
 Improved ink composition with new ionomers
o Next step: introduce beyond-state-of-the-art GDL
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Motivation
Performance targets clearly defined and well verifiable.

Determination of degradation rates is not well defined.

 How to determine if durability goals are achieved?
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Motivation
Performance targets clearly defined and well verifiable.

Determination of degradation rates is not well defined.

 How to determine if durability goals are achieved?

• j = 1 A/cm2 = const.
• Refresh interruptions

refresh steps
 www.DLR.de • Chart 7 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Motivation
Performance targets clearly defined and well verifiable.

Determination of degradation rates is not well defined.

 How to determine if durability goals are achieved?

Discrimination between reversible and irreversible degradation needed

• j = 1 A/cm2 = const.
• Refresh interruptions
 www.DLR.de • Chart 8 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Motivation
Performance targets clearly defined and well verifiable.

Determination of degradation rates is not well defined.

 How to determine if durability goals are achieved?

Discrimination between reversible and irreversible degradation needed

• j = 1 A/cm2 = const.
• Refresh interruptions

• How to determine irreversible

degradation?
• How to know if refresh procedure
leads to full recovery of reversible
losses?
www.DLR.de • Chart 9 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Durability test for automotive applications

For broader analysis use load cycle instead of constant load
• FC-DLC test according to FCH-JU StackTest project
Time Dwell Load
Step
[sec] [sec] [%]
1 0 15 0.0
2 15 13 12.5
3 28 33 5.0
4 61 35 26.7
5 96 47 5.0
6 143 20 41.7
20 min 7 163 25 29.2
8 188 22 5.0
9 210 13 12.5
1.00 A/cm2 10 223 33 5.0
Single FC-DLC cycle 11 256 35 26.7
0.84 A/cm2 12 291 47 5.0
13 338 20 41.7
14 358 25 29.2
15 383 22 5.0
0.59 A/cm2 16 405 13 12.5
17 418 33 5.0
18 451 35 26.7
19 486 47 5.0
0.26 A/cm2 20
21
533
553
20
25
41.7
29.2
22 578 22 5.0
23 600 13 12.5
0.05 A/cm2 24 613 33 5.0
25 646 35 26.7
26 681 47 5.0
0.00 A/cm2 27 728 20 41.7
28 748 25 29.2
29 773 68 5.0
30 841 58 58.3
31 899 82 41.7
32 981 85 58.3
33 1066 50 83.3
34 1116 44 100.0
35 1160 21 0.0
www.DLR.de • Chart 10 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Durability test for automotive applications

For broader analysis use load cycle instead of constant load
• FC-DLC test according to FCH-JU StackTest project
 Voltage values at different loads (pseudo pol-curves)

0.00 A/cm2
0.05 A/cm2

0.26 A/cm2

0.59 A/cm2

0.84 A/cm2

1.00 A/cm2
www.DLR.de • Chart 11 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Durability test for automotive applications

For broader analysis use load cycle instead of constant load
• FC-DLC test according to FCH-JU StackTest project
 Voltage values at different loads (pseudo pol-curves)

0.00 A/cm2
0.05 A/cm2

0.26 A/cm2

0.59 A/cm2

0.84 A/cm2

1.00 A/cm2

FC-DLC cycles
www.DLR.de • Chart 12 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Voltage Recovery
Soak time leads to significant recovery of voltage losses,
but does it lead to full a recovery?
Test bench parameter
during soak time

• Switch off load

• stop gas supply
• let cell cool down to RT
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Voltage Recovery
Soak time leads to significant recovery of voltage losses,
but does it lead to full a recovery?

Recovery due to soak time Quantification of recovery

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Voltage Recovery
Test of conditions that occur during soak time and could be the
reason for recovery

• OCV period (different times)

• low potential period, N2 purge
• reduction of Tcell (increasing RH)
• drying
• stop gas supply
• potential sweep
• purging anode with air
• test soak time duration
 www.DLR.de • Chart 15 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Voltage Recovery
Test of conditions that occur during soak time and could be the
reason for recovery
Recovery due to soak time

Potential change Humidification

• OCV period (different times)

• low potential period, N2 purge
• reduction of Tcell (increasing RH)
• drying
• stop gas supply
Drying Stopping gas supply
• potential sweep
• purging anode with air
• test soak time duration
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Voltage Recovery
Test of conditions that occur during soak time and could be the
reason for recovery

Recovery due to soak time

 Soak time duration (1 - 24 h) has little

influence
 Temporary increase of RH has largest
effect
 Combination of high RH and low
potentials similar to soak time at high
loads
 Reason for recovery at low loads unclear

Recovery by soak time could not be exceeded by any other procedure

 It is assumed that soak time leads to full recovery of reversible losses
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Determination of Irreversible Degradation

Use voltage values directly after refresh

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Determination of Irreversible Degradation

Use voltage values directly before refresh

 Large error due to different durations between refresh steps
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Determination of Irreversible Degradation

Use voltage values at e.g. 100 h after refresh

 Most promising to describe “irreversible” voltage losses
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Determination of Irreversible Degradation

• Irreversible degradation related to significant loss of ECSA on cathode

I/A
activation losses

U/V
 www.DLR.de • Chart 21 > Talk > DLR • European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference

Determination of Irreversible Degradation

• Irreversible degradation related to significant loss of ECSA on cathode

• Reversible degradation becomes faster upon operation
- Irreversible loss of surface polymer concentration in CL and MPL (XPS)

carbon

polymer
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Conclusions

o Reason for voltage recovery:

• Water management plays a role in voltage
recovery, especially at high loads
• Recovery at low load not yet explained

o Propose to use voltage loss diagrams (area specific

resistance change) instead of single value if possible

o „Irreversible“ voltage loss rate calculated at defined

times after refresh provide suitable values
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Acknowledgements

Thank you for your attention.

The research leading to these results has received funding from the European
Union’s Seventh Framework Programme (FP7/2007-2013) for Fuel Cell and
Hydrogen Joint Technology Initiative under Grant no 303452 (Impact).