2006 DOE Hydrogen Program Review

MEA & Stack Durability

for PEM Fuel Cells
3M/DOE Cooperative Agreement
No. DE-FC36-03GO13098
Project ID # FC8

Mike Hicks
3M Company
May 16, 2006

This presentation does not contain any proprietary or confidential information

Overview
Timeline

Barriers & Targets

9/1/2003 6/30/2007*
70% complete
* Revised end date subject to

A. Durability: 40k hrs

Team Members

DOE approval

Plug Power
Case Western Reserve
University
University of Miami

Budget
Total $10.1 M
DOE $8.08 M
Contractor $2.02 M
Funding received in
FY05: $2.43 M
Funding for FY06:
$2.60 M

MEA & Stack Durability for PEM Fuel Cells

Consultant
Iowa State University

3 Fuel Cell Components

Objectives
Develop a pathway/technology for stationary PEM fuel cell systems for enabling
DOEs 2010 objective of 40,000 hour system lifetime to be met
Goal: Develop an MEA with enhanced durability
Manufacturable in a high volume process
Capable of meeting market required targets for lifetime and cost
Optimized for field ready systems
2000 hour system demonstration

Focus to Date
MEA characterization and diagnostics
MEA component development
MEA degradation mechanisms
MEA nonuniformity studies
Hydrogen peroxide model
Defining system operating window
MEA and component accelerated tests
MEA lifetime analysis
MEA & Stack Durability for PEM Fuel Cells

3 Fuel Cell Components

Approach
To develop an MEA with enhanced durability .
Optimize System Operating
Conditions to Minimize
Performance Decay

Optimize MEAs and

Components for Durability

Utilize proprietary 3M Ionomer

Improved stability over baseline ionomer
Utilize ex-situ accelerated testing to age MEA components
Relate changes in component physical properties to changes in MEA
performance
Focus component development strategy
Optimize stack and/or MEA structure based upon modeling and
experimentation
Utilize lifetime statistical methodology to predict MEA lifetime under normal
conditions from accelerated MEA test data

MEA & Stack Durability for PEM Fuel Cells

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Accomplishments
GDL Characterization
Developed new test equipment to measure capillary pressure in GDLs
Membrane
Completed investigation of reinforced membranes reinforcement may not be necessary
for membrane durability
Identified membrane failure mode and implemented solution to mitigate it
Ongoing monitoring of membrane properties in accelerated tests
Membrane Degradation Mechanism
Analyzed experimental and literature data more than just end group degradation
Utilized ionomer model compounds to identify likely points of attack and provide insight
into ionomer degradation mechanism
Developed initial hydrogen peroxide model to study peroxide in operating fuel cell
MEA Nonuniformity Studies
Completed 121-channel segmented cell and investigated the effects of flow rate, load
setting and GDL type; determined high gas stoichiometry yields current uniformity
Utilized theoretical 3D fuel cell model to investigate effects of catalyst, membrane and
GDL nonuniformity; determined that electrode defects result in highly, nonuniform current
distribution
System Test
Initiated Saratoga system test with a preliminary, durable MEA design
MEA Lifetime Modeling
Demonstrated that load profile affects MEA durability
Developed initial lifetime prediction model to estimate MEA lifetime relative to DOEs 2010
stationary system goals
Related initial fluoride ion to lifetime method to increase sample throughput
MEA & Stack Durability for PEM Fuel Cells

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GDL Characterization Capillary Pressure

Solution
Design your own instrument
CWRU has designed, machined and
assembled the sample holders, load cell
and strain sensor
CWRU collaborated with Porous Materials
Inc, Ithaca, NY to fabricate the instrument
PMI will integrate the syringe pump, the
press and automation

Background
Measured GDL permeability in humid and
dry air
Humid air yields lower gas permeability
Pores fill with water
Problem
Need technique to characterize water
transport in GDL pores
There are no available instruments for
measuring capillary pressures for
hydrophobic porous media

Developed an instrument for

measuring Capillary Forces in
hydrophobic GDLs
New method to characterize
GDLs

MEA & Stack Durability for PEM Fuel Cells

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Reinforced Membrane Activities

Highest Stress

Lowest Stress

Channels
Lands

Evaluation of Various Reinforcing Members

Impedance (mcm2)

Membrane Stress Model

DuPont Nafion (NR-111)1

260 330

Ion Power Nafion (N111-IP)1

1330 +

Gore Primea1

400 470

3M Cast Nafion (1000 EW)

1200 +

160
140
120
100
80
60
40

Desired Result stronger and higher

conductivity than neat Nafion

20
0

10

15

20

25

30

35

Tear (MPa)

RH Cycle Test to Evaluate Hypothesis

Test Conditions:
80C
Cycle equally between 0 and 150% RH
Time to failure
(hours)

180

Hypothesis - Need reinforcing member to carry

stress to eliminate mechanical failure or
reduce mechanical failure rate

MEA (electrode and GDL) made

with:

Lines 3M Cast Nafion Membrane

Symbols Various reinforced membranes
with 3M Ionomer

200

Neat membrane most durable

No relationship between mechanical
props and durability
Tensile test does not predict
mechanical durability
Tear resistance does not predict
mechanical durability
Less shrinking does not correlate to
more mechanical durability
What is the benefit of reinforcement?

1. Gittleman et al, Fall AIChE Meeting, October 2005.

MEA & Stack Durability for PEM Fuel Cells

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40

Mitigation of Membrane Edge Failure in Modules

Relative MEA Failure Rate

Problem
In module testing, observe infant
mortality of MEAs due to edge failure at
the membrane catalyst interface
Solution
Developed edge protection component
for MEA

Active
Area

Site of
edge
failure

120
100
80
60
40

No Failures

20

Identified MEA
failure mode
Implemented a
solution to
significantly reduce
infant mortality
failure rate

w/o Edge Protection

MEA & Stack Durability for PEM Fuel Cells

w/ Edge Protection
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3M Ionomer Membrane Properties vs Decay

Membrane Aging Procedure
Received
Membrane
H+ Form

Pre-condition w/
H2SO4 (0.1M)
70C, 1 hour

H+ Form

Ion exchange w/
H2SO4 (0.1M)

70C, 2 hours

As Received

H2O2 (0.1M)

70C, 1 hour

H+ Form

120

0.3

131C

0.2

100

Weight [%]

0.4

Aging
experiments
in progress
No change
after 125 hrs

125C

Dynamic
Mechanical
Analysis

0.5

70C, ~ 35 hours

Degraded Sample @ 125 hrs

132C

0.6

Fe(II) Form

Degraded Membrane
Fe(II) Form

Measure degraded membrane

properties over time

Tan delta

Ion exchange w/ FeSO4 (0.1M)

80

Thermal
Gravimetric
Analysis

60

40

20

0.1

0.0
20

40

60

80

100

120

140

160

180

200

300

400

500

Temperature [C]

Temperature [C]

MEA & Stack Durability for PEM Fuel Cells

100

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600

Membrane Decay Mechanism Via Model Compounds

F- generated

Conventional Wisdom:
H2O2 generated during fuel cell
operation
HO or other radicals are
attacking species
-COOH end group unzipping
primary route

208th ECS Meeting, Abstract 1195,

Los Angeles, CA, October 2005

Non-zero intercept
Demands other degradation
mechanism(s)

[ -COOH]

Investigate alternative degradation mechanism(s) via

model compounds
Utilize analytical capabilities
Better isolation of effect from different reactive sites
Age MCs via Fentons test or UV light (200 - 2400 nm @ 100W)
MC1
O
HO

O
F
C

F2
C

F2
C

CF3

HO

CF3

F
C

F2
C

MC7
F2
C

F2
C

F2
C

F2
C

SO3H

F2
C

HO

F2
C

F2
C

F2
C

SO3H

CF3

MC4
F3C

MC3

MC2

OH

F3C

MC8
F2
C

F2
C

F2
C

F2
C

SO3H

MEA & Stack Durability for PEM Fuel Cells

F3C

F2
C

F
C

F2
C

F2
C

SO3H

CF3
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Model Compounds Relative Degradation Rates

MC3 > MC1 MC2 > MC4 > MC7 & MC8
MC3

MC1
O

O
HO

MC2

F2
C

F2
C

F2
C

SO3H

>HO

O
F
C

F2
C

F2
C

CF3

HO

F
C

CF3

>

F3C

F2
C

OH

>

F3C

F2
C

F2
C

F2
C

F2
C

SO3H

MC8
F2
C

F2
C

SO3H

F2
C

F3C

F2
C

F
C

COOH containing MCs exhibit low stability

Comparison of MC3 & MC4
Is it really a reactivity effect or solubility
effect
Is there a change in reactivity hydrolysis
products?
Hydrolysis observed (by NMR) for MC1
& MC2
Need to evaluate MC7 & MC8 for
hydrolysis

F2
C

F2
C

SO3H

CF3

MEA & Stack Durability for PEM Fuel Cells

F2
C

CF3

MC7

MC4

F2
C

Identified MC1 & MC2 Reaction Products

O
C

F3C

F3C

OH

CF2

MC3 Isomer Degradation

O
1

HO

11

CF3

CF2

CF2
CF2
2

CF

SO3H

HO

CF
CF3
5

SO3H

10

HO
F

SO3H

F
9

Same degradation rate

Decarboxylation is rate determining step
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Membrane Decay Mechanism Hydrogen Peroxide Model

Objective
To define simple model to study peroxide behavior in an MEA

Equations:

d
C
= Rate of production ( electrochemical +Chemical recombination )
dt H 2O2
Ionomer degradation + catalytic disproportionation
+ Rate of consumption
+ electrochemical reduction
+ Transport through the electrode ( Diffusion +Convection )

Geometry
O2 inlet
No peroxide

Model Output
Peroxide Concentration Profile as f(L)

Peroxide to
membrane
Z=
0

0.75 V =

Z=
1

Experiments to Determine Input Parameters

1. Rate of Peroxide Production
2. Rate of Peroxide Disproportionation
Model provides insight into hydrogen peroxide
distribution in an operating fuel cell and the
degradation of ionomer by hydrogen peroxide
MEA & Stack Durability for PEM Fuel Cells

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MEA Nonuniformity Studies

Motivation - MEA Durability
Is MEA durability a function of current
distribution/uniformity?
4.5

Current Density (A/cm2)

4.0

Increasing avg. current

3.5

V. Gurau, H. Liu and S. Kakac, A Two

Dimensional Non-Isothermal
Mathematical Model for Proton
Exchange Membrane Fuel Cells, AIChE
Journal, Vol. 44 (11), pp. 2410 2422,
1998

3.0
2.5
2.0
1.5
1.0
0.5
0.0
0

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Dimensionless Channel Length

Approach
Measure experimentally segmented cell
Theoretical modeling
MEA & Stack Durability for PEM Fuel Cells

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Segmented Cell
Outlet

A B C D E F G H I J K

Voltage (V)

0.85
0.80

210 sccm O2

0.75
0.70

1000 sccm Air

0.65

50 cm2, 121 segments

Fraction of Total Current at 0.66 V
(Segment Current/Total Current)

Filled Symbols Sum of Individual Segments

Hollow Symbols Fuel Cell (Segments shorted together)

0.90

1
2
3
4
5
6
7
8
9
10
11

0.24

Validation of Cell Design

0.95

Inlet

100 sccm Air

O2 Utilization =
0.99
0.96

0.56

500 sccm Air

0.60
0

10

15

20

Current (A)

Effect of Air Flow Rate on Current Distribution

0.20

200 sccm Air

0.31

0.16
0.12

Cell design validated

Design fuel cell systems to operate
at high stoichiometry for uniformity
Recently completed 121 channel
load

0.08
0.04
0.00

Inlet

100 sccm 200 sccm

Outlet

500 sccm 1000 sccm

MEA & Stack Durability for PEM Fuel Cells

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25

MEA Nonuniformity Studies

Variables Investigated
Ionic Conductivity
Catalyst Loading
GDL Porosity
Electrode Thickness
Membrane Thickness
GDL Thickness

Collector Plate
Hydrogen

Gas channel
Gas diffusion layer
Anode catalyst layer
Membrane
Cathode catalyst layer
Gas diffusion layer

Air
y

Collector Plate

Electrode Thickness
0.7859
0.6811
0.5763
0.4716
0.3668
0.2620
0.1572
0.0524
0.6

1.1338
0.9826
0.8314
0.6803
0.5291
0.3779
0.2268
1.2
0.0756

0.2
0.1

0.6
0.4
0.2

0
1.06

0
0.2

CL +1

1.02

0.6
0.8

0.2

1.04
0.4

CL +3

1.02

0.6
0.8

0.5890
0.5105
0.4320
0.3534
0.2749
0.1963
0.1178
0.0393
0.6

0.5

0.5

0.3
0.2
0.1

0.4
0.3
0.2
0.1

0
1.06

0
0.2
1.02

0.6
1

Surface defects
resulted in highly nonuniform current
distribution

0
1.06

0
0.2

1.04
0.4

0.5890
0.5105
0.4320
0.3534
0.2749
0.1963
0.1178
0.0393
0.6

0.4

0.8

0
1.06

1.04
0.4

CL -1/2

0.8

current density

0.3

current density

0.4

current density

0.5

current density

Gas channel

1.04
0.4

CL -1

MEA & Stack Durability for PEM Fuel Cells

1.02

0.6
0.8

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Saratoga System Test First Durable MEA Testing

Objective Investigate possible interaction between system
design and durable MEA design
80

70
0.8

50

Stack DC voltage

0.6

System Efficiency

Cell Ratio

40

0.4

30
20

System Restarts

Stack Cell Ratio

Stack Voltage (V)

System Efficiency (%)

60

0.2

10
0
0

100

200

Run Hours

300

400

0
500

No negative MEA System interaction

Program approach validated
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Solid Lines
Time

Fraction Failing

Predicted
Lifetime
70C
100% RH

Fraction Failing

.5
.3
.2
.1
.05
.03
.02

Decreasing Stress

.005
.003

Censored data
No censored data

.001

.1

10^01

.05
.03
.02

New 3M
PEM MEAs

~ 4x

.01
.005
.003
.001
10

20

50

Dotted Lines
Time

.01

Baseline
MEAs

.3
.2

.7

Comparison of
MEA Designs
.7
.5

Time

Modified Load Cycle

.98
.9

Weibull distribution
Arrhenius for temp
Humidity model for RH
Class model load profiles

.98
.9

Dashed Lines

0.5

Baseline Components

Model Assumes

Constant Load Cycle

0.5

I (A/cm2)

Near-OCV Load Cycle

0.5

I (A/cm2)

I (A/cm2)

Statistical MEA Lifetime Predictions from Accelerated Test Data

100

200

500

1000

Accelerated Lifetime (Hrs)

MEA & Stack Durability for PEM Fuel Cells

10^02

10^03

10^04

Accelerated Lifetime (Hrs)

10^05

10^06

Lifetime probability distribution

Reasonable predictive values
No OCV load cycle offers ~ 13X lifetime improvement
New MEAs with 3M ionomer ~ 4x more durable
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Fluoride Ion Mapping of Accelerated Test Data

Accelerated Lifetime (Hrs)

1.0E+05

Predicted Lifetime
New 3M PEM MEAs
70C
100% RH
Hollow symbols: In-Progress

1.0E+04

R2 = 0.77
1.0E+03

R2 = 0.89

1.0E+02

R2 = 0.83
1.0E+01

1.0E+00
0.00

0.01

0.10

1.00

10.00

I (A/cm2)

Initial Fluoride Release (g/min)

0.5
0

Near-OCV Load Cycle

Time

Pathway towards ~ 20,000 hour MEA lifetime with

3M PEM MEAs under accelerated, near-OCV load
cycle test conditions
Means to increase sample throughput

MEA & Stack Durability for PEM Fuel Cells

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Future Work To the End of the Project

MEA & Stack Development & Testing

MEA Component optimization & integration 3M

Saratoga stack tests Plug Power
Complete MEA evaluation in modules/single cells Plug Power
Select Final stack and MEA design and test Plug Power/3M

MEA Degradation Studies

Peroxide model CASE
Incorporate realistic kinetic and transport parameters
Model compounds CASE
Determine degradation kinetic constants
MEA nonuniformity studies 3M/Plug/University of Miami
Determine operating conditions/MEA designs that yield current distribution
uniformity
Post mortem analysis CASE/Plug Power
Mechanical properties-morphology relationship CASE

MEA Statistical Lifetime Predictions

MEA lifetime modeling 3M/Plug Power
MEA & Stack Durability for PEM Fuel Cells

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Project Summary
Relevance:

Developing MEA and system technologies to meet DOEs year 2010

stationary durability objective of 40,000 hour system lifetime. Providing
insight to MEA degradation mechanisms.

Approach:

Two phase approach (1) optimize MEAs and components for durability
and (2) optimize system operating conditions to minimize performance
decay.

Progress:

Demonstrated pathway towards 20,000 hour MEA lifetime with 3M

PEM MEAs under accelerated near-OCV load cycle test conditions.
Initiated durable MEA-stack system tests.

Accelerated Lifetime
Predictions (hrs)

FY 05

FY 06

DOE 2010
Goal (hrs)

16,000

> 20,000

40,000

Technology Transfer/Collaborations: Active partner with CWRU, Plug Power

and the University of Miami. Presented 9 presentations and 2 papers
on work related to this project in last 12 months.

Future Work:

Complete studies on MEA degradation mechanism. Select final MEA

and stack design and test system for 2,000 hours.

MEA & Stack Durability for PEM Fuel Cells

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Publications and Presentations

M. Yandrasits, Mechanical property measurements of PFSA membranes at elevated temperatures and
humidities, 2nd International Conference on Polymer Batteries and Fuel Cells, Las Vegas, NV, June 2005.
D. Stevens, M. Hicks, G. Haugen, J. Dahn, Ex situ and in situ stability studies of PEMFC catalysts: Effect of
carbon type and humidification on degradation of the carbon, J. Electrochem. Soc., 152 (12), A2309 (2005).
D. Schiraldi and C. Zhou, Chemical durability studies of PFSA polymers and model compounds under mimic
fuel cell membrane conditions, 230th ACS Meeting, Washington, D.C., August 2005.
M. Hicks, D. Pierpont, P. Turner, T. Watschke, M. Yandrasits, Component Accelerated Testing and MEA
Lifetime Modeling, 2005 Fuel Cell Testing Workshop, Vancouver, BC, September 2005.
J. Dahn, D. Stevens, A. Bonakdarpour, E. Easton, M. Hicks, G. Haugen, R. Atanasoski, M. Debe, Development
of Durable and High-Performance Electrocatalysts and Electrocatalyst Support Material, 208th Meeting of The
Electrochemical Society, Los Angeles, CA, October 2005.
D. Pierpont, M. Hicks, P. Turner, T. Watschke, Accelerated Testing and Lifetime Modeling for the Development
of Durable Fuel Cell MEAs, 208th Meeting of The Electrochemical Society, Los Angeles, CA, October 2005
(presentation and paper).
M. Hicks, K. Kropp, A. Schmoeckel, R. Atanasoski, Current Distribution Along a Quad-Serpentine Flow Field:
GDL Evaluation, 208th Meeting of The Electrochemical Society, Los Angeles, CA, October 2005 (presentation
and paper).
G. Haugen, D. Stevens, M. Hicks, J. Dahn, Ex-situ and In-situ Stability Studies of PEM Fuel Cell Catalysts: the
effect of carbon type and humidification on the degradation of carbon supported catalysts, 2005 Fuel Cell
Seminar, Palm Springs, CA, November 2005.
D. Pierpont, M. Hicks, P. Turner, T. Watschke, New Accelerated Testing and Lifetime Modeling Methods
Promise Development of more Durable MEAs, 2005 Fuel Cell Seminar, Palm Springs, CA, November 2005.
M. Hicks, R. Atanasoski, 3M MEA Durability under Accelerated Testing, 2005 Fuel Cell Durability, Washington,
DC, December 2005.
Z. Qi, Q. Guo, B. Du, H. Tang, M. Ramani, C. Smith, Z. Zhou, E. Jerabek, B. Pomeroy, J. Elter, "Fuel Cell
Durability for Stationary Applications - From Single Cells to Systems, 2005 Fuel Cell Durability, Washington,
DC, December 2005.

MEA & Stack Durability for PEM Fuel Cells

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Response to 2005 Reviewers Comments

Need to evaluate catalyst degradation; how does catalyst degradation affect

overall MEA durability?
Reported results of commercial Pt/C catalyst durability and degradation at 2004
HFCIT Review
Project not focused on development of Pt/C catalyst; separate 3M/DOE project
focused on catalyst durability (3M NSTF catalyst)
Need additional characterization of membrane physical properties and effect of
aging on these properties
Initiated task on measuring membrane mechanical properties & morphology as a
function of aging
Need to relate effect of component improvements to overall MEA improvements.
What component improvement added most value to MEA lifetime?
Integration of components is critical in terms of obtaining good MEA durability
Considering possible patent applications
Need to work on reinforced membranes.
Have evaluated reinforced membranes; results to be presented in the future
Development out of scope of project some work done at expense to 3M
Better description of lifetime model
Using std lifetime statistical analysis techniques; see W.Q. Meeker and L.A.
Escobar, Statistical Methods for Reliability Data, John Wiley and Sons, Inc. (1998)
Need to address other targets (cost/performance) in concert with durability
Reported performance at the 2005 DOE Hydrogen Program Review
Cost not a primary objective; it is used as a metric when deciding options
Too much emphasis on fluoride ion release.
Disagree
Very strong relationship between fluoride release and MEA lifetime
MEA & Stack Durability for PEM Fuel Cells

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Critical Assumptions and Issues

Validation of lifetime model analysis method
Testing baseline samples at normal test conditions
Comparison to field test data

Increasing sample throughput of improved durability MEAs

New, durable MEAs last too long
Use initial fluoride ion release as metric (reduces test time)
Plug Power test equipment online (adds more test equipment)

Understanding role of peroxide

Initial peroxide lifetime model established

Demonstrate benefit of new, more durable MEAs

Start lifetime accelerated tests of new MEAs
Apply lifetime model to new MEAs

MEA & Stack Durability for PEM Fuel Cells

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