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MEA & Stack Durability For PEM Fuel Cells
MEA & Stack Durability For PEM Fuel Cells
MEA & Stack Durability For PEM Fuel Cells
Mike Hicks
3M Company
May 16, 2006
Overview
Timeline
9/1/2003 6/30/2007*
70% complete
* Revised end date subject to
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
Consultant
Iowa State University
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
Approach
To develop an MEA with enhanced durability .
Optimize System Operating
Conditions to Minimize
Performance Decay
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
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
Highest Stress
Lowest Stress
Channels
Lands
Impedance (mcm2)
260 330
1330 +
Gore Primea1
400 470
1200 +
160
140
120
100
80
60
40
20
0
10
15
20
25
30
35
Tear (MPa)
180
200
40
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/ Edge Protection
8
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
132C
0.6
Fe(II) Form
Degraded Membrane
Fe(II) Form
Tan delta
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]
100
600
Conventional Wisdom:
H2O2 generated during fuel cell
operation
HO or other radicals are
attacking species
-COOH end group unzipping
primary route
Non-zero intercept
Demands other degradation
mechanism(s)
[ -COOH]
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
F3C
F2
C
F
C
F2
C
F2
C
SO3H
CF3
10
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
F2
C
F2
C
SO3H
CF3
F2
C
CF3
MC7
MC4
F2
C
F3C
F3C
OH
CF2
HO
11
CF3
CF2
CF2
CF2
2
CF
SO3H
HO
CF
CF3
5
SO3H
10
HO
F
SO3H
F
9
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
12
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0
Approach
Measure experimentally segmented cell
Theoretical modeling
MEA & Stack Durability for PEM Fuel Cells
13
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
0.65
0.90
1
2
3
4
5
6
7
8
9
10
11
0.24
0.95
Inlet
O2 Utilization =
0.99
0.96
0.56
0.60
0
10
15
20
Current (A)
0.20
0.31
0.16
0.12
0.08
0.04
0.00
Inlet
14
25
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
1.02
0.6
0.8
15
70
0.8
50
Stack DC voltage
0.6
System Efficiency
Cell Ratio
40
0.4
30
20
System Restarts
60
0.2
10
0
0
100
200
Run Hours
300
400
0
500
16
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
.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
0.5
I (A/cm2)
0.5
I (A/cm2)
I (A/cm2)
100
200
500
1000
10^02
10^03
10^04
10^05
10^06
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)
Time
18
19
Project Summary
Relevance:
Approach:
Two phase approach (1) optimize MEAs and components for durability
and (2) optimize system operating conditions to minimize performance
decay.
Progress:
Accelerated Lifetime
Predictions (hrs)
FY 05
FY 06
DOE 2010
Goal (hrs)
16,000
> 20,000
40,000
Future Work:
20
21
22
23