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!Premium Act
Programme Review Day 2012 - Brussels, 28 & 29 November
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PREdictive Modelling for Innovative Unit Management and ACcelerated Testing
procedures of PEFC
(256776)
Sylvie Escribano CEA
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• Duration: from 03/2011 to 02/2014
• Total budget: 5 370 190 € - FCH contribution: 2 513 251 €
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Programme Review Day 2012 - Brussels, 28 & 29 November
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1. project & partnership description
Improvement of stationary PEFC systems durability (40000h required!)
A reliable method to predict system lifetime, benchmark components and improve operating strategies
WP6 - Dissemination WP7 - Management
WP1 - Specifications
WP2 – Experiments under real operating
conditions
WP5 – Lifetime prediction
methodology
WP3 – Quantification of components degradation
WP4 – Predictive Modelling
IRD
IRD
DLR POLIMI
CEA
CEA CEA
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Programme Review Day 2012 - Brussels, 28 & 29 November
• Technical aspects
Two fuel cell stack technologies for stationary power applications:
DMFC and H2 reformate PEMFC CHP systems
Experimental investigation
Tools to quantify & correlate performance and components degradation to operating conditions
Multi-physics modelling
Tools to combine degradation phenomena and analyse their global impact on durability
• Expected achievements
Operating strategies, enhancing lifetime of given MEAs in given stack and system
Design of a lifetime prediction methodology based on coupled modelling and composite accelerated tests experiments (ranking of selected MEAs in real conditions and then following accelerated tests)
Premium Act/2 1. Project objectives & Approach
WP1 – Specifications
(from systems)
WP1 – Specifications
(from systems)WP2 –
Experiments under real operating
conditions
(systems, stacks & single cell real
ageing tests)
WP2 –Experiments under
real operating conditions
(systems, stacks & single cell real
ageing tests)
WP5 – Lifetime prediction
methodology
(SC specific tests: coupling,
validation, Acct)
WP5 – Lifetime prediction
methodology
(SC specific tests: coupling,
validation, Acct)
WP3 – Quantification of components degradation
(Ex-situ characterizations, locally resolved analysis)
WP3 – Quantification of components degradation
(Ex-situ characterizations, locally resolved analysis)
WP4 – Predictive Modelling
mechanistic model
+ MEA & cell model
WP4 – Predictive Modelling
mechanistic model
+ MEA & cell model
WP1 – Specifications
(from systems)
WP1 – Specifications
(from systems)WP2 –
Experiments under real operating
conditions
(systems, stacks & single cell real
ageing tests)
WP2 –Experiments under
real operating conditions
(systems, stacks & single cell real
ageing tests)
WP5 – Lifetime prediction
methodology
(SC specific tests: coupling,
validation, Acct)
WP5 – Lifetime prediction
methodology
(SC specific tests: coupling,
validation, Acct)
WP3 – Quantification of components degradation
(Ex-situ characterizations, locally resolved analysis)
WP3 – Quantification of components degradation
(Ex-situ characterizations, locally resolved analysis)
WP4 – Predictive Modelling
mechanistic model
+ MEA & cell model
WP4 – Predictive Modelling
mechanistic model
+ MEA & cell model
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Programme Review Day 2012 - Brussels, 28 & 29 November
• Ageing studies
Premium Act/2 1. Technical Accomplishments and Progress
4 Ballard Mark9SSL (110 cells)
Operating condition
tests according to CHP power profiles
t
I 400mA/cm²
18h
65mA/cm²
6h
DMFC systems
Field tests: IRD 1/2-1 KWDC
H2 65 %CO2 22 %CO 5 ppmCH4 3 %N2 10 %
fuel composition effect (CO, CO2, Air bleed)
Average cell degradation rate ~ 10µV/h @ 40A
conditions for DMFC SC tests
Aged DMFC MEAs for analyses Conditions and protocols for PEMFC single cells and stack tests ( aged PEMFC MEAs for analyses)
ICI
IRD
Soprano PEMFC systems
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Programme Review Day 2012 - Brussels, 28 & 29 November
• Ageing studies
Premium Act/2 1. Technical Accomplishments and Progress
DMFC MEA DURABILITY TEST [01]
Tcell = 75°C, lAir = 3.0, lCH3OH = 4.0, 1.0 M CH3OH
y = -0.0000118x + 0.4293912
R2 = 0.9144703
0.00
0.25
0.50
0.75
1.00
0 2,500 5,000 7,500 10,000
Hours @ 0.2 A/cm2
U [
V]
/ H
FR [W
/cm
2 ]
Voltage OCV HFR
High Frequency Resistance (HFR): y = 1.0E-0.7 * X + 0.1134
DMFC stack and single cells
Methodologies to analyse temporary and permanent degradation for stationary or cycling operation
Testing of refresh procedures Operating strategies to reduce temporary or overall degradation rate
Further interpretation of refresh procedures vs. temporary and permanent degradation
Development and application of other protocols and operating strategies
IRD
&
POLIMI
Cell voltage degradation for DMFC stack long term operation (< 12µV/h)
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Programme Review Day 2012 - Brussels, 28 & 29 November
Premium Act/2 1. Technical Accomplishments and Progress
• Ageing studies
@Imax= 89µV/h
@Imin= 30µV/h
PEMFC stack and single cells
LT PEM 5-layer Reference MEAs
Description Product ID Catalyst loading
Anode GDL Sigracet 35DC
Anode Catalyst Hispec 10000 0.3 mg PtRu/cm2
Membrane Nafion® N212CS
Cathode Catalyst Hispec 9100 0.5 mg Pt/cm2
Cathode GDL Sigracet 35DC
DMFC 5-layer Reference MEAs
Description Product ID Catalyst loading
Anode GDL Sigracet 35DC
Anode Catalyst Cabot Dynalyst 62RKR4 1.8 mg PtRu/cm2
Membrane Nafion® N115CS
Cathode Catalyst Cabot Dynalyst 65KR2 1.2 mg Pt/cm2
Cathode GDL Sigracet 35DC
XL
LT PEM 5-layer Reference MEAs
Description Product ID Catalyst loading
Anode GDL Sigracet 35DC
Anode Catalyst Hispec 10000 0.3 mg PtRu/cm2
Membrane Nafion® N212CS
Cathode Catalyst Hispec 9100 0.5 mg Pt/cm2
Cathode GDL Sigracet 35DC
DMFC 5-layer Reference MEAs
Description Product ID Catalyst loading
Anode GDL Sigracet 35DC
Anode Catalyst Cabot Dynalyst 62RKR4 1.8 mg PtRu/cm2
Membrane Nafion® N115CS
Cathode Catalyst Cabot Dynalyst 65KR2 1.2 mg Pt/cm2
Cathode GDL Sigracet 35DC
XL
H2 inlet
Air inlet
Single Cell - Reformate
H2: 79% CO2: 20% CH4: 1,3% CO: 26 ppm
Stfuel 1,2 Stair 2 P = 1,2 bar RHfuel 100% RHair 50% or 40% Tfuelcell : 75°C
SC voltage / load cycles high performance degradation rate
-1
-0,8
-0,6
-0,4
-0,2
0
0,2
0,4
0,6
0,8
0 0,2 0,4 0,6 0,8
U(V)
I(A
)
CV CAT BoT
CV CAT EoT
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
0 200 400 600 800 1000 1200 1400
i(mA/cm²)
U(V
)
75°C 100/40%RH 1.2b H2 pur
75°C 100/40%RH 1.2b H2 pur 1000h-2
75°C 100/40%RH 1.2b H2 reformé
75°C 100/40%RH 1.2b H2 reformé 1000h
but low permanent degradation of components properties (EoT diagnostics)
0
0,005
0,01
0,015
0,02
0 0,01 0,02 0,03 0,04 0,05 0,06
Re (Z)
- Im (Z)
1A reformate 1000h
1A H2 1000h
1A H2 BoT
Interpretation to be completed [ex-situ local observations & measurements] - Development and application of other protocols (incl. coupling higher [CO] & cycles) and operating strategies
Stack - Pure H2
Electrochemical diagnostics cell by cell
10 cells voltages during imin/imax load cycles
BoT H2 BoT reformate EoT H2 EoT reformate
CEA
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Programme Review Day 2012 - Brussels, 28 & 29 November
• Characterizations for degradation investigation and quantification
Premium Act/2 1. Technical Accomplishments and Progress
Vertical & lateral Chemical mapping Electron microscopy observations
Cathode:
C-Fiber Paper
Cathode: MPL
ATR IR (C-F bonds) macroscopic PTFE & ionomer distribution in the new and aged PEFC and DMFC electrode layers
Cathode: CL
Raman microscopic PTFE and C distribution of GDLs
XPS atomic concentrations of elements
Fresh PEMFC MEA
Anode (PtRu) Cathode (Pt)
SEM General aspect of the membrane and MEA
FEG-SEM Active layer structure
TEM + ulramicrotomy catalyst layer and particles
DLR CEA
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Programme Review Day 2012 - Brussels, 28 & 29 November
85 80 75 70 650.0
0.5
1.0
500 490 480 470 460 450
1.0
1.5
500 490 480 470 460 450
1.0
1.5
85 80 75 70 650.0
0.5
1.0
x10
Pt4f
Etch Time [s] 0
120
240
1140
2040
2940
4740
0.05 +/- 0.02 at%
Ru3p
CATHODE
(outlet)
ANODE
(outlet)
10
3 C
ounts
/s
0.0 at%
0.44 +/- 0.09 at%
Ru3p
10
3 C
ounts
/s
Binding Energy [eV]
0.40 +/- 0.06 at%
Pt4f
0
120
240
1140
2040
2940
4740
Binding Energy [eV]
AGED Micro Porous Layer (IRD-AALE cell6)
• Characterizations for degradation investigation and quantification
Premium Act/2 1. Technical Accomplishments and Progress
Fresh PEMFC MEA Cycled PEMFC MEA
85 80 75 70 650.0
0.5
1.0
500 490 480 470 460 4500.0
0.5
1.0
500 490 480 470 460 450
0.5
1.0
85 80 75 70 650.0
0.5
1.0
0.11 +/- 0.06 at%
Pt4f
Etch Time [s]
0
1800
3600
0.0 at%
0.0 at%
Ru3p
CATHODE
ANODE
10
3 C
ounts
/s
Ru3p
10
3 C
ounts
/s
Binding Energy [eV]
x10
0.14 +/- 0.06 at%
Pt4f
0
1800
3600
5400
Binding Energy [eV]
VIRGIN Micro Porous Layer (IRD-AB2F)
XPS detection of Ru cathode side
No main modifications : membrane not damaged, active layer structure similar to non aged
Analysis of other aged samples from stack and single cell DMFC & PEMFC
Impact of the testing conditions on the components degradation
Vertical & lateral Chemical mapping Electron microscopy observations DLR CEA
Aged DMFC stack (fuel starvation)
0
10
20
30
cat.
an
.
an
.
cat.
Reference
Inlet
Flow Field
Outlet
an
od
e
CCMMPL
IR P
eak A
reas o
f P
TF
E o
r N
afion
GDL
an
.
cat.
cath
od
e
cath
od
e
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
an
.
cat.
aged MEA
AALE - Cell 6
0
10
20
30MEA
ca
t.
an
.
Inlet
Flow Field
Outlet
ca
tho
de
an
od
e
CCMMPL
IR P
eak A
reas o
f P
TF
E o
r N
afion
GDL
an
.
ca
t.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.a
n.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
an
.
ca
t.
AB2F - Reference
IR-ATR changes due to ageing mainly in the CCMs
NA NA NA Aged Aged
Aged
NA Aged
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• Degradation models
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1. Technical Accomplishments and Progress
POLIMI
0,0 2,0x105
4,0x105
6,0x105
8,0x105
1,0x106
0,0
0,2
0,4
0,6
time / s
0.1A/cm²
0.2A/cm²
0.3A/cm²
0.4A/cm²
ce
ll vo
lta
ge
/ V
DLR
0 1x105
2x105
3x105
4x105
5,0x10-6
1,0x10-5
1,5x10-5
2,0x10-5
2,5x10-5
3,0x10-5
3,5x10-5
dis
tance fro
m m
em
bra
ne
in a
node C
L / m
t / s
0,00E+002,45E-034,90E-037,35E-039,80E-031,23E-021,47E-021,71E-021,96E-02
Ruthenium
volume fraction
Effect relevant mainly at high i
Water fluxes description
Ru-dissolution occurs first close to mb
Simulation of the flooding effect
DMFC cell modeling
Simulated __ and measured o water fluxes at cathode outlet
To be validated Evolution of physical parameters to be integrated for DMFC
degradation modelling
• Detailed basic model developed basis for degradation studies (transient behaviour, EIS)
• Degradation mechanism implemented • Dev of electrochemical impedance model
coupling phenomena interpretation
• Single cell model (incl. water transport)
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Degradation à I=0.6A/cm^2
0
100
200
300
400
500
600
0 200 400 600 800 1000 1200 1400 1600 1800
Temps (h)
Te
ns
ion
(m
V)
0.00E+00
5.00E+06
1.00E+07
1.50E+07
2.00E+07
2.50E+07
3.00E+07
Su
rfa
ce
sp
éc
ifiq
ue
(m
^2
/m^
3)
U (mV)
gamma_c (m 2̂/m 3̂)
• Degradation models
Premium Act/2
1. Technical Accomplishments and Progress
PEMFC cell modeling
-1.5-1
-0.50
0.51
1.5
x 10-3
1
1.5
2
2.5
x 10-5
-2
0
2
4
6
8
10
x 108
Largeur canal+dent (m)Epaisseur couche active (m)
Densité d
e c
oura
nt
(A/m
3)
Active layer thickness
Land - Channel - Land
-1.5-1
-0.50
0.51
1.5
x 10-3
1
1.5
2
2.5
x 10-5
-2
0
2
4
6
8
10
x 108
Largeur canal+dent (m)Epaisseur couche active (m)
Densité d
e c
oura
nt
(A/m
3)
Active layer thickness
Land - Channel - Land
Global degradation of the active surface area
Amplification of the initial heterogeneities
Related Pt active area
distribution -1.5
-1-0.5
00.5
11.5
x 10-3
1
1.5
2
2.5
x 10-5
0
0.5
1
1.5
2
2.5
x 107
Largeur canal+dent (m)Epaisseur couche active (m)
Surf
ace s
pécifiq
ue (
m2/m
3)
To be correlated with experimental degradation of components and performance regarding the different conditions and protocols
Global degradation of the cell voltage
Local current density distribution
after ageing Parameters degradation estimated for each local conditions
CEA
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2. Alignment to MAIP/AIP
• Correlation of the project with the corresponding Application Area (as
mentioned in MAIP/AIP documents)
• Application area: Stationary Power Generation
• “emphasis on long-term basic research to better understand degradation/failure mechanisms and the lifetime requirements of all fuel cell stack types (SOFC, MCFC, PEMFC), for different fuels and levels of power.”
• “For lifetime predictions, research is necessary to establish methodologies as well as tools for modelling, operational controls and diagnostics.”
Topic: “Fundamentals of fuel cell degradation for stationary power application”
“Research on critical parameters and operating conditions that impact degradation and life time of cells and stacks, for all power ranges and fuel cell technologies”
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2. Alignment to MAIP/AIP
• Detailed project activities & results versus MAIP/AIP document targets
Direct link between previously described activities & targets (Cf. approach slides)
• Application - µ-CHP systems with different requirements
- 2 Fuel Cell types / fuels : DMFC (Methanol) & PEMFC (reformate)
- Power ranges: from 500W stack to 30kWe PEM CHP syst.
• Technical activities
- FC tests (system, stack and cell levels): nominal and critical conditions
- Studies of the microstructure & properties before/after ageing
- Modelling of the degradation mechanisms
Identification of main parameters enhancing degradation
Development of accelerated tests
Proposal & validation of lifetime prediction methodology
Specific degradation
mechanisms for PEFC operating with methanol and reformate
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Premium Act/3
2. Alignment to MAIP/AIP
• Identify and comment on gaps/bottlenecks in RTD&D proposed by MAIP/AIP documents
• Most topics of Premium Act are considered in the MAIP/AIP
DMFC technology is not directly included in the implementation plan whereas currently subjected to a significant commercial interest
• Comments on priorities and topics possibly under/over-estimated in the AIPs in terms of technical challenge
• For stationary applications, degradation understanding and durability improvement are the right priorities
Durability of 40000 hours: too wide requirement
more focused targets to be proposed / specific application
technical challenges to be more related to components or operating conditions constraints
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Programme Review Day 2012 - Brussels, 28 & 29 November
•Training and Education
• Post-doctoral researchers, PhD and MSc students involved in activities at CEA, DLR & POLIMI
• Polimi personal exchange:
M. Zago DLR from 6/12 to 8/12
F. Bresciani IRD Fuel Cell 8/12 to 10/12
• Safety, Regulations, Codes and Standards
• Possibility to contribute to future standards definition thanks to project outcomes on traditional and accelerated testing & on degradation models
• Dissemination & public awareness
• Journal publication: Zago, M., Casalegno, A., Santoro, C., Marchesi, R. “Water transport and flooding in DMFC: Experimental and modeling analyses”, 2012, Journal of Power Sources 217 , pp. 381-391
• Premium Act results to be presented at FC papers & conferences (incl. exhibition for indust.) (All partners) [ex: FDFC 2013]
• Premium Act workshop
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3. Cross-cutting issues
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Programme Review Day 2012 - Brussels, 28 & 29 November
• Technology Transfer / Collaborations
• Interaction with EU projects
• Use of knowledge & results from DECODE project [degradation mechanisms, modelling data, investigation methods]
• Exchanges posssible with new projects e.g. IMPACT, IMPALA, PUMAMIND… [degradation, water management, modelling]
• Interactions at national level (French, German, Italian or Danish FC projects)
• Possible exchanges and use of knowledge & results from national funded or other collaborative projects (all partners)
• Interaction with the national Real FC project : exchanges regards experimental data and testing methodology (POLIMI - Italy)
• Interactions at international level
• Possible exchanges about methodologies (for all technical aspects of testing, characterization or modelling) thanks to:
• close direct relationships with other industrial groups, institutes or universities
• involvement in international working groups (IEA, standardization bodies…)
Premium Act/5 4. Enhancing cooperation and future perspectives
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• Project Future Perspectives
• Proposed future research approach and relevance & Need/opportunities [for increasing cooperation, building alliances & for international collaboration]
• RTD topics: Emphasis on fuel/methanol purity
Development of more generic ACCT for DMFC and PEMFC
• Premium Act: balanced consortium with 3 industries developing FC systems
possible extended collaboration for further optimisation of the FC systems studied
possible extension to other industries or institutes interested in the approach
• At international level: contribution to future definition of RCS (methanol purity, degradation tests or models)
• Possible contribution to the future FCH JU Programme
• Include research and demonstration of methanol/greenfuel based fuel cells e.g. DMFC in the implementation plan.
• Recommendations for projects dedicated to specific systems development:
• Proposition of; exp./model methodology for degradation study; ex-situ investigation methods and testing protocols; validated prediction methodology
Premium Act/5 4. Enhancing cooperation and future perspectives
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Thank you for your attention