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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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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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• 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)


(from systems)WP2 –

Experiments under real operating

conditions

(systems, stacks & single cell real

ageing tests)

WP2 –Experiments under

real operating conditions


ageing tests)


methodology

(SC specific tests: coupling,

validation, Acct)


methodology


validation, Acct)


(Ex-situ characterizations, locally resolved analysis)




mechanistic model

+ MEA & cell model


mechanistic model

+ MEA & cell model


(from systems)


(from systems)WP2 –

Experiments under real operating

conditions


ageing tests)

WP2 –Experiments under

real operating conditions


ageing tests)


methodology


validation, Acct)


methodology


validation, Acct)






mechanistic model

+ MEA & cell model


mechanistic model

+ MEA & cell model

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• 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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• Ageing studies


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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• 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



Anode Catalyst Cabot Dynalyst 62RKR4 1.8 mg PtRu/cm2


Cathode Catalyst Cabot Dynalyst 65KR2 1.2 mg Pt/cm2


XL

LT PEM 5-layer Reference MEAs



Anode Catalyst Hispec 10000 0.3 mg PtRu/cm2


Cathode Catalyst Hispec 9100 0.5 mg Pt/cm2


DMFC 5-layer Reference MEAs



Anode Catalyst Cabot Dynalyst 62RKR4 1.8 mg PtRu/cm2


Cathode Catalyst Cabot Dynalyst 65KR2 1.2 mg Pt/cm2


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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• Characterizations for degradation investigation and quantification


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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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


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

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cat.

an

.an

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cat.

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cat.

an

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cat.

an

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cat.

an

.

cat.

an

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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

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ca

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an

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ca

t.

an

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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


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


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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• 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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• 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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•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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• 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

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