degradation and reliability modelling of …chemeng.uwaterloo.ca/mfowler/degradation.pdf · bol...

DEGRADATION AND RELIABILITY MODELLING OF

POLYMER ELECTROLYTE MEMBRANE (PEM) FUEL CELLS

Michael Fowlermfowler@uwaterloo.ca

Michael Fowler – University of Waterloo

OUTLINE

• Introduction to Fuel Cell Technology• Endurance Run of a Single Cell• Reliability of Fuel Cells• Voltage Degradation in PEM Fuel Cells• Modelling of PEM Fuel Cell Degradation• Conceptual Reliability Analysis a of PEM

Fuel Cell Stack

Michael Fowler – University of Waterloo

SURVEY OF FUEL CELL DEVELOPERS

• “For continuous use products, one game changer may be accelerated testing of the fuel cell. There are currently no accurate models for forecasting failure modes, which is why our products are fairly short lived. We base their lifetime on actual data we have”

• Fuel Cell Industry Report, January 2002, Vol 3, No 1., Alexander Communications Group Inc.

Michael Fowler – University of Waterloo

WHY FUEL CELLS FOR POWER GENERATION

• High Efficiency• Low Environmental Burden and Emissions• High Reliability• Flexibility of Design• Easily RefuelledBARRIERS TO MARKET ACCEPTANCE OF

FUEL CELLS• Cost• Endurance and reliability• Refuelling infrastructure and ‘supply chain’

are not in place• Public Perception of hydrogen

Michael Fowler – University of Waterloo

GOALS

• Identify key failure modes associated with PEM fuel cells

• Develop a Generalized Steady State Electrochemical Degradation Model with ageing or voltage degradation terms

• Develop a conceptual model for fuel cell stack reliability

Michael Fowler – University of Waterloo

FUEL CELL OPERATION

Michael Fowler – University of Waterloo

PEM FUEL CELL SYSTEM

Exhaust

DC AC Power

Fuel: Natural Gas, Synthesis gas, landfill gas,

distillate, methanol, propane

Fuel Processor and Gas Clean-up

Hydrogen Rich Gas

Water

Fuel Cell Stack

Power Conditioner

Co-generationHeat

Exhaust

Energy

Air

AirExhaust

Michael Fowler – University of Waterloo

FUEL CELL HARDWARE

Michael Fowler – University of Waterloo

FUEL CELL TEST STATION

Michael Fowler – University of Waterloo

Labview VI – Monitoring System

Ideal and Actual Fuel Cell Voltage/Current Characteristics

0

0.2

0.4

0.6

0.8

1

1.2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Current Density (A/cm2)

Pot

entia

l (V

olta

ge)

0

5

10

15

20

Pow

er (w

atts

)

Polarization Curve (Operation Voltage)

Theoretical EMF or Ideal Voltage (open circuit voltage)

Region of Ohmic Polarization(Resistance Loss)

Region of Activation Polarization(Reaction Rate Loss)

Higher EfficiencyLarger Cell

Total Loss

Region of Concentration Polarization

(Gas Transport Loss)

Michael Fowler – University of Waterloo

VOLTAGE DEGRADATION CURVE FOR A SINGLE PEM CELL

(Operated at 80°C, 0.4 amp cm-2, 30 psig/30 psig, H2/Air – stoichiometric ratios 1.2/2)

0.000

0.100

0.200

0.300

0.400

0.500

0.600

0.700

0.800

0 200 400 600 800 1000 1200

Age (Hours)

Vol

tage

(V

olts

)

Michael Fowler – University of Waterloo

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

1200 1250 1300 1350 1400 1450 1500

Age (Hours)

Vol

tage

(V

olts

at

0.4

Am

ps/c

m2 )

Voltage Performance at End of Life

Michael Fowler – University of Waterloo

RELIABILITY JARGON

• Durability - ability to resist permanent change in performance over time, i.e. degradation or irreversible degradation. This phenomena is related to ageing.

• Reliability - The ability of an item to perform the required function, under stated conditions, for a period of time. Combination of degradation, and failure modes that lead to catastrophic failure.

• Stability - recoverable function of efficiency, voltage or

current density decay or reversible degradation.

Failure of the plate

Michael Fowler – University of Waterloo

E-TEK MEA

Michael Fowler – University of Waterloo

E-TEK MEA

Smooth, unbroken and even carbon fibres on gas diffusion layer.

Polymer and impregnation and no debris can be seen.

Michael Fowler – University of Waterloo

ENDURANCE TESTED MEA

Polymer Deposit Seenthrough-out Electrode

Debris seen in variousLocation. Likely sealoxidation products.

Michael Fowler – University of Waterloo

Seal Oxidation

Michael Fowler – University of Waterloo

SCORCHING ALONG THE EDGE

Michael Fowler – University of Waterloo

SCORCHING

Michael Fowler – University of Waterloo

SUMMARY OF OBSERVED FAILURE

Tear onDisassembly

Oxidation ofSeals can beseen on MEA

Flow Path can be seenimprinted on carboncloth. Morepronounced when wet.

Discolouration onEdge

Tear or Burn-throughon the edge of activeregion

Michael Fowler – University of Waterloo

FMEA OF A FUEL CELL

• Plate– Cracking – Scorching – Change in the Plate which will impact the MEA

• Dimensional changes (warping, erosion, misalignment) • Contamination or debris released

• Seal Failure• MEA

– Pinhole Formation– Shorting – Degradation of Voltage

Michael Fowler – University of Waterloo

VOLTAGE DEGRADATION

• Voltage Degradation will be the main factor governing the ‘life’ of the stack itself (i.e. time in service, performance and reliability at end of life)

• Degradation must be accommodated for in control systems

• Will be important in Life Cycle Analysis (especially the Life Cycle Costing)

Michael Fowler – University of Waterloo

DEGRADATION FAILURE MODES (leading to degradation of performance or durability)

• Kinetic or activation loss in the anode or cathode catalyst –Loss of Apparent Catalytic Activity

• Ohmic or resistive increases in the membrane or other components –Loss of Conductivity

• Decrease in the mass transfer rate of in the reactants flow channel or electrode –Loss of Mass Transfer Rate of Reactants

Michael Fowler – University of Waterloo

VOLTAGE DEGRADATION MODES

0

0.2

0.4

0.6

0.8

1

1.2

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Current Density (amp cm-2)

Pote

ntia

l (V

)

Conductivity Loss

Loss of Apparent Catalytic Activity

Loss of Rate of Mass Transport

BOL

Michael Fowler – University of Waterloo

VOLTAGE DEGRADATION CURVE FOR A SINGLE PEM CELL

(Operated at 80°C, 0.4 amp cm-2, 30 psig/30 psig, H2/Air – stoichiometric ratios 1.2/2)

0.000

0.100

0.200

0.300

0.400

0.500

0.600

0.700

0.800

0 200 400 600 800 1000 1200

Age (Hours)

Vol

tage

(V

olts

)

Michael Fowler – University of Waterloo

ACTIVITY TERM kcell(from the GSSEM) OF A SINGLE CELL

(Operated at 80°C, 0.4 amp cm-2, 30 psig/30 psig, H2/Air – stoichiometric ratios 1.2/2)

0.002

0.0022

0.0024

0.0026

0.0028

0.003

0 200 400 600 800 1000 1200

Age (Hours)

Act

ivit

y T

erm

kce

ll

Michael Fowler – University of Waterloo

RESISTANCE INCREASE CURVE OF A SINGLE CELL

(Operated at 80°C, 0.4 amp/cm2, 30 psig/30 psig, H2/Air – stoichiometric ratios 1.2/2)

0

0.5

1

1.5

2

2.5

3

3.5

4

0.00 200.00 400.00 600.00 800.00 1000.00 1200.00

Age (Hours)

Inte

rnal

Res

ista

nce

(moh

ms)

0

5

10

15

20

25

Lam

bda

Michael Fowler – University of Waterloo

SIMULATION OF A SINGLE CELL USING THE GSSEDM

0

0.2

0.4

0.6

0.8

1

1.2

0 0.2 0.4 0.6 0.8 1 1.2Current Density (Amp/cm2)

Po

ten

tial

(V

olt

)

0

5

10

15

20

25

30

Po

wer

(W

atts

)

BOL

1500 Hours

3000 Hours

4500 Hours

6000 Hours

Michael Fowler – University of Waterloo

RELIABILITY ANALYSIS

• Must account for stochastic behaviour of cells• Includes a Degradation Model’, (durability)

where ‘Failure’ is degradation to below threshold value for specific parameter (e.g.voltage, efficiency, power) Catastrophic failure of the MEA

• Goal of the analysis is to allow an understanding of the impact of design (e.g.redundancy - increase loading of catalyst) and operation changes (e.g. limitation of operating states) on EOL performance

Michael Fowler – University of Waterloo

RELIABILITY ANALYSIS

• Will require some type of ‘Degradation Model’, which allows reliability to be function of degradation evaluation (durability)

• ‘Failure’ is degradation to below threshold value for specific parameter (e.g. voltage, efficiency, power)

• Should account for stochastic behaviour of cells• Catastrophic failure of the MEA • Goal of the analysis is to allow an understanding of the

impact of design (e.g. redundancy - increase weight of catalyst)and operation changes (e.g. limitation of operating states) on EOL performance

Michael Fowler – University of Waterloo

STACK AGEING MODEL (100 CELLS – 100 cm2)

0

20

40

60

80

100

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Current Density (amp cm-2)

Vol

tage

(vo

lts)

0

1000

2000

3000

4000

5000

6000

7000

Pow

er (W

atts

)

BOL 1000 hours2000 hours 3000 hours4000 hours 5000 hours6000 hours 7000 hours8000 hours

80% Rated Power Spec

Michael Fowler – University of Waterloo

MODELLING OF STOCHASTIC BEHAVIOUR

Simulation 100 Cell Stack 50.56 cm2 Area, 3atmg, H2/Air SR 1.2/2

20

40

60

80

100

120

0 0.3 0.6 0.9 1.2 1.5

Current Density (Amps/cm2)

Vol

tage

(Vol

ts)

0

500

1000

1500

2000

2500

3000

3500

Po

wer

(W

atts

)

Variability in 110 cell Stack

Normalized Variability of a Single Cell

Stack

OPERATION WITH MEA FAILURE AND RENEWAL

100 Cell Stack, 100 cm2, MTTF 6430 hours

Michael Fowler – University of Waterloo

MTTF –MEAN TIME TO FAILURE

Michael Fowler – University of Waterloo

MEA RENEWAL VS NO RENEWAL

Michael Fowler – University of Waterloo

RENEWAL RATE VARIATION

40

45

50

55

60

65

70

0 1000 2000 3000 4000 5000 6000 7000Operating Time (hours)

Vol

tage

(vol

ts a

t 1am

p cm

-2)

W e i b u l l 4 3 3 0 h o u r M E ACharater is t ic Li fe Weibul l 6330 hourCharac te r i s t i c L i feN o r m a l 4 3 3 0 M e a nM E A M T T F90% Conf idence

N o r m a l 6 4 3 0 h o u r M e a nM T T FN o M E A R e p l a c e m e n t

Michael Fowler – University of Waterloo

VARIATION IN DEGRADATION RATES

40

45

50

55

60

65

70

0 2000 4000 6000 8000 10000

Operating Time (hours)

Vol

tage

(vol

ts a

t 1am

p cm

-2)

Half ConductivityDecay Rate

Half the ActivityDecay Term

Double Activity DecayTerm

Double ConductivityDecay Rate

90% ConfindenceRegion

Michael Fowler – University of Waterloo

MAJOR CONTRIBUTIONS OF THIS WORK

• Identification of key failure modes associated with PEM fuel cells

• Development of GSSEDM, modelling the performance of a cell with operating age

• Develop a conceptual model for fuel cell stack reliability.

Michael Fowler – University of Waterloo

Acknowledgement / References• NSERC, National Defence, Support of the Electrochemical Power

Sources Group at RMC.• Key References for Further Information:

– M.W. Fowler, R.F. Mann, J.C. Amphlett, B.A. Peppley and P.R. Roberge, “Incorporation of Voltage Degradation into a Generalized Steady State Electrochemical Model for a PEM Fuel Cell”, Journal of Power Sources, 106 (2002) 274-283.

– M.W. Fowler, John C. Amphlett, Ronald F. Mann, Brant A. Peppley and Pierre R. Roberge, “Issues Associated With Voltage Degradation in a Polymer Electrolyte Fuel Cell Stacks”, Journal for New Materials for Electrochemical Systems, 5 (2002) 255-262.

– Michael Fowler, Ronald F. Mann, John C. Amphlett, Brant A. Peppley and Pierre R. Roberge, Chapter 56 Conceptual reliability analysis of PEM fuel cells, Handbook of Fuel Cells – Fundamentals, Technology and Applications - Volume 3: Fuel Cell Technology and Applications, Edited by Wolf Vielstich, Hubert Gasteiger, Arnold Lamm., John Wiley & Sons Ltd., 2003. (In Press)

– Michael Fowler, “Demonstration of the Generalized Steady-State Electrochemical Model for a PEM Fuel Cell”, Proceedings - Canadian Hydrogen Conference, Victoria, British Columbia, 19 – 22 July 2001.

Michael Fowler – University of Waterloo

QUESTIONS

Michael Fowler – University of Waterloo

Measurement Error

0.15 psig0.5% of full scale*

TransducerPressure

0.1°C0.1°C (calibrated)Thermal CoupleTemperature

0.05mVVoltage

.025 Amps or

.0005 Amps cm-2

ShuntCurrent

0.05% of spanNational Instruments 5B30

Signal Processing

1.5 cc min-1 anode 5 cc min-1 cathode

1.5% of full scaleAalborg GFM 171Flow Meters

1.5 cc min-1 anode 5 cc min-1 cathode

1.5% of full scaleCole PalmerFlow Controllers

0.06 mohms2% of full scale3 mohm

HP 4328AResistance

Measurement Error

Stated ErrorDeviceFunction

Michael Fowler – University of Waterloo

• intrinsic reactivity (thermodynamic, chemical and physical instability), including material corrosion and degradation

• manufacturing irregularities and design flaws

• reactant contaminants (including those contaminants that may leach from the reactant storage and delivery systems)

• abusive handling• defect propagation

DETERIORATION CAN NOT BE AVOIDED

Michael Fowler – University of Waterloo

Instrument Error

y = 0.0004x + 3.0897

0

0.5

1

1.52

2.5

3

3.5

4

0 200 400 600 800 1000 1200

Age (Hours)

Inte

rnal

Res

ista

nce

(moh

ms)

Series1

Linear (Series1)

Michael Fowler – University of Waterloo

( ) ( )*OH

5422

½ 1030841529810582291 ppT..T-.-.E --Nernst lnln * +⋅×+×=

( )( )[ ] i- ck TG oeact ln ln-1 ln Aln 863.21108.62 1036.101

*cc

5-6

cc , 2

αα

η +′++⋅⋅+∆⋅⋅−= −

lnF2

R - ) F(4 ln

F2R

F2

*H

0a act, 2

iT

ckATG

aec

⋅⋅⋅+∆

−=η

V = E + η + η + ηCell Nernst act, a act, c ohmic

PEM MODEL DEVELOPMENT

Michael Fowler – University of Waterloo

)](ln[ )](ln[ 4*O321act 2

iTcTT ⋅+⋅+⋅+= ξξξξη

G

- 2G

- c

eec1 FF nα

ξ∆∆

=

TOTAL ACTIVATION OVERVOLTAGE

( )FnCαα

ξ C3

-1R

=

+=

FR

F2

R- 4 nCα

ξ

*H

-5cell 2

ln104.3 ln 0.000197 k cA ⋅×+⋅+=2ξ

( )( )( ) ( ) ( ) ( ) cln2

ln F

R2FR

2lnln *H

c

23

20*OH

1*H

0c2 22 F

RA

nFn

FR

kccknF

R cCC

n

ac

+

++

+

=−

+

ααξ

ααα

Michael Fowler – University of Waterloo

internal

protonelectronic

protonohmic

electronicohmicohmic

Ri

RRi

-

) (-

⋅=

+=

+= ηηη

A lr

R Mproton =

−

−−

+

−⋅

=

TT

Ai

AiT

Ai

rM 30325.3exp3634.0

303062.003.016.181

5.22

λ

TOTAL OHMIC OVERVOLTAGE

Michael Fowler – University of Waterloo

• proposed ageing rate (kDR) of is -0.055 µV/hr

• –0.0007 hr-1 for λDR

• term related to the loss of mass transport of reactants (not developed in this work)

AGEING PARAMETERS

Age??? DRage ×+= o

*H

-5cell 2

ln104.3 ln 0.000197 k k cAAge/TDR ⋅×+⋅++×=2oξ

Michael Fowler – University of Waterloo

0.40.45

0.50.55

0.60.65

0.70.75

0.80.85

0.90.95

11.05

1.1

0 200 400 600

Current Density (mA/cm2)

Pot

enti

al (V

olts

)

600 hour data BOL Data231 hour data GSSEM

6 0 0 H o u r E x p e r i m e n t a l D a t al a m b d a 1 2 . 5E p s i l o n 2 0 . 0 0 2 9 2

2 3 1 H o u r D a t al a m b d a 1 6 . 6E p s i l o n 2 0 . 0 0 3 0 1

G S S E M

B e g i n n i n g o f L i f e D a t al a m b d a 1 6 . 6E p s i l o n 2 0 . 0 0 3 1 1

SINGLE CELL DEGRADATIONH2/O2 30 psig/30psig 80oC

Michael Fowler – University of Waterloo

0.4

0.45

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1

1.05

1.1

0 200 400 600

Current Density (mA/cm2)

Pot

entia

l (V

olts

)

600 hour data High stoic ratio - 600 hour data BOL Data

6 0 0 h o u r D a t aS R 1 . 1 5 / 3l a m b d a 1 2 . 3E p s i l o n 2 . 0 0 3 0 3

2 2 7 h o u r D a t aS R 1 . 1 5 / 2l a m b d a 7 . 5E p s i l o n 2 0 . 0 0 3 2 0

6 0 0 h o u r D a t aS R 1 . 1 5 / 2 . 0l a m b d a 1 4 . 4E p s i l o n 2 0 . 0 0 3 0 1

SINGLE CELL DEGRADATIONH2/AIR 30 psig/30psig 80oC

Michael Fowler – University of Waterloo

LOSS OF APPARENT CATALYTIC ACTIVITY

• Catalyst sintering (catalyst migration or ripening)• Loss of catalytic or electrolyte material• Low levels of contaminants binding to active sites

• Contaminants from reactants (including dust)• Contaminants leached from fuel cell components

• Poor water management may contribute to effectiveness of catalytic sites (flooding and dehydration) or simply the presence of liquid water

• Degradation of Nafion in contact with active sites• Carbon Corrosion

Michael Fowler – University of Waterloo

Stack Ageing - Kinetic LossSingle Cell

0

0.2

0.4

0.6

0.8

1

1.2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5

Current Density (A/cm2)

Pot

enti

al (

Vol

tage

)

0

5

10

15

20

25

30

Pow

er (

wat

ts)

BOL 1000 Hours 2000 Hours 3000 Hours 4000 Hours 5000 Hours

LOSS OF APPARENT CATALYTIC ACTIVITY

Michael Fowler – University of Waterloo

LOSS OF CONDUCTIVITY

• Low levels of cation contamination reducing the proton conductivity (this cause may be accelerated by high hydration levels as the water acts as a source and pathway for contaminates)

• Changes to eletro-osmotic drag properties • Changes to the water diffusion characteristics of the

membrane• Corrosion of the plates leading to increased contact

resistance• Thermal or hydration cycling leading to mechanical

stress cycling resulting in delamination of the polymer membrane and catalyst

Michael Fowler – University of Waterloo

Stack Ageing- Loss of Conductivity

0

0.2

0.4

0.6

0.8

1

1.2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5

Current Density (A/cm2)

Pot

enti

al (

Vol

tage

)

0

5

10

15

20

25

30

Pow

er (

wat

ts)

BOL 1000 Hours 2000 Hours 3000 Hours 4000 Hours 5000 Hours

LOSS OF CONDUCTIVITY

Michael Fowler – University of Waterloo

LOSS OF MASS TRANSFER RATE

• Swelling of polymer materials in the active catalyst layer changing water removal characteristics

• Compaction of the gas diffusion layer due to mechanical stresses

• Surface chemistry changes in the gas diffusion layer making water removal more difficult

• Carbon Corrosion

Michael Fowler – University of Waterloo

Stack Ageing -Mass Transport Loss

0

0.2

0.4

0.6

0.8

1

1.2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6

Current Density (A/cm2)

Pot

enti

al (

Vol

tage

)

0

5

10

15

20

25

30

Pow

er (

wat

ts)

BOL 1000 Hours 2000 Hours 3000 Hours 4000 Hours 5000 Hours

LOSS OF MASS TRANSFER RATE OF REACTANTS

Michael Fowler – University of Waterloo

RELIABILITY BLOCK DIAGRAM