DEGRADATION AND RELIABILITY MODELLING OF …chemeng.uwaterloo.ca/mfowler/degradation.pdf · BOL...
Transcript of DEGRADATION AND RELIABILITY MODELLING OF …chemeng.uwaterloo.ca/mfowler/degradation.pdf · BOL...
DEGRADATION AND RELIABILITY MODELLING OF
POLYMER ELECTROLYTE MEMBRANE (PEM) FUEL CELLS
Michael [email protected]
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
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1.2
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Current Density (A/cm2)
Pot
entia
l (V
olta
ge)
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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)
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tage
(V
olts
)
Michael Fowler – University of Waterloo
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Age (Hours)
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tage
(V
olts
at
0.4
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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
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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)
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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
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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)
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Age (Hours)
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rnal
Res
ista
nce
(moh
ms)
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Lam
bda
Michael Fowler – University of Waterloo
SIMULATION OF A SINGLE CELL USING THE GSSEDM
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ten
tial
(V
olt
)
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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)
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Current Density (amp cm-2)
Vol
tage
(vo
lts)
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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
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Vol
tage
(Vol
ts)
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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
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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
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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
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1
1.52
2.5
3
3.5
4
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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
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0.65
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0.75
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0.95
1
1.05
1.1
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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
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Current Density (A/cm2)
Pot
enti
al (
Vol
tage
)
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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
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Current Density (A/cm2)
Pot
enti
al (
Vol
tage
)
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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
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Current Density (A/cm2)
Pot
enti
al (
Vol
tage
)
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30
Pow
er (
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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