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Stack Modeling and Diagnostics -- Fundamental Issues

Question: What are the important PEM Fuel Cell phenomena that require improved understanding through development of models or diagnostic tools?
• Membrane Electrode Assembly Design
– Optimizing reactant transport – Kinetics mechanisms – Liquid water effects

MEA/Flowfield Interactions
– Current distribution – Temperature distribution

Flowfield Design
– Liquid water release from diffusion media and movement through channels – Basic structure (e.g. serpentine, interdigitated …)

Durability
– Degradation mechanisms – Failure mechanisms
Mark Mathias Nov. 14, 2001
by: MFM page: 1

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

Potential Distribution in H2/Air Fuel Cell
0.8

1 A/cm2
0.6 0.4
DM CL

Cathode solid phase potential Membrane CL DM Ecell H
+

Potential (V)

0.2 0 -0.2 -0.4 -0.6 -10 10 30 50

Anode solid phase potential Anode overpotential

Eeq

Electrolyte phase potential Cathode overpotential

70

90

110

130

150

Nominal cell thickness

Cathode layer optimization is critical for H2/Air Anode layer becomes important for reformate application
file: Modeling and Diagnostic Needs date: Nov. 8, 2001 by: MFM page: 2

MEA Design
• How can we determine which transport process is rate-limiting?
– Diagnostic approaches needed – Understand nature of O2 transport limitations in catalyst layer (ionomer vs. water film)

How can we optimize proton conductivity and gas permeance distributions in electrodes?
– Characterization methods needed to measure these quantities – Understand interaction with anode/cathode water management strategy

Diff.-Med.
H2 O H2

Anode
H2 → 2H+ + 2eH+

Membrane
H2 O

Cathode

Diff.-Med.
H2 O O2

back-diffusion ½O + 2H+ + 2e- → H O 2 2 H+ ca. 3H2O electro-osmosis H+

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

by: MFM

page: 3

MEA Design -- Continued
• What are the kinetics mechanisms on C-supported Pt in PEM?
– – – Reliable engineering descriptions needed (in-situ vs. ex-situ) Understand dependence on ionomer type and catalyst properties Understand dependence on local water concentration

How can we optimize liquid water transport through catalyst layer and diffusion media?
– – – – What is the nature of flooding (catalyst layer, diffusion media, interface between the two)? How do we describe transport through these layers (ie. wicking properties within and between layers)? What are the critical material properties and how do we measure them? Understand history-dependent liquid water effects and impact on multiple steadystates and dynamic responses

Diff.Med.

Anode

Membrane

Cathode

Diff.Med.

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

by: MFM

page: 4

MEA/Flowfield Interactions
• How can we specify in-plane layer property requirements?
– Understand how in-plane transport requirements depend on land width – Understand how diffusion media requirements depend on flow-field type (interdigitated, serpentine, etc…) – Characterization methods needed (properties vs. compression)

How do we control current density distribution?
– Measurement methods needed – Understand material properties and interfacial resistances

How do we control MEA temperature?
– Measurement methods needed for interfacial and bulk thermal conductivities – Understand material properties and interfacial resistances – Understand dominant heat transfer modes

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

by: MFM

page: 5

Flowfield Design
• How can we speed liquid water release from diffusion media?
– – – Understand effect of diffusion media structure and properties on water emergence Understand velocity requirements for water removal Characterization/visualization methods needed Understand rivulet vs. plug flow Understand liquid movement in bends and turns Understand effects of plate and diffusion media hydrophobicity Characterization/visualization methods needed

How does liquid water move through channels?
– – – –

cathode DM

H2O

What are the advantages of various flowfield designs, e.g. serpentine vs. interdigitated.
– – Understand effects on gas distribution Understand effects on liquid water transport
date: Nov. 8, 2001 by: MFM page: 6

file: Modeling and Diagnostic Needs

Durability
• What are key degradation mechanisms and their relative contribution to MEA degradation? How do we design to mimimize them?
– – – – Understand sintering and influence of support and operating conditions Understand electrode ionomer loss Understand peroxide formation chemistry and impact on ionomer loss Understand change in material hydrophobic properties and effects on performance – Understand degradation of contact resistances

What are key failure mechanisms and how do we slow them?
– Why do membrane holes form? (Mechanical or chemical mechanisms) – Why do catalyst layers delaminate? – Understand effects of geometry, operating conditions, and compression

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

by: MFM

page: 7

Final Comments
• On Model Verification -- PEM modeling art is way ahead of experimental verification. Using polarization curves to “verify” 1+D models is insufficient. Verification should include high-frequency resistance, changes in reactant concentration (e.g. pure O2, helox), measurement of water balance, etc. On Experimental Approaches -- Key will be to experimentally isolate phenomena in processes that are naturally tightly coupled and complex. Clever experiments are needed. On CFD -- Useful for small-scale (50 cm2) work, requires computation time or model formulation advances to become a practical design tool on the full-active-area scale. On AC Impedance -- Not much has been learned yet using this technique, due to experimental difficulties and lack of models. On Current Distribution -- Improved methods are needed, less-intrusive less-cumbersome than those known. High frequency resistance distribution badly needed.

• •

file: Modeling and Diagnostic Needs

date: Nov. 8, 2001

by: MFM

page: 8

Voltage Loss Contributions in H2/Air
Assumptions: • negligible ηH2 • only Eloss,kinetic at 0.02 A/cm2 • Tafel slope of 66 mV/dec
H2/Air at s=2/2 and 150kPa, Tcell=80C, dewpts.=80/80C
0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0.00 0.50 1.00

0.4/0.4 mgPt/cm

2

ORR kinetics losses
(i0=1.7x10 A/cm
-9 2 Pt)

voltage loss [V]

total ohmic losses

mass tx losses RΩ,membrane (ca. 0.1 S/cm)
1.50 2.00 i [A/cm ]
2

• major η-losses for ORR (0.44V at 1 A/cm2 ≈ 37% η-loss (Eeq ≈ 1.184V)) • for 50 → 25µm membrane: remaining 0.025V membrane loss (no dry-out effect)
→ note: total ohmic Eloss at 1 A/cm2 ≈ 0.050V (ca. 0.025V add. Rcontact)
file: Modeling and Diagnostic Needs date: Nov. 8, 2001 by: MFM page: 9

• unaccounted for tx-losses of ca. 0.07V at 1 A/cm2 (H+, O2)