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Membrane Issues for

PEM Fuel Cells

Mark Roelofs
DuPont Fuel Cells, Wilmington, DE

NSF Workshop
Arlington, Virginia
November 14, 2001
Membrane Issues

• Water
• Higher Temperature
• Lifetime
• Fuel crossover
• Cost
Membrane Structures

PerFluoroSulfonate Ionomer (PFSI) Acid-doped polymer
e.g. Nafion e.g. PolyBenzImidazole doped with phosphoric acid
PBI/H3PO4
H H2PO4 • xH3PO4 H
CF2 CF2 CF2 CF
x y N N
O
CF2 N N
FC CF3 n
H
O H H2PO4 • xH3PO4
CF2
CF2
sulfonated aromatic ionomer
SO3H e.g. Sulfonated poly(p-phenylene ether sulfone)
SPPSU
O
S O O
O
SO3H
Water Issues

• For PerFluoro Sulfonate Ionomers
(PFSI) and some sulfonated aromatic 1000.000
systems
Note log scale
• Humidification requirement 100.000
– conductivity requires contact with
liquid water or water vapor at > ~80

Conductivity (mS/cm)
10.000
RH.
– Water management system
1.000
> FC system cost ↑ 120 C
> specific power ↓ 0.100
150 C
80 C
• Dimensional changes in membrane
with water content 0.010
– stresses at electrode/membrane
interface and at the gasket
0.001
– electrode debonding from membrane 0 20 40 60 80 100
with CCM RH (%)
– buckling and cracking of carbon
paper from shrinking membrane
Water Issues (continued)

• Electro-Osmotic water Drag (EOD)
– Each proton transported drags 1 to 5 water molecules
> Both aromatic sulfonates and PFSI: EOD increases with increasing
temperature and water content.
– Necessitates anode humidification system for hydrogen & reformate.
– Degrades system efficiency for DMFC

• Water requirement makes for poor dynamic response of stack
– Chasms of dry-out (conductivity loss) or flooding on either side of the
operating point.
– Water content depends on diffusion, evaporation, condensation.
> non-linear and slow response of system to current changes.

• Need for faster diffusion of cathode water back to anode =>
thinner membranes
– manufacturing, fuel permeation, lifetime problems

• Wanted: conductivity without water
Advantages of HT Operation
HT in the context of Proton Exchange Membrane (PEM):
Fuel cell operation 100 - 200 0C versus 60 – 80 oC for standard Nafion®

• Better anode kinetics in the presence of CO
– Much simplified fuel processor
– Reduction in anode catalyst requirement
• Smaller heat exchangers
– Utilizing stack heat - heat building or car interior
– Rejecting stack heat – radiators
– Cooling reformate feed?
• Potential to eliminate water management system
• These allow for the FC System:
– Increased system reliability
– Lower cost in $/Wh
– Higher power density W/Liter
• Fuel Neutral
Reformate’s “CO Problem”

• Reforming
– fuel, steam, air → H2 , CO2, CO (1 400 Zawodzinski,
to 20%) Gottesfeld et al. '97

Voltage Loss from CO (mV)
• CO binds to Pt at anode, covers 50 ppm CO
300
sites needed for hydrogen 200 ppm CO
oxidation.
Acceptable
• Standard Remove-it Fix: 200 Loss Level
– Add water gas shift reactors to
get CO below ~200 ppm
100
– Add preferential oxidizer (Pt) to
further lower CO below 10 ppm.
• Higher-Temperature Fix: 0
– CO desorbs from Pt at higher 75 100 125 150 175
temperature.
Temperature (C)
– Run FC at 120 to 200 oC
Simplification of BOP with CO Tolerance

75% reduction in size of fuel processor

• Steam reformed MeOH
with no partial
oxidation: 1% CO
• 120°C stack: Elimination
of Selective
(Preferential) Oxidation
and Low Temp. Shift
Reactors
• 150°C stack: Also
elimination of High
Temp. Shift Reactor
T.J. Flynn, R.M. Privette, M.A. Perna, K.E. Kneidel, D.L. King,
and M. Cooper, Compact Fuel Processor for Fuel Cell-Powered
Vehicles, SAE International, SAE Technical Paper Series,
Report No. 1999-01-0536, reprinted from Fuel Cell Power for
Transportation (SP-1425), 1999.
Standard PFSI not suitable for HT

• Near-saturated water for conductivity
• Vapor pressure of liquid water increases exponentially with
temperature
– 80 °C → 7 psi 150 °C → 69 psi
• FC operation with high water vapor pressure is unattractive
– Air compressors and water condensers
> cost ↑,
> energy efficiency ↓
> specific power ↓

• Very short lifetime reported for PFSI at high temp. with high
RH.
PFSI = PerFluoro Sulfonate Ionomers
Challenge of HT Electrolyte

• Norby’s “Gap Chart”
– There is only one widely
recognized low-vapor pressure
proton conductor in the 100 - 200
oC range with the requisite

conductivity: H3PO4.

• On the left: oxides which only
work at greater than 500 oC.
• On the right: systems that rely on
water below 100 oC, or systems
with low conductivity.

• Humidity increases conductivity
for many systems.
– Required for some – Nafion®.
– Sufficient at low humidity – H3PO4.
Potential Routes to HT Membranes

Class Liquid Doped Polym. Solid-State Composite HT Ionomer
Electrolyte Electrolyte e.g. Filled PEM
Example H3PO4 PBI/H3PO4 CsHSO4 Nafion®/SiO2 Unknown
or Zr(HPO4)2
Who IFC Case Western, Cal Tech DeNora,
Celanese DuPont

Issues Highly corrosive Leachable at Superprotonic Probable Conductivity
Features highest doping conductivity at operation at without water
levels >140 °C 100-110 °C
High cathode High cathode Modest Pressurize for Thermal and
overpotential overpotential conductivity: <20 adequate hydrolytic
due to without catalyst mS/cm hydration stability
adsorption coating
Potentially Mechanically PEM failure Mechanical
corrosive weak; due to creep reinforcement
Processability
Lifetime
• Lifetime in FC
– Generally acknowledged that:
– PFSI better than aromatics
• All membranes have lifetime issues
• Thermal stability
– e.g. Kopitzke & Linkous et al. 2000
– C-S bond homolysis for sulfonated
aromatics.
– Nafion® anhydrous
– Relevance?
• Oxidative stability
– Can it be empirically predicted from
functional groups?
– What are the nature of free radicals
generated, and do they diffuse out of
the electrodes?
• Creep
• Accelerate what?

water vapor
Lifetime – Membrane Thinning

• ABB Membrel PEM electrolyzer
operated by SWB GmbH
– Stucki, Scherer et al. 1998
• 5 years electrolyzing water to H2 +
O2
– 400 mA/cm2, 80 oC
– Pt catalyst at hydrogen electrode
• PFSI shows >50 % thickness loss
• -SO3H lost at same rate as

thickness (µm)
thickness
• Fluoride detected in water effluent
• Erosion of membrane from
hydrogen-electrode side
• Most thinning near oxygen-output
end
Electrode / Membrane Interface

• Traditionally, PFSI used as binder and ion-conductor in electrode
– Makes acceptable interface to PFSI membrane
– Ionic contact resistance low and stable with time

• New non-PFSI membranes (e.g. aromatic sulfonate)
– High ionic contact impedance between PFSI-based electrodes &
aromatic sulfonate membrane.
– Desirable for the electrode ion-conductor be the same as the
membrane?
> new polym. electrolyte must also develop electrode fabrication method.
– Not desirable to be the same?
> e.g. PBI/H3PO4 good O2 barrier – don’t use in cathode?
> Performance advantages using different electrolytes in electrodes vs
memb.?

• Methods for “compatibilizing” membrane surface with electrode
ionomer/binder.
Fuel Crossover
Equivalent
Current
density
Fuel Membrane and Conditions (mA/cm2) Reference
NR-112 @ 22 C, 50% RH, 1 atm H2 differential
hydrogen pressure 0.4 DuPont est.
NR-111 @ 22 C, 50% RH, 1 atm H2 differential
hydrogen pressure 0.6 DuPont est.
N117 @81 C, 15 M permeation data extrapolated to 1
methanol M MeOH differential conc. 289 Cruickshank & Scott (1998)

methanol N112 @130 C, 2 M MeOH conc., 500 mA/cm2 DMFC 110 Arico, Antonucci et al. (2000)
methanol 1 M MeOH conc, N117?, 80 C, open-circuit DMFC 95 Ren, Gottesfeld, et al.(2000)

• Hydrogen & reformate
– not generally accepted as a problem for defect-free membranes
– potential problem for very thin membranes – damage?
• Direct Methanol
– a significant problem
– lowers fuel efficiency
– cathode mixed potential lowers cell potential
– Indirect - increased water transport to cathode lowers energy efficiency
Cost

• “The cost of Nafion® membrane is about $100/kW for a
typical reformed hydrogen PEM fuel cell system. This
represents about 3% of the system cost.”
– http://www.fuelcells.dupont.com/
Supplementary Slides
References

• S. Stucki, G.G. Scherer, S. Schlagowski, and E. Fischer, PEM water electrolysers: evidence for membrane
failure in 100 kW demonstration plants. J. Appl. Electrochem., 1998. 28: p. 1040-1049.
• R.W. Kopitzke, C.A. Linkous, and G.L. Nelson, Thermal stability of high temperature polymers and their
sulfonated derivatives under inert and saturated vapor conditions. Polymer Degradation and Stability, 2000.
67: p. 335-344.
• T. Norby, Solid-state protonic conductors: principles, properties, progress and prospects. Solid State Ionics,
1999. 125: p. 1-11.
• X. Ren and S. Gottesfeld, Electro-osmotic Drag of Water in Poly(perfluorosulfonic acid) Membranes. J.
Electrochem. Soc., 2001. 148(1): p. A87-A93.
• M. Ise, K.D. Kreuer, and J. Maier, Electroosmotic drag in polymer electrolyte membranes: an
electrophoretic NMR study. Solid State Ionics, 1999. 125: p. 213-223. 1.
• A.S. Arico, P. Creti, E. Modica, G. Monforte, V. Baglio, and V. Antonucci, Investigation of direct methanol
fuel cells based on unsupported Pt-Ru anode catalysts with different chemical properties. Electrochim. Acta,
2000. 45: p. 4319-4328.
• J. Cruickshank and K. Scott, The degree and effect of methanol crossover in the direct methanol fuel cell. J.
Power Sources, 1998. 70: p. 40.
• X. Ren, P. Zelenay, S. Thomas, J. Davey, and S. Gottesfeld, Recent advances in direct methanol fuel cells at
Los Alamos National Labortory. J. Power Sources, 2000. 86: p. 111-116.
• T.A. Zawodzinski, C. Karuppaiah, F. Uribe, and S. Gottesfeld. Aspects of CO Tolerance in Polymer
Electrolyte Fuel Cells: Some Experimental Findings. in Proc. Symp. on Electrode Materials and Processes
for Energy Conversion and Storage IV 1997: The Electrochemical Society 97-13: p. 139-146.