Hydrocarbon Membrane Project: FC7 Chris J. Cornelius, Cy H. Fujimoto, Michael A. Hickner Sandia National Laboratories Chemical and Biological Technologies P.O. Box 5800 Albuquerque, NM 87185 May 16 th 2006 This presentation does not contain any proprietary or confidential information Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.
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Hydrocarbon Membrane · 2006-06-02 · DOE Fuel Cell Program Hydrocarbon Membrane Project: FC7 Chris J. Cornelius, Cy H. Fujimoto, Michael A. Hickner Sandia National Laboratories
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DOE Fuel Cell Program
Hydrocarbon MembraneProject: FC7
Chris J. Cornelius, Cy H. Fujimoto, Michael A. Hickner
Sandia National LaboratoriesChemical and Biological Technologies
P.O. Box 5800Albuquerque, NM 87185
May 16th 2006
This presentation does not contain any proprietary or confidential information
Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company,for the United States Department of Energy under contract DE-AC04-94AL85000.
Substituting SDAPPe and SDAPPf within the electrode layers can improve or approach same performance as a Nafion based MEA. However, fuel cell performance is dependent on electrolyte type, loading, and hydrogen fuel cell operating temperature.
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DOE Fuel Cell Program
Fuel Cell PerformanceO.5V with 30wt% Nafion Electrodes
0
200
400
600
800
1000
1200
1400
1600
1800
50 60 70 80 90 100 110 120 130
Temperature (°C)
Cur
rent
Den
sity
(mA
/cm
2 )
100% RH
75% RH
50% RH
25% RH
Nafion 112 SDAPP4 (2.5mil)
0.4 mg Pt/cm2
high stoic H2/Air flow
8
0
200
400
600
800
1000
1200
1400
1600
1800
50 60 70 80 90 100 110 120 130
Temperature (°C)
Cur
rent
Den
sity
(mA
/cm
2)
100% RH75% RH50% RH25% RH
DOE Fuel Cell Program
0
100
200
300
400
500
600
700
800
900
1000
50 60 70 80 90 100 110 120 130
Temperature (°C)
Cur
rent
Den
sity
(mA
/cm2 )
100% RH
75% RH
50% RH
Fuel Cell PerformanceO.5V with 30wt% Nafion vs non-Nafion Electrodes
Nafion 112 SDAPP4 (2.5mil)
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0.4 mg Pt/cm2
high stoic H2/Air flow
0
200
400
600
800
1000
1200
1400
1600
1800
50 60 70 80 90 100 110 120 130
Temperature (°C)
Cur
rent
Den
sity
(mA
/cm
2)
100% RH75% RH50% RH25% RH
DOE Fuel Cell Program
SDAPP electrodes provide good porosity and do not significantly impede electrochemistry within the electrode structures.
A v e ra g e T a fe l S lo p e (1 0 -2 0 m A )
O 2 A ir O 2 A irN 1 1 2 N a f io n 3 0 % N a f io n E le c tro d e s -8 7 .5 -8 3 .5 -5 9 .1 -5 1 .2S D A P P 3 0 % S D A P P E le c tro d e s -8 3 .1 -7 9 .3 -6 3 .1 -6 7 .6
5 0 R H 1 0 0 R H
Fuel Cell PerformanceDevelopment of Non-Nafion MEAs
10
Electrons
Reactants & Water
H2O, O2, H2 H2O
H +
e -
Protons
Electrons
Reactants & Water
H2O, O2, H2 H2O
H +H +
e -e -
Protons
DOE Fuel Cell Program
Fuel Cell Performance50%RH Nafion & Non-Nafion Electrodes on N112
11
N112 with 30wt% Nafion Anode and Cathode
N112 with 15wt% SDAPPf Anode and Cathode
N112 with 15wt% SDAPPf Anode and 30wt% Nafion Cathode
N112 with 30wt% SDAPPf Anode and Cathode
80oC & 50%RH
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 400 800 1200 1600 2000
Current Density (mA/cm2)
Cel
l Pot
entia
l (V)
120oC 50%RH
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 400 800 1200 1600 2000
Current Density (mA/cm2)
Cel
l Pot
entia
l (V)
DOE Fuel Cell Program
0.00E+00
5.00E-05
1.00E-04
1.50E-04
2.00E-04
2.50E-04
3.00E-04
60 80 100 120 140Temperature (°C)
Hyd
roge
n Pe
rmea
bilit
y (c
m2 /s
)
Nafion 112SDAPP2SDAPP3SDAPP4
Hydrogen CrossoverMEA & PEM Testing
0.00E+00
5.00E-14
1.00E-13
1.50E-13
2.00E-13
2.50E-13
3.00E-13
3.50E-13
0 20 40 60 80 100
Relative Humidity
Gas
Per
mea
biity
mol
e cm
/ kP
.
0
0.5
1
1.5
2
2.5
3
3.5
Rat
io N
112
Per
m/S
andi
a P
erm
Sandia Nafion Ratio
In collaboration/Contract with Giner Electrochemical Systems
(cycling) and chemical)– Minimize interfacial resistance and
improve adhesion of PEM and catalyst layer
Future WorkImproving Fuel Cell Membranes
O2
19
24.5
270n*
Ph Ph
Ph
S
Ph Ph
Ph
F F
F F
*
PhPh
Ph
*
PhPh
Ph
*
5.2n*
Ph Ph
Ph
S
Ph Ph
Ph
*
n
PhPh
Ph
*
PhPh
Ph
*
F F
FF
H2
94
99
H2 and O2 Permeability Units in Barrer10-10cm3/cm2 s cm of Hg (at STP)
16
DOE Fuel Cell Program
SummaryHydrocarbon Membrane
Relevance:Identify and Answer fundamental issues with Nafion and alternative PEM and MEA fuel cell implementation
Approach:Develop a Structure-Property-Performance relationship of alternative PEMs in order to mitigate poor fuel performance relative to DOE targets.
Technical Accomplishments and Progress:Capabilities Established: Material design and synthesis, characterization, device testing, system performance measurements, and predictions
Technology Transfer & Collaborations:Active involvement with industry and academia$50K$50K award award by Lockheed Martin under a Shared Vision to initiate the by Lockheed Martin under a Shared Vision to initiate the understanding of hydrocarbon PEM scaleunderstanding of hydrocarbon PEM scale--up. up.
Proposed Future Research:Continue structure property function improvements to achieve DOE fuel cell goals
17
DOE Fuel Cell Program
Reviewer’s CommentsResponse to Previous Year Review
1.Relevance to overall DOE objectives – (Weight - 20%)• Key technology that must be enhanced.Key technology that must be enhanced.We have taken our first generation membrane and are adding functionalities to improve conductivity, durability, and performance.
2.Approach to performing the R&D – (Weight - 20%)•• Separate MEA interface from bulk PEM propertiesSeparate MEA interface from bulk PEM properties•• Improve Conductivity (low RH) then Electrode InterfaceImprove Conductivity (low RH) then Electrode InterfaceResearch goals separate PEM from MEA interface. New Chemistry initiated during the next fiscal years is expected to address 2010 DOE performance targets.
3.Technical Accomplishments and Progress toward overall project and DOE goals – (Weight - 35%)•• Measure conductivity of new membranes as a function of T and RMeasure conductivity of new membranes as a function of T and RH in order to H in order to separate PEM versus MEA advances.separate PEM versus MEA advances.Research goals separate PEM from MEA interface. New Chemistry initiated during the next fiscal years is expected to address 2010 DOE performance targets.
18
DOE Fuel Cell Program
Reviewer’s CommentsResponse to Previous Year Review
4.Technology Transfer / Collaborations with industry / universities / other laboratories – (Weight - 10%)•• Need to develop industrial contactsNeed to develop industrial contacts•• Develop collaboration on MEA durability and electrode integratDevelop collaboration on MEA durability and electrode integrationionWe have taken our first generation membrane and are adding functionalities to improve conductivity, durability, and performance.
5.Proposed Future Research approach and relevance –(Weight - 15%)•• Need more aggressive challengesNeed more aggressive challenges•• Too Broad Too Broad –– optimize PEM then electrodeoptimize PEM then electrodeResearch goals separate PEM from MEA interface. New Chemistry initiated during the next fiscal years is expected to address 2010 DOE performance targets of performance, durability, and cost).
19
DOE Fuel Cell Program
Publications and PresentationsMarch 2005 - Present
PublicationsHickner, Michael A.; Fujimoto, Cy H.; Cornelius, Christopher J. “Transport in
sulfonated poly(phenylene)s: Proton conductivity, permeability, and the state of water” Polymer (accepted April 18th, 2006).
Fujimoto, Cy H.; Hickner, Michael A.; Cornelius, Christopher J.; Loy, Douglas A. “Ionomeric Poly(phenylene) Prepared by Diels-Alder Polymerization: Synthesis and Physical Properties of a Novel Polyelectrolyte” Macromolecules(2005), 38(12), 5010-5016.
PresentationsFall 2006: FuelCell 2000 (2), ECS (1) and ACS (1)
Technical Advances(pre-patents): 3
PublicationsHickner, Michael A.; Fujimoto, Cy H.; Cornelius, Christopher J. “Transport in
sulfonated poly(phenylene)s: Proton conductivity, permeability, and the state of water” Polymer (accepted April 18th, 2006).
Fujimoto, Cy H.; Hickner, Michael A.; Cornelius, Christopher J.; Loy, Douglas A. “Ionomeric Poly(phenylene) Prepared by Diels-Alder Polymerization: Synthesis and Physical Properties of a Novel Polyelectrolyte” Macromolecules(2005), 38(12), 5010-5016.
PresentationsFall 2006: FuelCell 2000 (2), ECS (1) and ACS (1)
Technical Advances(pre-patents): 3
20
DOE Fuel Cell Program
Critical Assumptions & IssuesHydrocarbon Membrane
1. Achieving Adequate Proton Conductivity• Proton Mobility and Acidity – current synthetic method is amenable for
inclusion of more acidic groups – current approaches are in the correct direction to achieve goal.
• Improved Morphology – improvements in structure will enhance proton conduction via better utilization of proton carrying groups to improve low RH fuel cell function.
• Interface versus Bulk - Separate MEA (interface) from PEM (bulk) to understand interrelationships. Improving proton conductivity and transport properties within the electrode (low RH & Durability).
2. Mechanical and Chemical Durability• Mechanical – Improving flexibility of PEM backbone to accommodate cyclic
stress and asymmetric water induced stresses.• Chemical – Improving stability with more chemically stable monomers
1. Achieving Adequate Proton Conductivity• Proton Mobility and Acidity – current synthetic method is amenable for
inclusion of more acidic groups – current approaches are in the correct direction to achieve goal.
• Improved Morphology – improvements in structure will enhance proton conduction via better utilization of proton carrying groups to improve low RH fuel cell function.
• Interface versus Bulk - Separate MEA (interface) from PEM (bulk) to understand interrelationships. Improving proton conductivity and transport properties within the electrode (low RH & Durability).
2. Mechanical and Chemical Durability• Mechanical – Improving flexibility of PEM backbone to accommodate cyclic
stress and asymmetric water induced stresses.• Chemical – Improving stability with more chemically stable monomers
Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company,for the United States Department of Energy under contract DE-AC04-94AL85000.
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