Hydrocarbon Membrane · 2006-06-02 · DOE Fuel Cell Program Hydrocarbon Membrane Project: FC7...

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.


OverviewHydrocarbon Membrane

Timeline• Start Date: 3/15/05• End date: 9/30/06•• Project Completion (FY06): Project Completion (FY06): 50%50%

Budget• Total project funding

− DOE share: $300K− Contractor share: $0K

• Funding received in FY05: $150K•• Funding for FY06: Funding for FY06: $150K$150K

Partners• Interactions and Collaborations

Automotive & FC Stack Producer (Independent Testing & DOE Call Partners)Academia (Virginia Tech, CWRU, Clemson, UK - Jun Jin)

Technical BarriersBarriersBarriers: A, B, C, D, F, I

• High Temperature Membranes for Distributed Power Applications

• Advanced Membrane R&D• Membrane Materials,

Components, Processes• Advanced MEA Meeting 2010

Targets• Direct Methanol Fuel Cells• Auxiliary/Portable Power

2


ObjectivesResearch Program Goals – DOE 2010 Targets

Overall • Membrane Conductivity (0.1, 0.7, & 0.01 S/cm @ Target, RT, -20oC)• Operating Temperature (<= 120oC & 1.5 kPa abs)• Catalyst Loading (0.3 g/kW)• Fuel Cell Performance (400 mA/cm2 and 320 mW/cm2 @ 0.8V)• Membrane cost ($40/m2)• Hydrogen and Oxygen Crossover (2 mA/cm2)• Survivability (-40oC to 120oC)• Durability (5000 hrs @ <= 80oC & 2000 hrs @ >= 80oC)

2006 • Synthesize and Characterize SDAPP physical properties.• Demonstrate SDAPP (Sulfonated Diels-Alder Polyphenylene) PEM fuel

cell performance (1st Generation).• Continue developing structure-property performance PEM and fuel cell

relationships to create improvements in PEM materials.

2007 • Membrane Conductivity and Fuel Cell Performance• Survivability (-40 oC to 120 oC), Degradation, and Durability Studies• Catalyst Loading and Membrane Cost

3


• Thermal & Chemical Stability(Thermal, Chemical, Processing)

• Low Fuel Cross-Over(Low O2 & H2 - Tunable)

• Gas Transport(Electrode & PEM)

• Low Interfacial Resistance(MEA – Electrodes)

• Chemical Diversity and High MW• Proton Conductivity & Morphology

• Thermal & Chemical Stability(Thermal, Chemical, Processing)

• Low Fuel Cross-Over(Low O2 & H2 - Tunable)

• Gas Transport(Electrode & PEM)

• Low Interfacial Resistance(MEA – Electrodes)

• Chemical Diversity and High MW• Proton Conductivity & Morphology

nSO3H

HO3S

ApproachHydrocarbon Membrane - SDAPP

1st Generation Sulfonated Diels-Alder Polyphenylene (SDAPP)

4


Fuel Cell PerformanceDevelopment of Non-Nafion MEAs

5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 500 1000 1500 2000 2500current density (mA/cm2)

cell

pote

ntia

l (V)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

HFR

( Ω-c

m2 )

N112 30% NafElect.

SDAPP 30%Naf Elect.

SDAPP 30%SDAPP Elect.



SDAPP4 Membrane 1 mil thick80°C cell temperatureH2 200sccm Air 500 sccm20 psig50% RH gas feeds


0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 200 400 600 800

Current Density (mA/cm2)

Cel

l Pot

entia

l (V)

29 w t % Nafion 1100 0.2 mg Pt/cm2 on Nafion 112

7 w t % SDAPPe 0.4 mg Pt/cm2 on SDAPP4

16 w t % SDAPPe 0.4 mg Pt/cm2 on Nafion 112

120°C Cell temperatureH2 200sccm Air 500 sccm

20 psig50% RH gas feeds

• Highly sulfonated samples do show good high temperature & low RH fuel cell performance.

• Enhanced performance due in part to our new alternative binders.


6


Fuel Cell Performance50% RH @ 80 oC and 120 oC

120oC80oC

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 200 400 600 800 1000Current density (m A/cm 2)

Cel

l pot

entia

l (V)

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

HFR

(-c

m2 )

SDAPP 2.2 IEC mem - 30wt % SDAPPf3 elect

Nafion 112 mem - 30 wt % Nafion elect

SDAPP 2.2 IEC mem - 15 wt % SDAPPe elect

0.0

0.7

1.0

0.9

0.8

0.6

0.5

0.3

0.1

0.4

0.2

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 500 1000 1500 2000

Current density (m A/cm 2)

Cel

l pot

entia

l (V)

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

HFR

( ℵ-c

m2 )

Nafion 112 mem - 30 wt% Nafion elect

SDAPP 2.2 IEC mem - 15 wt % SDAPPe elect

SDAPP 2.2 IEC mem - 30wt % SDAPPf3 elect

SDAPP 2.2 IEC mem - 15 wt % SDAPPf3 elect

Cel

l Pot

entia

l (V)

Cel

l Pot

entia

l (V)

Nafion 112 - 30wt% Nafion Elec.SDAPP4 – 15wt% SDAPPe Elec.SDAPP4 – 30wt% SDAPPf3 Elec.SDAPP4 – 15wt% SDAPPf3 Elec.

Nafion 112 - 30wt% Nafion Elec.SDAPP4 – 15wt% SDAPPe Elec.SDAPP4 – 30wt% SDAPPe Elec..

HFR

(ohm

*cm

2 )

HFR

(Ohm

*cm

2 )

0 500 200015001000Current Density (mA/cm2)

0.0

0.7

1.0

0.9

0.8

0.6

0.5

0.3

0.1

0.4

0.2

0 200 1000800400 600Current Density (mA/cm2)

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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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


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)

9

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


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


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Electrons

Reactants & Water

H2O, O2, H2 H2O

H +

e -

Protons

Electrons

Reactants & Water

H2O, O2, H2 H2O

H +H +

e -e -

Protons


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


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


Cel

l Pot

entia

l (V)


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

Barriers Addressed– O2 and H2 Crossover– Fuel Cell Performance– Thermochemical Stability

Barriers Addressed– O2 and H2 Crossover– Fuel Cell Performance– Thermochemical Stability

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Fuel Cell PerformanceIncreasing Durability & Conductivity

In collaboration/Contract with Dr. Deck – Virginia Tech

• Polymerization yielded solid polymer• Incorporation into DA PEM - TBD • Physical Properties - TBD

Barriers Addressed– Conductivity– Fuel Cell Performance– Thermochemical Stability

Barriers Addressed– Conductivity– Fuel Cell Performance– Thermochemical Stability

7

C7F7

FF

30%C7F7

C7F7

C7F7

C7F7

C7F7

O

OC

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Fuel Cell PerformanceIncreasing Conductivity – Ullman Reaction

Br Br

O3S

SO3

N

N

HO3S

SO3H

In collaboration/Contract with Dr. Litt - CWRU

• Polymerization yielded solid polymer/ionomer• MW - TBD • IEC & Conductivity – TBD• Physical Properties - TBD

Barriers Addressed– Conductivity– Fuel Cell Performance– Membrane Cost

Barriers Addressed– Conductivity– Fuel Cell Performance– Membrane Cost

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Fuel Cell PerformanceImproving PEM Morphology & Function - AFM

In collaboration/Contract with Dr. Perahia - Clemson

Barriers Addressed– Conductivity– Fuel Cell Performance– Membrane Cost & Durability

Barriers Addressed– Conductivity– Fuel Cell Performance– Membrane Cost & Durability

Ion Transport

RandomBlock

Ion Transport

RandomBlock

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Enhanced Acidity & Hydration– Acid Groups– Organic-Inorganic Composites

Gas Transport– Tailoring polymers for Electrode and

PEM utilization

Structure-Property-Function– Structured Materials (sulfonation) – Improved Stability (Mechanical

(cycling) and chemical)– Minimize interfacial resistance and

improve adhesion of PEM and catalyst layer

Enhanced Acidity & Hydration– Acid Groups– Organic-Inorganic Composites

Gas Transport– Tailoring polymers for Electrode and

PEM utilization

Structure-Property-Function– Structured Materials (sulfonation) – Improved Stability (Mechanical

(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)

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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

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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.

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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).

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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

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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

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AcknowledgementsHydrocarbon Membrane – Project: FCP5

Thank you for your attention

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.

Sandia National LabsPaul Dailey

Virginia TechProfessor Eva MarandProfessor Paul DeckWill JamesBrian HickoryJessica PriceMariam Konate

ClemsonProfessor Dvora PerehiaLilin He

Case Western Reserve UniversityProfessor Morton Litt

Giner ElectrochemicalSystems, LLC

Cortney Mittelsteadt

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Hydrocarbon Membrane · 2006-06-02 · DOE Fuel Cell Program Hydrocarbon Membrane Project: FC7...

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