HighTemperatureMembraneWorkingGroupMeeting,WashingtonDC,May18,2009

IntegrationofNonTraditional MembranesintoMEAs
YuSeungKim
SensorsandElectrochemicalDeviceGroup LosAlamosNationalLaboratory

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Outline

Background MEAFabrication Part1.MembraneElectrodeInterface

Interfacialresistancemeasurement ImpactofpoorMEAadhesion MethodofimprovingMEAadhesion

Part2.NonPFSAIonomers
Ionomertocatalystratio Dispersingagent Oxygenpermeability Chainmobility

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IonomerBinderforNonTraditionalMembranes
MEA for PEMFCs Membrane
HT Ionomer Binder HT Membrane

High proton conductivity at low RH Good thermal/electrochemical stability Low reactant permeability Low electronic conductivity

Ionomer Binder
High proton conductivity at low RH Good thermal/electrochemical stability High reactant permeability Good catalyst-ionomer interaction

Ionomerbinderhavingdissimilarstructurewithmembranesmaybe desirable.

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StrugglingforRobustMEAFabrications

Gubleretal.,Hotpressingofradiationgraftedmembraneswasnotsuccessfulin our laboratory.SuccessfulfabricationofhotpressedMEASwaspossiblewhenthinner membraneswithlowerdegreeofgraftingwereused FuelCells,(2005)5,317. Baeetal.,TheMEAcomposedofSPSgPPcompositemembranemaysufferfromthe heterogeneousinterfacialstructureincreasingthecontactresistancebetweenmembrane andcatalystlayer J.Memb.Sci.(2003),220,75. Lufranoetal.Poorelectrode/electrolyte(sulfonatedpolysulfone)contactcausedfromthe assemblyofanonperfluorinatedmembranewithacatalyticlayercontainingNafionionomer andlowchainsmobilityoftheseglassypolymers J.Appl.Sci.(2000)77,1250. LeNinivinetal.OptimizationofElectrodemembraneinterfaces(sulfonatedpolyphenylene) isnecessary J.Appl.Electrochem.(2004)34,1159. Vernonetal...WiththisinmindoptimizationofMEAfabricationprocessesas wellasthe developmentofmorecompatibleionomermaterialsintheelectrodesmayproducevery significantimprovementsinperformanceforthehybridmembraneMEA J.PowerSources (2005)139,141151. Besseetal...Wehaveobservedthatthefuelcellperformancesofourpolyimidemembranes arerelativelydependentofprelimianryacidtreatment.Inorder toimprovethe electrode/membraneinterface,athinsulfonatedpolyimidelayerwasdepositedonthe electrodesurfacebeforemakingtheassembly NewMater.Electrochem.Sys.(2001),346.
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LANLMEAProcessingforNonTraditionalMembranes

DirectMembranePainting

Y.S.Kim,J.Electrochem.Soc.151,A2150(2004)

Decaltransfer(Hotpressing)

Wilson,USPatent5,211,984(1993)

Catalystinkisdirectlypaintedonto membranesusingvacuumplate Simpleprocess Difficulttocontrolcatalystloading Difficulttoprocesshighlywater swollenmembrane Easytoisolatemembraneproperty MostlyusedforDMFCapplications

Catalystinkispaintedondecalthen transfertomembraneusinghot pressing Complexprocedure Precisecontrolofcatalystloading Easytoprocesshighlywaterswollen membrane Electrodeadhesiontomembraneis critical Difficulttoisolatemembrane property MostlyusedforPEMFCapplications

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DirectMembranePainting

+
Electrolyte dispersion
Nafion 5% Water/alcohol >90%

Add water Mixing

Catalyst Ink

Pt black catalyst

Teflon masking sheet

current

time

Vacuum table Ink Painting 75-80oC

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Cell break-in

DecalTransfer(Hotpressing)

Glycerol TBAOH Mixing

+
Electrolyte dispersion
Nafion 5% Water/alcohol >90%

Supported catalyst
Pt 20% Carbon 80%

Catalyst Ink

Decal painting & drying

current

time

Cell break-in

Drying
75oC/30 min Under vacuum

Acidification
0.5M H2SO4 1.5 h Water for 1.5 h at boiling temp.
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Hot pressing
210oC few min.

TwoMajorIssueswithDissimilarIonomerBinders
Interfacial Delamination
HT Ionomer Binder HT Membrane

GDL

anode membrane cathode

Poor Performance due to lack of Understanding of electrode structure Carbon
Membrane-electrode interface Catalyst/support dispersity Catalyst-ionomer interaction Ionomer morphology Porosity Reactant/water permeability Catalyst solubility Ionomer relaxation etc

Pt
Binder

(K.More,DOEHydrogenandFuelCellsAnnualReport(2005))
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MeasurementofInterfacialResistance,Rinterface
Rinterface =NonmembraneResistance ElectronicResistance
Non-membrane Resistance
0.30 Y = 7.2 x 10-4+0.035
0.12

Electronic Resistance

0.25

0.10

HFR ( cm2)

0.20

0.08

0.15

Voltage (V)

metal sheet replaced cell (including catalyst layers) electronic resistance (27 cm 2)

0.06
cell 1 cell 2 cell 3

0.10

0.04

0.05

non-membrane resistance (35 cm2)

0 50 100 150 200 250 300 350

0.02

metal sheet replaced cell (excluding catalyst layers)

0 5 10 15 20 25

0.00

0.00

Wet membrane thickness (m)

Current (A)

Rinterface for the example is 8 mcm2

Ref. Y.S. Kim and B.S. Pivovar, J. Electrochem. Soc. (2007) 154, B739.
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Rinterface betweenHCmembraneandNafionElectrode
1: BPSH-30 2: BPSH-35 3: BPSH-40 4: Nafion

Conductivity, , and Interfacial Resistance, Rinterface

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 50 100 150 200 250 4
0.08 0.07 0.06 0.05 0.04 0.03 0 3 2 1 4 2 4

Membrane

(mS/cm)

Rinterface (mcm2)

1 2

HFR ( cm )

BPSH30 BPSH35 BPSH40 Nafion

39 54 78 111

17 31 43 8

Membrane Thickness (m)

SulfonatedPoly(Aryleneether)Sulfone(BPSHx)*
O O S O2 co O

O
HO 3 S

SO 2 SO 3 H

1-x

*Ref. M. Hickner et al. Chem. Rev. 104, 4587, 2004

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ImpactofMembraneElectrodeIncompatibilityonDecalTransfer

Electrode transfer @ 210oC hot pressing

Nafion memb./Nafion electrode

Membrane

Tg* (oC)

Requiredhotpressing Temp.(oC)

BPSH30 BPSH35 BPSH40 Nafion

BPSH/Nafion electrode

260 266 271 120

280
285
>295
140210

HighTgHCmembranesrequirehigherhot pressingtemperature. Hotpressingtemp.increaseswithdegreeof sulfonation. LowsurfaceadhesionpropertyofHCmembranes makesdifficultto100%electrodetransfer.

Ref. F.Wang et al. J. Memb. Sci. (2002), 197, 231.

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Method of Improving Interfacial Adhesion: 1. Thin Coating Layer

Thin coating layer system*

Current density (A/cm 2)
BPSH/Nafion electrode with thin coating layers
0.25 0.20 0. 20 0.15 0. 15 0.10 0. 10

0.2

Anode catalyst layer

Low swelling PEM layer

Proton exchange membrane

Low swelling PEM layer

Cathode catalyst layer

0.1 0.0 1000 1250 1500 1750 2000

250

500

750

Time (hour)

*Y.S. Kim and B.S. Pivovar, US Patent Applications, LANL (2006)

Stable DMFC performance (and HFR) was obtained with thin coating layer system.

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HFR (Ohm cm 2)

0.05 0. 05

LANLMEAFabricationStepsusingNontraditionalMembranes
Is your membrane highly water swollen? (i.e. >35 wt.%) no Direct membrane painting yes Decal Transfer Are the electrodes adhered after acidification? no Plasticized electrode* yes

Does HFR increase over time (under fully humidification)? no MEA testing

yes

Thin layer coating*

MEA testing

* LANL Intellectual properties

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 Part1.MembraneElectrodeInterface

Interfacialresistancemeasurement ImpactofpoorMEAadhesion MethodofimprovingMEAadhesion

Part2.NonPFSAIonomers

IonomertoCatalystRatio DispersingAgent OxygenPermeability ChainMobility

Electrode formulation & testing conditions for electrode studies

Catalyst: Carbon supported platinum (20 wt.%) Catalyst loading: 0.2 mg/cm2 Anode ionomer: Commercial Nafion dispersion Membrane: Nafion 212 MEA fabrication: LANL proprietary Cell temperature: 80oC Anode humidity bottle temperature: 105oC Back pressure: 20 or 30 psi Break in time: >14 h

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NonPFSAElectrode Fact&Motivation
1.0 0.9 0.8 Nafion bonded Pt/C (Pt: 0.2 mg/cm2)
O

BPSH35
O SO2 O 1-x O HO3S SO2 SO3H x

Cell potential (V)

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Nafion
BPSH-35 bonded Pt/C (Pt 0.2 mg/cm )
CF2 CF2 CF x CF2 CF CF3 y n z O(CF2)2 SO3 H
- +
2

OCF2

Membrane: Nafion 212

80oC

Current density (A/cm2)

Electrodebondedbyhydrocarbonionomer(similarconductivityto Nafion)showedmuchinferiorperformance totheelectrodebondedbyNafionionomer. Noelectrodeionomerisavailableforhightemperaturemembranes wherethePFSAionomercannotbeused.

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EffectofIonomerContentonFuelCellPerformance

BPSH-35-bonded Electrode
0.9 0.8 0.7 Ionomer content wt.% 21 29 35

ionomer

Density (g/cm3) 2 1.3

Wt.%

Vol.%

Cell Potential (V)

0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.1 0.2 0.3 0.4 0.5
o Cell temp. 80 C with cathode bypass; backpressure: 30/30 psig 2 Catalsyt : 20% Pt/C (ETEK): 0.2/0.2 mgpt/cm , ionomer: BPSH-35

Nafion BPSH35

29 21 29 35

30 27 40 53

0.6

0.7

Current density (A/cm2)

DuetothelowerdensityofBPSH35,electrodewithlessamountofBPSH35performedbetter. OptimumBPSH35contentis~21wt.%(~27vol.%).

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SANS Study of Nafion Dispersion

1
Line represents slope corresponding to sharp interface between solvent and Nafion

NMPdispersion:CoreShellCylinder
*Structuresarevisualaidsreflectingcurrentunderstanding,andmaybelaterupdated

102

d/D (cm )

-1

0.1

12 27

39

0.01

0.001 0.001

Sharpinterfacebetweencoreandshell SLD*ofcore=~calculatedNafion backbone SLDofshell=~solvent Nosolventpenetrationintothecore Solventpenetratessidechains(lowslope)

0.01 0.1 1

q (A )

-1

Glyceroldispersion:CylinderModel
148

Solvent NMP Ethyleneglycol Water/IPA(2:3) Butanediol Glycerol

Slope
1.7
2.0
2.0
3.3
3.5

28

LessphaseseparationbetweenNafion backbone andsidechains GlycerolappearstopenetrateNafion lessthan NMP(highslope),butsomepenetrationmayoccur

*Moreinformation:FC_16ChristinaJohnston,LANL,Wed.9:00AM.
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Effect of Dispersing Agent on Electrode Performance

Initial Performance
0.90

Durability (potential cycling)

Water/1-propanol/2-propanol
1.1 1.0 0.9 0.8

IR-corrected polarization curves

Nafion electrode
0.85 0.80

Initial After 1000 cycles After 3000 cycles After 10000 cycles

EIR-corrected (V)

Cell potential

0.7 0.6 0.5 0.4 0.3 0.2

0.75 DISPERSION 0.70 N-methylpyrrolidone water/2-propanol (1:3) glycerol

1 A cm-2: 60 mV loss

0.65

o Cell temp. 80 C with fully humidified; backpressure: 30/30 psig

2
Catalsyt : 20% Pt/C (ETEK): 0.2/0.2 mgpt/cm , ionomer: Nafion 212

0.1 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

2

1.6

1.8

2.0

0.60

Current density (A/cm )

0.1

Glycerol
1.1 1.0 0.9 0.8

i (A/cm2)

Cell potential

Electrodes from NMP (and waterisopropanol) dispersion exhibits good ORR kinetics while electrode from glycerol dispersion have relatively good mass transfer. Electrode from water/2propanol showed poor potential cycling durability while electrode from glycerol showed good durability.
* More information: FC_16 Christina Johnston, LANL, Wed. 9:00 AM.
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Initial After 1000 cycles After 3000 cycles After 10000 cycles

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
2

1 A cm-2: 30 mV loss

1.6

1.8

2.0

Current density (A/cm )

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HC Ionomer Dispersion in Various Dispersing Agent*

EW 670 1519 670 1519 670 1519 670 1519 483 670 670 1519 670 1519 670 1519 Dispersing Dispe Mechanical Wettability medium rsion property 1,4 butanediol NA NA Ethylene + Tough Good glycol
Propylene + Tough Good glycol
Glycerol + Tough Good + + Water/iso + Brittle Poor propanol (1:1) NMP + Tough Good + DMSO + + DMAc + +
0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 0.40 0.35 0.30 0.25 0.20
o Cell temp. 80 C with fully humidified; backpressure: 30/30 psig 2 Catalsyt : 20% Pt/C (ETEK): 0.2/0.2 mgpt/cm , ionomer: BPSH-35

IR-corrected polarization curves

EIR-corrected (V)

DISPERSION DMAc water/2-propanol (1:1) glycerol

0.01

0.1

i (A/cm )

*Y.S. Kim, T. Rockward, and K.S. Lee, US Patent Pending, LANL (2009)

Dispersing agent effect is much greater for BPSH 35 electrode than Nafion but similar trend. We have difficulties using waterbased dispersion due to poor mechanical properties and poor wettability.

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ChronoamperometryofOxygenonPt/Nafion andPt/6F40
glass

120

Pt/Nafionelectrode

40

Pt/6F40electrode

Ionomer

Oxygen

Pt

0.3 V 30 Current (nA) Current (nA) 80 cv limiting 0.4 V current 40

0.4 V 0.3 V
60 C, 60% RH, 100 m (diameter) Pt UME (microdisk) Film thickness: Nafion 13.5 m, 6F40 - 26.5 m ;

20 cv limiting current

10

0 0 0.4 t
-1/2

0.8 /s
-1/2

1.2

0 0

0.4 t
-1/2

0.8 (s
-1/2

1.2

SignificantlyloweroxygenreductioncurrentsforthePt/6F40thanthoseforpt/Nafionindicates significantlyloweroxygenpermeabilityof6F40tooxygen. NonlineariltyandcurrentdecreaseofPt/Nafionbeyondthecvlimitingcurrentindicates significantpolymerchainreorganizationofNafionduringchromoamperometryprocess.

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EffectofCathodeHumidificationonFuelCellPerformance
0.9 0.8 0.7 no humidified cathode fully humidified cathode 0.6

0.5

Cell potential (V)

0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0

0.4

du e R

RH d ce

0.3

0.2 cell temp. 80oC 2 0.1 catalsyt : 0.2 mg/cm Pt/C membrane Nafion 212 electrode binder:BPSH-35 (27 vol.%) back pressure 30 psig 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Current density (A/cm 2)

HydrocarbonbondedelectrodeshowsbetterperformanceatlowRHconditions,duetobetter masstransfer GoodchancetoreplacePFSAbondedelectrodewiththermallystableHC bondedelectrodefor hightemp.andlessRHfuelcells

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HFR ( cm )

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EffectofHydrophobicityofPolymers
PFSA
1.0 0.9 0.8 0.7 PFSA

Fully humidified cathode

Cell potential (V)

0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 biphenyl Hexafluoro Decafluoro

Decafluoro based Polyaromatic

0.1

0.2

0.3

0.4

0.5

0.6

0.7
2

0.8

0.9

1.0

Current density (A/cm )

Hexafluoro bisphenol based Polyaromatic

1.0 0.9 0.8 0.7 PFSA

No humidifed cathode

Cell potential (V)

0.6 0.5 Decafluoro 0.4 0.3 0.2 0.1 0.0 0.0 biphenyl

Biphenyl based Polyaromatic

Hexafluoro

0.1

0.2

0.3

0.4

0.5

0.6

0.7
2

0.8

0.9

1.0

Courtesy: Profs. McGrath (VT) and Lee (GIST)

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Current density (A/cm )

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StateofWaterinESF100andBPSH35using2HNMR
Neat water

ESF-100

BPSH-35

BPSH35hasmoreboundwaterthanESF100whichpossiblyprohibitsoxygentransport.

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EffectofChainMobilityonBreakinProcess
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Nafion BPSH-35 Nafion 6F-40

Break in at 0.7 V

Nafion

CF2

CF2

CF x

CF2 CF

yn z O(CF2)2 SO3-H+

OCF2

CF3

Beforebreakin

Afterbreakin

current (A)

Pt
SO3H
6F-40 BPSH-35 0 20 40 60 80

Pt
SO3H

BPSH35
time (h)

SO2

O 1-x

O HO3S

SO2 SO3H x

Beforebreakin

Afterbreakin

Pt
SO3H

Pt
SO3H

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Summary

PooradhesionbetweenmembraneandelectrodemayresultinprematureMEAfailure (poorelectrodetransfer)duringMEAprocessingorgradualinterfacialdelaminationduring longtermfuelcelloperation. Interfacialadhesioncanbeenhancedbythincoatinglayersorplasticizationofelectrode. Todate,propertiesandinteractionofnonPFSAionomerbinderswithfuelcellcatalystare poorlyunderstood. SANSresultsindicatedthatdispersedandsolidionomerhaddifferentstructure(size, micelleformationandphaseseparation)andmechanicalpropertiesdependingon dispersingagent. SolidNMRstudyindicatedthatstateofwatermaybeimportantfactorforelectrode floodingwhichhaveobservedasapredominantfactor.Electrode performanceincreased withfluorinationofpolymers. Sidechainmobilitymaygivecriticalinfluenceonelectrodeperformance.More investigationisneededinthisarea.

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Acknowledgments

BryanS.Pivovar(NREL)
JamesE.McGrath(VirginiaTech)
ChulSungBae(UNLV)
MichaelGuiver(CanadaNRC)
JaeSukLee(GIST)
KwanSooLee(GIST,LANL)
TommyRockward(LANL)
AndreaLabourieu(LANL)
BruceOrler(LANL)
CindyWelch(LANL)
MarilynHawley(LANL)
RexHjelm(LANCE,LANL)
ChristinaJohnston(LANL)
JerzyChilstunoff(LANL)
NancyGarlend (DOEEEREProgram)

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