2016 DOE Fuel Cell Technologies Office Annual Merit Review

2016 DOE Hydrogen and Fuel Cells Program Review

XYZ Thrust Area Co-ordinatorRod amp Adam FC PAD Directors

Wednesday June 8th 2016

FC136 ndash FC-PAD Components and Characterization

Presenter Karren L More Tuesday June 6th 2017

This presentation does not contain any proprietary confidential or otherwise restricted information

12017 DOE Fuel Cell Technologies Office Annual Merit Review

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Part of

FC-PAD Consortium to Advance Fuel Cell Performance and Durability

Approach Objectives

bull Improve component stability and durability Couple national lab capabilities with funding bull Improve cell performance with optimized opportunity announcements (FOAs) for an influx of

transport innovative ideas and research bull Develop new diagnostics characterization tools

and models

Consortium fosters sustained capabilities and collaborations

Structured across six component and cross-cutting thrusts

Core Consortium Team

Prime partners added in 2016 by DOE solicitation (DE-FOA-0001412)

2wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Part of

FC-PAD Consortium to Advance Fuel Cell Performance and Durability

Approach Objectives

bull Improve component stability and durability Couple national lab capabilities with funding bull Improve cell performance with optimized opportunity announcements (FOAs) for an influx of

transport innovative ideas and research bull Develop new diagnostics characterization tools

and models

Consortium fosters sustained capabilities and collaborations

Structured across six component and cross-cutting thrusts

Core Consortium Team

Prime partners added in 2016 by DOE solicitation (DE-FOA-0001412)

2wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

FC-PAD Consortium - Overview

Fuel Cell Technologies Office (FCTO) bull FC-PAD coordinates activities related to fuel cell performance and durability bull The FC-PAD team consists of five national labs and leverages a multishy

disciplinary team and capabilities to accelerate improvements in PEMFC performance and durability

bull The core-lab team consortium was awarded beginning in FY2016 builds upon previous national lab (NL) projects

bull Provide technical expertise and harmonize activities with industrial developers bull FC-PAD serves as a resource that amplifies FCTOrsquos impact by leveraging the

core capabilities of constituent members

3wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

4

FC-PAD Consortium Relevance and Objectives Overall Objectives bull Advance performance and durability of polymer electrolyte membrane

fuel cells (PEMFCs) at a pre-competitive level bull Develop the knowledge base and optimize structures for more durable

and high-performance PEMFC components bull Improve high current density performance at low Pt loadings bull Loading 0125 mgPt cm2 total bull Performance 08 V 300 mA cm2

bull Performance rated power 1000 mW cm2

bull Improve component durability (eg membrane stabilization self-healing electrode-layer optimization)

bull Provide support to industrial and academic developers from FOA-1412 bull Each thrust area has a sub-set of objectives which support the overall

performance and durability objectives

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

5

FC-PAD Overview and Relevance

Timeline Barriers Project start date 10012015 Project end date 09302020

Budget bull FY17 project funding $5150000 bull As proposed 5-year consortium with

quarterly yearly milestones amp GoNo-Go bull Total Expected Funding $25M (NLs only)

PartnersCollaborations (To Date Collaborations Only)

bull IRD Fuel Cells Umicore NECC GM TKK USC 3M JMFC WL Gore Ion Power Tufts KIER PSI UDelaware CSM SGL NPL NIST CEAULorraine

bull Partners added by DOE DE-FOA-0001412

bull Cost $40kW system $14kWnet MEA

bull Performance 08 V 300 mA cm2

bull Performance rated power 1000 mW cm2 (150 kPa abs)

bull Durability with cycling 5000 (2020) ndash 8000 (ultimate) hours plus 5000 SUSD Cycles

bull Mitigation of Transport Losses bull Durability targets have not been met

bull The catalyst layer is not fully undershystood and is key in lowering costs by meeting rated power

bull Rated power low Pt loadings reveals unexpected losses

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

6

FC-PAD Objectives How We Get There bull Develop the knowledge base and optimize structures for more durable and

high-performance PEMFC components bull Understanding Electrode Layer Structure o Characterization bull New Electrode Layer Design and Fabrication o Stratified (Spray Embossed Array) Pt - Deposition Jet Dispersion bull DefiningMeasuring Degradation Mechanisms o Membrane Catalyst Pt-alloy dissolution

FC-PAD Presentations bull FC135 FC-PAD Fuel Cell Performance and Durability Consortium (Rod Borup LANL)

ndash Overview Framing Approach and HighlightsDurability bull FC136 FC-PAD Components and Characterization (Karren L More ORNL)

ndash Concentration on Catalysts and Characterization bull FC137 FC-PAD Electrode Layers and Optimization (Adam Weber LBNL)

ndash Concentration on Performance - MEA construction and modeling bull FC155 (3M) FC156 (GM) FC157 (UTRC) FC158 (Vanderbilt) FOA-1412 Projects

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

FC-PAD Component Characterization - Capabilities

Thin film characterization

Advanced microscopy amp spectroscopy

AST DevelopmentRefinement

Synchrotron X-ray techniques Time-resolved on-line ICP-MS

7wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress AST Development amp Refinement New catalyst durability AST is 5X faster than old AST and 70

20X faster than FCTT durability protocol 60

50

40

30

20

10

0

06 -10V cycles 30000 cycles 06 -095V cycles 30000 cycles Target ndash 133 hr Target ndash 50 hr

bull Square wave lowers test duration from 133 to 50 hours (does not include characterization time)

bull Square wave still representative of drive cycle 80

70degradation 60

bull AST reflective of Pt dissolution and independent 50

E

CSA

Loss

ECS

A Lo

ss

FCTT Drive cycle TEC10E20E

Old AST (5X) TEC10E20E

New AST (25X) TEC10E20E

New AST Low flow 4-serp (25X) TEC10E20E

0 500 1000 1500 2000 2500

New AST E-carbon

New AST V-carbon

New AST EA-carbon

0 10000 20000 30000 40000

of carbon type

Other durability protocols under development and refinement

40

30

bull Membrane durability 20

bull Carbon durability 10

0

bull SUSD protocols bull Freeze protocols bull Drive cycle protocols

PtC 015mgPtcm2

Time (hrs)

of Potential Cycles

8wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Aqueous Stability of PtCo Alloys Time-Resolved On-Line ICP-MS Measurements

Objectives bull Real time measurements of Pt and Co dissolution

under cyclic potentials bull Resolve anodic vs cathodic dissolution of Pt and Co Catalysts bull TEC36E52 Pt3CoHSC 465 wt Pt

47 wt Co 57 nm TEM bull Umicore Elyst P30 0670 275 wt Pt

3 wt Co 44 nm TEM bull Catalyst-ionomer ink deposited on GC at

2 microg-Ptcmsup2

ICP-MS Agilent 7500ce Octopole Cell BASi

bull Co dissolution observed at all potentials bull Distinct peaks in anodic and cathodic dissolution of Pt

above 09 V bull Potential dependent dissolution rates of Pt and Co

9wwwfcpadorg

10

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress Dissolution of Pt from UmicorePt7Co3C Cathode Catalyst on Stair-Case Potentials

Cathodic dissolution not significant for UPL lt09 V in square wave potentials

bull Distinct anodic and cathodic peaksbull Anodic peaks higher at higher potentialsbull Highest cathodic peak on potential step from 08 to 075 V

bull ~3-time higher Pt dissolution during cathodic than anodic steps stair-case potential 1 V UPL

bull Both anodic and cathodic Pt dissolution rates (amount dissolved divided by cycle time) increase at higher potential steps

Peak cathodic dissolution rate depends on the initial potential and the potential step

0

1

2

3

4

5

6

7

8

9

10

04 05 06 07 08 09 1

PeakCatho

dicP

tDissolutio

nRa

tengh-

1

Step-downPotentialV

50mVstep100mVstep150mVstep200mVstep300mVstep600mVstep

Peak cathodic rate reaches a

maximum at 065-075 V step down

potential

50 mV stair-case180 s hold

SquareWaveUPLvaries120shold

wwwfcpadorg

11

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress Dissolution of Co from UmicorePt7Co3C Cathode Catalyst on Stair-Case Potentials

Break-in protocol requires gt1-h conditioning on 04-10 V square wave potentials

bull Anodic Co dissolution rate nearly constant for potentials up to 08 V

bull Anodic peaks observed at potentials gt08 Vbull Highest cathodic peak on potential step from 08 to 06 V

bull Comparable Co dissolution during anodic and cathodic steps

bull Anodic and cathodic Co dissolution rates (amount dissolved divided by cycle time) lowest for 200 mV potential step

Peak cathodic dissolution rate depends on the initial potential and the potential step

00

05

10

15

20

25

30

35

40

45

04 05 06 07 08 09 1

PeakCatho

dicC

oDissolutionRa

tengh-

1

Step-downPotentialV

100mVstep

150mVstep

200mVstep

300mVstep

600mVstep

Break-in (04-1 V 180s hold)

200 mV stair-case 180 s hold

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Extensive Study of PtCo Catalysts

Catalyst Supplier

CatalystHSAC Catalyst Loading (mgPtcm2) amp ECSA (m2

PtgPt)

Membrane

Umicore PtCo (Elyst Pt30 0670) spray-coated CCL NREL

01 amp 37 Nafion 211

IRD (EWII) Pt3Co (IRD SOA catalyst) IRD-prepared MEA

02 amp 41 Reinforced

GM - SOA GM SOA PtCo catalyst GM-prepared MEA

01 amp 43 DuPont XL-100

MEAs characterized bull Conditioned BOL bull NEW Catalyst AST bull OLD Catalyst AST bull 1200 hr Wet Drive Cycle

06 -10V cycles 30000 cycles

Target ndash 133 hrs

06 -095V cycles 30000 cycles

Target ndash 50 hrs

12

Old triangle-wave catalyst AST New square-wave catalyst AST

wwwfcpadorg

11

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress Dissolution of Co from UmicorePt7Co3C Cathode Catalyst on Stair-Case Potentials

Break-in protocol requires gt1-h conditioning on 04-10 V square wave potentials

bull Anodic Co dissolution rate nearly constant for potentials up to 08 V

bull Anodic peaks observed at potentials gt08 Vbull Highest cathodic peak on potential step from 08 to 06 V

bull Comparable Co dissolution during anodic and cathodic steps

bull Anodic and cathodic Co dissolution rates (amount dissolved divided by cycle time) lowest for 200 mV potential step

Peak cathodic dissolution rate depends on the initial potential and the potential step

00

05

10

15

20

25

30

35

40

45

04 05 06 07 08 09 1

PeakCatho

dicC

oDissolutionRa

tengh-

1

Step-downPotentialV

100mVstep

150mVstep

200mVstep

300mVstep

600mVstep

Break-in (04-1 V 180s hold)

200 mV stair-case 180 s hold

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Extensive Study of PtCo Catalysts

Catalyst Supplier

CatalystHSAC Catalyst Loading (mgPtcm2) amp ECSA (m2

PtgPt)

Membrane

Umicore PtCo (Elyst Pt30 0670) spray-coated CCL NREL

01 amp 37 Nafion 211

IRD (EWII) Pt3Co (IRD SOA catalyst) IRD-prepared MEA

02 amp 41 Reinforced

GM - SOA GM SOA PtCo catalyst GM-prepared MEA

01 amp 43 DuPont XL-100

MEAs characterized bull Conditioned BOL bull NEW Catalyst AST bull OLD Catalyst AST bull 1200 hr Wet Drive Cycle

06 -10V cycles 30000 cycles

Target ndash 133 hrs

06 -095V cycles 30000 cycles

Target ndash 50 hrs

12

Old triangle-wave catalyst AST New square-wave catalyst AST

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Extensive Study of PtCo Catalysts

Catalyst Supplier

CatalystHSAC Catalyst Loading (mgPtcm2) amp ECSA (m2

PtgPt)

Membrane

Umicore PtCo (Elyst Pt30 0670) spray-coated CCL NREL

01 amp 37 Nafion 211

IRD (EWII) Pt3Co (IRD SOA catalyst) IRD-prepared MEA

02 amp 41 Reinforced

GM - SOA GM SOA PtCo catalyst GM-prepared MEA

01 amp 43 DuPont XL-100

MEAs characterized bull Conditioned BOL bull NEW Catalyst AST bull OLD Catalyst AST bull 1200 hr Wet Drive Cycle

06 -10V cycles 30000 cycles

Target ndash 133 hrs

06 -095V cycles 30000 cycles

Target ndash 50 hrs

12

Old triangle-wave catalyst AST New square-wave catalyst AST

wwwfcpadorg

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress Extensive Study of PtCo Catalysts

segmented PtC 3D surfaces

SOA Pt-CoHSAC Fresh MEA

bull Avg PtCo particle sizebull 44nm diameter

bull Avg PtCo compositionbull 85 Pt ndash 15 Co

bull majority of PtCoparticles are insideHSAC support

bull 77 within corebull 23 on surface

rotation animation

STEM-BF image

volume clipping animation

single z-slice

single z-slice

PtCo NPs located at surface

internal PtCo NPs

13 wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Extensive Study of PtCo Catalysts

at

Co

BOL 1200hr wet drive cycle

50nm 50nm

BOL 45nm

Square-wave AST 51nm

Triangle-wave AST 50nm

Wet Drive Cycle 74nm

36

30

24

18

12

6

0

equivalent diameter (nm)

bull Significant increase in PtCo particle size from 45nm to ~74nm during 1200 hr wet drive cycle Significant drop in Co content within CCL shyaverage particle composition changes from 85Pt15Co to ~95Pt5Co

bull Significant Pt-enrichment of most particles (except for very large particles)

BOL triangle square wet drive

0 5 10 15 20 25 30

14wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Extensive Study of PtCo Catalysts

at

Co

BOL 1200hr wet drive cycle

50nm 50nm

BOL 45nm

Square-wave AST 51nm

Triangle-wave AST 50nm

Wet Drive Cycle 74nm

36

30

24

18

12

6

0

equivalent diameter (nm)

bull Significant increase in PtCo particle size from 45nm to ~74nm during 1200 hr wet drive cycle Significant drop in Co content within CCL shyaverage particle composition changes from 85Pt15Co to ~95Pt5Co

bull Significant Pt-enrichment of most particles (except for very large particles)

BOL triangle square wet drive

0 5 10 15 20 25 30

14wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

single z-slice

internal PtCo NPs

Technical Progress Extensive Study of PtCo Catalysts

SOA Pt-CoHSAC Wet Drive cycle 1200 hrs

bull Avg PtCo particle size bull 75nm diameter

bull Avg PtCo composition bull 95 Pt ndash 5 Co

bull Some change of PtCo particles from inside to surface of HSAC support bull 65 remain in core bull 35 on surface

single STEMBF image

single z-slice

PtCo NPs located at surface

segmented PtC 3D surfaces

15

rotation animation volume clipping animation

Increased PtCo particles on surface of HSAC after testing due to Pt and Co dissolution

wwwfcpadorg

16

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Pt and Co mol fractions in particles and d-spacing calculated from fit to position of WAXS (111) peak ndash PtCo catalysts become more ldquoPt-likerdquo during ASTs

2210

2215

2220

2225

2230

2235

2240

2245

2250

00

01

02

03

04

05

06

07

08

09

10

d-sp

acin

g(Aring

)

Mol

eFr

actio

nPtmolfraction Comolfraction d-spacing(ang)

Technical Progress Extensive Study of PtCo Catalysts

wwwfcpadorg

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress Co Loss During ASTs

SOA PtCo exhibits improved initial performance (ECSA) compared to other PtCoHSAC catalysts but after 30000

cycles ECSA values are the same

Performance (ECSA) loss can be directly attributed to extensive Co loss from

catalystCCL into membrane during AST

0

10

20

30

40

50

60

70

80

0 5000 10000 15000 20000 25000 30000 35000

ECSA(m

2 gm)

ofPotenalCycles (squarewaveAST)

PtHSAC

GMSOAPtCoHSAC

UmicoreElystPtCoHSAC

IRDldquospongyrdquoPtCoHSAC

0

5

10

15

20

PtC

o R

atio

in C

CL

Umicore 7030

Umicore 8020

Umicore 9010

IRD 6040

IRD 6634

IRD 8218

GM SOA 9515

GM SOA 8911GM SOA

8515

PtCo Powder

BOL MEA

Square-wave AST

Wet Drive Cycle

17 wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Au

Technical Progress Quantifying Co Loss to Membrane

Method

bull Au-coat MEAs for internal standard (should not use Cu Pt C)

bull Acquire EDS maps of cathode catalyst layer(CCL) and membrane

bull Assume most Pt lost redeposits in ldquoPt-bandrdquo in membrane near the CCL calculate Pt migration from cathode into membrane usingAu referencestandard

bull Use average PtCo ratio in untested CCL and amount of Co in tested CCL to calculate ~Co in membrane

sputtered

~1-2 nm Au

W Bi GE Gray and TF Fuller Electrochemical and Solid-State Letters 10 (5) B101 (2007)

DA Cullen R Koestner RS Kukreja ZY Liu S Minko O Trotsenko A Tokarev L Guetaz HM Meyer III CM Parish and KL More Journal of the Electrochemical Society 161 (10) F1111 (2014)

18wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Au

Technical Progress Quantifying Co Loss to Membrane

Method

bull Au-coat MEAs for internal standard (should not use Cu Pt C)

bull Acquire EDS maps of cathode catalyst layer(CCL) and membrane

bull Assume most Pt lost redeposits in ldquoPt-bandrdquo in membrane near the CCL calculate Pt migration from cathode into membrane usingAu referencestandard

bull Use average PtCo ratio in untested CCL and amount of Co in tested CCL to calculate ~Co in membrane

sputtered

~1-2 nm Au

W Bi GE Gray and TF Fuller Electrochemical and Solid-State Letters 10 (5) B101 (2007)

DA Cullen R Koestner RS Kukreja ZY Liu S Minko O Trotsenko A Tokarev L Guetaz HM Meyer III CM Parish and KL More Journal of the Electrochemical Society 161 (10) F1111 (2014)

18wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Quantifying Co Loss to Membrane Umicore GM XL square 1600

1400

1200CCL 1000

800

600

400

200

0 60 membrane

near cathode 1600

1400

1200

1000

800 membrane 600

near 400 co

unts

coun

tsanode

200

0 60

Umicore

Co-Kα1

Pt-Lα1

cathode mem near cat mem near an anode

65 70 75 80 85 90 95 100 keV GM XL square

cathode mem near cat mem near an anode

Co-Kα1

Pt-Lα1

19

65 70 75 80 85 90 95 100 keV

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Quantifying Co Loss

Co migration from cathode to membrane nominal loading

-BOL conditionedshy(mgcm2)

GM XL (square wave)

01

0018

Umicore (triangle wave)

01

0025

AST STEMEDS

quantification

32 Pt loss

50 Co loss

28 Pt loss

52 Co loss

Loss to membrane (mgcm2)

0032

0009

0028

0013

remaining cathode

content(mgcm2)

0068 Pt

0009 Co

0072 Pt

0012 Co

Next step - how much Co remains within the ionomer in CCL

20wwwfcpadorg

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress RDE Testing - Film Deposition Impurities

bull RDE technique used by basicapplied science community for PEMFC electrocatalyst screening bull Standard test protocol and best practices can enable procedural consistency and less variability bull Test protocol and best practices validated at NREL and ANL using poly-Pt PtC-TKK JM Umicore

3 film depositiondrying methods Cell and Electrolyte Impurity Levelsmdash evaluated NREL poly-Pt specific activity as a diagnostic

SAD (stationary air-dry)

RAD (rotational air-dry)

SIPAD (stationary IPA dry)

Statistical reproducibility Poly-Pt specific activity Poly-Pt specific activity NREL inter-lab comparison

RDE cell configurations used at NREL and ANL

Nafion-based Rotational Air Drying (N-RAD) most reliable method for routine screening

SS Kocha K Shinozaki JW Zack D Myers N Kariuki T Nowicki V Stamenkovic Y Kang D Li and D Papageorgopoulos ldquoBest Practices and Testing Protocols for Benchmarking ORR

RHE No Salt Bridge SCE Salt Bridge HgHg2SO4 Salt BridgeActivities of Fuel Cell Electrocatalysts using RDErdquo Electrocatalysis (2017) DOI ECCL NREL ESC ANL HFCM ANL

CE

RE (RHE) WE

(RDE)

21 wwwfcpadorg

22

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress TF-RDE Protocols and BaselinesRDE Protocols

Statistical Reproducibility PtC Specific Activity (micromicroAcm2Pt)

at NREL (Rotational Air Dry or N-RAD technique)

PtC mass activity (mAmgPt) Inter-lab comparison(N-RAD technique)

464 wt Pt d~25nm 376 wt Pt dlt2nm 472 wt Pt d~49nm

Gas N2 or O2

Temperature rtRotation Rate [rpm] 1600

Potential Range [V vs RHE] minus001 to 10 (anodic)Scan Rate [Vs] 002

Rsol measurement method i-interrupter or EIS (HFR)iR compensation applied during measurement

Background Subtraction LSV (O2)minusLSV (N2)

ORRCVBreak-inORR Protocol Details

wwwfcpadorg

0

300

600

900

1200

1500

1800

TKKPtHSC Umi5PtHSC Umi5PtCoHSC

MassA

cltvity(m

AmgPt)

NafionFree5SIPADRDE

NafionBased5RADRDE

NafionBasedMEA

Test protocol and best practices validated at NREL and ANL

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Ionomer-TM Effect on ORR Kinetics RDE 60

50

ORR Kinetics on bare and

Film Pt Ni2+

OR

R k

inet

ic1

i at0

9 V

40

30

20 Film Pt

10 Pt

00 0 001 002 003

W-frac12

004 005

Pt Ni2+

006

Cur

rent

0

9 V

(Ac

m2 )

ik gt 20 mAcm2 indicative of ldquocleanrdquo system 25 2

PFSA thin film-coated Poly-Pt with 10 mM Ni2+ in

23

15 electrolyte 1

05 Studies on Co2+ underway 0

Bare Pt Pt-Ionomer Bare Pt in 10 Pt-Ionomer Film mM Ni2+ Film in 10 mM

Ni2+

wwwfcpadorg

22

2016DOEFuelCellTechnologiesOfficeAnnualMeritReview

Technical Progress TF-RDE Protocols and BaselinesRDE Protocols

Statistical Reproducibility PtC Specific Activity (micromicroAcm2Pt)

at NREL (Rotational Air Dry or N-RAD technique)

PtC mass activity (mAmgPt) Inter-lab comparison(N-RAD technique)

464 wt Pt d~25nm 376 wt Pt dlt2nm 472 wt Pt d~49nm

Gas N2 or O2

Temperature rtRotation Rate [rpm] 1600

Potential Range [V vs RHE] minus001 to 10 (anodic)Scan Rate [Vs] 002

Rsol measurement method i-interrupter or EIS (HFR)iR compensation applied during measurement

Background Subtraction LSV (O2)minusLSV (N2)

ORRCVBreak-inORR Protocol Details

wwwfcpadorg

0

300

600

900

1200

1500

1800

TKKPtHSC Umi5PtHSC Umi5PtCoHSC

MassA

cltvity(m

AmgPt)

NafionFree5SIPADRDE

NafionBased5RADRDE

NafionBasedMEA

Test protocol and best practices validated at NREL and ANL

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Ionomer-TM Effect on ORR Kinetics RDE 60

50

ORR Kinetics on bare and

Film Pt Ni2+

OR

R k

inet

ic1

i at0

9 V

40

30

20 Film Pt

10 Pt

00 0 001 002 003

W-frac12

004 005

Pt Ni2+

006

Cur

rent

0

9 V

(Ac

m2 )

ik gt 20 mAcm2 indicative of ldquocleanrdquo system 25 2

PFSA thin film-coated Poly-Pt with 10 mM Ni2+ in

23

15 electrolyte 1

05 Studies on Co2+ underway 0

Bare Pt Pt-Ionomer Bare Pt in 10 Pt-Ionomer Film mM Ni2+ Film in 10 mM

Ni2+

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Technical Progress Ionomer-TM Effect on ORR Kinetics RDE 60

50

ORR Kinetics on bare and

Film Pt Ni2+

OR

R k

inet

ic1

i at0

9 V

40

30

20 Film Pt

10 Pt

00 0 001 002 003

W-frac12

004 005

Pt Ni2+

006

Cur

rent

0

9 V

(Ac

m2 )

ik gt 20 mAcm2 indicative of ldquocleanrdquo system 25 2

PFSA thin film-coated Poly-Pt with 10 mM Ni2+ in

23

15 electrolyte 1

05 Studies on Co2+ underway 0

Bare Pt Pt-Ionomer Bare Pt in 10 Pt-Ionomer Film mM Ni2+ Film in 10 mM

Ni2+

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

24

Proposed Future Work bull Catalysts and Catalyst Layers o Characterize new catalysts incorporated into MEAs and new CCL architectures before and after ASTs

(ANL BNL Umicore etc) o Work with FOA partners and implement FC-PAD capabilities to characterize novel catalystsMEAs o Coordinate characterization results with refined models bull Testing and AST Refinement o Quantify the effect of Co and Ce in the ionomer and how it affects performance (both sheet resistance and

local oxygen resistance) o Complete 5000 hr benchmarking test o Initiate durability testing using a differential cell (currently using GMs 5cm2 cell) and validate using new

10cm2 differential cell hardware o Understand the effect of Co alloying on carbon corrosion at 30C bull Dissolution Studies o Correlate Pt and Co dissolution with extent of oxidation and oxide structure for PtCo alloy catalysts o Measure Pt re-deposition rates as a function of potential using on-line ICP-MS for input to catalyst

degradation models

o On-line ICP-MS measurements of Pt and TM dissolution as a function of catalyst particle size and support o EXAFS analysis of changes in Pt and Co coordination and bonding after AST

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

25

Summary bull RelevanceObjective o Optimize performance and durability of fuel-cell components and assemblies bull Approach o Use synergistic combination of modeling and experiments to explore and optimize component

properties behavior and phenomena bull Technical Accomplishments o Understanding of the aqueous stability of PtCo alloys using time-resolved on-line ICP-MS

measurements o Refinement of catalyst durability AST to better simulate FCTT drive cycle protocol o Extensive characterization of multiple PtCo catalysts showed performance loss correlation with

accelerated Co leachingdissolution o Quantification of Co loss from CCL to membrane during AST o Initiated work with FOA partners bull Future Work o Further our understanding of Pt-alloy durability by incorporating new catalystMEAs in FC-PAD o Elucidate critical bottlenecks for performance and durability from ink to CCL formation to

conditioning to testing o Use critical characterization data as input for multiscale modeling of cell and components o Expand dissolution studies to better understand the behavior of Pt-based TM catalysts

wwwfcpadorg

2016 DOE Fuel Cell Technologies Office Annual Merit Review

Acknowledgements

DOE EERE Energy Efficiency and Renewable Energy Fuel Cell Technologies Office (FCTO)

bull Fuel Cells Program Manager amp Technology Manager o Dimitrios Papageorgopoulos o Greg Kleen

bull Organizations we have collaborated with to date

bull User Facilities o DOE Office of Science SLAC ALS-LBNL APS-ANL LBNL-Molecular Foundry CNMSshy

ORNL CNM-ANL o NIST BT-2

26