DOE's Fuel Cell Catalyst R&D Activities · DOE’s fuel cell catalyst R&D activities . Nancy L. Garland . ... • Develop electrocatalysts with reduced precious metal

1 | Fuel Cell Technologies Program eere.energy.gov

U.S. Department of Energy Fuel Cell Technologies Program

U.S. Department of Energy Polymer Electrolyte Membrane Fuel Cell Catalyst Development Activities

DOE’s fuel cell catalyst R&D activities Nancy L. Garland

Department of Energy Kick-off Catalyst Working Group Arlington, VA May 14, 2012


Tech

nolo

gy

Bar

riers

*

Econ

omic

&

Inst

itutio

nal

Bar

riers

Fuel Cell Cost & Durability Targets*:

Stationary (1–10 kWe Residential CHP + DG with NG): $1,000-$1,700/kW depending on scale, 60,000-hr durability by 2020

Vehicles: $30/kW, 5,000-hr durability

Safety, Codes & Standards Development

Domestic Manufacturing & Supplier Base

Public Awareness & Acceptance

Hydrogen Supply & Delivery Infrastructure

Hydrogen Threshold Cost $2 – 4 /gge, (dispensed and untaxed)

Key Challenges

Technology Validation:

Technologies must be demonstrated under real-world

conditions. Assisting the growth of early

markets will help to overcome many

barriers, including achieving

significant cost reductions through

economies of scale.

Market Transformation

* Targets and metrics are being updated

Hydrogen Storage Capacity Target: > 300-mile range for vehicles—without compromising interior space or performance

DOE’s Hydrogen & Fuel Cells Program addresses the key challenges facing the widespread commercialization of fuel cells.

Source: US DOE 10/2011


• Catalyst is highest stack cost at high production volumes.

Catalysts dominate FC issues

• Learning Demonstration project indicates durability needs to be increased.

• Catalyst degradation is a key aspect of performance loss.

DOE is investigating • Cost reduction by decreasing Pt

loading: – Extended Pt surfaces – Platinum alloy catalysts, including

core-shell concepts – Non-PGM catalysts – Hybrid catalysts

• Durability improvement by: – More stable structured alloys – Addition of catalyst functionality to

reduce the severity of conditions at the electrodes during start-up/shut-down cycles

– More stable catalyst supports

500,000 systems/year (2010)


Approach Extended Surfaces

Core-shell particles

Dealloyed Particles

Non-PGM Catalysts

Activity + + + Needs improvement

Durability + ?? ?? Needs improvement

Mass transport - + + ? Other Activities in

MEAs not as high as those in RDE experiments

Activities in MEAs not as high as those in RDE experiments

Evaluation of catalyst approaches


Characteristic Units Target 2017

Platinum group metal total content a g / kW rated ≤ 0.125

Platinum group metal total loading a mg PGM / cm2 electrode area ≤ 0.125

Loss in catalytic (mass) activity b % mass activity loss < 40%

Catalyst support stability c % mass activity loss < 10%

Mass activity d A / mg PGM @ 900 mViR-free ≥ 0.44

Non-Pt catalyst activity per volume of supported catalyst d, e

A / cm3

@ 800 mViR-free ≥ 300

Catalyst Targets (from MYRD&D Plan)

a PGM content and loading targets may have to be lower to achieve system cost targets. b DDurability measured in a 25-50 cm2 MEA during triangle sweep cycles at 50 mV/s between 0.6 V and 1.0 V at 80°C, atmospheric

pressure, 100% relative humidity, H2 at 200 sccm and N2 at 75 sccm for a 50 cm2 cell. Based on U.S. DRIVE Fuel Cell Tech Team Cell Component Accelerated Stress Test and Polarization Curve Protocols

c Durability measured in a 25-50 cm2 MEA during a hold at 1.2 V in H2/N2 at 80°C, 150 kPa, 100% relative humidity. Based on U.S. DRIVE Fuel Cell Tech Team Cell Component Accelerated Stress Test and Polarization Curve Protocols (http://www.uscar.org/commands/files_download.php?files_id=267), Catalyst Support Cycle and Metrics (Table 2). Activity loss is based on loss of mass activity, using initial catalyst mass, at end of test.

d Test at 80°C H2/O2 in MEA; fully humidified with total outlet pressure of 150 kPa; anode stoichiometry 2; cathode stoichiometry 9.5. (as per Gasteiger et al. Applied Catalysis B: Environmental, 56 (2005) 9-35) .

e Volume = active area * catalyst layer thickness


Task Approach Activities

Catalysts/ Electrodes

• Develop electrocatalysts with reduced precious metal loading, increased activity, improved durability /

3M: Advanced Cathode Catalysts and Electrodes

stability, and increased tolerance to air, fuel, and system-derived impurities

3M: Durable Catalysts for Fuel Cell Protection During Transient Conditions

• Develop supports with reduced corrosion, lower cost, and increased non-PGM catalyst loading

ANL: Polymer Electrolyte Fuel Cell Lifetime Limitations: The Role of Electrocatalyst Degradation

• Optimize electrode design and assembly Argonne National Laboratory: Nanosegregated Cathode Catalysts with Ultra-Low Platinum Loading

• Develop anodes for fuel cells operating on non-hydrogen fuels

BNL: Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on High-Stability Low-Cost Supports

GM: High-Activity Dealloyed Catalysts

lIT: Synthesis and Characterization of Mixed-Conducting Corrosion Resistant Oxide Supports

Los Alamos National Laboratory: The Science and Engineering of Durable Ultralow PGM Catalysts

Los Alamos National Laboratory: Engineered Nano-scale Ceramic Supports for PEM Fuel Cells

Northeastern University: Development of Novel Non-Pt Group Metal Electrocatalysts for PEMFC Applications

NREL: Extended, Continuous Pt Nanostructures in Thick, Dispersed Electrodes

NREL: WO3 and HPA Based System for Ultra-High Activity and Stability of Pt Catalysts in PEMFC Cathodes

University of South Carolina: Development of Ultra-Low Platinum Alloy Cathode Catalyst for PEM Fuel Cells

Current Fuel Cell Activities (from MYRD&D Plan)

7 | Fuel Cell Technologies Program eere.energy.gov 7 7

Thank you

http://www.eere.energy.gov/hydrogenandfuelcells

http://www.eere.energy.gov/hydrogenandfuelcells�


Extended Surface Catalysts : Nanostructured thin film (NSTF) catalysts

0.00 0.03 0.06 0.09 0.12 0.15 0.18 0.210.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9Pt3Ni7(A) after surface

energy treatment(open - XRFsolid - ICP)

Pt3Ni7(B) as-madePt3Ni7(A) as-made

PtCo(B)

3

2 Pt68(CoMn)324 3 4

13

1714

Nominally Standard NSTF whiskersMultiple MEA's, Test Stations, LotsNumber of samples = N

10 629

29

Comparison PtNi and PtCoMn Activities-graph 15, data 6

Mas

s Ac

tivity

(A/m

g Pt)

(105

0 se

c)

Pt Loading in PtM or PtCoMn (mg/cm2)

1

DOE 2015 Target

0 1 2 3 4 5 6 7 8 9 10 110.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

7.5 psig, 2/2.5 stoich, 67%RH, 80oC NSTF PtCoMn 0.05/0.10 mgPt/cm2 PEM: 3M 20 micron; GDL: 3M Std.

GM Short Stack NSTF A/C: 0.05/0.10 mg/cm2

13 µm PEM

GM Test of 3M MEAs:50cm2, two cells, 3M Protocol

3M Test of 3M MEAs:50cm2, two cells,

3M Protocol

Specifc Power Density Projections- graph 18

Cell V

olta

ge (V

)

Power / Total Loading (kW/gPt )

0.125 gPt/kWrated

0.2 gPt/kWat 650 mV

3M has developed NSTF Pt and Pt alloy catalysts on crystalline organic supports: Eliminates carbon corrosion issues, demonstrates higher

resistance to Pt dissolution, and reduces rates of degradation of the membrane by chemical attack

ORR mass activities > 0.43 A/mgPGM for surface-energy-treated Pt3Ni7 alloy catalyst

Ultra-thin catalyst layer enables higher J(A/cm2) below 0.2 mg/cm2 Requires different water management under cool/wet conditions High volume roll-to-roll production scale-able with standard

technology

805 Nanostructured Thin Film Electrocatalysts - Current Status and Future Potential, T 9:00

3M

http://www.electrochem.org/meetings/scheduler/abstracts/220/0805.pdf�








Synthesized novel, extended-Pt catalysts and incorporated them into thick, dispersed electrodes for improved mass transport/water management Deposited Pt on multiple substrates: carbon nanotubes, TiO2-coated Si nanowires, Cu nanowires, Ag nanowires and nanoplates NREL has demonstrated: •Pt deposited on Ag nanowires by spontaneous galvanic displacement (SGD) displays activity as high as 1,300 µA/cm2 Pt.

•Improved stability for SGD-deposited Pt nanowire catalysts compared to Pt/C.

NREL is developing extended thin film structures

2005 Stack Status

440280110

im0.9V [mA/mgPt]

2005 Cell Status

DOE2015 Target

5nm

2015 Target

808 Electrochemically Available Surface Area and Mass and Specific Activities of Extended Surface Pt Nanostructures T 10:00



Improving Pt monolayer electrocatalysts for the ORR BNL Core-shell particles

Pt-ML on bimetallic core

STEM image

EELS intensities for Pt, Ir, and Ni before (middle) and after 50K cycles (lower panel)

PGM MA: 0.76 A/mg

SA: 0.80 mA/cm2 PGM MA: 0.57 A/mg

Pt-ML on hollow Pd core

Lowering noble metal content, increasing activity and stability by smooth surface morphology, mass-saving geometry and composition, induced lattice contraction in cores

0

100

200

300

400

0 50000 100000 150000 200000 250000

Pt/Pd9Au/C (0.105 mg

Pt cm-2)

Pt/Pd9Au/C (0.101 mg

Pt cm-2)

Pt(H)/Pd/C (0.099 mgPt

cm-2)

30% Pt/C (0.102 mgPt

cm-2)

mas

s ac

tivity

/ A

mg

Pt-1

at 0

.9V

number of potential cycles

Pt shell protected by the core; No dissolution of Pt ML; Loss of Pd

induces contraction of Pt ML thus increasing stability and activity

2ML Ir around Ni

Complete stability of improved Pt ML/Pd/C in 200,000 cycles 0.6-1.0 V at Toyota Motor Company

1057 Bimetallic Core-Protected Platinum Monolayer Shell Electrocatalysts for Fuel-Cell Cathode W 16:40


http://www.bnl.gov/�


Pt-ML on Pd wires electrodeposited on C

Electrodeposited Pd NWs on carbon NPs. FFT indicates (111) facets

Pt MA: 1.74 A/mg Pt SA: 0.76 mA/cm2 PGM MA: 0.39 A/mg

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.0

0.2

0.4

0.6

0.8

1.0

H2/O2

After 10000 cycles; 80 oC, 0.1 mg/cm2 Pt + Pd, 0.04 mgPt/cm2

Powe

r Den

sity

, W/c

m2

E, V

j, A/cm2

MEA 5 cm2 Cathode total metal loading 0.1 mg/cm2

on Toray paper PGM MA: 1.2 A/mg at 0.85 V

Improving Pt Monolayer Electrocatalysts for the ORR

1058 Pt Monolayer on Electrodeposited Pd Nanostructures-Advanced Cathode Catalysts for PEM Fuel Cells W 17:00










http://www.bnl.gov/�


Pt Co Pt Fe Co

Pt Co Ni Pt Fe Ni

Colloidal solvo - thermal approach for monodispersed PtM and PtMN NPs with controlled size and composition

Efficient surfactant removal

2. Surface chemistry PtxM(1-x) N

Dissolution of 3d elements leads to Pt-skeleton

1. Particle size effect

Optimal particle size ~ 6 nm

3. Composition effect Pt

Optimal composition of Pt-ternary NPs is Pt3MN

Co Ni Pt3NiCo

4. ORR activity

Pt< Pt3FeCo < Pt3FeNi < Pt3Co < Pt3CoNi

Impr

ovem

ent f

acto

r vs.

Pt

1

2

3

4

5

Mas

s ac

tivity

A/m

g Pt

1.0

0.5

1.5

2.0

Pt/C Pt3FeCo/C Pt3CoNi/C Pt3FeNi/C

Nanosegregated catalysts: binary and ternary systems:

~ 200°C Pt3M1N2 (NM = Fe, Co, and/or Ni)

Oleylamine oleic acid

~ 150°C

Pt-bimetallic NPs (IF~2.5) vs. Pt/C

Pt-ternary (IF~5) vs. Pt/C

1005 Rational Design and Synthesis of Pt-Bimetallic Electrocatalysts, W 8:40



General Motors is developing dealloyed catalysts [PtM3 → ~Pt2M, M= Cu,Co,Ni,Fe,V] to increase ORR activity above that of Pt or standard Pt-alloy particles •Dealloyed PtCu3 catalysts have greater initial ORR activity (0.69 A/mgPt) than dealloyed PtCo3 (0.37 A/mgPt), but dealloyed PtCo3 shows better stability against voltage cycling

•Detailed characterization (electron microscopy and x-ray absorption spectroscopy) are providing insights towards combining the attributes of activity and durability in a single catalyst. The roles of different particle morphologies are being investigated

•Dealloying conditions are being modified to improve manufacturability and to mitigate negative effects of excess alloying-element ions, which leach to the membrane

De-alloyed Nanoparticles

HAADF STEM images of (left) single-alloy-core particle in D-PtCu3 and (right) multiple-alloy-core particle in D-PtCo3. Both show Pt-only shells.

GM 50 cm2 fuel cells; cycling 0.6-1.0 V, 50 mV/s

1110 X-ray Absorption Spectroscopy Investigation on Activity and Durability of De-Alloyed Pt3Co Cathodic Catalysts. Th 12:00





Synthesis of Pt/PPY nanowires using multi-potential steps and Pt sputter deposition

Ceria/Carbon Bead SA ~ 60 - 75 m2/g

Mill

Ce/C Powder SA ~ 70 - 90 m2/g

Pt-Ce/C Powder ~ 4 - 9 wt% Pt

Pt

•DFT modeling show that smaller Pt nanotubes are stable only for larger coverage and symmetric structures

•(6,6) Pt nanotube binds O more strongly than Pt(111)

•(13,13) Pt nanotube binds O similar or slightly more weakly than Pt(111)

Synthesis of 2-nm ceria supports on carbon

PPY nanowires Pt-coated PPY nanowires

PPY electrodeposition

Theoretical Modeling of Novel Pt Nanoparticles

LANL - Durable Ultralow PGM Catalysts

1213 Ultra-Low Pt Load Catalysts Based on Electrochemically Synthesized Polypyrrole Nanowires F 14:00

1/4

1/2

http://www.lanl.gov/�



NE - Non-PGM Catalysts

Non-PGM ORR catalyst based on melamine precursors prepared at MSU showed good activity and durability under catalyst durability protocol, however poor durability under C-corrosion conditions

• GDEs were prepared for melamine-based catalyst using NTCNA’s spray system.

• MEAs were prepared with NRE211 as the electrolyte and JMFC GDE anodes.

RDE data

Fuel Cell data –Nissan Tech. Center

Catalyst durability test protocol Carbon corrosion test protocol

Mechanistic Studies

1069 Reasons for Kinetic Facility of Oxygen Reduction and Development of Non-Precious Cathode Catalysts for Alkaline Membrane Fuel Cell W 16:40



0 200 400 600 800 1000 1200 14000.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8 05/04/2011, Initial FePyP Cathode 07/13/2011, Best FePyP Cathode 07/22/2011, CoPyP Cathode 09/26/2011, Best CoPyP cathode

@ 1

220

mA/

cm2

@ 9

20 m

A/cm

2

Volta

ge /

V

Current Density / mA/cm2

LBNL - 3D Non-PGM Catalyst

Schematic of oxygen, proton, electron, and water transport in the thin redox polymer and the catalyst layer.

Current collector

Electrolyte phase + gas pores

CatalystCatalyst support

High activity and turnover within the catalyst layer

Decent initial (>20 hr) stability

Changing inks, metal center, loading and mediator leads to better performance

Molecular catalysts dispersed in ionomer film over carbon particles

1154 Electroreduction of Molecular Oxygen by Water-Soluble Metal Porphyrins in Trifluoromethane Sulfonic Acid Solution, Th 16:40














The University of South Carolina, in collaboration with Yonsei University (S. Korea) is developing two types of ultra-low loading Pt catalysts: (i) Hybrid cathode catalyst (HCC)

combines a non-PGM carbon composite catalyst (CCC) as a support for a PGM-based catalyst to obtain ultra-low Pt loading.

(ii) Pt and Pt-M alloy catalysts are deposited on activated graphitic carbon support, Pt-M/AGC.

The Pt-Co HCC catalyst and Pt-M/AGC catalyst had mass activities in the range of 0.38 to 0.44 A/mgPGM at loadings of 0.1 mgPGM/cm2 approaching the DOE target.

USC - Hybrid Catalysts

After 30,000 cycles

Mass activity at 0.9 V ECSA in MEA

DOE target ≤ 40% loss ≤ 40% loss

Pt3M/AGC 34% loss

(from 0.41 to 0.27 A/ mgPt)

30% loss (from 29.5 to

20.8 m2/g)

Durability of Mass Activity of Pt3M Catalyst

0.1 10.84

0.86

0.88

0.90

0.92

0.94

0.96

0.380.154

iR-c

orre

cted

cell p

oten

tial (

V)

Mass activity (A mgPt-1)

Pt-Co/CCS Pt2Ni Commercial Pt/C

0.454

1008 Development of Ultra-Low Pt Alloy Cathode Catalyst for PEM Fuel Cells, W 10:00



0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

0 2000 4000 6000 8000 10000

Pulse #

ECSA

Nor

mal

ized

to B

OL

( ∆%

) FC18446, 10 ug

FC 18448, 10 ug

FC 18496, 10 ug

FC 18504, 10 ug

FC17939, 2 ug

FC18245, 2ug

Pt surface area loss rate: ~ 2% per 1,000 cycles

3M

Samples with 2 and 10 μg/cm2 of protective catalyst endured 10,000 cycles to 1.4 V OER catalyst decay rate: ~30%.

Absence of hydrogen and simultaneous presence of oxygen in separate regions of the anode results in cathode potential > 1.23 V during transients and startup/shutdown.

3M approach: modify both anode and cathode catalysts to enable PEM fuel cell systems to weather the conditions in the fuel cell at voltages beyond the thermodynamic stability of water during the transient periods.

To achieve this goal 3M will develop two major concepts:

1. Cathode catalysts with high oxygen evolution reaction (OER) activity

2. Anode catalysts with low oxygen reduction (ORR) reaction activity

3M – Protect catalysts during transient conditions

1106 Catalyst Durability for Fuel Cells under Start-up/Shut-down conditions Th 10:40


• 3M Company R. Atanasoski, M. Debe • Argonne National Laboratory N. Markovic • Brookhaven National Laboratory R. Adzic • General Motors F. Wagner • Lawrence Berkeley National Laboratory J. Kerr • Los Alamos National Laboratory F. Garzon • National Renewable Energy Laboratory B. Pivovar • Northeastern University S. Mukerjee • University of South Carolina B. Popov

Acknowledgements


NREL team is investigating heteropolyacids and tungsten oxide catalyst supports to increase stability and activity of Pt catalysts. •Expected to increase stability due to their higher corrosion resistance and the strong catalyst -support interaction.

•Initial tests indicate the Pt/WOX catalysts are more corrosion resistant than Pt/C, with corrosion not occurring until above 1.6V

Carbon catalyst support degradation affects durability

21 | Fuel Cell Technologies Program eere.energy.gov 9

Colloidal solvo - thermal approach for monodispersed PtM NPs with controlled size and composition

Efficient surfactant removal

Temperature induced segregation Agglomeration prevented

Optimized annealing temperature 400-500o

C

(b)

Surface chemistry

PtxM(1-x) NPs

Dissolution of 3d elements leads to Pt-skeleton

Co KαPt Lα

Pt Co

ANL Nanosegregated Catalysts for ORR

0

100

200

300

400

Impr

ovem

ent F

acto

r(v

s. P

t/C)

Mas

s A

ctiv

ity ( A

/g) before

after

0

2

4

6

Pt/C acid leachedPtNi/C

acid leached/annealePtNi/C

c

0.1M HClO4 60o

C @ 0.95V, 20mV/s

x6 Activity

Documents

DOE's Fuel Cell Catalyst R&D Activities · DOE’s fuel cell catalyst R&D activities . Nancy L. Garland . ... • Develop electrocatalysts with reduced precious metal