LANL Fuel Cell Research1HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007

Program Kick-off Meeting Arlington, Virginia, February 13-14, 2007

Advanced Cathode Catalysts - Brookhaven National Laboratory -- University of New Mexico - Oak Ridge National Laboratory

Debbie Myers - Argonne National Laboratory - University of Illinois Urbana-Champaign -

Piotr Zelenay - Los Alamos National Laboratory

Hydrogen, Fuel Cells and Infrastructure Technologies

Radoslav Adzic Paolina Atanassova Cabot Superior MicroPowders

Plamen Atanassov Karren More

Andrzej Wieckowski Yushan Yan University of California – Riverside

This presentation does not contain any proprietary or confidential information

Objectives

Main objective:

Develop oxygen reduction reaction (ORR) catalyst, alternative to pure platinum, capable of fulfilling cost, performance and durability requirements established by the DOE for the polymer electrolyte fuel cell (PEFC) cathode

Other objectives:

• Investigate new catalyst supports and electrode structures for maximum catalyst utilization

• Determine ORR mechanisms on newly developed catalysts through extensive physicochemical characterization, electrochemical and fuel cell testing

• Optimize catalysts, supports, and electrode structures for maximum activity and/or utilization

• Determine catalyst stability and minimize performance loss over time • Assure path forward for fabrication and scale-up of viable catalysts

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 2

Technical Targets & Barriers

DOE Technical Targets

• Precious metal loading: ~ 0.25 mg/cm2

(with ~ 0.05 mg/cm2 anode) • Cost: < 5 $/kW • Activity (precious-metal based catalysts): 0.44 A/mgPt at 0.90 ViR-free

720 μA/cm2 at 0.90 ViR-free

• Activity (precious-metal free catalysts): > 130 A/cm3 at 0.80 ViR-free

• Durability with cycling: 5,000 hours at T ≤ 80°C 2,000 hours at T > 80°C

• Electrochemical surface area (ESA) loss: < 40%

Technical Barriers Addressed

• A. Durability (catalyst, electrode layer) • B. Cost (catalyst, MEA) • C. Electrode Performance (ORR overpotential, O2 mass transport)

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 3

Approach

Three classes of ORR catalysts

• Oxygen catalysts with ultra-low platinum content • New-generation chalcogenides • Non-precious metal/heteroatomic polymer nanocomposites

Novel electrode structures for cathode catalysts

• Open-frame catalyst structures • Conductive-polymer nanofibers and nanotubes for non-precious metal

cathode structure

Extensive catalyst characterization

Catalyst performance durability

• Fuel cell performance durability • Catalyst dissolution rates and mechanisms

Fabrication & scale-up of practically viable cathode catalysts

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 4

LANL Fuel Cell Research

Participating Organizations

– catalysts with ultra-low Pt content; Radoslav Adzic (PI)

– new-generation chalcogenides; Andrzej Wieckowski (PI)

– non-precious metal composites; Piotr Zelenay (lead-PI)

– open-frame catalyst structures; Plamen Atanassov (PI)

– nanostructure catalyst supports; Yushan Yan (PI)

– characterization & durability; Debbie Myers (PI)

– characterization; Karren More (PI) - planned start in FY08

– fabrication & scale-up; Paolina Atanassova (PI)

HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 5

0

0.1M HClO4; 20mV s

Catalysts: Materials with Ultra-low Pt Content

-2

-4

-6

j / m

Acm

-2

Pt10/C/

0 2 4 6

0

40

80

120

160 Ni Au Pt

-2 @ 0.90 V 1.5 µgPt cm-2 & 2.3 µgAu cm-2

Pt/Au Ni/C

Inte

nsity

(Cou

nts)

Distance (nm)

1060 µA cm

0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

E / V RHE E / V RHE

0.8Re /Pd/C is ~20× that of Pt/C

Pt10/C

Pt )ML 20/C

/ 4

-1

Pt mass-activity of Pt 0.2

(Re0.2 0.8 /Pd

0.1 M HClO20 mV s

0

-2

-4

-6

j / m

Acm

-2

Stabilization of PtMLcontent in PtML (i) mixed Pt-metal monolayer catalysts, (ii) non-precious-metal core/precious-metal shell nanoparticle

(iii) (iv) Pd alloy catalysts

LANL Fuel Cell Research

/Me/C and Pt/C, and reduction of noble metal catalysts using

catalysts, stabilization of Pt/C by Au clusters,

HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 6

Catalysts: New-generation Chalcogenides

RRDE: Au disk at 1600 rpm; 0.1 M H2SO4-1

2

-8.0

-6.0

-4.0

-2.0

0.0

2.0

Se/Ru(ZrO2); Ru:ZrO2

Se/Ru(ZrO2); Ru:ZrO2

ZrO2

Se/Ru

-2

0.60 V 0.70 V 0.70 V

Se/Ru(ZrO2 2 )

, 20 mV s2-3 nm Se/Ru decorating ZrO solid matrix

= 1.5 = 1.0

j / m

A cm

Transmission Electron Microscopy: ) (~ 20 nm ZrO particle size

0.00 0.20 0.40 0.60 0.80 1.00

E / V vs. RHE

•

• ZrO2

LANL Fuel Cell Research

Modification of electronic properties of Ru by homogeneous mixing with Fe-group metals; protection of the nanoparticle interior by Ru skin

matrix for high dispersion and possible increase in Se durability

HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 7

LANL Fuel Cell Research8HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007

Catalysts: Non-precious Metal Composites

Time (hours)0 50 100 150 200

Cur

rent

Den

sity

(A cm

-2)

0.00

0.05

0.10

0.15

0.20

0.25

0.4 V

10%Co-PPY-XC72(0.2 mg cm-2 Co)

PyrolizedCoTPP

(2 mg cm-2)

H2 / air; 80°C

• Novel strategies for the preparation of nanoporous heteroatomic polymers and non-precious-metal incorporation into polymer matrix

• Activity enhancement: (i) ORR mechanism understanding, (ii) effective active-site entrapment, (iii) major cathode-structure re-design

Novel Electrode Structures

Conductive NanostructuresOpen-frame Catalyst Structures

PPY nanotubes by electrochemical polymerization

PPY nanowires by chemical polymerization

Electrode structures for (i) improved oxygen transport and precious-metal catalystutilization, (ii) increased non-precious catalyst loading, (iii) tunable

hydrophobicity/hydrophilicity, (iv) enhanced stability, (v) efficient H2O management

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 9

0 1 2 3 4 5 6

ACNT-1

ACNT-2

R (Å)

FT (χ

·k2 )

Fe-Fe

Fe-N

Extensive Catalyst Characterization

ACNT -ACNT-1 - ACNT without nitrogen during synthesis ACNT-2 - nitrogen-incorporated ACNT

X-ray Absorption Spectroscopy for Determining Atomic Structure (Example: ANL)

iron-aligned carbon nanotube catalyst

EXAFS Analysis of ACNT-1

0.00052.564.5Fe-Fe σ2R (Å)CNShell

0.00051.954.2Fe-N σ2R (Å)CN

EXAFS Analysis of ACNT-2 Shell

FT (χ

·k 2 )

ACNT-1

ACNT-2

Fe-Fe

Fe-N

0 1 2 3 4 5 6 R (Å)

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 10

MM G

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5

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Task Leads & Schedule

LANL Fuel Cell Research 11HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007

6.3

6.2

6.1

CSMP

5.3

5.2

5.1

ANL LANL

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UIUC

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1.1

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16151413121110987654321

QUARTERTASKS & LEADS

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MM G6.2

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M5.2

M5.1

ANLLANL

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MM GM GM4.1UNM

MM GM G3.

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QUARTERTASKS& LEADS M – milestone

G – go/no-go decision

FY 2007 Milestones & Go/No-Go Decisions

Task 1: Nanoparticle Catalysts with Ultra-low Platinum Content • Synthesis of Pt-metal monolayer catalyst(s) • Synthesis of core-shell nanoparticle catalyst(s) • Synthesis of Au-modified Pt nanoparticle catalyst • Synthesis of Pd alloy nanoparticle catalyst(s)

Task 2: New-Generation Chalcogenides • Synthesis of Te/Ru nanoparticle catalysts • Synthesis of Se/Me/Ru and Te/Me/Ru nanoparticle catalysts

Task 3: Non-precious Metal/Heteroatomic Polymer Nanocomposites • Synthesis of heteroatomic polymer with mesoporous carbon structure

(G - material properties) • Synthesis of heteroatomic polymer(s) on carbon nanotube structure

(G - material properties)• Synthesis of heteroatomic polymer using novel techniques (G - material

properties) • Integration of non-precious metals and alloys into heteroatomic polymer

(G - material properties)

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 12

FY 2007 Milestones & Go/No-Go Decisions

Task 4: Novel Electrode Structures for Cathode Catalysts • Synthesis of Pt and PGM alloy nanoparticle catalysts with open frame

structures • Synthesis of polypyrrole nanotubes/nanofibers using both chemical and

electrochemical oxidation with template approach and deposit non-precious metal catalyst into polymer matrix (G - conductivity)

Task 5: Catalyst Performance Durability – ongoing, no milestones

Task 6: Fabrication and Scale-up of Practically Viable Cathode Catalysts • Evaluate powder synthesis approach for catalyst material(s) and report

results (G - catalyst morphology, performance)

Note: Modifications to scope of work may be needed as a result of:

(a) reduced project funding(b) delay in contracts

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 13

Project Funding Estimate

Source Period Amount, $

DOE

2011

2010

2009

2008

2007

$70,000

2,200,000

2,200,000

2,150,000

1,980,000

2007-2011 8,600,000 (96%)

Recipients 2007-2011 360,000 (4%)

TOTAL 2007-2011 8,960,000 (100%)

LANL Fuel Cell Research HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007 14

LANL Fuel Cell Research15HFCIT Program Kick-off Meeting, Arlington, VA, February 13-14, 2007

Thank You & Good Luck!