fuel cell seminar energy expositions -...

November 11, 2014 Copyright 2014 Pajarito Powder, LLC 1

Deployment of Non‐Platinum Catalysts for PEM Fuel CellsAlexey Serov, Pajarito Powder LLC and UNM Teams

Fuel Cell Seminar & Energy Expositions


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts• Successes• Challenges


PPC Introduction

PPC founded to:Create & ManufactureAffordable Fuel Cell

Catalystsin Commercial Quantities


PPC Introduction

PPC founded to:Create & ManufactureAffordable Fuel Cell

Catalystsin Commercial Quantities

1.5gr

50gr10gr

0.3

0.4

0.5

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0.7

0.8

0.9

1

0 0.5 1 1.5I (A/cm2)

E (V

olts

, unc

orre

cted

)

Interbatch 1Intrabatch 2AIntrabatch 2BIntrabatch 2CInterbatch 3 (100kg Precursor batch)

Testing conditions0.5bar O2 100%RH 80oC 211 membrane, 45wt% Nafion 1100Anode = 0.2mgPt/cm2

Cathode = 2.3mgcat/cm2

US20080312073A1,WO2012174335A2,WO2013116754A1,WO2012174344A2,WO2014062639A1,WO2014011831A1,WO2014085563A1,WO2014113525A1,


Non‐PGM Catalysts

Polypyrrole

Polyaniline


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism


Active Site Identification

• Electrochemical Analysis– Rotating Ring and Rotating Disk Electrode (RRDE and RDE)

• Ab‐initio calculations ‐ Density Functional Theory (DFT)• Multiple chemical species & Activity correlation

– X‐Ray Photoelectron Spectroscopy (XPS)– Aberration Corrected Transmission Electron Microscopy (ACTEM)

– Raman Spectroscopy– Mössbauer Spectroscopy – X‐Ray Absorption Spectroscopy (XAS)

– Electrochemical XAS (e‐XAS)• Good statistical analysis and correlation of all of the above!


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology


Pore Structures


Pore Structure Role


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making non‐PGM catalysts


Making Non‐PGM Catalysts

• Multiple ways to make non‐PGM catalysts– Need to bring precursors together on nano‐scale then react them to make active sites

– Some processes are very complex with iterations of mixing, cooking, pyrolysis, etching.

– Commonality:• Similar precursors

– M/N/C compounds (ex: cyanamide) & Metal salts +N/C compounds• Mixing• Pyrolysis at 800‐950C• Etch excess metal particles


Sacrificial Support Method

Template: monodispersedamorphous silica

infused with transition metal saltand N-C precursor

pyrolyzedin inert atmosphere

silicaetched by HFand removed

Fumed Silica: BET-SA ~50-400 m2/g

N-C Precursor:1,4-Phenylenediamine3-Hydroxytyramine 4-Aminoantipyrine Diethanolamine N-Hydroxysuccinimide PhenanthrolineCarbendazime

TemplatedSelf-supported

Non-PGM CatalystMetals: Ce, Zr, V, Ti, Ta, Nb, W, Mo, Fe, Ru, Co, Ni, Cu

Alexey Serov


SSM Catalyst Evolution

Ball‐Mill Pyrolysis Etching Centrifuge Filter Dry Pyrolysis

Silica Infused with precursors

Pyrolizedinfused silica

Etched pore structure

Porous non-PGM catalyst

Pore structure evolution

Pyrolized pore structure


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HFR

(mΩ

-cm

2 )

Cel

l Vol

tage

(V)

Current Density (A/cm2)

55% Nafion

45% Nafion

35% Nafion

~ 0.92 V OCV Catalyst loading is 4 mgcatalyst/cm2

0.60

0.70

0.80

0.90

0.001 0.01 0.1 1

IR-fr

ee C

ell V

olta

ge (V

)

iR-free Current Density (A/cm2)

55% Nafion

45% Nafion

35% Nafion

Conditions: Tcell=80C, 100% RH 1.5 bar total pressure. Anode: 0.4 mg cm-2 (Pt/C),Cathode: 4mg cm-2

Meets DoE target of 100 mA/cm2 at 0.8ViR-free in Oxygen

Iron Nicarbazin Catalyst

Fe +

DOE EERE Project ID# FC086 AMR 2013 report, NTCNA testing



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HFR

(mΩ

-cm

2 )

Cel

l Vol

tage

(V)

Current Density (A/cm2)

Beginning of Life (BoL)End of Life (EoL)

Conditions: Tcell=80C, 100% RH 1.5 bar total pressure. Anode: 0.4 mg cm-2 (Pt/C),Cathode: 4mg cm-2.

Load cycling AST – Good!

Minimal change in performance is observed after 10,000 potential cycles (load cycling) from 0.6 to 1.0V.


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rent

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sity

(mA

/cm

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Potential (V)

after 0 cycles

after 50 cycles

after 100 cycles

after 200 cycles

after 500 cycles

after 1000 cycles

Start/Stop AST – Good!


EXAFS

ECSA

0.2 V

1.1 V

Durability under start/stop similar to Pt/CDurability under start/stop similar to Pt/C


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts


100mL

500mL

1L

1”x 6”

6”x 30”

2000mL

500mL

15mL 50mL

0.5L

20L

Batch Size

0.5 g

50 g

100 g

Scale‐up process


0.3

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0.6

0.7

0.8

0.9

1

0 0.5 1 1.5I (A/cm2)

E (V

olts

, unc

orre

cted

)

Interbatch 1Interbatch 2Intrabatch 3AIntrabatch 3BIntrabatch 3CInterbatch 4 (100kg Precursor batch)

Testing conditions0.5bar O2 100%RH 80oC 211 membrane, 45wt% Nafion 1100Anode = 0.2mgPt/cm2

Cathode = 2.3mgcat/cm2

Improved inter-batch variability illustrated by Samples 1, 2, 3 and 4 Improved intra-batch variability (<5% @0.4V) illustrated by GDEs made from Sample 3

Improved performance for different sources of precursors, see Sample 4

1.5gr

50gr

10gr

5% I error bars

-5-4-3-2-10

0 0.5 1E, V (vs RHE)

Cur

rent

Den

sity

, m

A/cm

2 A @ 10mV/sB @ 10mV/sC @ 10mV/s

1600RPM, O2

RDE Proprietary

50+ Grams Scale‐Up


Proprietary

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cted

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Gen1Gen1AGen1BGen2Gen2AGen2BTargets

211 Nafion, 45wt% 1100 EW, 4mg/cm 2

catalyst, 25BC GDL, 100% RH, 2.5bar AirI

II

Improved formulation

Catalyst formulation leading to MEA performance improvementsDoE Target I met, without iR correction – 60% improvement towards target II

US20080312073A1,WO2012174335A2,WO2013116754A1,WO2012174344A2,WO2014062639A1,WO2014011831A1,WO2014085563A1,WO2014113525A1,


Proprietary

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0.01 0.1 1I (A/cm2)

E(V

olts

, iR

unc

orre

cted

)

Gen1Gen1AGen1BGen2Gen2AGen2BTargets

211 Nafion, 45wt% 1100 EW, 4mg/cm 2

catalyst, 25BC GDL, 100% RH, 2.5bar Air

I

II

Improved formulation

Catalyst formulation leading to MEA performance improvementsDoE Target I met, without iR correction – 60% improvement towards target II


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts• Successes


Non‐PGM ORR catalysts

• Characterization techniques developed• Mostly likely active site/s identified• Iterative approach to synthesis

– Key factors hypothesized– Catalysts made– Catalysts characterized

• Correct surface chemistry • Porosity

– Key factors identified24


Commercialization

25

43rd Tokyo Motor Show

Precious Metal Free Fuel Cell Electric Vehicle

20132013A. Serov, M. Padilla, A.J. Roy, P. Atanassov, T. Sakamoto, K. Angewandte Chemie Intern. Ed., (2014) DOI: 10.1002/anie.201404734

B. Pivovar, Alkaline Membrane Fuel Cell Workshop Final Report

NREL/BK-5600-54297


PPC Capabilities

• Multiple non‐PGM catalyst production methods and formulations scaled to 25‐100gr

• Fixed Product Line (200gr/day capacity)– NPC‐2000 & 1000: non‐platinum, drop‐in fuel cell catalysts with different performance/price points

– PHC‐3000: Ultra low loaded platinum content catalyst for higher performance

• Custom Catalyst Design• Contract Manufacturing

26


Outline

• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts• Successes• Challenges and Limits


Limits

• Pt/C activity per gram likely unachievable• BUT, Cost/Performance parity exists today

– $/kW to improve dramatically at scale

• Additional work is needed– Electrode must be re‐optimized for non‐PGM– Additional durability and stability testing

28

$‐$40$80

10 1,000 100,000Monthly Production (Kg)

Price/kW

($USD

) NPC‐2000 Pt Catalyst


Thanks

• Verge Fund• US Department of Energy, EERE Program• University of New Mexico

• Profs. Plamen Atanassov, Alexey Serov, and Kateryna Artyushkova• New Mexico State University

• Prof. Boris Kiefer

• Northeastern University• Prof. Sanjeev Mukerjee and several students

• Michigan State University• Prof. Scott Calabrese Barton and Nate Leonard

• Los Alamos National Laboratory• Drs. Piotr Zelenay, Hoon Chung, and Gang Wu

• Nissan technical Center North America• Drs. Nilesh Dale, Ellazar Niangar, and Taehee Han


Questions?

Alexey Serov, Chief Scientist ([email protected])

Pajarito Powder, LLC317 Commercial St. NE

Albuquerque, NM 87102, USA+1 (505) 293‐5367

www.pajaritopowder.com

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