Messe Sauber Agentur | Home - World of Energy SolutionsMaking Non-PGM Catalysts • Multiple ways to...

October 8, 2014 Copyright 2014 Pajarito Powder, LLC 1

Precious Metal Free Fuel Cell Catalysts, Concepts and Limits

Barr Halevi, Pajarito Powder LLC

World of Energy Solutions


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 & Manufacture

Affordable Fuel Cell Catalysts

in Commercial Quantities

Piotr Zelenay


PPC Introduction




Mix PrecursorsBall-Mill

Precrusor storagePrecursor vacuum drying

Pyrolysis Furnace 1

HF storageSlurry mixingFilter

Waste container

Atmospheric OvenPyrolysis Furnace 2

Weighing

Di storage

Milled mix storage

P1, boat, dateLabe; sits on shelf in jar

Pyrolyzed storage

Labe; sits on shelf in jar

Etched storage

Labeled, sits on shelf in jar

2-4 P2s

Testing:BET

ConductivityCharring

MEA

P2 storage

Decide P2, P1, and etching

Packaging ShippingQuality Assurance

Ball-Mill

HNO3 storage


PPC Introduction






Pyrolysis Furnace 1


Waste container


Weighing

Di storage

Milled mix storage


Pyrolyzed storage


Etched storage


2-4 P2s

Testing:BET


MEA

P2 storage



Ball-Mill

HNO3 storage

1.5 gr

50 gr

10 gr


PPC Introduction






Pyrolysis Furnace 1


Waste container


Weighing

Di storage

Milled mix storage


Pyrolyzed storage


Etched storage


2-4 P2s

Testing:BET


MEA

P2 storage



Ball-Mill

HNO3 storage

1.5 gr

50 gr

10 gr

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.5 1 1.5I (A/cm

2)

E (

Volts, uncorr

ecte

d)

Interbatch 1

Intrabatch 2A

Intrabatch 2B

Intrabatch 2C

Interbatch 3 (100kg Precursor batch)

Testing conditions

0.5bar O2 100%RH 80oC 211

membrane, 45wt% Nafion 1100

Anode = 0.2mgPt/cm2

Cathode = 2.3mgcat/cm2


PPC Introduction






Pyrolysis Furnace 1


Waste container


Weighing

Di storage

Milled mix storage


Pyrolyzed storage


Etched storage


2-4 P2s

Testing:BET


MEA

P2 storage



Ball-Mill

HNO3 storage

1.5 gr

50 gr

10 gr

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.5 1 1.5I (A/cm

2)

E (

Volts, uncorr

ecte

d)

Interbatch 1

Intrabatch 2A

Intrabatch 2B

Intrabatch 2C

Interbatch 3 (100kg Precursor batch)

Testing conditions

0.5bar O2 100%RH 80oC 211


Anode = 0.2mgPt/cm2


US20080312073A1,WO2012174335A2,W

O2013116754A1,WO2012174344A2,WO20

14062639A1,WO2014011831A1,WO20140

85563A1,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 – Dm X-Ray Absorption Spectroscopy (DXAS)

– Electrochemical XAS (e-XAS)

• Good statistical analysis and correlation of all of the above!


H2O

T.S. Olson, S. Pylypenko, J.E. Fulghum, P.

Atanassov, Journal of the Electrochemical

Society, 157 (2010) B54-B63

Oxygen Reduction

Reaction on Non-PGM

Catalysts • Bi(+?) -functional Mechanism

• Two(+?) types of Active Sites

Multifunctional Site/s


Density-Functional-Theory (DFT).

• Generalized Gradient Approximation (PBE).

• 3-d periodic boundary conditions.

• Plane-waves.

• Spin polarized: Co.

• PAW-potentials.

• Fermi-smearing (σ=0.025 eV)

Boris Kiefer

Surfaces:

• Graphene (32 atoms).

• 14 A vacuum.

• Molecule(s) pre-optimized.

• Dipol correction.

DFT: Fe(N-C)4 Most Likely


DFT: Fe(N-C)4 Most Likely

Possible electron arrangements in

3d orbitals of Fe+2 in Fe-N4 sites: a)

high spin, b) intermediate spin,

and c) low spin states, and d)

electronic density of states (DOS)

of Fe in graphitic Fe-N4 sites S. Kattel, P. Atanassov and B. Kiefer, PCCP 13800-13806


3963984004024041500

2000

2500

3000

nitrile

pyridinic

Nx-Fepyrrolic

quaternary

graphitic

Binding energy, eV

cp

s

7067087107127147167187202600

2700

2800

2900

3000

3100

Fe-Nx

Fe

Fe oxides

satellites

Binding energy, eVc

ps

a)

XPS: Fe(N-C)x Exist

Kateryna Artyushkova

b)


DFT calculations of XPS binding energy shifts

Both Me-N2 and Me-N4

centers are present but their

relative amount changes

upon exposure to oxidizing

atmosphere –stabilization of

N4 centers

Vacuum

3963984004024044063200

3400

3600

3800

4000

4200

Binding energy, eV

cp

s

O2, 60oC

Polypyridine

Bipyridine-Fe

N- pyridinic

N- pyridinic

N-Fe

Ambient pressure XPS

K. Artyushkova, B. Kiefer, B. Halevi, A. Knop-Gericke, R. Schlogl and P.

Atanassov, Chem. Comm, 49 (2013) 2539 – 2541

Me-N4 Me-N2 Me-N2

theory +1.1eV 0.8eV 1.0eV

experiment +0.9-1.1eV

XPS & DFT: Matching


Gerd Duscher Matt Chisholm

ACTEM images proves Nitrogen & Iron single sites in graphene

ACTEM – Fe/N Sites Exist


The relative content of D1 or D2 is high,

demonstrating the successful integration

of the majority of the iron in FeNxCy

molecular sites during pyrolysis.

The existence of Fe-N coordinations by

Mössbauer spectra, (doublets) is also

supported by the Fe-N binding energy in

XPS at 399.6 eV.

Pyridinic &

disordered

Fe-Nx

Fe-Nx

Frederic Jaouen, U Montpellier

Mössbauer: Fe(N-C)4


Sanjeev Mukerjee

Fe2+-N4 active site at

0.3 V undergoes redox

transition to a penta-

coordinated

(H)O−Fe3+−N4 at 0.90 V

DXAS – Fe(N-C)x & Fe-Fe


U. Tylus, Q. Jia, K. Strickland, N. Ramaswamy, A. Serov, P. Atanassov and

S. Mukerjee, J. Phys. Chem. C, 118 (2014) 8999-9008

eXAS – mechanism?

Oxygen Reduction

Reaction on Non-PGM

Catalysts

• Bi(+?) -functional

Mechanism

• Two(+?) types of Active

Sites


Outline

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


Pore Structures


Pore Structure Role


Kateryna Artyushkova

Structure-to-Property Relationships

-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

PC 1 (53.56%)

PC

2 (

20.0

3%

)

E 1/2

N 1s %

N cyano

N pyridinic

N-Fe N pyrrolic

N quaternary

N graphitic

PC153.6%

PC220.0%

Worseperformance

Bestperformance

Polymers

Low MW organics

Chelates

Different Active Sites


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


edge defects

in-plane

defects

Different Active Sites

• Edge less stable, more active

• In-plane more stable, less active

• Need in-plane for stable/durable

catalysts!


Sacrificial Support Method

Template:

monodispersed

amorphous silica

infused with

transition metal salt

and N-C precursor

pyrolyzed

in inert

atmosphere

silica

etched by HF

and removed

Fumed Silica:

BET-SA ~50-400 m2/g

N-C Precursor:

1,4-Phenylenediamine

3-Hydroxytyramine

4-Aminoantipyrine

Diethanolamine

N-Hydroxysuccinimide

Phenanthroline

Carbendazime Templated

Self-supported

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

Alexey Serov

October 8, 2014 Copyright 2014 Pajarito Powder, LLC 27 Ball-Mill Pyrolysis Etching Centrifuge Filter Dry Pyrolysis

SSM Catalyst Evolution

Silica Infuse d with precursors

Pyrolize d infused silica

Etched pore structure

Porous

non - PGM catalyst

Pore structure evolution

Pyrolized pore structure


Precipitated Silica:

Sponge-like

Fumed Silica:

Sponge-like

ECS PEFC SHORT COURSE 2013,

SFO (T.J. Schmidt & H.A. Gasteiger)

Typical Pt/C

Primary particle size:

10-40nm

Sacrificial support allows for pore size

tailoring to match current Pt/C catalysts

Evonik

Aerosil

SSM Pore Structure


0

100

200

300

400

500

0

0.2

0.4

0.6

0.8

1

0 0.5 1 1.5 2

HF

R (mΩ

-cm

2)

Ce

ll V

olt

ag

e (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-f

ree

Ce

ll V

olt

ag

e (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 2103 report, NTCNA testing



0

100

200

300

400

500

0

0.2

0.4

0.6

0.8

1

0 0.5 1 1.5 2

HF

R (mΩ

-cm

2)

Ce

ll V

olt

ag

e (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.


-30

-20

-10

0

10

20

30

0 0.2 0.4 0.6 0.8 1

Cu

rre

nt

De

ns

ity (

mA

/cm

2)

Potential (V)

after 0 cycles

after 50 cycles

after 100 cycles

after 200 cycles

after 500 cycles

after 1000 cycles

Start/Stop AST – Good!


Dm EXAFS

ECSA

0.2 V

1.1 V

Durability under start/stop similar to Pt/C


Volumetric Projection

Volumetric Projections

Volumetric Current (A/cm3)

0.01 0.1 1 10 100 1000

Voltage (

V),

iR

-fre

e

0.70

0.75

0.80

0.85

0.90

0.95

MEA 2

MEA 10

MEA 14

Sanjeev Mukerjee, NEU

Sample mV @ 200 A/cm3

A/cm3 @ 0.8 V (iR free)

MEA 2 809 400

MEA 10 796 150

MEA 14 810 400


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

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.5 1 1.5I (A/cm

2)

E (

Volts,

un

corr

ecte

d)

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

Testing conditions

0.5bar O2 100%RH 80oC 211


Anode = 0.2mgPt/cm2


Improved inter-batch variability illustrated by Samples 1, 2, 3 and 4 Improved intra-batch variability (


Proprietary

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.2 0.4 0.6 0.8 1

I (A/cm 2 )

E (V

olts, iR

un

co

rre

cte

d)

Gen1 Gen1A Gen1B Gen2 Gen2A Gen2B Targets

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 improvements DoE Target I met, without iR correction – 60% improvement towards target II

US20080312073A1,WO2012174335A2,W

O2013116754A1,WO2012174344A2,WO20

14062639A1,WO2014011831A1,WO20140

85563A1,WO2014113525A1,


Proprietary

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0.01 0.1 1

I (A/cm 2 )

E (V

olts, iR

uncorr

ecte

d)

Gen1 Gen1A Gen1B Gen2 Gen2A Gen2B Targets

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 improvements DoE 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 identified

39


Commercialization

40

43rd

Tokyo Motor Show

Precious Metal Free Fuel Cell Electric Vehicle

2013 A. 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 no-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 41


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 43

$-

$40

$80

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

Pri

ce/k

W

($U

SD) NPC-2000 Pt Catalyst


Thanks

• Verge Fund

• US Department of Energy, Energy Efficiency and Renewable Energy 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?

Barr Halevi, CTO & President ([email protected])

Pajarito Powder, LLC

317 Commercial St. NE

Albuquerque, NM 87102, USA

+1 (505) 293-5367

www.pajaritopowder.com
mailto:[email protected]://www.pajaritopowder.com/

Messe Sauber Agentur | Home - World of Energy SolutionsMaking Non-PGM Catalysts • Multiple ways to...

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Transcript of Messe Sauber Agentur | Home - World of Energy SolutionsMaking Non-PGM Catalysts • Multiple ways to...