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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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 2
Outline
• What are non-PGM ORR catalysts? • Identifying the active site/s and mechanism • Key morphology • Making deployable non-PGM catalysts • Successes • Challenges
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 3
PPC Introduction
PPC founded to: Create & Manufacture
Affordable Fuel Cell Catalysts
in Commercial Quantities
Piotr Zelenay
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 4
PPC Introduction
PPC founded to: Create & Manufacture
Affordable Fuel Cell Catalysts
in Commercial Quantities
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 5
PPC Introduction
PPC founded to: Create & Manufacture
Affordable Fuel Cell Catalysts
in Commercial Quantities
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
1.5 gr
50 gr
10 gr
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 6
PPC Introduction
PPC founded to: Create & Manufacture
Affordable Fuel Cell Catalysts
in Commercial Quantities
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
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 7
PPC Introduction
PPC founded to: Create & Manufacture
Affordable Fuel Cell Catalysts
in Commercial Quantities
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
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
US20080312073A1,WO2012174335A2,W
O2013116754A1,WO2012174344A2,WO20
14062639A1,WO2014011831A1,WO20140
85563A1,WO2014113525A1,
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 8
Non-PGM Catalysts
Polypyrrole
Polyaniline
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 9
Outline
• What are non-PGM ORR catalysts? • Identifying the active site/s and mechanism
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 10
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!
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 11
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 12
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 13
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 14
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)
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 15
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 16
Gerd Duscher Matt Chisholm
ACTEM images proves Nitrogen & Iron single sites in graphene
ACTEM – Fe/N Sites Exist
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 17
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 18
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 19
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 20
Outline
• What are non-PGM ORR catalysts? • Identifying the active site/s and mechanism • Key morphology
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 21
Pore Structures
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 22
Pore Structure Role
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 23
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 24
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 25
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!
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 26
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 28
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 29
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 30
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.
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 31
-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!
DOE EERE Project ID# FC086 AMR 2103 report, NTCNA testing
Dm EXAFS
ECSA
0.2 V
1.1 V
Durability under start/stop similar to Pt/C
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 32
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 33
Outline
• What are non-PGM ORR catalysts? • Identifying the active site/s and mechanism • Key morphology • Making deployable non-PGM catalysts
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 34
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 35
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
membrane, 45wt% Nafion 1100
Anode = 0.2mgPt/cm2
Cathode = 2.3mgcat/cm2
Improved inter-batch variability illustrated by Samples 1, 2, 3 and 4 Improved intra-batch variability (
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 36
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,
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 37
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 38
Outline
• What are non-PGM ORR catalysts? • Identifying the active site/s and mechanism • Key morphology • Making deployable non-PGM catalysts • Successes
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 39
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 40
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 41
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 42
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 43
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 44
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
October 8, 2014 Copyright 2014 Pajarito Powder, LLC 45
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/