Fuel Cell Seminar Energy Expositions -...
Transcript of 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
November 11, 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
November 11, 2014 Copyright 2014 Pajarito Powder, LLC 3
PPC Introduction
PPC founded to:Create & ManufactureAffordable Fuel Cell
Catalystsin Commercial Quantities
November 11, 2014 Copyright 2014 Pajarito Powder, LLC 4
PPC Introduction
PPC founded to:Create & ManufactureAffordable Fuel Cell
Catalystsin Commercial Quantities
1.5gr
50gr10gr
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0 0.5 1 1.5I (A/cm2)
E (V
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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,
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Non‐PGM Catalysts
Polypyrrole
Polyaniline
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Outline
• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism
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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!
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Outline
• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology
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Pore Structures
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Pore Structure Role
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Outline
• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making non‐PGM catalysts
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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
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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
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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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0
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HFR
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-cm
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Cel
l Vol
tage
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Current Density (A/cm2)
55% Nafion
45% Nafion
35% Nafion
~ 0.92 V OCV Catalyst loading is 4 mgcatalyst/cm2
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0.70
0.80
0.90
0.001 0.01 0.1 1
IR-fr
ee C
ell V
olta
ge (V
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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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DOE EERE Project ID# FC086 AMR 2103 report, NTCNA testing
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Cel
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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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Cur
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sity
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/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!
DOE EERE Project ID# FC086 AMR 2103 report, NTCNA testing
EXAFS
ECSA
0.2 V
1.1 V
Durability under start/stop similar to Pt/CDurability under start/stop similar to Pt/C
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Outline
• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts
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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
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0.3
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0.5
0.6
0.7
0.8
0.9
1
0 0.5 1 1.5I (A/cm2)
E (V
olts
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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
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Proprietary
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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,
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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
November 11, 2014 Copyright 2014 Pajarito Powder, LLC 23
Outline
• What are non‐PGM ORR catalysts?• Identifying the active site/s and mechanism• Key morphology• Making deployable non‐PGM catalysts• Successes
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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
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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
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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
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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
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Limits
• Pt/C activity per gram likely unachievable• BUT, Cost/Performance parity exists today
– $/kW to improve dramatically at scale
• Additional work is needed– Electrode must be re‐optimized for non‐PGM– Additional durability and stability testing
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$‐$40$80
10 1,000 100,000Monthly Production (Kg)
Price/kW
($USD
) NPC‐2000 Pt Catalyst
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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
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Questions?
Alexey Serov, Chief Scientist ([email protected])
Pajarito Powder, LLC317 Commercial St. NE
Albuquerque, NM 87102, USA+1 (505) 293‐5367
www.pajaritopowder.com