Deployment of Non Platinum Catalysts

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 2

PPC Introduction PPC founded to: Create & Manufacture Affordable Fuel Cell Catalysts in Commercial Quantities 50gr 10gr 1.5gr E (Volts, uncorrected) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 Testing conditions 0.5bar O 2 100%RH 80 o C 211 membrane, 45wt% Nafion 1100 Anode = 0.2mg Pt/cm 2 Cathode = 2.3mg cat/cm 2 Interbatch 1 Intrabatch 2A Intrabatch 2B Intrabatch 2C Interbatch 3 (100kg Precursor batch) 0 0.5 1 1.5 I (A/cm 2 ) US20080312073A1,WO2012174335A2,W O2013116754A1,WO2012174344A2,WO20 14062639A1,WO2014011831A1,WO20140 85563A1,WO2014113525A1, November 11, 2014 Copyright 2014 Pajarito Powder, LLC 4

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! November 11, 2014 Copyright 2014 Pajarito Powder, LLC 7

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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 12

Sacrificial Support Method Fumed Silica: BET-SA ~50-400 m 2 /g Template: monodispersed amorphous silica Alexey Serov infused with pyrolyzed transition metal salt in inert and N-C precursor atmosphere N-C Precursor: 1,4-Phenylenediamine 3-Hydroxytyramine 4-Aminoantipyrine Diethanolamine N-Hydroxysuccinimide Phenanthroline Carbendazime silica etched by HF and removed Templated Self-supported Non-PGM Catalyst Metals: Ce, Zr, V, Ti, Ta, Nb, W, Mo, Fe, Ru, Co, Ni, Cu November 11, 2014 Copyright 2014 Pajarito Powder, LLC 13

SSM Catalyst Evolution Pore structure evolution Silica Infused with precursors Pyrolized infused silica Pyrolized pore structure Etched pore structure Porous non-pgm catalyst Ball Mill Pyrolysis Etching Centrifuge Filter Dry Pyrolysis November 11, 2014 Copyright 2014 Pajarito Powder, LLC 14

Iron Nicarbazin Catalyst Fe + Cell Voltage (V) 1 0.8 0.6 0.4 ~ 0.92 V OCV Catalyst loading is 4 mg catalyst /cm 2 55% Nafion 45% Nafion 35% Nafion Conditions: T cell =80C, 100% RH 1.5 bar total pressure. Anode: 0.4 mg cm -2 (Pt/C), Cathode: 4mg cm -2 500 400 300 200 HFR (mω-cm 2 ) IR-free Cell Voltage (V) 0.90 0.80 0.70 55% Nafion 45% Nafion 35% Nafion 0.2 100 0 0 0 0.5 1 1.5 2 Current Density (A/cm 2 ) DOE EERE Project ID# FC086 AMR 2013 report, NTCNA testing 0.60 0.001 0.01 0.1 1 ir-free Current Density (A/cm 2 ) Meets DoE target of 100 ma/cm 2 at 0.8V ir-free in Oxygen November 11, 2014 Copyright 2014 Pajarito Powder, LLC 15

Load cycling AST Good! 1 0.8 Beginning of Life (BoL) End of Life (EoL) 500 400 Cell Voltage (V) 0.6 0.4 Conditions: T cell =80C, 100% RH 1.5 bar total pressure. Anode: 0.4 mg cm -2 (Pt/C), Cathode: 4mg cm -2. 300 200 HFR (mω-cm 2 ) 0.2 100 0 0 0.5 1 1.5 2 0 Current Density (A/cm 2 ) DOE EERE Project ID# FC086 AMR 2103 report, NTCNA testing Minimal change in performance is observed after 10,000 potential cycles (load cycling) from 0.6 to 1.0V. November 11, 2014 Copyright 2014 Pajarito Powder, LLC 16

Start/Stop AST Good! 30 ECSA 20 Current Density (ma/cm 2 ) 10 0-10 after 0 cycles after 50 cycles after 100 cycles -20 after 200 cycles after 500 cycles after 1000 cycles -30 0 0.2 0.4 0.6 0.8 1 Potential (V) EXAFS 1.1 V 0.2 V DOE EERE Project ID# FC086 AMR 2103 report, NTCNA testing Durability under start/stop similar to Pt/C November 11, 2014 Copyright 2014 Pajarito Powder, LLC 17

50+ Grams Scale Up E (Volts, uncorrected) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 Testing conditions 0.5bar O 2 100%RH 80 o C 211 membrane, 45wt% Nafion 1100 Anode = 0.2mg Pt /cm 2 Cathode = 2.3mg cat /cm 2 Interbatch 1 Interbatch 2 Intrabatch 3A Intrabatch 3B Intrabatch 3C Interbatch 4 (100kg Precursor batch) Current Density, ma/cm 2 5% I error bars 0 0.5 1 1.5 I (A/cm 2 ) 0-1 -2-3 -4-5 RDE 1600RPM, O 2 A @ 10mV/s B @ 10mV/s C @ 10mV/s 0 0.5 1 E, V (vs RHE) Proprietary 50gr 10gr 1.5gr 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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 20

Improved formulation E (Volts, ir uncorrected) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 I Gen1 Gen1A Gen1B Gen2 Gen2A Gen2B Targets 211 Nafion, 45wt% 1100 EW, 4mg/cm 2 catalyst, 25BC GDL, 100% RH, 2.5bar Air 0 0.2 0.4 0.6 0.8 1 I (A/cm 2 ) II Proprietary US20080312073A1,WO2012174335A2,W O2013116754A1,WO2012174344A2,WO20 14062639A1,WO2014011831A1,WO20140 85563A1,WO2014113525A1, Catalyst formulation leading to MEA performance improvements DoE Target I met, without ir correction 60% improvement towards target II November 11, 2014 Copyright 2014 Pajarito Powder, LLC 21

Improved formulation E (Volts, ir uncorrected) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 211 Nafion, 45wt% 1100 EW, 4mg/cm 2 catalyst, 25BC GDL, 100% RH, 2.5bar Air I Gen1 Gen1A Gen1B Gen2 Gen2A Gen2B Targets 0.01 0.1 1 I (A/cm 2 ) II Proprietary Catalyst formulation leading to MEA performance improvements DoE Target I met, without ir correction 60% improvement towards target II November 11, 2014 Copyright 2014 Pajarito Powder, LLC 22

Outline What are non PGM ORR catalysts? Identifying the active site/s and mechanism Key morphology Making deployable non PGM catalysts Successes November 11, 2014 Copyright 2014 Pajarito Powder, LLC 23

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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 24

Commercialization Precious Metal Free Fuel Cell Electric Vehicle 43 rd Tokyo Motor Show B. Pivovar, Alkaline Membrane Fuel Cell Workshop Final Report NREL/BK-5600-54297 2013 A. Serov, M. Padilla, A.J. Roy, P. Atanassov, T. Sakamoto, K. Angewandte Chemie Intern. Ed., (2014) DOI: 10.1002/anie.201404734 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 25

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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 27

Limits Pt/C activity per gram likely unachievable BUT, Cost/Performance parity exists today $/kw to improve dramatically at scale Price/kW ($USD) $80 $40 $ Additional work is needed NPC 2000 Pt Catalyst 10 1,000 100,000 Monthly Production (Kg) Electrode must be re optimized for non PGM Additional durability and stability testing November 11, 2014 Copyright 2014 Pajarito Powder, LLC 28

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 November 11, 2014 Copyright 2014 Pajarito Powder, LLC 29

Questions? Alexey Serov, Chief Scientist (aserov@pajaritopowder.com) Pajarito Powder, LLC 317 Commercial St. NE Albuquerque, NM 87102, USA +1 (505) 293 5367 www.pajaritopowder.com November 11, 2014 Copyright 2014 Pajarito Powder, LLC 30