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Low-Noble-Metal-Content Catalysts/Electrodes for Hydrogen Production by Water Electrolysis
P. I. Name: Kathy AyersOrganization: Proton OnSite
Date: June 11th, 2015Project ID: PD098
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Overview
2012 MYRDD Plan
Budget
• Project Start: 28 June 2012• Project End: 13 Aug 2015• Percent complete: 92%
Timeline Barriers
Partners• Brookhaven National Lab
• G. Capital Cost
Characteristics Units2011
Status2015
Target2020
TargetHydrogen Levelized Cost d
(Production Only) $/kg 4.2 d 3.9 d 2.3 d
Electrolyzer System Capital Cost$/kg$/kW
0.70 430 e, f
0.50 300 f
0.50 300 f
%(LHV) 67 72 75kWh/kg 50 46 44% (LHV) 74 76 77kWh/kg 45 44 43
Table 3.1.4 Technical Targets: Distributed Forecourt Water Electrolysis Hydrogen Protoduction a, b, c
System Energy Efficiency g
Stack Energy Efficiency h• Total Funding Spent*
– $996,357• Total Project Value
– $1,150,000• Cost Share Percentage
– 0% (SBIR)
*As of March 31, 2015
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• Reduction of greenhouse gas emissions through renewable hydrogen production– Currently produced from fossil fuels– Also provides transportation benefit
• Only current technology at relevant scale
Relevance: PEM Electrolysis
Proton 1 MW fluids system Controls/
electronicsPage 3
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
S40 H6M C30 0.5 MW 1 MW 2 MW 2 MW Adv
% o
f Bas
elin
e C
ost/k
W
0%
20%
40%
60%
80%
100%
2008 Baseline
2012 Bipolar Plate
2015 Release
Projected Next Gen
% B
asel
ine
Cost
Implementation Timeline
Balance of stackBalance of cellMEA
Relevance: Catalyst Loading • Catalyst becomes a key cost driver at MW scale
– 30% stack cost reduction possible vs. 2012 baseline
BoP cost/kg decreases dramatically with scale
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Relevance: EU Competition Growing
* 2015 FCH-JU data
• Need to maintain competitive position in U.S. for energy storage and other applications
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Approach:• Reduce electrode cost through highly active core shell
catalysts and advanced deposition methods– Lowest catalyst loading in combination– Addresses both PGM usage and labor costs
Phase II Project Objectives• Automate cathode process and scale up• Downselect promising anode electrode configurations• Operate 500 hours with cost-reduced electrodes.• Demonstrate feasibility for 80% electrode cost reduction
Previous methods produced imperfect structure and mixing
Defect-induced partial alloying eliminated.
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Approach: Manufacturing and GDL Selection• Ultrasonic spray deposition identified as approach for high-
throughput and low labor• Phase 1: MPLs result in better distribution of catalyst near
membrane; need repeatable hydrophilic layer• Phase 2: Equipment procurement, transfer process
Ultrasonic spray deposition schematic11SPIE Newsroom. DOI: 10.1117/2.1200903.1555
Ultrasonic printer at Proton OnSite (left) and nozzle with GDL material (right).
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Approach: Anode• No commercial MPL options for anode GDLs
– Custom MPL from 3rd party supplier– In house fabrication of TiOx MPLs– Non-MPL options: binder changes– Alternate catalysts– Print parameters
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Approach: Task Summary• Task 1.0 Cathode Catalyst
– Technology transfer – Scale-up
• Task 2.0 Cathode Manufacturing– Deposition verification– Manufacturing development
• Task 3.0 Anode Catalysts– Evaluation of synthesized
catalysts– Evaluation of novel
manufacturing methods
• Task 4.0 Anode Electrode– Ink formulation for anode
catalysts – Anode GDE fabrications – Structural and component
characterization• Task 5.0 Cell Development
and Testing– Anode GDL development – Cathode GDE incorporation – Durability and post-operation
assessment• Task 6.0 Cost Analysis
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Accomplishments: Year 1 Milestones
Task # Milestone Description Status6 Project Kick-off: Proton, BNL 100%
1Demonstrate successful cathode catalystsynthesis and electrode manufacture at Proton 100%
3Complete study of TiOx-supported Ru@Ircatalysts in solution electrochemical cells. 100%
4Demonstrate uniform and robust catalyst layeron Ti GDLs 100%
1Complete scale up synthesis of cathodecatalysts to 10 – 100 g batch level 100%
5Complete cell design analysis for cathodeconfiguration 100%
Milestones in green accomplished since last AMR
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Accomplishments: Year 2 MilestonesTask
# Milestone DescriptionDue Date / Completion
2Downselect optimal cathode material and processfor reliable production 100%
4,5Demonstrate improved activity and durability ofselected anode GDE samples in cell 100%
6 Provide initial cost assessment via H2A model 100%2,4,5 Identify key issues for enhancing durability 100%
4,5Achieve >100 hours durability of developed anodecatalyst/GDE 10%
2,4,5Demonstrate process capability for large activearea electrodes 100%
2,4,5 Achieve 500 hours of operation at 89 cm2 cell level 50%
6
Evaluate the benefits of selected anodecatalysts/electrodes over the baseline in costreduction or efficiency boost. 8/30/2015
6 Complete Final Reporting 8/30/2015
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1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Cell
Pote
ntia
l (V)
Current density (A/cm2)
1/10th Loading Baseline Catalyst
1/10th Loading Core-Shell Material
Baseline
Technical Accomplishments: Catalyst• Core shell cathode catalyst demonstrates activity advantage • Enables lower loadings at equivalent performance
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Technical Accomplishments:Scale Up/Tech Transfer
Safety-qualified hydrogen reducing furnace
Color transformation: dark brown to green
1
1.2
1.4
1.6
1.8
2
2.2
0 0.5 1 1.5 2
Cel
l Pot
entia
l (V)
Current Density (A/cm2)
Scaled-up cathode material(1/10th loading)Baseline
• Scaled process from 1 to 10 g• Performance met baseline
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1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
0 0.5 1 1.5 2
Cell
Pote
ntia
l (V)
Current Density (A/cm2)
Commercial MPL 1Commercial MPL 2Commercial MPL 3Custom Spray MPL (downselect)Baseline
Technical Accomplishments: Manufacturing• Downselected printing manufacturing method,
catalyst, and MPL for cathode • Durability demonstrated to >500 hours
Commercial MPLs not ideal for electrolysis. Spray-deposited MPL shows good performance.
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• Large active area electrode qualified using full loaded cathodes (~700 cm2 area sprayed).
1.7
1.8
1.9
2.0
2.1
2.2
2.3
0 200 400 600 800 1000 1200
Cell
Pote
ntia
l (V)
Time (hours)
Sprayed CathodeSprayed Cathode (repeat)Baseline
Repeatable baseline performance demonstrated on electrodes cut from large active area print using advanced manufacturing techniques.
Technical Accomplishments: Scale Up
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Technical Accomplishments: OER Catalyst• RuO2 and Ru@IrO2 catalysts synthesized,
characterized, and electrochemically tested
TEM images of uniform ordered RuO2 particles
Ru enhances OER activity, but IrO2 catalysts downselected because of stability
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Technical Accomplishments: Anode• Resolved early mass
transport issues• Anode MPL shown to not
impact cell resistance1.4
1.5
1.6
1.7
1.8
1.9
2
2.1
0 0.5 1 1.5 2
Cell
Pote
ntia
l (V)
Current Density (A/cm2)
MEA baseline (50C)
MEA w/ Anode MPL
1.70
1.75
1.80
1.85
1.90
1.95
2.00
2.05
2.10
0 100 200 300 400 500
Cell P
oten
tial a
t 1.8
A/c
m2
(V)
Time (min)
MPL only: no transport issues
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Technical Accomplishments: Anode • Proton-made anode MPLs and BNL electrodepositing
process enable lower catalyst loadings on the anode
Repeatable baseline performance is achieved using low-loaded anodes.
1.51.61.71.81.92.02.12.22.32.4
0 0.5 1 1.5 2
Cell
Pote
ntia
l (V)
Current Density (A/cm2)
Anode MPL Formula 1 - 1/5 LoadingAnode MPL Formula 2 - 1/5 LoadingBNL Electrodeposited Anode - 1/4 LoadingBaseline
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• Advanced approach provides large competitive advantage at MW scale
• Capital cost impact larger than implied by H2A model
Technical Accomplishments: Cost
0 1 2 3 4 5Year After Implementation
Scenario 1 Cumulative Savings
Scenario 2 Cumulative Savings
Remaining investment for Scenario 1: MW program
Remaining investment for Scenario 2: this approach
Several million $ in savings in 3-4 years
Electricity $/kg H2Baseline $0.06/kWh $5.10Advanced $0.06/kWh $4.98
$/kW Delta: ~$150
Savi
ngs
in s
tack
cos
ts, $
mill
ions
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Future Work• Task 2: Cathode Manufacturing
– Scale-up down selected cathode configuration to multi-cell commercial stack platform
• Task 3: Develop Anode Catalysts– Optimize durability and performance of electrodeposited
anodes for long-term testing• Task 4: Anode Electrode Fabrication
– Downselect anode MPL configuration• Task 5: Cell Development and Testing
– Final demonstration with cost-reduced electrodes• Task 6: Cost Analysis
– Refine the impact of design changes on the $/kg of H2Page 20
Collaborators• Brookhaven National Lab
– Synthesis and characterization of core shell catalyst materials
– Development of electrode formulations and application methods on GDLs for low catalyst loading
• University of Connecticut (not funded by this project)– Paseoguilari group: MPL development– Maric group: synergistic alternate anode project
• Printer and accessory suppliers• Proton cell stack supply chain
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Technology Transfer Activities
• Successfully transferred Brookhaven catalyst synthesis to Proton and scaled up batch size
• Exploring manufacturing options for the core-shell cathode catalyst
• Optimizing custom MPL configurations for anode and cathode
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Summary• Relevance: Demonstrates pathway to reducing stack capital cost• Approach:
– Optimize anode catalyst formulation and utilization for 80% cost reduction– Identify optimum configuration for manufacturable, ultra-low loaded cathode
• Technical Accomplishments:– Completed scale up synthesis of cathode catalysts– Identified multiple pathways for 80% cost-reduced anode– Downselected a manufacturable ultra-low loaded cathode. Showed > 500 hrs
durability in production quality hardware– Demonstrated process capability for large active area electrodes
• Collaborations:– Brookhaven National Labs – catalyst and formulation development– University of Connecticut – MPL development
• Proposed Future Work:– Downselect anode MPL configuration for long-term testing– Manufacture large active area cost reduced electrodes for final demonstration– Perform cost analysis
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Acknowledgments
The Proton Team• Everett Anderson• Blake Carter• Chris Capuano• Luke Dalton• Nem Danilovic• Morgan George• Judith Manco• Mike Niedzwiecki• Mike Parker• Julie Renner• Andy Roemer
Our Collaborators• Jia Wang• Yu Zhang
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