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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