DEVELOPING IMPROVED MATERIALS TO SUPPORT THE HYDROGEN ECONOMY
Michael Martin Edison Materials Technology Center

May 16-19, 2006

Project ID# PDP18
This presentation does not contain any proprietary or confidential information

Objectives

Edison Materials Technology Center (EMTEC) will use, Hydrogen, Fuel Cells & Infrastructure Technologies Program Multi-Year Research, Development and Demonstration Plan goals to find and fund projects to stimulate near term manufacturing based commercialization potential.
Feasibility projects with job creation potential Cross cutting breakthrough materials technology Will use EMTEC Core Technology (CT) model
EMTEC - Accelerating Technology to Market
Target Technologies and Barriers

Target Technology

H2 Generation from Renewable Liquid Feedstocks H2 Generation by Water Electrolysis H2 Generation by Photoelectrochemical Electrolysis H2 Separation Materials H2 Generation from Biomass and Coal H2 Storage by New Materials and Concepts H2 Processing: Sensors, Delivery, Purification

DOE Barrier Addressed

Fuel Processor Capital Costs Renewable Integration Materials Efficiency, Bulk Materials Synthesis, Device Configuration Designs Cost, Impurities Capital Cost and Efficiency Efficiency, Cost, Weight and Volume Durability, Cost
EMTEC is one of 7 State of Ohio Edison Centers
Established in 1987 by Ohio Gov. Celeste 501c(3) Not for Profit
Membership Based with Over 140 Industry, University, and Government Members Virtual We Own no Major Capital Equipment Access to Over $2B in State-Of-The-Art Facilities Significant Experience in Ceramics, Metals, Polymers, and many Material Processes

Approach

EMTEC solicits and evaluates projects that: Have Industry Relevance Are Appropriately Resourced Have EERE Hydrogen Goal Alignment Addresses DOE Barriers Have Commercialization Viability EMTEC has extensive experience managing collaborative technology projects EMTEC has developed a business model for selection and management of core technology
EMTEC Proposal Flow Chart
Project Execution Whitepapers Request For Proposal Propose New Projects Technology Transfer

- Industry

PRINCIPALS - Academia

Project Closeout

ACTIVITIES

Project Approval

- Industry Task Leader - Principal Investigator - Project Teams - Staff

Commercialization

- Government - Staff
- EMTEC - Fuel Cell Oversight Committee
- EMTEC - Principal Investigator - Project Teams - Staff

- Industry - Staff

Status and Budget

Status

3 RFP Rounds 114 White Papers and Proposals Reviewed 42 Site visits performed 23 Projects funded

Budget

FY04: $2.945 Million FY05: $2.961 Million FY06: ~$2.5 Million Contractor cost share > $7 million State of Ohio cost share: > $2 Million
Interactions - Collaborations
State of Ohio Department of Development Technology Division State of Ohio Department of Development Third Frontier USAF AFRL Technology Transfer program Procurement Technical Assistance Center (PTAC) Manufacturing Small Business Development Center (MSBDC) Materials Technology Liaison at AFRL Technical Steering Committee (TSC)

Key Accomplishments

Catacel H2 Reformation Product Developed Faraday Tunable Catalytic Loading Process Developed Makel Prototype H2 Sensor Developed and Automotive Testing Initiated Participant with Argonne National Laboratory on R&D 100 Application MWOE Pilot Scale PEC H2 Production Operational Powdermet Microballoon H2 Storage Verified NexTech H2 Safety Sensor Performance Verified PET Advanced Reel-to-Reel Electrolyzer Manufacturing Process Developed

Novel Stackable Structural Reactor (SSR) for Low-cost Hydrogen Production - Catacel Corp DOE Barriers Addressed: Fuel Processor Manufacturing, Operation and Maintenance Total project value: $234,352 Novel Stackable Structural Reactor (SSR) for low-cost stationary hydrogen production Intended to be a drop-in replacement for the loose ceramic catalyst media in the stationary steam reforming process Accomplishment: H2 Reformation Product Developed Future Work: Installation and testing in steam reformer
Nanocatalyst Development Employing Electrically Mediated Processing for Hydrogen Generation Faraday Technology DOE Barrier Addressed: Fuel processor manufacturing Total project value: $360,287 A low-cost, mass production fabrication technology for catalyzation of membrane electrode assemblies (MEA) for PEM (Proton Exchange Membrane) electrolyzers and regenerative fuel cells Collaborators include Precision Energy Technologies (PET) Accomplishment: Tunable catalytic loading process developed Future work: Optimize catalytic loading
Take-up Reel Urethane Seal (V-belt) Guide Roller (2X) Gas diffusion electrode Source Reel

V-belt Pulley (4X)

Variable Speed Plating Drum

Anode Assembly

Plating Solution

FLOW PATH

Low Cost MEMS Hydrogen Sensor for Transportation Safety Makel Engineering DOE Barriers Addressed: Control and safety Total project value: $260,727 Advanced hydrogen sensor system for hydrogen powered transportation applications Provides the means for low cost, compact, low power consumption, and miniaturized systems suitable for mass production Accomplishment: Prototype H2 sensor developed and automotive testing initiated Future Work: Final product testing and market development

Schottky Diode

Resistor

Heater

Development of Improved Materials for Integrated Photovoltaic - Electrolysis Hydrogen Generation Systems - MWOE
DOE Barriers Addressed: Renewable integration, system efficiency Total project value: $674,875 Small scale manufacturing process for Integrated Photovoltaic Electrolysis (IPE) panel This technology produces hydrogen from water using sunlight Collaborators on project include the University of Toledo, Energy Photovoltaic, Inc, and National Renewable Energy Laboratory Accomplishment: Pilot scale IPE H2 production operational Future Work: Improve solar-to-hydrogen efficiency
High Strength, Low-Cost Microballoons for Hydrogen Storage - Powdermet Inc. DOE Barriers Addressed: Cost, weight and volume, energy efficiency Total project value: $218,267 Nanocomposite high-strength coatings on light weight, low strength microballoons by chemical vapor deposition for high volume, low-cost hydrogen storage Collaborators on project include Air Force Research Laboratory and Hy-Energy LLC. Accomplishment: High strength microballoon H2 storage verified Future Work: Design, build and test H2 storage systems
New Materials Offer Breakthrough for Hydrogen Storage HyEnergy LLC DOE Barriers Addressed: Hydrogen Storage Total project value: $232,588 PCT isotherm shows

Multiple phase transitions Reversibility Total capacity > 3% Individual phases offer higher potential capacity
Future Work: Phase identification, isolation and phase-specific PCT evaluation
Novel Ceramic Hydrogen Sensors for Fuel Cell Applications NexTech Materials DOE Barriers Addressed: Control and safety Total project value: $215,073 Novel ceramic sensor for hydrogen safety; low-cost sensor technology with improved gas sensitivity, selectivity, and response time Safe practices in the production, storage, distribution and use of hydrogen are essential for a hydrogen economy Accomplishment: H2 safety sensor performance verified Future Work: Completion of prototype assembly and testing

Normalized Resistance

1.0 0.8 0.6 0.4 0.2 0.500

1% H2 200ppm CO 0.5% CH4

Time (minutes)
Reel-to-Reel Electrolyzer MEA Processing Precision Energy & Technology DOE Barriers Addressed: Fuel processor manufacturing Total project value: $216,897 Develop continuous reel-to-reel manufacturing equipment and and control processes to bring lower cost commercialization for hydrogen producing membranes Thermal, pressure and speed control for catalyst application and MEA assembly Accomplishment: Advanced reelto-reel electrolyzer manufacturing process developed Future Work: Equipment and process optimization and testing

Program Summary

Hydrogen Program Performance
H1-01 H1-092A H1-11 H1-15 H1-162A H2-202A H2-15 H2-21 H2-12 H2-3

Project Title

Nanocatalyst Development Employing Electrically Mediated Processing for Hydrogen Generation (I) Novel Spiral Stackable Reactor (SSR) for Low-Cost Hydrogen Production (II) Commercialization of EM Solid State Welding for High Pressure Hydrogen Storage (I) Low Cost MEMS Hydrogen Sensor for Transportation Safety (I) Development of Improved Materials for Integrated PhotovoltaicElectrolysis Hydrogen Generation Systems (I-II) Regenerative Solid Oxide Fuel Cell (II) High Temperature Electrochemical Cells for Hydrogen Production and Regenerative Fuel Cell Systems (I) Novel Ceramic Hydrogen Sensors for Fuel Cell Applications (I) High Strength, Low Cost Microballoons for Hydrogen Storage (I) Hydrogen Storage Using Porous Silicon (I)

Applicant

Faraday Catacel Corp IAP Research Inc. Makel Engineering MWOE UDRI NexTech NexTech Powdermet Dephi

Project Match Funding Ratio
$ 360,287 $ 528,737 $ 324,769 $ 260,727 $ 674,875
$ 390,000 $ 215,000 $ 215,073 $ 218,267 $ 216,742

2.89 2.17 3.25 1.99 2.08

1.95 2.15 2.15 2.23 2.46
I - Phase I II - Phase II III = Phase III
LEGEND Excellent / Outstanding OK / Good Caution / Watch / Needs Improvement Problems / Unacceptable Not Applicable / TBD
On Schedule On Cost Meeting Objective Comm. Potential Reinvest. Position Prtnr/Chmpn
H2-08 H2-22 H2-18 H2-11 H2-16
Electrochemical Coal Gasification with Novel Electrodes (I) Fabrication of Metal-Carbon Nanostructure Composites (I) Novel Materials for Reversible Hydrogen Storage (I) Development of Complex Metal Hydrides for Hydrogen Storage Applications (I) Novel Intermediate-Temperature Reversible SOFC for a Renewable Energy System that can Co-produce Power and Hydrogen (I) Reel to Reel Processing for Continuous Thermal Pressing of the Catalyst Film onto a Membrane for High Volume, Low Cost Commercialization of Hydrogen Generating MEAs (I) Electrochemical Conversion of Biomass to Hydrogen (I) Improved Liquifaction Process (I)
Ohio Univ. Univ. of Toledo Hy-Energy GFS Chemicals NFCRC
$ 70,070 $ 73,334 $ 232,588 $ 197,092 $ 224,085 2.00 1.55 2.09 2.18 2.24

H2-23 H3-14 H2-2

PET TMI Praxair
$ 201,897 $ 162,000 $ 200,804

2.21 1.62 2.01

H3-19 H3-3 H3-7 H3-13 H3-5
Methanol Reformed Hydrogen For Portable PEM Fuel Cell Systems (I) Development of High Pressure Electrolyzers for Backup Power Systems (I) Scalable Steam Methane Reformer System for Distributed Hydrogen Production (I) Low-Cost Manufacturing of Multi-Fuel Reactors for an Innovative HighEfficiency Planar Reformer (I) Innovative and Cost-Effective Micro-Process for Roll-to-Roll Solution Casting of Multi-Layer PEMS (I)
Protonex Proton Energy Catacel Corp Delphi Chemsultants
$ 264,573 $ 207,526 $ 209,998 $ 219,084 $ 203,657 2.65 2.10 2.10 2.19 2.11

Summary

EMTEC manages an ongoing program with a DOE cooperative agreement in Hydrogen, Fuel Cells & Infrastructure Technologies Every project targets at least one DOE technical barrier Successful projects will generate jobs and marketable products or processes

Future Plans

Select at least four projects for Phase II nearterm commercialization development Aggressively participate in R&D 100 applications relevant to Phase II projects Release Round 4 RFP that stresses product development and near term job creation Watch for RFP: ~ August 2006

Response to Comments

Key Reviewer Comments Projects do not share DOEs research goals EMTEC Response This program focuses on commercialization of nearterm technologies aligned with DOE hydrogen goals Project alignment with barriers are now better described $200k for commercial feasibility + $400k for product development spreads risk and magnifies opportunities
Projects not well aligned with DOE barriers Why not fund fewer projects at higher levels

II.K.5 Developing Improved Materials to Support the Hydrogen Economy*
Durability/Operability Control and Safety Device Configuration Designs System Design and Evaluation Grid Electricity Emissions System Efficiency Electricity Costs Variation in Standard Practice of Safety Assessments for Components and Energy Systems System Weight and Volume High-pressure Conformability Materials of Construction System Life-Cycle Assessments Lack of Understanding of Hydrogen Physisorption and Chemisorption Reproducibility of Performance Charging/Discharging Rates Hydrogen capacity within the storage medium (Doped and Undoped Alanates) Facility of hydrogen Desorption and Adsorption in Optimized Systems Renewable Integration Electricity Costs High-Purity Water Availability Fuel Cell Manufacturing and Process Costs Fuel Cell/Stack Durability Fuel Cell Electrode Performance Feedstock Issues Carbon Dioxide Emissions Impurities High Cost and Low Energy Efficiency of Hydrogen Liquefaction Fuel Processor Manufacturing Thermal, Air and Water Management

Michael Martin

EMTEC (Edison Materials Technology Center) 3155 Research Blvd. Dayton, OH 45420 Phone: (937) 259-1365; Fax: (937) 259-1303 E-mail: hydrogen@emtec.org
DOE Technology Development Manager: Pete Devlin
Phone: (202) 586-4905; Fax: (202) 586-9811 E-mail: Peter.Devlin@ee.doe.gov
DOE Project Officer: Jill Gruber
Phone: (303) 275-4961; Fax: (303) 275-4753 E-mail: Jill.Gruber@go.doe.gov

Contract Number: DE-FC36-04GO14215 Start Date: March 1, 2004 Projected End Date: Continuing 2007
*Congressionally directed project

Objectives

Manage ongoing projects. Collect and review monthly project reports for go/no-go results. Initiate Phase II projects as appropriate. Prepare quarterly program reports from individual project reports; evaluate projects for potential Phase II awards.
Technical Barriers and Technical Targets
EMTEC will solicit and fund hydrogen infrastructure related projects that have a near-term potential for commercialization. The subject technology must be related to the U.S. Department of Energy (DOE) hydrogen economy goals as outlined in the Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year Research, Development and Demonstration Plan (MYPP). Preference will be given to cross cutting materials development projects that lead to the establishment of manufacturing capability and job creation. Specific barriers from the MYPP for the projects include: Capital Costs Operation and Maintenance (O&M) On-Board Hydrogen Storage System Cost

Approach

EMTEC has used the U.S. Department of Energy hydrogen economy goals as outlined in the MYPP to find and fund projects with near-term commercialization potential. A request for proposal (RFP) process aligned with this plan requires performance-based objectives with go/no-go technology-based milestones. EMTEC manages this project for the DOE using the protocols that include a RFP solicitation process, white papers and proposals with peer technology and commercialization review (including DOE ), EMTEC project negotiation and definition and DOE cost share approval. Our RFP
FY 2007 Annual Progress Report

DOE Hydrogen Program

II.K Hydrogen Production / Production-Crosscutting
approach specifies proposals/projects for hydrogen production, hydrogen storage or hydrogen infrastructure processing which may include sensor, separator, compression, maintenance, or delivery technologies. EMTEC is especially alert for projects in the appropriate subject area that have cross cutting materials technology with near-term manufacturing opportunities. To date, EMTEC has selected projects which have been continuing development projects preparatory to commercialization. EMTECs overriding objective is technology commercialization.

Martin Edison Materials Technology Center
Nanocatalyst Development Employing Electrically Mediated Processing for Hydrogen Generation
Faraday Technology, Inc. Project Number: EFC-H1-1-2A Project in Negotiation for Phase II
Objectives The overall objective of the project is to develop a low-cost, mass fabrication technology for catalyzation of MEAs for proton exchange membrane (PEM) electrolyzers and regenerative fuel cells, a technology that directly supports the development of the hydrogen economy. This project meets the mission of EMTEC which is to improve the methods by which the quality of processed materials is determined, improve the current materials processing operations relative to quality, cost or responsiveness and develop alternative materials processing methods and/or operations. This project will meet the challenge of reducing electrolyzer cost by developing lower cost materials with improved manufacturing capability. T he overall objective for P hase II is to complete the development of a manufacturing process for fabricating MEAs for electrolyzers and regenerative fuel cell systems with an optimized bi-functional oxygen electrode .

Accomplishments

EMTEC hosted the 2nd Membrane Electrode Assemblies (MEAs) Manufacturing Symposium, August 22-24, 2006 at the DoubleTree in downtown Dayton, OH. This symposium drew 151 participants from multiple countries. EMTEC continued the planning and organizing efforts for the 3rd MEA Manufacturing Symposium, to be held August 2123, 2007, at the Dayton Marriott. EMTEC hosted another highly successful half-day Fuel Cell Manufacturing Short Course on March 6, 2007 at the Engineers Club of Dayton, OH. This course was presented by fuel cell expert, Dr. Jack Brouwer of the National Fuel Cell Research Center, University of California, Irvine. EMTEC attended and presented at the DOE Hydrogen Program review May 11, 2007. EMTEC continued the negotiations for competitively selected Round 1, 2, and 3 Phase II proposals, culminating in a total of four Phase II projects to date. Individual progress reports for the active projects funded through this period are included in this report. EMTEC hosed a new event entitled 1st Ohio Summit on Supply Chain Opportunities in Alternative Energy June 19-20, 2007 in Dayton OH. This highly successful event included sessions on alternative energy from hydrocarbon sources, wind, solar, biomass, and fuel cells/hydrogen. This event drew 168 participants and 27 exhibitors.

1. US Patent application 11/191683 filed 7/27/05, Reactor Having Improved Heat Transfer. 2. US Trademark application 78/710819 filed 9/12/05 for SSR.
Commercialization of Electromagnetic (EM) Solid State Welding for High Pressure Hydrogen Storage
IAP Research, Inc. Project Number: EFC-H1-11-1A Project Completed
Low Cost MEMS Hydrogen Sensor for Transportation Safety
Makel Engineering, Inc. (MEI) Project Number: EFC-H1-15-2A Awarded Phase II
Objectives The objective of this project is the development of a low-cost, high performance hydrogen safety sensor for hydrogen-powered vehicles. The proposed system meets a need for a low cost sensor for on-vehicle safety, pipeline/fueling station monitoring for hydrogen distribution, and has the potential for use in closed-loop fuel cell control loops. In order to meet this emerging market need, MEI is adapting our hydrogen sensing technology and integrating recently developed hydrogensensitive nanomaterials into a highly manufacturable system platform. MEI will work with our partners to produce a second generation prototype system that will be tested on hydrogen-powered vehicles. Accomplishments Phase I of this project was highly successful and culminated in an R&D100 award. A team consisting of Argonne National laboratory, MAKEL Engineering Inc and EMTEC completed sufficient industrial development and commercialization of Argonne sensor technology to qualify for the coveted R&D100 award for a nanostructured hydrogen sensor. This Argonne press release describes the technology. Phase II of this project will continue industrial application development by MEI.
sensor fabrication changes to optimize performance and manufacturing cost; then, it will be used to collect calibration data on beta-prototype sensors. The latest design for the hydrogen sensor printed circuit board includes the final design for the 555 timer circuit as well as the detection circuit which will sound a piezo-buzzer and turn on a light emitting diode when a pre-set level of H2 has been reached. The next design iteration will include an onboard relay which will integrate NexTechs sensor into a control system which would automatically shut down the system once the pre-set level of H2 has been detected. This relay has been ordered and will be tested in a bread-boarded circuit before the PCB design is redrawn. A new method for temperature compensation of the sensor signal was developed. The new method is a proportional correction which more accurately compensates temperature fluctuations during both baseline and response conditions. The previous method was a linear offset compensation which worked well to correct the baseline signal, but adversely affected the signal during a response if the temperature was greatly deviated from the average. A meeting with Precision Joining Technologies, Inc. (Dayton, OH) was set up for June 6, 2007 to discuss NexTechs needs for joining the sensor elements to the TO8 headers. Several attempts were made by NexTech to attach the sensors using soldering techniques, but the quality of the connection was not satisfactory for long-term stability. Precision Joining has a vast experience in joining similar types of metals using their portfolio of welding processes. An alpha-prototype sensor fabricated using a yttriastabilized zirconia tubular support was tested with a reduced power consumption of only 398 mW. This is the first generation of NexTech hydrogen sensors which have operated at less then 400 mW. The reduction in power consumption is due to improved physical contact of the heater to the inside wall of the tube providing very efficient heat transfer from the resistive coil to the dense substrate.

Development of Improved Materials for Integrated Photovoltaic-Electrolysis Hydrogen Generation Systems
Midwest Optoelectronics, LLC Project Number: EFC-H1-16-2A Project Completed
Regenerative Solid Oxide Fuel Cell (RSOFC)
University of Dayton Research Institute Project Number: EFC-H2-20-2A Project Completed
High Temperature Electrochemical Cells for Hydrogen Production and Regenerative Fuel Cells
NexTech Materials Ltd. Project Number: EFC-H2-15-1C Project Completed
Novel Ceramic Hydrogen Sensors for Fuel Cell Applications
NexTech Materials Project Number: EFC-H2-21 Awarded Phase II
Objectives Develop ceramic-based sensor formulation that is sensitive to low concentrations of hydrogen in air (1,000 ppm 1%) for use as a safety sensor. Demonstrate that sensor does to give false alarms in the presence of interference gases (CO, CH4, volatile organic compounds, etc.). Demonstrate response time of less than 30 seconds in the presence of 1% hydrogen. Test proposed novel platform for improved hydrogen sensor. Fabricate a prototype based on the best performing sensor system and platform.
Accomplishments More tests were conducted to verify the timer circuit design used to control the power to the NiCr heater in the electronics package. The final components were verified and a 150 hour test was conducted. This final design will be on the printed circuit boards used for beta-prototypes. Additional testing was done to validate and verify the effect of relative humidity on the performance of the sensor. A test matrix was established to test the impact of the design specifications on performance of the sensor in both wet and dry environments. The assembly of the expanded hydrogen sensor test stand is nearly complete and the first round of sensors is scheduled to be loaded in early June 2007. This stand will be used first to evaluate various
High Strength, Low Cost Microballoons for Hydrogen Storage
Powdermet Inc. Project Number: EFC-H2-15 Awarded Phase II
Objectives The goal of this project is to prove the concept and validate a system that delivers 4 wt% hydrogen stored in microballoons, including all balance of plant components and attachment specifications to a current fuel cell stack. This goal has two components: (1) storing at least 6 wt% hydrogen in coated microballoons

and (2) mechanical analysis, balance of plant components and construction of a 4 wt% black box prototype hydrogen delivery system. Specific objectives in support of these goals are: 1. Scale-up carbon microballoon scaffold production. 2. Scale-up SiC coating of carbon microballoons. 3. Demonstrate 2.5-3 GPa coating strength SiC on 1 mm carbon microballoons. 4. Fill microballoons with H2 at 8-15,000 psi. 5. Design hydrogen testing apparatus for crushing microballoons in a detector chamber. 6. Verify 6-9 wt% H2 in 1 mm SiC microballoons. 7. Cost analysis and trade study on hydrogen filled microballoons vs. other competing technologies.
appears acceptable, but permissible diameter variation needs to be considered further.
Electrochemical Coal Gasification with Novel Electrodes
Ohio University Project Number: EFC-H2-08 Project Completed
Fabrication of Metal-Carbon Nanostructure Composites
The University of Toledo Project Number: EFC-H2-22 Project Completed
8. Determine the balance of plant components for a 4 wt% H2 system. 9. Build a working prototype hydrogen delivery system black box. Accomplishments A major change in project status was reported at the review meeting on March 30. A realistic fuel cell mission for this project involves a 50 W fuel cell that consumes ~2 g H2/hr. The corresponding microballoon consumption is ~65 cm3/hr or <1 L for a 12-hour mission. Although original objectives included preparation and filling of 40 L of microballoons per day, a net throughput of ~2 L per day of H2-filled microballoons suffices to operate two missions per day by conclusion of this project. Moreover, a volume of 65 cm3 that contains 40 cm3 H2 at 9,000 psi suffices to operate the prototype hydrogen delivery system for one hour, thus permitting validation of the systems operation. These microballoons are assumed to contain 10 wt% H2. For comparison, it has been assumed that balloons containing 6 wt% H2 would permit completion of a system that contains 4 wt% H2. Dimensional requirements for microballoons have been specified provisionally by a scaling analysis. Our target is to deliver microballoons (2+/-0.5) mm diameter to the hydrogen delivery device. Hydrogen content of balloons with variable radius r varies as r3 if all balloons are at constant pressure. The delivery device must accept variation in balloon diameter and amount of hydrogen. These variations can be compensated by adjusting the feed rate, which varies as 1/r3. But released pressure also cocks the feed device in a pneumatic model, where length of a constant-force spring would increase with balloon radius. Details are in the review presentation. Thomas Willis showed that balloon capture mechanisms and hydrogen feed regulators probably can accommodate a radius variation of +/- 25%, although this is a much larger variation than had been supposed. A target diameter of ~2 mm

Novel Materials for Reversible Hydrogen Storage
Hy-Energy LLC. Project: EFC-H2-11 Project Completed
Development of Complex Metal Hydrides for Hydrogen Storage Applications
GFS Chemicals, Inc. Project Number: EFC-H2-11-1A Project Completed
Novel Intermediate-Temperature Reversible SOFC for a Renewable Energy System that can CoProduce Power and Hydrogen
UC-Irvine, National Fuel Cell Research Center Project Number: EFC-H2-16
Objectives Evaluate novel reversible solid oxide fuel cell (SOFC) materials sets produced with wet-chemicalroute synthesis through preliminary manufacturing (dry pressed button cells) and performance tests; Select the best performing materials sets for manufacturability, performance and stability features; Manufacture planar anode-supported reversible SOFC button cells using the selected materials set by tape-casting, screen-printing, and co-firing processes; Accomplish electrochemical and stability tests of planar anode-supported reversible SOFC button cells; and Investigate market and commercialization potential of reversible SOFC technology.
Accomplishments In this reporting period significant progress has been made. The major successful accomplishments are:
1. Completed the composite cathode of SSC with LSGMC compositional matrix tests and determined the optimal composite cathode composition; 2. Pretreated the yttrium-doped strontium titanate (SYT) sample in a reducing atmosphere and conducted the four-terminal DC conductivity measurements; 3. Successfully fabricated flat/non-warping composite anode substrates of SYT with LSGMC and LDC by using an in-house tape-caster; 4. Submitted two papers for reporting of results on: (a) the electro-catalytic properties of the SSC-LSGMC composite cathodes, and (b) the emission of criteria pollutants from the glycine-nitrate combustion processes.
Accomplishments Experimental system designed and assembled. Preliminary candidate materials identified.
Tests conducted at low pressure showed encouraging results. Because of this, we upgraded the system to test at pressures up to 400 psig. Tests on the same materials at higher pressure showed that they did not perform as well as they did at low pressure. Initial attempts to modify the materials to optimize highpressure performance were not successful. Remaining materials development work will focus on modifying the materials so that performance at high pressure can be optimized. Process development work indicates that the hydrogen liquefaction process will need to be redesigned to take full advantage of the improved ortho-para conversion process. Because some of these process changes could be significant, the next phase of this project will emphasize process development to design an optimized process. The cost of retrofitting existing processes appears to be prohibitive because of required downtime for installation. Further materials development work will focus on developing a material that meets or exceeds the best-performing materials studied to date while also optimizing the materials for the current process conditions. If this can be accomplished, a successful retrofit is more likely. There is a potential economic benefit based on the results of Task 1. Using the best results to date, it could be possible to reduce hydrogen liquefaction power consumption by more than 1 kWh/kg.

Reel to Reel Processing for Continuous Thermal Pressing of the Catalyst Film onto a Membrane for the High Volume, Low Cost Commercialization of Hydrogen Generating Membrane Electrolyte
Precision Energy and Technology Project Number: EFC-H2-23 Project Completed
Electrochemical Conversion of Biomass to Hydrogen
Technology Management, Inc. Project Number: EFC-H3-14 Project Completed
Improved Hydrogen Liquefaction Process
Praxair, Inc. Project Number: EFC-H2-2
Objectives Reduce the cost for hydrogen liquefaction. Reduce the electrical power consumption for hydrogen liquefaction. Increase the liquid hydrogen production rate for existing plants. Reduce hydrogen distribution costs.
Methanol Reformed Hydrogen For Portable PEM Fuel Cell Systems
Protonex Technology Corporation Project Number: EFC-H3-19 Project Completed
Development of High Pressure Electrolyzers for Backup Power Systems
Proton Energy Systems, Inc. Project Number: EFC-H3-3 Project Completed
This project will attempt to improve the electrical efficiency of hydrogen liquefaction. Our goal is to reduce the power consumption by about 20%. If this can be accomplished, assuming that the current efficiency is 25%, the final efficiency would be over 30%, which will exceed the 2010 target. Improving efficiency will reduce cost as long as the added capital cost is low enough. Therefore, maintaining low capital cost is another important goal of the project. Any improvement made in this project will apply to both small-scale (existing) and large-scale (future) plants.
Manufacturing UltraCells Reformed Methanol Micro Fuel Cells
UltraCell Corporation Project Number: EFC-H3-34-1B Newly Awarded
Recast Single and Multilayer Membranes Water uptake and fuel cell performance of selected recast membranes were tested during the reporting period. It was found that composite films containing ZrSPP showed increased water uptake as compared to those cast from neat Nafion solutions. Also, fuel cell tests with a 5-layer composite membrane revealed reduced sensitivity to dehydration due presumably to improved water back-diffusion in the multilayer structure. Further details are given below. Membrane Water Uptake Good water sorption is one of the most important properties of PEM membranes. Selected membranes were equilibrated with liquid water at 25C, weighed, dried at 100C, and then reweighed. The water uptake was calculated from the dry and wet membrane weights (mdry and mwet, respectively) as:

W = mwet mdry mdry

Low-Cost Manufacturing of Multi-Fuel Reactors for an Innovative High-Efficiency Planar Reformer

Delphi Automotive Systems, Inc. Project Number: EFC-H3-13-1B Project in Renegotiation
Scalable Steam Methane Reformer System for Distributed Hydrogen Production
Catacel Corporation Project Number: EFC-H3-07-1A
Objectives The overall objective of this Phase I project is to demonstrate the technical and commercial feasibility of a scalable steam methane reformer system for the distributed production of hydrogen. Accomplishments NexTech has been working on a new lowtemperature shift catalyst, and is expected to deliver it to Catacel for testing in early May. Considerable effort has been expended to solve the leaky heat exchanger problem. Roughly 30% of the units constructed currently have no leaks.
An Innovative and Cost Effective Micro-Process for Roll-To-Roll Solution Casting of Multi-Layer Proton Exchange Membranes with Superior Performance, Transport and Mechanical Properties in High Temperature/Low RH Operating Environments
Chemsultants International, Inc. Project Number: EFC-H3-5-1A
It can be seen that changing the annealing temperature in the range of 130-160C does not alter significantly water uptake. It is evident, however, that the addition of ZrSPP particles to Nafion induces a significant increase in membrane water content, for both a homogeneous zirconium dispersion and for a 5-layer film. Fuel Cell Tests Anode and cathode Pt/C powder electrodes were hot-pressed onto the opposing surfaces of a 5-layer Nafion-zirconium membrane to create a fuel cell MEA (with an electrode area of 5.0 cm2). The catalyst loading was 0.4 mg Pt/cm2 for both the anode and the cathode. The 5 cm2 cell was run at 80C with a hydrogen flow rate of 100 sccm and an air flow rate of 500 sccm. After a break-in (conditioning) period, the cell was run with full (100%) humidification of the reactant streams. When the power output stabilized, voltage-current data were collected. The voltage from the 5-layer membrane was lower than that from the Nafion 212 membrane at the same current density. This is due to the greater thickness (and greater electrical resistance) of the 5-layer membrane (90 m), as compared to Nafion 212 (70 m in thickness). The water vapor content of the hydrogen feed stream was reduced to 50% relative humidity (RH) and the fuel cell performance curves for the 5-layer and Nafion 212 membranes were recorded (after sufficient time for equilibration of the MEA at the new humidity condition). The power output for the commercial Nafion decreased significantly, while the fuel cell performance of the 5-layer membrane remained

Objectives Prove the feasibility of a new manufacturing process for roll-to-roll production of multi-layer PEMs based on interspersed, discrete layers of hydrophilic zirconium particles and recast Nafion polymer developed by Case Western Reserve University that will be solution cast in a layered structure via a novel, advanced process to manufacture thin caliper (12-20 um) membranes. Accomplishments Some initial incompatibility between Nafion and the zirconium phosphate sulfophenylphosphonate (ZrSPP) particles was previously observed. Attempts were made to correct this phenomenon by converting the acid form to the tetraalkylammonium salt prior to addition to the Nafion. However, other rheology issues were found to be unsolvable with the TEA. As a result the tetraethyl ammonium ZrSPP was converted to the acid form for further evaluation.
unchanged with the decrease in anode humidity. This experiment suggests that the multi-layered membrane structure is helping to promote water back-diffusion from the cathode to the anode during fuel cell operation. Thus, the 5-layer Nafion/zirconium membrane is less sensitive to the anode humidification level. Also, the fuel cell open circuit voltage with the multilayer membrane was significantly higher than that with commercial Nafion 212. This suggests that reactant gas crossover is reduced in the multi-layer composite membrane. More testing is needed to confirm the observed behavior and additional fuel cell experiments are planned for the near future. Lab Cast Membranes Multi-layered Nafion membranes incorporating the ZrSPP particles were produced in the laboratory and tested for mechanical strength and layer uniformity. The targeted total thickness was 2.0 mil (.002 inches). The membranes were cast from DuPont DE-2021 aqueous Nafion solution, 20% solids, with certain percentages of ZrSPP (acid form) on solids. Each individual layer was dried for 15 minutes at 70C prior to casting the next layer. After the final layer was dried, the entire membrane was annealed at 140C for 1 hour. Optical Microscopy The prepared films were embedded in microcrystalline wax and cross-sectioned to allow examination of the layered structure with a microscope. Optical microscopy was performed using an Olympus BX41 microscope with an Insight 14-bit Mosaic Cmount digital camera in conjunction with SpotTM Image Capture Software. Three and five-layered Nafion/ ZrSPP composite membranes were prepared in the above manner and viewed under the microscope. Optical micrographs showed the layered structures and an even distribution of layers within the membranes. In addition, the measurements obtained for each layer with the microscope software program correlate exactly with the micrometer readings taken after each casting pass. Dispersibility of ZrSPP The ZrSPP (acid form) material was finely ground with a mortar and pestle and wet with several drops of deionized water. The particles were very hygroscopic and attracted the water easily. After being placed in a sonicating bath for 15 minutes, the solution turned to a clear gel. The gel was left overnight and sonicated once more prior to addition of the Nafion solution. This process seemed to enhance the dispersability of the nanoparticles in the Nafion solution. Previous attempts at adding the nanoparticles to the Nafion solution resulted in large aggregates and non-dispersed material settling out of solution. Membranes made with the new method were much improved and defects were minimal.

Mechanical Testing Tensile testing of one and two layered Nafion films with various ZrSPP loadings was performed. Testing was done on both wet and dry membranes. Results show that tensile strength is reduced when membranes are in the wet state. In addition, tensile strength and elongation are reduced upon increased loading of ZrSPP nanoparticles for the 1-layer films. However, addition of layers seems to strengthen the membranes slightly by maintaining the tensile strength even after increasing the ZrSPP loading. Results indicate that addition of ZrSPP in a layered structure does not necessarily impede tensile strength. This will be a positive factor if the conductivity and/or water management of the 3- or 5-layer systems proves better than that of standard Nafion 212. Lab Casting of Multilayered (Seven Layers of Alternating Neat and Filled Nafion) Membrane In preparation for casting of seven or more alternating layers of Nafion (DE-2021) and Nafion/ ZrSPP composite material, an application thickness study was performed. The bird film applicator gap was incrementally increased and dried thickness of the film measured using a laboratory micrometer. Due to the leveling effects of the 20% solids Nafion solution, a maximum value of approximately 0.70 mils can be obtained from one coating pass. This is a usual phenomenon for solutions with lower viscosity and solids content. The thickness data shows that very thin layers can be obtained with the DE-2021 Nafion solution, allowing for subsequent building up of layers numbering seven or ten fold.
Nanofiber Paper for Efficient Hydrogen Generation
Inorganic Specialists, Inc. Project Number: EFC-H3-6-1B
Objectives Demonstrate nanofiber paper for hydrogen production, and compare it to existing products. Develop continuous nanofiber papermaking for the hydrogen generation application. Compare different methods of catalyst deposition for its impact on hydrogen generation efficiency.
Notre Dames Activity In general, the Notre Dame work plan is to hold one electrode (the anode) constant, making it larger than the cathode specimens so that the anode is not the limiting factor in electrolysis experiments. Then a series of catalyzed nanofiber paper and commercial electrodes will be tested against this standard for the production of hydrogen, and the relative performance will be evaluated.
But before implementing this plan, we need to verify that the nanofiber mat will not degrade under the test conditions where gas is being generated. Gas generation (especially at high rates) generates tremendous microscopic pounding on an electrode surface, and so corrosion (abrasion) of the electrode is a major issue. This factor has to be understood before we move on to the more refined issue of comparing different catalyzed samples. An initial test to determine the onset potential for H2 evolution and the carbon stability in a wet electrochemical cell was carried out. The medium consisted of 0.5 M H2SO4 at an overpotential of 1.7 V vs. saturated calomel electrode. A conductive inert backing of e-beam deposited gold (Au) on stainless steel (SS) was prepared, but the 150 nm thickness of Au was not able to withstand rapid gas generation at high overpotentials. This result showed us it would be wise to do our nanofiber mat testing in a type of cell where the mat can be mechanically supported. A suitable cell fixture was purchased from H-Tec. This cell should allow for the nanofibers to have the maximum available support due to the use of a perforated metal sheet that physically holds the nanofibers close to the membrane and eliminates possible break-up of the mat during the rapid bubble formation expected. Two 80 cm3 gas storage tanks were also purchased from H-Tec. Inorganic Specialists Development Work We have been thrown off from our schedule by about a month by a fortuitous development. Applied Sciences has introduced a new nanofiber, PR-25, which is smaller in diameter than the PR-24 product we had previously been using. It is also at least 50 times more conductive. Since most nanofiber paper applications benefit from high conductivity, we have made the decision to switch to using PR-25. This has required some adjustment; PR-25 processes differently from the PR-24 that we are used to, and so the trip to Southeast Nonwovens was postponed until April as we did the work to adjust how we disperse the fiber, and make sure the new fiber releases well from the papermaking support. That development work is now essentially complete. The advent of this high-conductivity fiber opens up new options; it allows us to design the electrolysis electrode according to Notre Dames preference, which is to have a nanofiber gas diffusion layer (GDL) combined with a nanofiber catalyst support. We could not do this previously because the GDLs we had made out of PR-24 were not conductive enough. But now we are making and will test a bi-layer electrode consisting of a thick, hydrophobic PR-25 GDL which will have a thin top layer of catalyzed hydrophilic nanofibers.

For the initial testing, a 11x11 15-mil thick nanofiber GDL sheet was prepared and treated with a teflon binder to make it water-repellent. This sheet has one extremely smooth (almost glossy) face on it. Samples were cut from this sheet, and a thin layer (0.1 mil) of either catalyzed or uncatalyzed hydrophilic PR-24 nanofibers were deposited onto the smooth GDL face. This creates a bi-layer nanofiber electrolysis electrode, with a thick hydrophobic GDL and a thin hydrophilic surface layer. The uncatalyzed version was prepared so that a catalyst dispersion could be sprayapplied. The catalyzed PR-24 nanofibers that were applied to one of these GDLs were prepared by the microwave procedure alluded to earlier. The PR-25 nanofiber sheet we are testing has been made robust, with a 10% binder content applied in such a way as to retain conductivity. We have placed it in an ultrasonic bath to simulate the high agitation of gas evolution, and it held together nicely. Thus, we are hopeful for its performance in an actual electrolysis cell. Work by Inorganic Specialists for Related Programs Nanofiber paper samples for hydrogen electrolysis from ammonia were prepared and sent to Professor Botte at Ohio University in Athens. Professor Botte will electroplate her catalyst onto these materials, and test them in her EMTEC-funded work. We are furnishing her three types of nanofiber paper. We expect her results will provide both of us with valuable information on how to tailor nanofiber paper for electrolysis. We have recently sold sheets of hydrophobic-treated nanofiber paper to an automotive manufacturer for evaluation as gas diffusers in fuel cells. This is another potential fuel cell-related product for nanofiber paper. Graftech in Parma, OH has expressed interest in the papermaking approach as a way to make a high thermal conductivity material from nanofibers. This would be a special high density nanofiber paper developed in a state-funded project in association with Applied Sciences and the National Composite Center. It now seems likely that Graftech will authorize some funds to support the development of continuous papermaking. We plan on using their funds to buy items that will support papermaking in general (such as equipment for feedstock preparation) that are not provided in the EMTEC project. This leverages resources so that both projects benefit. Publications/Presentations

1. A presentation at CARBON 2007 in Seattle in July has been scheduled. Also, some of our nanofiber fuel cell work will be presented in a talk by Notre Dame at the Electrochemical Society meeting in Chicago in May.
to steam and condenser to condense excess/unreacted H2O were installed and connections were made. Calibration was carried out with a hydrogen-helium mixture in the range 1-30% H2. The experimental conditions were as follows: pre-heater temperature: 400C; reactor temperature: 600C; helium flow rate: 204 sccm; percent weight increase of the sample: 3234%, equivalent to the theoretically predicted value. Two observations are worth reporting. At a preheater temperature of 300C and a reactor temperature of 50C, condensation of the water was observed on the outside walls of the reactor. This could be due to the presence of water in the line (used for verifying the proper functioning of the HPLC pump). This also implies that water was allowed to react with nano iron even before the data was collected. This led to lower hydrogen generation from MSR in one case. In the next run, it was made sure that there was no water in the line to begin with, by ramping the pre-heater to above 100C first, which was then connected to the reactor. Under these conditions the increase in sample weight after MSR was equivalent to 32.1% close to the theoretical value. However, it was observed that the stainless steel filter holding the sample also increased due to oxidation by steam under the employed conditions (from 10.04 g to 10.324 g), there by liberating additional hydrogen. Analysis of the gas chromatograph data also confirmed this as the amount of hydrogen generated was more than theoretically possible if the MSR of nano Fe alone was taken into consideration. To avoid this, we plan to employ a ceramic boat as container for nano Fe. Design and Construction of a Solar Reactor In order to eliminate the currently used heat source for initiating and sustaining the MSR reaction, we envision utilizing a solar concentrator and designing a small prototype hydrogen generation set-up based on the solar-powered MSR technique. A design for the solar concentrator to facilitate MSR was arrived at during the meeting with Replex Inc. at Mount Vernon, OH. A 46.5-in diameter shallow polycarbonate reflector with a focal length of 36-in is being fabricated and mounted by Replex. This will be delivered to the University of Toledo for temperature profile determination and parameter optimization for the MSR reactions.

Objectives The objective of this project is the development and demonstration of a low-cost, high-flux, nano-enabled tubular membrane technology for the purification/ separation of hydrogen obtained by steam methane
reforming. The proposed membrane will incorporate lower cost porous ceramic supports and inorganic separation membrane technologies which were developed independently by MetaMateria Partners (MMP) and Professor Henk Verweij of The Ohio State University (OSU), respectively. The layered inorganic composite will enable the selective diffusion of hydrogen gas at commercial rates. After successful demonstration of the technology in Phase I using a simulated reformer gas stream, Phase II will focus on manufacturing scaleup and commercialization of the technology. Accomplishments A decision was made not to proceed with an injection die designed for producing four alumina tubes per injection. After completing the design, it was determined that sufficient similarities existed in the design and dimensions to an injection die MMP already possessed for production of cathode support tubes that was used in a project funded through the Army TankAutomotive and Armaments Command. A decision was made to utilize this die rather than incur the expense of having a new die custom manufactured. The die has two cavities, each of which is about 30 in length. After the development problems are resolved with the support tubes using a smaller 8 die, the 30 dual cavity die can also be used to produce tubes in quantity to support the further needs of the project. The development work on the support tubes was focused on elimination of 30 to 50 micron diameter surface pores in the support tubes. The elimination of these large pores is vital to being able to lay down defect-free coatings. The AKP-30 intermediate layer does not fully fill these large surface pores. In order to understand and eliminate the source of these pores, several approaches were investigated. While pores in ceramic bodies can result from a number of different phenomena, including micelles, aggregates, poor mixing and gas-evolving reactions, the most common is probably trapped air that is retained in the slurry due to its high viscosity. The viscosity of the injection slurry can be adjusted by either changing the solids loading, the pH or through the addition of organic surfactants. Changing the solids loading of the slurry may have the undesired effect of causing drying cracks to develop and can also affect the drying and sintering shrinkage of the body. The MMP process utilizes organic additives that act as surfactants to lower the slurry viscosity and improve solids loading; however, these surfactants had not yet been optimized for use with the tabular alumina used in this project. Zeta potential measurements are used to measure the interaction of the individual particles in a suspension as a function of either pH or surfactant concentration. The zeta potential as a function of pH for the as-received alumina powder was obtained. This curve was measured using a Colloidal Dynamics Zeta Probe. The zeta potential becomes more negative as the pH increases.