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Basic Research Needs For the Hydrogen Economy Presentation for Basic Energy Sciences Advisory Committee Basic Research Needs For the Hydrogen Economy Presentation for Basic Energy Sciences Advisory Committee Meeting Harriet Kung (DOE/BES) harriet. [email protected] doe. gov October 20, 2003 Basic Energy Sciences Serving the Present, Shaping the Future

Hydrogen: A National Initiative “Tonight I'm proposing $1. 2 billion in research funding so Hydrogen: A National Initiative “Tonight I'm proposing $1. 2 billion in research funding so that America can lead the world in developing clean, hydrogen-powered automobiles… With a new national commitment, our scientists and engineers will overcome obstacles to taking these cars from laboratory to showroom, so that the first car driven by a child born today could be powered by hydrogen, and pollution-free. ” President Bush, State-of the-Union Address, January 28, 2003 Basic Energy Sciences Serving the Present, Shaping the Future

Drivers for the Hydrogen Economy: • Reduce Reliance on Fossil Fuels • Reduce Accumulation Drivers for the Hydrogen Economy: • Reduce Reliance on Fossil Fuels • Reduce Accumulation of Greenhouse Gases 20 Actual Projected 18 Air 16 14 12 Domestic Production Marine s hicle Ve eavy H 10 8 6 Offroad - Light Trucks Rail 4 Cars 2 Passenger Vehicles Millions of Barrels per Day 22 0 1975 1980 1985 1990 1995 2000 2005 2010 2015 2020 2025 Year Basic Energy Sciences Serving the Present, Shaping the Future

The Hydrogen Economy solar wind hydro H 2 O nuclear/solar thermochemical cycles Bio- and The Hydrogen Economy solar wind hydro H 2 O nuclear/solar thermochemical cycles Bio- and bioinspired automotive fuel cells H 2 gas or hydride storage H 2 stationary electricity/heat generation fossil fuel reforming production 9 M tons/yr consumer electronics storage 4. 4 MJ/L (Gas, 10, 000 psi) 8. 4 MJ/L (LH 2) use in fuel cells $3000/k. W 40 M tons/yr 9. 72 MJ/L $35/k. W (Transportation only) (2015 Freedom. CAR Target) (Internal Combustion Engine) Basic Energy Sciences Serving the Present, Shaping the Future

Fundamental Issues The hydrogen economy is a compelling vision: - It provides an abundant, Fundamental Issues The hydrogen economy is a compelling vision: - It provides an abundant, clean, secure and flexible energy source - Its elements have been demonstrated in the laboratory or in prototypes However. . . - It does not operate as an integrated network - It is not yet competitive with the fossil fuel economy in cost, performance, or reliability - The most optimistic estimates put the hydrogen economy decades away Basic Energy Sciences Serving the Present, Shaping the Future

Basic Research for Hydrogen Production, Storage and Use Workshop, May 13 -15, 2003 Millie Basic Research for Hydrogen Production, Storage and Use Workshop, May 13 -15, 2003 Millie Dresselhaus George Crabtree Michelle Buchanan (ORNL) Workshop Chair: Associate Chairs: (MIT) (ANL) Breakout Sessions and Chairs: Hydrogen Production Tom Mallouk, PSU & Laurie Mets, U. Chicago Hydrogen Storage and Distribution Kathy Taylor, GM (retired) & Puru Jena, VCU Fuel Cells and Novel Fuel Cell Materials Frank Di. Salvo, Cornell & Tom Zawodzinski, CWRU EERE Pre-Workshop Briefings: Hydrogen Storage Jo. Ann Milliken Fuel Cells Nancy Garland Hydrogen Production Mark Paster Plenary Session Speakers: Steve Chalk (DOE-EERE) -- overview George Thomas (SNL-CA) -- storage Scott Jorgensen (GM) -- storage Jae Edmonds (PNNL) -- environmental Jay Keller (SNL-CA) – hydrogen safety Basic Energy Sciences Serving the Present, Shaping the Future CHARGE: To identify fundamental research needs and opportunities in hydrogen production, storage, and use, with a focus on new, emerging and scientifically challenging areas that have the potential to have significant impact in science and technologies. Highlighted areas will include improved and new materials and processes for hydrogen generation and storage, and for future generations of fuel cells for effective energy conversion.

Basic Research for Hydrogen Production, Storage and Use Workshop 125 Participants: Universities National Laboratories Basic Research for Hydrogen Production, Storage and Use Workshop 125 Participants: Universities National Laboratories Industries DOE: SC and Technology Program Offices Other Federal Agencies - including OMB, OSTP, NRL, NIST, NSF, NAS, USDA, and House Science Committee Staffer Remarks from News Reporters: American Institute of Physics Bulletin of Science Policy News Number 71 “Dresselhaus remarked that there were some “very promising” ideas, and she was more optimistic after the workshop that some of the potential showstoppers may have solutions. ” “… solving the problems will need long-term support across several Administrations. Progress will require the cooperation of different offices within DOE, and also the involvement of scientists from other countries, …” C&E News June 9, 2003 “MOVING TOWARD A HYDROGEN ECONOMY” DOE Workshop Brings Together Scientists to Prioritize Research Needs for Switching to Hydrogen Economy. Basic Energy Sciences Serving the Present, Shaping the Future

Workshop Goals To identify: • Research needs and opportunities to address long term “Grand Workshop Goals To identify: • Research needs and opportunities to address long term “Grand Challenges” and to overcome “show-stoppers. ” • Prioritized research directions with greatest promise for impact on reaching long-term goals for hydrogen production, storage and use. • Issues cutting across the different research topics/panels that will need multi-directional approaches to ensure that they are properly addressed. • Research needs that bridge basic science and applied technology. Basic Energy Sciences Serving the Present, Shaping the Future

Hydrogen Production Panel Chairs: Tom Mallouk (Penn State), Laurie Mets (U of Chicago) Current Hydrogen Production Panel Chairs: Tom Mallouk (Penn State), Laurie Mets (U of Chicago) Current status: • Steam-reforming of oil and natural gas produces 9 M tons H 2/yr. • We will need 40 M tons/yr for transportation. • Requires CO 2 sequestration. Alternative sources and technologies: Coal: • Cheap, lower H 2 yield/C, more contaminants. • R&D needed for process development, gas separations, impurity removal. Solar: • Widely distributed carbon-neutral; low energy density. • PV/electrolysis current standard – 15% efficient. • Requires 0. 03% of land area to serve transportation. Nuclear: Abundant; carbon-neutral; long development cycle. Basic Energy Sciences Serving the Present, Shaping the Future catalysis,

Priority Research Areas in Hydrogen Production Fossil Fuel Reforming • For the next decade Priority Research Areas in Hydrogen Production Fossil Fuel Reforming • For the next decade or more hydrogen will mainly be produced using fossil fuel feedstocks. • Development of efficient inexpensive catalysts will be key. • Modeling and simulation will play a significant role. Inspired by quantum chemical calculations, Ni surface-alloyed with Au (black) on the left is used to reduce carbon poisoning of catalyst, as verified experimentally on the right. Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Production Solar Photoelectrochemistry/Photocatalysis • Power conversion efficiency (10%) needs Priority Research Areas in Hydrogen Production Solar Photoelectrochemistry/Photocatalysis • Power conversion efficiency (10%) needs to be increased by reducing losses. • Spectral response needs to be extended into the red. • Costs need to be reduced in the production of the transparent anode. Low cost Ti. O 2 porous nanostructures allow deep light penetration into dyesensitized solar cells to increase their efficiency. Photochemical solar cells or Grätzel cells use cheap porous Ti. O 2 with a huge surface area (see right). Dye additives allow absorption of visible light to better match solar spectrum (left). Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Production Bio- and Bio-inspired H 2 Production • • Priority Research Areas in Hydrogen Production Bio- and Bio-inspired H 2 Production • • Biological systems (plants, microbes) can produce hydrogen from H 2 O. Nanostructured catalysts can mimic biological systems for H 2 production. Biomimetic catalysts may play important roles in future electrochemical and photochemical hydrogen-related processes. Synthetic catalysts, such as water oxidation catalysts based on the design of the natural photosynthesis II Mn cluster (upper left) or hydrogen activation catalysts based on the design of the natural reversible Ironhydrogenase H-cluster (lower right), show promise in mimicking many of the catalytic properties of their natural counterparts. Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Production Nuclear and Solar Thermal Hydrogen to split H Priority Research Areas in Hydrogen Production Nuclear and Solar Thermal Hydrogen to split H 2 O Nanostructures may allow the high efficiency achieved in thermochemical hydrogen production cycles to occur under less severe environmental conditions. • Operation at high temperature (500950 ºC) for thermal hydrogen production cycles places severe demands on reactor design and on materials. • Use of solar concentrator technology needs to be explored. • Efforts to lower operating temperatures offer major challenges for catalyst development. Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Production Fossil Fuel Reforming Molecular level understanding of catalytic Priority Research Areas in Hydrogen Production Fossil Fuel Reforming Molecular level understanding of catalytic mechanisms, nanoscale catalyst design, high temperature gas separation Solar Photoelectrochemistry/Photocatalysis Light harvesting, charge transport, chemical assemblies, bandgap engineering, interfacial chemistry, catalysis and photocatalysis, organic semiconductors, theory and modeling, and stability Ni surface-alloyed with Au to reduce carbon poisoning Bio- and Bio-inspired H 2 Production Microbes & component redox enzymes, nanostructured 2 D & 3 D hydrogen/oxygen catalysis, sensing, and energy transduction, engineer robust biological and biomimetic H 2 production systems Nuclear and Solar Thermal Hydrogen Thermodynamic data and modeling for thermochemical cycle (TC), high temperature materials: membranes, TC heat exchanger materials, gas separation, improved catalysts Basic Energy Sciences Serving the Present, Shaping the Future Dye-Sensitized Solar Cells Synthetic Catalysts for Water Oxidation and Hydrogen Activation

Hydrogen Storage Panel Chairs: Kathy Taylor (GM, retired), Puru Jena (Virginia Commonwealth U) Current Hydrogen Storage Panel Chairs: Kathy Taylor (GM, retired), Puru Jena (Virginia Commonwealth U) Current Technology • Tanks for gaseous or liquid hydrogen storage. • Progress demonstrated in solid state storage materials. Target Applications • Transportation: on-board vehicles storage. • Non-transportation: applications for hydrogen production/delivery. System Requirements • Demand compact, light-weight, affordable storage. • System requirements set for Freedom. CAR: 4. 5 wt% for 2005, 9 wt% for 2015. • No current storage system or material meets all targets. (Currently: Solid Storage 3%; Liquid and Gas Storage 4%) Volumetric Energy Density MJ / L system 30 Energy Density of Fuels gasoline liquid H 2 20 compressed gas H 2 proposed DOE goal 10 chemical hydrides 0 0 complex hydrides 10 20 30 Gravimetric Energy Density MJ/kg system 40

High Gravimetric H Density Candidates Based on Schlapbach and Zuttel, 2001 Basic Energy Sciences High Gravimetric H Density Candidates Based on Schlapbach and Zuttel, 2001 Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Storage Metal Hydrides and Complex Hydrides • Metal hydrides Priority Research Areas in Hydrogen Storage Metal Hydrides and Complex Hydrides • Metal hydrides such as alanates allow high hydrogen volume density, but temperature of hydrogen release also tends to be high. • Nanostructured materials may improve absorption volume. • Incorporated catalysts may improve release. Using Neutrons to “See” Hydrogen The large neutron cross sections of hydrogen and deuterium make neutrons an ideal probe for in situ studies of hydrogen-based chemical reactions, surface interactions, catalytic reactions and of hydrogen in penetrating through membranes. Basic Energy Sciences Serving the Present, Shaping the Future

Carbon Nanotubes for Hydrogen Storage • The very small size and very high surface Carbon Nanotubes for Hydrogen Storage • The very small size and very high surface area of carbon nanotubes make them interesting for hydrogen storage. • Challenge is to increase the H: C stoichiometry and to strengthen the H —C bonding at 300 K. A computational representation of hydrogen adsorption in an optimized array of (10, 10) nanotubes at 298 K and 200 Bar. The red spheres represent hydrogen molecules and the blue spheres represent carbon atoms in the nanotubes, showing 3 kinds of binding sites. (K. Johnson et al. ) Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Storage Nanoscale/Novel Materials • Nanoscale materials have high surface Priority Research Areas in Hydrogen Storage Nanoscale/Novel Materials • Nanoscale materials have high surface areas, novel shapes, with properties much different from their 3 D counterparts – especially useful for catalysts and catalyst supports. • Enhanced hydrogen adsorption on high surface area nanostructures may be attained by selective manipulation of surface properties. • Nanostructures also have other opportunities for use for hydrogen storage. Nanostructures such as cup-stacked carbon nanofibers (less than 10 nm diameter) and other high surface area structures are being developed to support tiny nanocatalyst particles (2 nm) in the regions between the cups. Results obtained thus far are encouraging for specific applications. Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Storage Theory and Modeling Model systems for benchmarking against Priority Research Areas in Hydrogen Storage Theory and Modeling Model systems for benchmarking against calculations at all length scales, integrating disparate time & length scales, first principles methods applicable to condensed phases First principles density functional theory shows that neutral Al. H 4 dissociates into Al. H 2 + H 2 but that ionized Al. H 4 - tightly binds 4 hydrogens. Calculations further show that Ti substitutes for Na in Na. Al. H 4 and weakens the Al-H ionic bond, thus making it possible to dramatically lower the temperature of H 2 desorption (by approximately 100°C). (unpublished calculations of P. Jena, co-chair of Hydrogen Storage Panel). Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Hydrogen Storage Metal Hydrides and Complex Hydrides Degradation, thermophysical properties, Priority Research Areas in Hydrogen Storage Metal Hydrides and Complex Hydrides Degradation, thermophysical properties, effects of surfaces, processing, dopants, and catalysts in improving kinetics, nanostructured composites Neutron Imaging of Hydrogen Nanoscale/Novel Materials Finite size, shape, and curvature effects on electronic states, thermodynamics, and bonding, heterogeneous compositions and structures, catalyzed dissociation and interior storage phase Na. BH 4 + 2 H 2 O 4 H 2 + Na. BO 2 Theory and Modeling Model systems for benchmarking against calculations at all length scales, integrating disparate time & length scales, first principles methods applicable to condensed phases Cup-Stacked Carbon Nanofiber Basic Energy Sciences Serving the Present, Shaping the Future H Adsorption in Nanotube Array

Fuel Cells and Novel Fuel Cell Materials Panel Chairs: Frank Di. Salvo (Cornell), Tom Fuel Cells and Novel Fuel Cell Materials Panel Chairs: Frank Di. Salvo (Cornell), Tom Zawodzinski (Case Western Reserve) Current status: • • Engineering investments have been a success. Limits to performance are materials, which have not changed much in 15 years. 2 H 2 + O 2 2 H 2 O + electrical power + heat Challenges: • Membranes • Operation in lower humidity, strength and durability. • Higher ionic conductivity. • Cathodes • Materials with lower overpotential and resistance to impurities. • Low temperature operation needs cheaper (non- Pt) materials. • Tolerance to impurities: CO, S, hydrocarbons. • Reformers • Need low temperature and inexpensive reformer catalysts. Basic Energy Sciences Serving the Present, Shaping the Future

Priority Research Areas in Fuel Cells Electrocatalysts and Membranes Oxygen reduction cathodes, minimize rare Priority Research Areas in Fuel Cells Electrocatalysts and Membranes Oxygen reduction cathodes, minimize rare metal usage in cathodes and anodes, synthesis and processing of designed triple percolation electrodes Low Temperature Fuel Cells ‘Higher’ temperature proton conducting membranes, degradation mechanisms, functionalizing materials with tailored nanostructures Solid Oxide Fuel Cells 2 -5 nm 20 -50 mm H 2 Intake Serving the Present, Shaping the Future Cathod O 2 Anode Catalys Membranes e Intak ts e Internal view of a PEM fuel cell Source: T. Zawodzinski (CWRU) Mass of Pt Used in the Fuel Cell a Critical Cost Issue Theory, modeling and simulation, validated by experiment, for electrochemical materials and processes, new materials-all components, novel synthesis routes for optimized architectures, advanced Source: H. Gasteiger (General Motors) in-situ analytical tools Basic Energy Sciences Controlled design of triple percolation nanoscale networks: ions, electrons, and porosity for gases Electrons Water YSZ Electrolyte for SOFCs Porosity can be tailored Source: R. Gorte (U. Penn)

High Priority Research Directions • Low-cost and efficient solar energy production of hydrogen • High Priority Research Directions • Low-cost and efficient solar energy production of hydrogen • Nanoscale catalyst design • Biological, biomimetic, and bio-inspired materials and processes • Complex hydride materials for hydrogen storage • Nanostructured / novel hydrogen storage materials • Low-cost, highly active, durable cathodes for lowtemperature fuel cells • Membranes and separations processes for hydrogen production and fuel cells • Analytical and measurement technologies • Theory, modeling, and simulation Basic Energy Sciences Serving the Present, Shaping the Future

Cross-Cutting Research Directions • Catalysis - hydrocarbon reforming - hydrogen storage kinetics - fuel Cross-Cutting Research Directions • Catalysis - hydrocarbon reforming - hydrogen storage kinetics - fuel cell and electrolysis electrochemistry • Membranes and Separation • Nanoscale Materials and Nanostructured Assemblies • Characterization and Measurement Techniques • Theory and Modeling • Safety and Environment Basic Energy Sciences Serving the Present, Shaping the Future

Messages § Enormous gap between present state-of-the-art capabilities and requirements that will allow hydrogen Messages § Enormous gap between present state-of-the-art capabilities and requirements that will allow hydrogen to be competitive with today’s energy technologies § production: 9 M tons 40 M tons (vehicles) § storage: 4. 4 MJ/L (10 K psi gas) 9. 72 MJ/L § fuel cells: $3000/k. W $35/k. W (gasoline engine) § Enormous R&D efforts will be required § Simple improvements of today’s technologies will not meet requirements § Technical barriers can be overcome only with high risk/high payoff basic research § Research is highly interdisciplinary, requiring chemistry, materials science, physics, biology, engineering, nanoscience, http: //www. sc. doe. gov/bes/ hydrogen. pdf computational science § Basic and applied research should couple seamlessly Basic Energy Sciences Serving the Present, Shaping the Future

Inter-Agency Coordination DOE • Hydrogen Program Management Plan- EERE, FE, NE, SC • EERE Inter-Agency Coordination DOE • Hydrogen Program Management Plan- EERE, FE, NE, SC • EERE Grand Challenge Solicitation on Hydrogen Storage (~ $150 M for 5 years) OSTP Hydrogen R & D Task Force Group • DOC, DOD, DOE, DOT, DOS, CIA, EPA, NASA, NIST, NSF, USDA • Develop Taxonomy of Research Directions to Facilitate Inter-Agency Coordination IPHE (International Partnership for the Hydrogen Economy) • IPHE Ministerial Meeting and Hydrogen Economy Dialogue, November 2003 • To Organize, Evaluate and Coordinate Multinational Research, Development and Deployment Programs DOE/European Commission • Implementing Agreement on Hydrogen Research and Applications • Topics include: Hydrogen Production, Carbon Sequestration, Storage, Delivery, Fuel Cells, Codes and Standards, Economic/Cost Modeling IEA Hydrogen Coordination Group • Hydrogen & Fuel Cells Technology and Policy Programs in IEA Member Countries Basic Energy Sciences Serving the Present, Shaping the Future

Outreach OMB/OSTP Briefing / SC Briefing March APS • DCMP Invited Symposium- Dresselhaus, Norskov, Outreach OMB/OSTP Briefing / SC Briefing March APS • DCMP Invited Symposium- Dresselhaus, Norskov, Gasteiger, Gust, Gratzel • Wednesday evening plenary? Energy Secy Abraham invited MRS, ACS will have symposia Council for Chemical Research Physics Today- article by Dresselhaus, Buchanan, Crabtree Nova- consultants are Nate Lewis, Millie Dresselhaus Jim Lehrer Newshour Interviews by Brazil Major TV Talk Show / Newspaper Basic Energy Sciences Serving the Present, Shaping the Future