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Presentation for Basic Energy Sciences Advisory Committee Meeting Harriet Kung (DOE/BES)

Basic Research Needs For the Hydrogen Economy. Presentation for Basic Energy Sciences Advisory Committee Meeting Harriet Kung (DOE/BES) harriet.kung@science.doe.gov October 20, 2003. Hydrogen: A National Initiative.

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Presentation for Basic Energy Sciences Advisory Committee Meeting Harriet Kung (DOE/BES)

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  1. Basic Research Needs For the Hydrogen Economy Presentation for Basic Energy Sciences Advisory Committee Meeting Harriet Kung (DOE/BES) harriet.kung@science.doe.gov October 20, 2003

  2. 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

  3. Drivers for the Hydrogen Economy: 22 20 18 16 14 12 10 8 Actual Projected 6 Off Off - - road road 4 Cars Air Passenger Vehicles 2 Domestic Domestic 0 Production Production Heavy Vehicles Marine Marine 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 2020 2025 Millions of Barrels per Day Light Trucks Rail Year • Reduce Reliance on Fossil Fuels • Reduce Accumulation of Greenhouse Gases

  4. solar wind hydro automotive fuel cells consumer electronics H2 H2O H2 nuclear/solar thermochemical cycles stationary electricity/heat generation fossil fuel reforming use in fuel cells storage Bio- and bioinspired 4.4 MJ/L (Gas, 10,000 psi) 8.4 MJ/L (LH2) production $3000/kW 9M tons/yr $35/kW (Internal Combustion Engine) 40M tons/yr (Transportation only) 9.72MJ/L (2015 FreedomCAR Target) The Hydrogen Economy gas or hydride storage

  5. 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

  6. Basic Research for Hydrogen Production, Storage and Use Workshop, May 13-15, 2003 Workshop Chair: Millie Dresselhaus (MIT) Associate Chairs: George Crabtree (ANL) Michelle Buchanan (ORNL) 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 DiSalvo, Cornell & Tom Zawodzinski, CWRU EERE Pre-Workshop Briefings: Hydrogen StorageJoAnn Milliken Fuel CellsNancy Garland Hydrogen ProductionMark Paster 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. 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

  7. 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.

  8. 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.

  9. Hydrogen Production Panel Panel Chairs: Tom Mallouk (Penn State), Laurie Mets (U of Chicago) • Current status: • Steam-reforming of oil and natural gas produces 9M tons H2/yr. • We will need 40M tons/yr for transportation. • Requires CO2 sequestration. • Alternative sources and technologies: • Coal: • Cheap, lower H2 yield/C, more contaminants. • R&D needed for process development, gas separations, catalysis, 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.

  10. 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.

  11. 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 TiO2 porous nanostructures allow deep light penetration into dye-sensitized solar cells to increase their efficiency. Photochemical solar cells or Grätzel cells use cheap porous TiO2 with a huge surface area (see right). Dye additives allow absorption of visible light to better match solar spectrum (left).

  12. Priority Research Areas in Hydrogen Production • Bio- and Bio-inspired H2 Production • Biological systems (plants, microbes) can produce hydrogen from H2O. • Nanostructured catalysts can mimic biological systems for H2 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 Iron-hydrogenase H-cluster (lower right), show promise in mimicking many of the catalytic properties of their natural counterparts.

  13. Priority Research Areas in Hydrogen Production Nuclear and Solar Thermal Hydrogen to split H2O Nanostructures may allow the high efficiency achieved in thermo-chemical hydrogen production cycles to occur under less severe environmental conditions. • Operation at high temperature (500-950 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.

  14. 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 Bio- and Bio-inspired H2 Production Microbes & component redox enzymes, nanostructured 2D & 3D hydrogen/oxygen catalysis, sensing, and energy transduction, engineer robust biological and biomimetic H2 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 Ni surface-alloyed with Au to reduce carbon poisoning Dye-Sensitized Solar Cells Synthetic Catalysts for Water Oxidation and Hydrogen Activation

  15. Hydrogen Storage Panel 30 Energy Density of Fuels gasoline 20 compressed gas H2 liquid H2 Volumetric Energy Density MJ / L system proposed DOE goal 10 chemical hydrides 0 20 0 10 30 40 complex hydrides Gravimetric Energy Density MJ/kg system 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 FreedomCAR: 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%)

  16. High Gravimetric H Density Candidates Based on Schlapbach and Zuttel, 2001

  17. Priority Research Areas in Hydrogen Storage Using Neutrons to “See” Hydrogen • 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. 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.

  18. 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.)

  19. Priority Research Areas in Hydrogen Storage • Nanoscale/Novel Materials • Nanoscale materials have high surface areas, novel shapes, with properties much different from their 3D 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 10nm diameter) and other high surface area structures are being developed to support tiny nanocatalyst particles (2nm) in the regions between the cups. Results obtained thus far are encouraging for specific applications.

  20. 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 AlH4 dissociates into AlH2 + H2 but that ionized AlH4- tightly binds 4 hydrogens. Calculations further show that Ti substitutes for Na in NaAlH4 and weakens the Al-H ionic bond, thus making it possible to dramatically lower the temperature of H2 desorption (by approximately 100°C). (unpublished calculations of P. Jena, co-chair of Hydrogen Storage Panel).

  21. 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 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 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 Neutron Imaging of Hydrogen NaBH4 + 2 H2O 4 H2 + NaBO2 Cup-Stacked Carbon Nanofiber H Adsorption in Nanotube Array

  22. Fuel Cells and Novel Fuel Cell Materials Panel Panel Chairs: Frank DiSalvo (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. 2H2 + O2 2H2O + 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.

  23. H2 Intake Membranes O2 Intake Cathode Anode Catalysts Internal view of a PEM fuel cell Water Electrons 2-5 nm 20-50 - mm 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 nano-structures Solid Oxide Fuel Cells Theory, modeling and simulation, validated by experiment, for electrochemical materials and processes, new materials-all components, novel synthesis routes for optimized architectures, advanced in-situ analytical tools Controlled design of triple percolation nanoscale networks: ions, electrons, and porosity for gases Source: T. Zawodzinski (CWRU) Mass of Pt Used in the Fuel Cell  a Critical Cost Issue YSZ Electrolyte for SOFCs Porosity can be tailored Source: H. Gasteiger (General Motors) Source: R. Gorte (U. Penn)

  24. 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 low-temperature fuel cells • Membranes and separations processes for hydrogen production and fuel cells • Analytical and measurement technologies • Theory, modeling, and simulation

  25. • 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 Cross-Cutting Research Directions

  26. 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: 9M tons  40M tons (vehicles) • storage: 4.4 MJ/L (10K psi gas) 9.72 MJ/L • fuel cells: $3000/kW $35/kW (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, computational science • Basic and applied research should couple seamlessly http://www.sc.doe.gov/bes/ hydrogen.pdf

  27. 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

  28. 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 Outreach

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