presentation for basic energy sciences advisory committee meeting harriet kung (doe/bes)

Basic Energy SciencesBasic Energy SciencesServing the Present, Shaping the FutureServing the Present, Shaping the Future

Presentation forBasic Energy Sciences Advisory Committee Meeting

Harriet Kung (DOE/BES)[email protected]

October 20, 2003

Basic Research Needs For the Hydrogen Economy


“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

Hydrogen: A National InitiativeHydrogen: A National Initiative


Energy Source

% of U.S. Electricity

Supply

% of Total U.S. Energy

SupplyOil 3 39Natural Gas 15 23Coal 51 22Nuclear 20 8Hydroelectric 8 4Biomass 1 3Other Renewables 1 1

Drivers for the Hydrogen Economy:Drivers for the Hydrogen Economy:

0

2

4

6

8

10

12

14

16

18

20

22

1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 2020 2025

Mil

lio

ns

of

Ba

rre

ls p

er

Da

y

Domestic ProductionDomestic

Production

Actual Projected

Light Trucks

Heavy Vehicles

Year

Air

MarineMarine

RailOff-roadOff-road

Cars

Pa

ss

en

ge

r V

eh

icle

s

• Reduce Reliance on Fossil Reduce Reliance on Fossil Fuels Fuels • Reduce Accumulation of Reduce Accumulation of Greenhouse GasesGreenhouse Gases


The Hydrogen EconomyThe Hydrogen Economysolarwindhydro

fossil fuelreforming

nuclear/solar thermochemical

cycles H2

gas orhydridestorage H2

automotivefuel cells

stationaryelectricity/heat

generation

consumerelectronics

H2O

production storageuse

in fuel cells

Bio- and bioinspired

9M tons/yr

40M tons/yr(Transportation only)

9.72 MJ/L(2015 FreedomCAR Target)

4.4 MJ/L (Gas, 10,000 psi) 8.4 MJ/L (LH2) $3000/kW

$35/kW(Internal Combustion Engine)


Fundamental IssuesFundamental 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 prototypesHowever . . .

- 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


Workshop Chair: Millie Dresselhaus (MIT)Associate Chairs: George Crabtree (ANL)

Michelle Buchanan (ORNL)

Basic Research for Hydrogen Production, Basic Research for Hydrogen Production, Storage and Use Workshop, May 13-15, 2003Storage and Use Workshop, May 13-15, 2003

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) -- overviewGeorge Thomas (SNL-CA) -- storageScott Jorgensen (GM) -- storageJae Edmonds (PNNL) -- environmentalJay Keller (SNL-CA) – hydrogen safety

Breakout Sessions and Chairs:Hydrogen Production

Tom Mallouk, PSU & Laurie Mets, U. ChicagoHydrogen Storage and Distribution

Kathy Taylor, GM (retired) & Puru Jena, VCUFuel Cells and Novel Fuel Cell Materials

Frank DiSalvo, Cornell & Tom Zawodzinski, CWRU

EERE Pre-Workshop Briefings:

Hydrogen Storage JoAnn Milliken Fuel Cells Nancy GarlandHydrogen Production Mark Paster


Basic Research for Hydrogen Production, Basic Research for Hydrogen Production, Storage and Use WorkshopStorage and Use Workshop

125 Participants: UniversitiesNational Laboratories Industries DOE: SC and Technology Program Offices Other Federal Agencies - including OMB, OSTP, NRL, NIST, NSF, NAS, USDA, and House Science Committee Staffer

Univ22%

Industries 7%

Labs 28%

DOE28%

Other Agencies

12%Foreign

3%

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.


• 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.

Workshop GoalsWorkshop Goals

To identify:


Hydrogen Production PanelHydrogen Production Panel

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.

Panel Chairs: Tom Mallouk (Penn State), Laurie Mets (U of Chicago)


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.

Priority Research Areas in Hydrogen ProductionPriority Research Areas in Hydrogen Production

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.


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).


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.


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.


Fossil Fuel ReformingMolecular level understanding of catalytic mechanisms, nanoscale catalyst design, high temperature gas separation

Solar Photoelectrochemistry/PhotocatalysisLight harvesting, charge transport, chemical assemblies, bandgap engineering, interfacial chemistry, catalysis and photocatalysis, organic semiconductors, theory and modeling, and stability

Bio- and Bio-inspired H2 ProductionMicrobes & 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 HydrogenThermodynamic data and modeling for thermochemical cycle (TC), high temperature materials: membranes, TC heat exchanger materials, gas separation, improved catalysts


Dye-Sensitized Solar Cells

Ni surface-alloyed with Au to reduce carbon poisoning

Synthetic Catalysts for Water Oxidation and Hydrogen Activation

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%)

Hydrogen Storage PanelHydrogen Storage PanelPanel Chairs: Kathy Taylor (GM, retired), Puru Jena (Virginia Commonwealth U)

Gravimetric Energy DensityMJ/kg system

Volu

metr

ic E

nerg

y D

en

sit

yM

J /

L s

yste

m

0

10

20

30

0 10 20 30 40

Energy Density of Fuels

proposed DOE goal

gasoline

liquid H2

chemicalhydrides

complex hydrides

compressed gas H2


High Gravimetric H Density CandidatesHigh Gravimetric H Density Candidates

Based on Schlapbach and Zuttel, 2001


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” HydrogenUsing Neutrons to “See” Hydrogen

NaAlH4 X-ray view NaAlD4 neutron viewNaAlH4 X-ray view NaAlD4 neutron view

H D C O Al Si Fe

X ray cross section

Neutron cross section

H D C O Al Si Fe

X ray cross section


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.

Priority Research Areas in Hydrogen StoragePriority Research Areas in Hydrogen Storage


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.)

Carbon Nanotubes for Hydrogen StorageCarbon 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.


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.


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.

• 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.


Theory and ModelingModel 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).


Metal Hydrides and Complex HydridesDegradation, thermophysical properties, effects of surfaces, processing, dopants, and catalysts in improving kinetics, nanostructured composites

Nanoscale/Novel MaterialsFinite size, shape, and curvature effects on electronic states, thermodynamics, and bonding, heterogeneous compositions and structures, catalyzed dissociation and interior storage phase

Theory and ModelingModel systems for benchmarking against calculations at all length scales, integrating disparate time & length scales, first principles methods applicable to condensed phases


Fuel PEFC

Fuel (NaBH4)

Spent fuel

Fuel CellVehicle

Fuel

Spent fuelrecovery

(NaBO2)

Service Station

Borohydride Production

(Mg)

H2

(MgO)

Fuel PEFC

Fuel (NaBH4)

Spent fuel

Fuel CellVehicle

Fuel

Spent fuelrecovery

(NaBO2)

Service Station

Borohydride Production

(Mg)

H2

(MgO)

NaAlH4 X-ray view NaAlD4 neutron viewNaAlH4 X-ray view NaAlD4 neutron view

H D C O Al Si Fe

X ray cross section


H D C O Al Si Fe

X ray cross section


NaBH4 + 2 H2O 4 H2 + NaBO2

H Adsorption in Nanotube Array

Neutron Imaging of Hydrogen

Cup-Stacked Carbon Nanofiber


Fuel Cells and Novel Fuel Cell Materials PanelFuel Cells and Novel Fuel Cell Materials Panel

Current status: • Engineering investments have been a

success. • Limits to performance are materials, which

have not changed much in 15 years.

Panel Chairs: Frank DiSalvo (Cornell), Tom Zawodzinski (Case Western Reserve)

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.

2H2 + O2 2H2O + electrical power + heat


Electrocatalysts and MembranesOxygen 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 CellsTheory, 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

Priority Research Areas in Fuel CellsPriority Research Areas in Fuel Cells

Source: H. Gasteiger (General Motors)

Mass of Pt Used in the Fuel Cell a Critical Cost Issue

1.4

1.2

1

0.8

0.6

0.4

0.2

0

g Pt/k

W

Ecell (V)0.55 0.60 0.65 0.70 0.75 0.80

2-5 nm

20-50 -m

Controlled design of triple percolation nanoscale networks: ions, electrons, and porosity for gases

YSZ Electrolyte for SOFCs

Porosity can be tailored

Internal view of a PEM fuel cell

H2Intake Anode Catalysts Cathode O2

Intake

Electrons Water

Membranes

Source: T. Zawodzinski (CWRU)

Source: R. Gorte (U. Penn)


High Priority Research DirectionsHigh 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


Cross-Cutting Research DirectionsCross-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


MessagesMessages

http://www.sc.doe.gov/bes/hydrogen.pdf

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


Inter-Agency CoordinationInter-Agency CoordinationDOE• 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


OutreachOutreachOMB/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

presentation for basic energy sciences advisory committee meeting harriet kung (doe/bes)

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