Hydrogen Storage for Transportation Applications

1
Hydrogen Storage for Transportation Applications

• James Wang
• Sandia National Laboratories
• Livermore, California

Presentation at Energy and Nanotechnology
Strategy for the Future Conference Center for
Nanoscale Science and Technology, Rice
University, Houston, TX, May 4, 2003
2
Acknowledgements
George Thomas, Hydrogen Storage Workshop, Hilton
Head, SC, 2/28/2002 JoAnn Milliken, Hydrogen
Storage Workshop, Argonne, IL, 8/14/2002 Petrovic
Milliken, DOE Fossil Energy/Nanoscience
Workshop, Napa, CA, 3/31-4/2/2003 Jay Keller,
G-CEP Hydrogen Conference, Stanford, CA, 4/15/2003
3
President Bush Launches the Hydrogen Fuel
Initiative
"Tonight I am proposing 1.2 billion in research
funding so that America can lead the world in
developing clean, hydrogen-powered
automobiles. "A simple chemical reaction between
hydrogen and oxygen generates energy, which can
be used to power a car producing only water, not
exhaust fumes. "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. "Join me in this important
innovation to make our air significantly cleaner,
and our country much less dependent on foreign
sources of energy."
2003 State of the Union Address January 28, 2003
From Patrovic Milliken (2003)
4
What are the issues we trying to solve?

• Energy security transportations dependence on
  petroleum
• Increasing dependence on foreign oil,
  particularly from unstable regions
• Vulnerable domestic international energy
  infrastructures
• Oil and natural gas pipelines
• Few and vulnerable ports of entry
• Urban air pollution
• Criterion gas emission (NOx, HC, PM, CO )
• Threat of climate change
• Atmospheric concentration of CO2, CH4

5
Why Hydrogen? Its abundant, clean, efficient,
and can be derived from diverse domestic
resources.
Biomass
.
Transportation
Hydro Wind Solar
HIGH EFFICIENCY RELIABILITY
Nuclear
Oil
Distributed Generation
ZERO/NEAR ZEROEMISSIONS
Coal
With Carbon Sequestration
Natural Gas
From Patrovic Milliken (2003)
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National Hydrogen Roadmap

• Major Findings
• Widespread use of hydrogen will affect every
  aspect of the U.S. energy system from production
  through end-use.
• Conversion
• Conversion of hydrogen into useful forms of
  electricity and thermal energy involves the use
  of fuel cells, reciprocating engines, turbines,
  and process heaters.

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National Hydrogen Roadmap (cont)

• Conversion
• Government should assist in developing
  better information on the fundamental properties
  of hydrogen combustion and materials,
  electrochemistry, and interfaces for fuel cells.
• Applications
• Ultimately, consumers should be able to use
  hydrogen energy for transportation, electric
  power generation, and portable electronic

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On-Board Hydrogen Storage Challenge

• The low volumetric density of gaseous fuels
  requires a storage method which densifies the
  fuel.
• This is particularly true for hydrogen because of
  its lower energy density relative to hydrocarbon
  fuels
• 3 MJ/l (5000 psi H2), 8 MJ/l (LH2) vs. 32 MJ/l
  (gasoline)
• Storing enough hydrogen on vehicles to achieve
  greater than 300 miles driving range is
  difficult.
• Storage system adds an additional weight and
  volume above that of the fuel.

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How large of a gas tank do you want?
Volume Comparisons for 4 kg Vehicular H2 Storage
Schlapbach Züttel, Nature, 15 Nov. 2001
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DOE Hydrogen Storage RD Program Approaches

• Carbon
• Kinetics/Mechanistic Studies
• Process RD
• Structure/Property Analyses

• Chemical Storage (2004)
• NaBH4 Process Chemistry
• Life-Cycle Analyses
• Other Hydrides

Standard Testing Procedures/Facilities

• Complex Metal Hydrides
• NaAlH4 System Integration
• Hydride Materials RD
• Kinetics/Mechanistic Studies

• Compressed/Liquid Tanks
• 5,000/10,000 psi Tanks
• Semi-Conformal System
• Tank Liners/Overwrap Materials
• Insulated Pressure Vessels
• Unusual Shapes

• Advanced Concepts (2004)
• TBD

From Patrovic Milliken (2003)
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Compressed H2 Storage
Compressed/Liquid Hydrogen Storage

• Type IV all-composite tanks are available at
  5000 psi (350 bar)
• 10,000 psi tanks being developed

Packaging volume and safety are key issues
Liquid H2 Storage

• Liquifying H2 requires substantial energy
• Boil-off is an issue for non-pressurized
  insulated tanks

From Patrovic Milliken (2003)
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Reversible Metal Hydride System
Sodium alanate doped with Ti is a reversible
material hydrogen storage approach.
Low hydrogen capacity and slow kinetics are
issues
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Irreversible Chemical Hydrides
Three Approaches
Regeneration costs are a major issue
From Patrovic Milliken (2003)
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From JoAnn Milliken (2002)
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Single-Wall Carbon Nanotubes

• Hydrogen storage capacity around 4 wt at ambient
  temperature and moderate pressure
• Higher reported storage capacities of 8-10 wt.
  have been difficult to reproduce
• Low cost high volume fabrication processes are
  not yet available for carbon nanotubes

C. Liu, Y.Y. Fan, M. Liu, H.T. Cong, H.M. Cheng,
and M.S. Dresselhaus, Hydrogen Storage in
Single-Walled Carbon Nanotubes at Room
Temperature, Science, 286, 1127-1129 (1999).
From Patrovic Milliken (2003)
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The most promising technologies are the farthest
from commercialization
From George Thomas (2002)
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From JoAnn Milliken (2002)
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Current Status of Hydrogen Storage Systems and
Materials
From Patrovic Milliken (2003)
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Advanced Concepts Discussed at DOE Hydrogen
Storage Workshop in August 2002

• Crystalline Nanoporous Materials
• Polymer Microspheres
• Self-Assembled Nanocomposites
• Advanced Hydrides
• Inorganic Organic Compounds
• BN Nanotubes
• Hydrogenated Amorphous Carbon
• Mesoporous Materials
• Bulk Amorphous Materials (BAMs)
• Iron Hydrolysis
• Nanosize Powders
• Metallic Hydrogen
• Hydride Alcoholysis

From Patrovic Milliken (2003)
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Materials with High Formula Weight Hydrogen
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Hydrogen Adsorption by Boron Nitride Nanotubes
R. Ma, Y. Bando, H.Zhu, T. Sato, C. Xu, and D.
Wu, Hydrogen Uptake in Boron Nitride Nanotubes
at Room Temperature, J. Am. Chem. Soc., 124,
7672-7673 (2002).
From Patrovic Milliken (2003)
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Hydrogen Storage by Palladium Nanoparticles in
Zeolite NaY
N. Nishimiya, T. Kishi, T. Mizushima, A.
Matsumoto, and K. Tsutsumi, Hyperstoichiometric
Hydrogen Occlusion by Palladium Nanoparticles
Included in NaY Zeolite, Journal of Alloys and
Compounds, 319, 312-321 (2001).
From Patrovic Milliken (2003)
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General Motors Gravimetric Energy Density vs.
Volumetric Energy Density of Fuel Cell Hydrogen
Storage Systems

40
35
Advanced
30
LH2 Tank
SysWt 8.2
25
.
LH2
Gravimetric Energy Density
MJ/kg
20
SysWt 4.2
CGH2 SysWt 3.7 700bar
DOE-Goal SysWt6.0
15
10
5
0
20
15
0
5
10
25
30
Volumetric Energy Density MJ/l
LT- Metal
HT MT- Metal
Hydride
Hydrides
SysWt 3.3 - 3.4
SysWt 1.2
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Summary

• Hydrogen storage is one of the highest technical
  priorities of the DOE Office of Hydrogen, Fuel
  Cells and Infrastructure Technologies.
• Todays hydrogen storage technologies dont meet
  the vehicle requirements (FreedomCAR goals).
• New materials and/or new technical approaches are
  required to meet hydrogen storage targets for
  vehicular fuel cell systems.
• Nanotechnology may play an important role in new
  storage materials development.
• Timing in successfully meeting the required
  hydrogen storage targets is important to the
  success of fuel cell vehicles and hydrogen
  economy.