2006 Annual DOE Hydrogen

Program Merit Review

Hydrogen Storage
Sunita Satyapal
Carole Read
Grace Ordaz
George Thomas1

1 Retired, on assignment to DOE, Washington DC

 Outline

¾ Challenges
¾ Goals and Targets

¾ Strategy
¾ Focus on Materials-based Technologies

¾ Results: Progress in the last year

¾ R&D Examples
¾ Programmatic Accomplishments

¾ Future Plans
 Hydrogen Storage: The “Grand Challenge”

On-board hydrogen storage to meet all performance (wt, vol,

kinetics, etc.) , safety and cost requirements and enable a more
than 300 mile driving range.

Targets 2010 2015

System Gravimetric Capacity 6 wt.% 9 wt.%
(net)= “specific energy” (7.2 MJ/kg) (10.8 MJ/kg)
(2.0 kWh/kg) (3.0 kWh/kg)
System Volumetric Capacity 1.5 kWh/L 2.7 kWh/L
(net)= “energy density” (5.4 MJ/L) (9.7 MJ/L)
(45 g/L) (81 g/L)
Storage system cost $4/kWh $2/kWh
(~$133/kg H2) ($67/kg H2)

More targets and explanations at www.eere.energy.gov/hydrogenandfuelcells/

 Targets are for Storage System

Today’s gasoline tank system:

Reminder:
System
Targets
System includes material, tank, and balance
of plant- e.g. insulation, sensors, regulators,
first charge, any byproducts/reactants, etc.

Material capacities must be

higher!
 Energy Density (Volumetric Capacity) is Critical!

Today’s Vehicle
(system)
6 Hydrogen Densities of Materials
Gasoline 200
NH3BH3(3)

Hydrogen volume density (kgH2 m-3)

Mg(OMe)2.H2O
TiH2
5 Mg2NH4
AlH3
Fuel Cell Efficiency, 150 LiNH2(2)
(kWh/L)

MgH2
NH3BH3(2)
Conformable Tanks LaNi5H6
LiBH4
NaBH4 C8H18 CH4 (liq)
FeTiH1.7 decaborane
NH3 C2H6
(kWh/L)

100 11M aq NaBH4KBH4 C2H5OH

4 LiAlH4 CH OH
3
C 3H8
Density

CaH2 2015 system targets

LiNH2(1) NaAlH4 liquid
NH3BH3(1) hydrogen
2015 Target 50
NaH
hexahydrotriazine
2010 system targets
Density

3 (system) 700 bar

EnergyEnergy

350 bar

0
Liquid H2 (20K, 1 bar) 0 5 10 15 20 25 100
30
2 Hydrogen mass density (mass %)

Compressed H2 (300K)
Select materials with capacities
1 700 bar
higher than system targets
350 bar

0
200 400 600 800 1000

(bar)
Pressure (bar)
See http://www.eere.energy.gov/hydrogenandfuelcells/storage/current_technology.html
 Current Status
No storage technology meets 2010 or 2015 targets

Current Cost Estimates

(based on 500,000 units)

700 bar
350 bar
Liquid H2
Complex Hydride
Chemical Hydride
$0 $5 $10 $15 $20
2015 target
$/kWh
2010 target

Note: Estimates from developers. To be periodically updated.

Costs exclude regeneration/processing. Complex hydride system data projected. Data points include analysis results.
 Strategy and Program Plans
• Focus is materials-based
technologies
• Systematic approach
• Robust theory/simulation and
rapid screening
• Tailor properties
• Capacity, T, P, energies

• Centers of Excellence ($5-6M/yr) plus independent

projects, launched at $150 M over 5 years (plan- subject to
appropriations)

• ~ 40 universities, 15 companies, 10 federal labs

(including 17 new BES awards)
• Diverse portfolio addresses NAS
recommendations Yacobsen, Rice U.

“…DOE should continue to elicit new concepts and ideas, because success in overcoming the major
stumbling block of on-board storage is critical for the future of transportation use of fuel cells.” (NRC Report,p.44)
 Strategy & Results
Broad Portfolio Focused on Materials Technologies

Challenges are technology specific: Pros and Cons for each

Tanks (to 10,000 psi), Chemical hydrides (CH), Metal Hydrides (MH), Carbon/Sorbents (S)

Key 2010 Targets: Tanks CH MH S

Volume (1.5 kWh/L) H M M M/H

Weight (2.0 kWh/kg) M M M/H M

Cost ($4/kWh) M/H M/H* M/H M/H

RD&D Plan: Tasks in each area

www.eere.energy.gov/ Refueling Time (3 L L M/H M
hydrogenandfuelcells
min, for 5 kg)
Discharge Kinetics L M M M
Thermal Mgmt:
Key Issues (0.02 g/s/kW)
for MH
(CH, C) Durability (1000 L M M M
cycles)

H = High (Significant challenge) M/H = Medium/High M = Medium L = Low (minimal challenge)

For CH, MH and S- assessment based on potential to meet targets, though systems not yet demonstrated in most cases.
*For CH: Storage system may meet cost but fuel cost of $2-$3/kg is challenge for CH regeneration.
 Hydrogen Storage Budget

DOE- EERE DOE- Office of Science

FY2007 Budget Request = $34.6M FY2007 Budget Request = $50.0M
FY2006 Funding = $26.6M FY2006 Funding = $32.5M

35.0 50.0
30.0 30.0 29.9 34.6 50.0
45.0
30.0
26.6 40.0
32.5
25.0 22.4 35.0

30.0
20.0
M$ M$ 25.0
15.0 13.2 20.0
15.0
10.0
10.0

5.0 5.0
0.0
0.0 2006 2007
2004 2005 2006 2007
Carbon-based Materials Metal Hydrides
Chemical Hydrogen Storage Compressed/Tanks Planned funding for Basic Science in
New Materials & Concepts Test/Analysis/Support Hydrogen Storage in FY06: $7.13M
Budget Request
 Results: Examples of Progress (2005-2006)
New materials with higher capacities being found

Material Capacities for Hydrogen Storage

Chemical H2 Carbon/ Sorbents & New
Advanced Metal Hydrides
Storage Materials
Li Mg Amides Metal/carbon hybrids, MetCars
~5.5wt%, ~2.8 kWh/L (>200 C) Phenanthraline/ organic 6 to > 8wt%*, ~1.3* kWh/l
Alane (*theory)
liquids
~7-10 wt%, ~5 kWh/L (<150 C) ~7 wt%,~1.8 kWh/L Bridged catalysts
Li borohydrides (>150 C) IRMOF-8
>9 wt%, ~3.5 kWh/l (~350 C) ~1.8 wt.%,~0.3 kWh/L
(room T)
Destabilized Binary hydrides Ammonia
~5-7wt%, ~2-3 kWh/L (250 C) Borane/Scaffolds Metal-Organic Frameworks
LiMgAlane, M-B-N-H IRMOF-177
~6 wt%,~2-4 kWh/L ~7 wt%, ~1 kWh/L
~ 7-8.8 wt%, > 1.3 kWh/L (<100 C) (77 K)
(~150-340 C)

Note: Material capacities only. No balance of plant. Estimates for volumetric capacities.

We are excited by these results but there are still issues…

Next steps: Operability (Temperature, pressure, kinetics, etc.)
 Results: Advanced Metal Hydrides
Na Ca
• Rapid Screening: Theory and Experiment
• More than 980 ternary phase systems K Mg
searched (alkali/alkaline earth alanates) K
• No stable mixtures found under UOP
Li Mg
conditions (~90 atm) Ca
Preliminary Assessment Na
No alanate mixtures likely to meet DOE
targets Li K Ca
Sachtler, et al, UOP
H

High Throughput Screening Reversible wt-%H 4. 5

4
SP02
P07 8 3.5
Li
3
Al18Li2Si6
6 Li13Si4 2.5
Al3Li12Si4 Li22Si5
Li4Al9 Li7Si3 2
4 Li3Al2 Li12Si7
Al3Li7Si4 AlLi5Si2 1.5
LiAl
Al2Li3Si2
Al3Li8Si5 NaAlH4 1
2
0.5
AlLiSi
0
0 Na
SP01
0.0dC
6
5
Al Si
LiAlH4
4
3
Mg(AlH4)2
2
1 Mg

Lemmon, Rubinsztajn, Cui & Zhao (GE)

 Results: Destabilized hydrides and
nano-engineering
E.g., New system (11.4 wt. % and 0.095 kg/L) – LiBH4 / MgH2
Temperature (°C)
500 400 300 200 100 20
14
LiBH4
LiH

H2 Capacity (wt.% - material basis)

Dehydrogenated 12 System
0 M + 1/2H2
LiBH4/MgH2
Requirement
State
10
LiBH4/MgS
Alloy 8
ENERGY

MgH2 LiBH4/MgF2
MAx+1/2H2 Dehydrogenated LiBH4/Mg2Si
6 MgH2/Si
State LiBH4 /Mg2Cu
NaAlH4
4 LiH/Si
(meas. at JPL)
Mg2NiH4 VH2

MH + xA Hydrogenated 2
ZrNiH3
State LiNiH5
0
1.0 1.5 2.0 2.5 3.0 3.5
-1
<100 nm 1000/T 1 bar (K )

• Demonstrated “destabilization” to
enable lower T
– Showed ~9-10 wt.% LiBH4/MgH2
– Can reduce T by ~ 240 C
– But kinetics slow
Long H-diffusion
distances in bulk
Short H-diffusion
distances in • Next steps: Enhance kinetics by nano-
materials: nanoparticles: fast engineering
reduced H-exchange rate hydrogen exchange

Vajo, Olsen, et al, HRL

Metal Hydride Center J. Vajo, S. Skeith, and F. Mertens, J. Phys. Chem. B, 109, 3719-3722 (2005).
 Results: Chemical Hydrogen Storage

• Organic liquids: >7 wt.%, 69 g/L • NH3BH3 in mesoporous scaffolds:

• 1.5 wt% more than FY05 • >6 wt% material capacity
• > 100 catalysts screened • H2 release at < 80 C
• > Dehydrogenation with 10x less • Reduced borazine formation
Pt in catalysts

H H H H H H
B N B N B N
N B N B N B
N B N B N B N
Æ 2.x H2 + H
B N B N B N
N B N B N B
B N B N B N
N H H H H H H x

Phenanthrolene
Autrey, Gutowski, et al, PNNL
Chemical CoE

Cooper, Pez, et al, Air Products

O PtBu2
Rapid dehydrogenation catalysts
demonstrated H
Ir
U. of Washington, Chemical CoE
H
O PtBu2

Original catalyst development- Jensen, et al (U HI)

 Results: Carbon and Sorbents

Carbon Center & New Materials:

• >7 wt.% at 77K shown on MOFs

(> 30 g/L)
• Several cycles reversibility
shown
Yaghi, Matzger
(UCLA, U MI)
• Four-fold enhancement in H2 102.0

101.5

storage via “spillover”

mass (%)
101.0

100.5

100.0

99.5
0 20 40 60 80 100 120 140
time (min)

Yang, et al
(U MI)
Y. Li and R.T. Yang, JACS (2006)
Yaghi, et al
A.G. Wong-Foy, A.J. Matzger, O.M. Yaghi, JACS (2006)
 Results: Designing tailored nanostructures
Yakobson, Ding, Lin
Rice University
Carbon Center

CNT “Carpet”
Tour, et al, Rice U.

NREL-Carbon Center
Potential for 6.1-7.7 wt% V
MetCars Yakobson, et al
Y. Zhao, A.C. Dillon, Y.-H. Kim, M.J.
Heben, S.B. Zhang, in prep

Theoretical modeling conducted to predict optimum structures and storage capacities

 Results: Testing and Analysis
Analysis & modeling underway to determine material property requirements to
meet system targets. Preliminary results shown.

Test facility completed, SwRI Overall efficiency analyses underway

(Coordination with H2A)
700

0.4
50% Market Share
600

Primary Energy Consumed, MJ/kg H2

Distribution
Storage 447
500
Production

400 0.6

300
0.5 206
8.4
8.4 85
200
22 36

100
175 175 187 175 175

0
R. Page, M. Miller, SwRI cH2-350bar cH2-700bar LH2 SBH MgH2
Preliminary estimates based on developer
regeneration efficiency analyses

Sensitivity analysis to Minimum Delivery P

8 bar
(0.5 kg/min)
determine impact of key 3 bar Vacuum
1.5
parameters Hydrogen Refueling
2.0 0.5 kg/min
Rate (8 bar)

Materials with > 7 wt% likely even Kinetic Enhancement

2X 5X
10 X
for 2007 targets (4.5 wt%) (8 bar, 0.5 kg/min) 1X

S. Lasher, et al, TIAX Storage Systems

1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3
Analysis Working Recoverable Medium Storage Capacity (%)
Group R. Ahluwalia, et al, Argonne
 Programmatic Accomplishments

• IPHE Hydrogen Storage

Conference
– Leveraging global activities
– See www.iphe.net
• Expanded Basic Science
• Theory Focus Session
– May 18, 2006
• Updated Targets & Multiyear Plan • Water Availability Model
– New versions on web – For hydrolysis
• Addressing NAS • Paper on Ammonia
recommendations (e.g. revolving – Draft on web for public comment
solicitation for new concepts)
• Updated Roadmap & Targets
– New versions on web
• Joint Tech Team meetings
– Defining requirements
See: www.eere.energy.gov/hydrogenandfuelcells/
 Hydrogen Storage – Future Plans

Ammonia Paper
IPHE Hydrogen
Released for
Storage Conference
Comment
Lucca, Italy
Solicitation
Released Full Proposals
Centers of Due
Excellence
Launched Pre-Proposals Pre-Proposals
Due Due

2005 2006 2007

Mar Jun Sep Dec Mar Jun Sep Dec Mar

Theory Focus Release

Testing Updated Session Solicitation *
Workshop Roadmap
Test Facility Go/No Go
Validation Single - walled
Storage Systems
Nanotubes
Analysis Working
Group Launched
Cryo-compressed
Tank Assessment
*Subject to appropriations
 Current Solicitations
1) Applied Research and Development (EERE)
– Up to $6M total ($2M planned in FY07, subject to appropriations)
Complements current DOE Centers of Excellence & existing Independent projects:
– Material discovery
– Engineering Science (including materials safety properties)
– Systems, safety and environmental analyses
– 3-6 awards at $200-400k/yr for 2-5 years
– Preproposals due June 7

2) Basic Science (Office of Science, BES)

– Up to $52.5M total ($17.5M/yr starting in FY07, subject to appropriations)
– Novel Materials for Hydrogen Storage
– Functional Membranes
– Nanoscale Catalysts
– Preproposals due July 6

See http://www.grants.gov or follow links from www.hydrogen.energy.gov

 Summary
• New Materials & Concepts are critical- address volumetric
capacity, T, P, kinetics, etc. (not just wt. %!)

• Basic science is essential to develop fundamental

understanding & complements applied research &
development
• Engineering issues need to be considered
– System issues, thermal mgmt, safety, refueling, testing, etc
• Examples of Essential Capabilities:
– Modeling & Analysis
– Combinatorial/high throughput methods
– Material properties measurements
– Standardized & accurate testing
 For More Information
Hydrogen Storage Team

Sunita Satyapal, Team Leader Grace Ordaz

Overall Storage/ FreedomCAR Tech Chemical Hydrides,Chemical Hydrogen
Team/International Storage Center of Excellence
202-586-2336 202-586-8350
sunita.satyapal@ee.doe.gov grace.ordaz@ee.doe.gov

Carole Read George Thomas*

Metal Hydrides, Metal Hydride Center On Assignment to DOE
of Excellence *retired, Sandia
202-586-3152 202-586-8058
carole.read@ee.doe.gov george.thomas@ee.doe.gov
New Hire
Carbon/Sorbents, Carbon
Center of Excellence
see www.eere.energy.gov/hydrogenandfuelcells/
(closes May 19)

Jesse Adams James Alkire Paul Bakke

303-275-4954 303-275-4795 303-275-4916
jesse.adams@go.doe.gov jim.alkire@ee.doe.gov paul.bakke@go.doe.gov

Basic Science: Harriet Kung Tim Fitzsimmons

(harriet.kung@science.doe.gov)
or (tim.fitzsimmons@science.doe.gov)

www.hydrogen.energy.gov
Additional Information
 Hydrogen Storage “Grand Challenge” Partners

Centers of Excellence Independent Projects

New Materials & Concepts
Alfred University
Metal Hydride Carbon Materials Chemical
Carnegie Institute of Washington
Center Center Hydrogen Center Cleveland State University
Michigan Technological University
National Laboratory: National Laboratory: National TOFTEC
Sandia-Livermore NREL Laboratories: UC-Berkeley
Los Alamos UC-Santa Barbara
Industrial partners: Industrial partners: Pacific Northwest University of Connecticut
General Electric Air Products & University of Michigan
HRL Laboratories Chemicals Industrial partners: University of Missouri
Intematix Corp. Intematix Corp. High-Capacity Hydrides
Universities: Millennium Cell UTRC
Universities: CalTech Rohm & Haas UOP
CalTech Duke US Borax Savannah River NL
Stanford Penn State Carbon-based Materials
Pitt/Carnegie Rice Universities: State University of New York
Mellon Michigan Northern Arizona Gas Technology Institute
Hawaii North Carolina Penn State UPenn & Drexel Univ.
Illinois Pennsylvania Alabama Chemical Hydrogen Storage
Nevada-Reno California-Davis Air Products & Chemicals
Utah Federal Lab Partners: UCLA RTI
Lawrence Livermore Pennsylvania Millennium Cell
Federal Lab Partners: NIST Washington Safe Hydrogen LLC
Brookhaven Oak Ridge OffBoard, Tanks, Analysis & Testing
JPL Gas Technology Institute (w/Delivery)
NIST Lawrence Livermore
Oak Ridge Quantum
Savannah River Argonne Nat’l Lab & TIAX LLC
SwRI