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!

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

) NH3BH3(3) -3 Mg(OMe)2.H2O m 2 TiH2 5 AlH3 ) Mg2NH4 LiNH (2) Fuel Cell Efficiency, 150 MgH 2

L 2 / NH3BH3(2) h Conformable Tanks LiBH4 ity (kgH LaNi5H6 NaBH4 C8H18 CH4 (liq)

W decaborane FeTiH1.7 NH3 C2H6 100 KBH C2H5OH 4 11M aq NaBH4 4 LiAlH4 C H CH3OH 3 8 y (k CaH t 2 2015 system targets i lume dens NaAlH LiNH2(1) 4 liquid o

v NH3BH3(1) hydrogen NaH 2015 Target en 50 hexahydrotriazine g 2010 system targets 700 bar Dens 3 (system) dro 350 bar Hy ergy 0 n 0 5 10 15 20 25 10030 E Liquid H2 (20K, 1 bar) 2 Hydrogen mass density (mass %) Compressed H (300K) Energy Density (kWh/L) Energy Density 2 Select materials with capacities 1 700 bar 1 higher than system targets 350 bar

0 200200 400 600 800 1000 Pressure (bar)(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) L M M M Thermal Mgmt: Discharge Kinetics 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 H Carbon/ Sorbents & New Advanced Metal Hydrides 2 Storage Materials

Li Mg Amides Metal/carbon hybrids, MetCars ~5.5wt%, ~2.8 kWh/L (>200 C) 6 to > 8wt%*, ~1.3* kWh/l Phenanthraline/ organic (*theory) Alane liquids ~7-10 wt%, ~5 kWh/L (<150 C) ~7 wt%,~1.8 kWh/L Bridged catalysts Li borohydrides (>150 C) IRMOF-8 ~1.8 wt.%,~0.3 kWh/L >9 wt%, ~3.5 kWh/l (~350 C) (room T) Destabilized Binary hydrides Ammonia ~5-7wt%, ~2-3 kWh/L (250 C) Borane/Scaffolds Metal-Organic Frameworks IRMOF-177 LiMgAlane, M-B-N-H ~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 conditions (~90 atm) Ca Mg 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 Li 3.5 3 Al18Li2Si6 6 Li13Si4 2.5 Al3Li12Si4 Li22Si5 Li4Al9 Li7Si3 2 4 Li3Al2 Li12Si7 Al3Li7Si4 AlLi5Si2 1.5 LiAl Al3Li8Si5 NaAlH 1 Al2Li3Si2 4 2 0.5 AlLiSi 0 0 Na SP01 0.0dC 6 5 Al Si 4 3 2 LiAlH4 Mg(AlH1 Mg 4)2

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 LiBH LiH 4 s)s)

ii System Dehydrogenated 12 LiBH4/MgH2 0 M + 1/2H Requirement

2 basbas

State alal

ii 10 terter LiBH4/MgS

mama 8 Alloy MgH2 - - LiBH4/MgF2 MAx+1/2H2

Dehydrogenated %% LiBH /Mg Si 4 2 MgH /Si State t.t. 6 2 (w(w LiBH4 /Mg2Cu NaAlH4 tyty ii 4 LiH/Si cc ENERGY (meas. at JPL) aa Mg NiH pp 2 4 VH2 Hydrogenated 2 MH + xA Ca Ca 22 ZrNiH3 LiNiH State HH 5 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 Short H-diffusion distances in bulk 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 N B N B N B BN BN BN H Æ 2.x H2 + 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

t Rapid dehydrogenation catalysts O P Bu2 demonstrated H Ir U. of Washington, Chemical CoE H t O P Bu2

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 H 102. 0 2 101. 5 )

storage via “spillover” % 101. 0

ass ( 100. 5 m 100. 0

99. 5 0 2 0 4 0 6 0 8 0 100 120 140 tim e ( m in )

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 Y. Zhao, A.C. Dillon, Y.-H. Kim, M.J. Yakobson, et al 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 2 Distribution H Storage

/kg 447

J 500 Production , M d 400 0.6 ume s

300 gy Con 0.5 206 8.4 8.4 85

y Ener 200 22 36 imar r P 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 (0.5 kg/min) 8 bar 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 2 X 5 X Kinetic Enhancement 10 X for 2007 targets (4.5 wt%) (8 bar, 0.5 kg/min) 1 X 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 [email protected] [email protected]

Carole Read George Thomas* Metal Hydrides, Metal Hydride Center On Assignment to DOE of Excellence *retired, Sandia 202-586-3152 202-586-8058 [email protected] New Hire [email protected] 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 [email protected] [email protected] [email protected]

Basic Science: Harriet Kung Tim Fitzsimmons or ([email protected]) ([email protected]) www.hydrogen.energy.gov Additional Information Hydrogen Storage “Grand Challenge” Partners

Independent Projects Centers of Excellence New Materials & Concepts Metal Hydride Carbon Materials Chemical Alfred University 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