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-1-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Hydride DevelopmentHydride Development
for Hydrogen Storagefor Hydrogen Storage
Jim WangJim Wang
Sandia National LaboratoriesLivermore, California
May 24-27, 2004 Sandia Team Sandia Team .
Mark Allendorf
Ray Baldonado
Bob Bastasz
Tim Boyle
Daniel Dedrick
Karl Gross (consultant)
Steve Karim
Jay Keller
Weifang Luo
Eric Majzoub
Tony McDaniel
Tina Nenoff
Vidvuds Ozolins (consultant)
Mark Phillips
Bill Replogle
Gary Sandrock (consultant)
Brian Somerday
Scott Spangler
Ken Stewart
Roland Stumpf
Konrad Thuermer
Jim Voigt
Jim Wang
Ken Wilson
Nancy Yang
This presentation does not contain any proprietary information.
-2-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Delivery of
Storage
System
High Capacity
Materials
Research &
Development
StructureProperties
MaterialCompatibility,Synthesis &
ContaminationStudies
StorageSystem Design
FundamentalModeling
Approach: Science-based Materials DevelopmentApproach: Science-based Materials Development
Objective: Meet/Exceed DOE 2010 FreedomCAR
on-board hydrogen storage targets
-3-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
BudgetBudget
• FY04 Materials R&D Funding $1,700K
49%
14%
22%
15%
High Capacity
Materials
DevelopmentFundamental
Mechanisms &
ModelingCompatibility,
Synthesis &
ContaminationsEngineering
Science
High Capacity
Materials R&D
Fundamental
Mechanisms &
Modeling
Compatibility,
Synthesis &
Contaminations
Engineering
Science
= 63%R&D
on NewMaterials
-4-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Technical Barriers and TargetsTechnical Barriers and Targets
• DOE Technical Barriers for Reversible Solid-State Material
Hydrogen Storage Systems
• Inadequate hydrogen capacity and reversibility
• Un-demonstrated materials cycle-life
• Lack of understanding of hydrogen physisorption and chemisorption
• Lack of standard test protocols and evaluation facilities
• Un-defined dispensing technology
• DOE Technical Target for Reversible Solid-State Hydrogen
Storage System in 2010
• 6 wt.% minimum reversible hydrogen stored per system
• Refueling rate at 1.5 Kg H2 per minutes
-5-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Equipment and experimental work:
• Experiments follow Standard Operating Procedures (SOPs)
• All equipment calibrated and can be traced to NIST standards
• Laboratory safety issues are reviewed in full group biweekly meetings
Lessons learned:
• Sodium-alanates are air and water sensitive
• Procedures established for proper preparation and handling, storage and disposalof sodium-alanate materials
Insights and Management of Safety issues:
• Actively participates in DOE H2 Safety, Codes and Standards program
• Studied interaction of alanates with container vessel materials
• Sponsored alanate safety testing by Thiokol Corp
• Exchange safety information with other researchers in the hydrogen community
Project SafetyProject Safety
-6-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Project TimelineProject Timeline
2004 2005Q3 Q4 Q2Q1
PCT &PerformanceAnalysis of
Amides
CompleteInitial
ThermalPropertiesof Amides
High Temp& PressureSynthesis
of NewComplexHydrides
Large BatchProductionof Alanates
CompleteInitial
ReversibleBorohydride
Studies
CompleteInitial
ContaminationStudies
CompleteInitial
Substituted Li-Amide Studies
CompleteInitial
AlanatesModeling
OptimizedNon-reactive
doping
Long-termCycle-Life
Measurements
InitialModeling ofSubstitutionMechanism in
Amides
Continue NewHydrogenStorage
MaterialsExploration
-7-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
1.High Capacity Storage Materials Research
• Developed Mg modified Li-amide providingreversible 5 wt% hydrogen storage at 700 psibelow 200C with potential for up to 10.4 wt% ifthe second reaction step is included.
• A new high temperature/ high pressure hydrogentest facility had been assembled and tested fornew alanates development.
• Facility at BNL has been established to study thefeasibility of decreasing the stability of NaBH4for reversible reactions.
Technical AccomplishmentsTechnical Accomplishments
-8-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
New Complex Hydrides (Progress @ Sandia)New Complex Hydrides (Progress @ Sandia)
NaAlH4
Modified Li Amides with Mg ~ 5wt%
-9-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
New Complex Hydrides (P-C-T Diagram)New Complex Hydrides (P-C-T Diagram)
Improved lithium amide operating conditions at lower
temperature and higher pressure
0
20
40
60
80
100
0 1 2 3 4 5 6 7
H wt%
Press
ure, b
ar
220oC
285oC
Li2NH + H
2 LiNH
2 + LiH ( 6.5wt% )
Total of 11.5wt% if 2nd reaction is included*.
* P. Chen et al, Nature,
420, 21 (2002) 302
Sandia Mg Modified Li-Amide Reaction
5 wt% reversible H2
-10-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
New Complex Hydrides (New Complex Hydrides (VanVan’’tt Hoff Plot) Hoff Plot)
10 atm
3 atm
1 atm
30 atm
*
-1
-0.5
0
0.5
1
1.5
2
1 1.5 2 2.5 3 3.5 4
1000/T, oK
Log P
, at
m
LaNi5 HMgH2
NaAlH4
CaNi5 H6
Na3AlH6
200o C 100 o C 25
oC
LaNi4H 5
Mg2 NiH4
6
Modified
Li-Amide
Li-Amide
Mg modified Li-amides by SNL have potential
to meet DOE targets
-11-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Search for New Search for New AlanatesAlanates (Material Synthesis Equipment) (Material Synthesis Equipment)
•Higher pressure and higher temperature Capabilities
Test Cell capabilities:
Hydrogen pressure up to 30,000 psig
Temperature control up to 700 C
Cell door can be locked for safety
High-Temperature High-Pressure Hydride lab has been
developed and assembled for new alanates development
-12-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
2. Structure Properties and Modeling
• Demonstrated that Ti did not incorporate into
the lattice of Ti exposed NaAlH4 single
crystal materials.
• Gained insight from modeling of the role of Ti
in hydrogen sorption process on Al surfaces.
• Experimentally verified mass transport of
AlHx in Na alanate reversible reactions.
Technical Accomplishments Technical Accomplishments (cont(cont’’d)d)
-13-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Ti-doped Sodium Alanates (Structure Properties)Ti-doped Sodium Alanates (Structure Properties)
XRD Rietveld refinement of pure and 'Ti exposed' NaAlH4
using NIST Si standard reference.
Crystals of NaAlH4 exposed to Ti duringgrowth from THF
X-ray diffraction shows no evidence of Ti incorporation in the
lattice when doped by this method
Crystals of pure NaAlH4 from THF
-14-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Ti-doped Sodium Alanates (Fundamental Mechanisms)Ti-doped Sodium Alanates (Fundamental Mechanisms)
First principles calculations (VASP):
• H adsorption stabilizes Ti at Al andAl3Ti surfaces
• Ti reduces H2 sorption barriers atAl surfaces
Al with Ti dopantNaH
H2-gasdissociation/recombination
Ti
segregation
AlHx
Al transport
NaAlH4
AlHx
barrier
HTi
Al
H2 chemi-sorption well
H2 gas
Alreactionpath
TiAl
AlH
H chemisorbed
without Ti
with Ti
Ti activates H sorptionTi activates H sorption
at Al surfaceat Al surface
-15-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Ti-doped Sodium Alanates (Fundamental Mechanisms)Ti-doped Sodium Alanates (Fundamental Mechanisms)
Al mass transport likely by AlHx
AlNaH
H2-gas
AlHx
Al transport
NaAlH4
AlHx
STM picture of Alsurface pitted inhydrogen environment
Strong signal from AlHx species => Al-hydrideis volatile at 150C and likely mobile at lower T
Thermal Desorption Spectroscopyof Na-alanate
AlHx
-16-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
3. Compatibility, Synthesis, ContaminationStudies & New Capabilities
• A wet chemistry nano-materials synthesisfacility has been established and is ready fornano-sodium alanate and lithium amidematerials production.
• Methods using IR spectroscopy are beingdeveloped to monitor the effects ofcontaminants
• New kinetic, P-C-T and cycle-life instrumentsadded to the existing capabilities.
Technical Accomplishments Technical Accomplishments (continued)(continued)
-17-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
In situ XRD: Full Scans < 1 minute
leverages DP funding
• In situ XRD system
Extensive Experimental Capabilities AddedExtensive Experimental Capabilities Added
Hydride labs are being expanded
• 2 cycle life instruments
• 2 air-less sample preparation stations
High-pressure kinetics stations
• 5 manual kinetics systems (including 3 new ones)
Fully automated PCT instrument
• 1 automated PCT instrument
-18-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
4. Materials Engineering Properties
• Measurements of thermal conductivity,packing density, and expansion of sodiumalanates has been completed.
• An empirical predictive model to optimizepressure and temperature for charging &discharging of hydrogen from alanates hasbeen developed to aid in scaled upoperating conditions.
Technical Accomplishments Technical Accomplishments (continued)(continued)
-19-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Engineering Properties (Thermal Conductivity)Engineering Properties (Thermal Conductivity)
Properties relevant for3 wt% alanate
Low thermal conductivity of sodium alanate will be a
design challenge for H2 storage systems.
-20-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Engineering Properties (Container Wall Pressure)Engineering Properties (Container Wall Pressure)
Higher pressure will be expected for alanate storage
systems at high H2 wt% and high packing densities.
10002.31.2
1002.40.9
Pressure (psia)*Wt%*Density(g/cc)
Initial data:
*Maximum wt% and pressure
attained during experimental set
-21-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Engineering Properties (Empirical Modeling)Engineering Properties (Empirical Modeling)
Rate = k * F(C) * F(P)
n = 1 or 2;
b = 1 or –1;
C: H-wt %;
k = ko exp(-Qa/RT)
k: rate constant;
ko: pre-exponential factor;
Qa: activation energy
Peq: From K. Gross, Appl. Physics,
2001. (Van’t Hoff plot).
No hysteresis was considered.
Alanate DesorptionSimulation
Rate = k *Cn * b * ln (P/Peq)
NaH + 1/3 Al + _ H2 1/3 Na3AlH6
1/3 Na3AlH6 + 2/3 Al + H2 NaAlH4
0
0.5
1
1.5
2
2.5
0 0.4 0.8 1.2 1.6
Time, hours
H w
t%
experiment
calculated
125oC
An empirical charging/discharging kinetic model has been developed
-22-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Engineering Science (Empirical Modeling continued)Engineering Science (Empirical Modeling continued)
0.001
0.01
0.1
1
10
100
0 5 10 15 20
Papp, bar
Rat
e, H
wt%
/ h
ou
r
NaAlH4
80C
100C
120C
140C
Na3AlH6
120C
140C
160C
180C
Calculated Desorption Rates at
Hwt% = 3.2 for NaAlH4
Hwt% = 1 for Na3AlH6
Various Temperatures and Pressures
NaAlH4 Formation Rate At Variou
Temperature and Pressure
0
1
2
3
4
5
6
7
8
9
10
0 20 40 60 80 100 120
Papp, Bar
Rate
H w
t %
/ h
ou
r
140C
160C
120C
100C
80C
60C
[H] = 2.9 wt%
Charge optimizationCharge optimizationDischarge estimationDischarge estimation
This model can be used to optimize storage system design
-23-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Interactions and CollaborationsInteractions and Collaborations
University of Hawaii: Mechanisms of Ti-doping enhanced kinetics
University of Geneva (IEA): New Complex Hydrides
Tohoku University (IEA): Li-Amides Characterization
University of Singapore: Li-Amides Synthesis and Performance
Brookhaven National Laboratory – Reversible Borohydrides
Denver University: Electron Spin Resonance measurements
Lawrence Livermore: Solid-State Nuclear Magnetic Resonance
NIST: Neutron Diffraction and Scattering Spectroscopy
UCLA: Ab Initio Calculations
UTRC: Materials Purity Issues and Safety Testing
-24-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Response to previous YearResponse to previous Year’’ Reviewers Reviewers’’ Comments Comments
1. Many positive comments - Our approach validated
2. Need to expand materials search
• More than 60% budget on new materials R&D in FY04
• Exciting results from modified lithium amides
3. More basic science needs to be done
• Added more expertise in modeling, surface science andreaction chemistry in FY04
4. More thermodynamics to investigate Ti-doping
• Measurements are currently underway
5. Extend collaborations and team work
• Focus and strength of our DOE Metal Hydride virtualCenter of Excellence.
6. Continue engineering materials investigation
• Much progress made and ongoing
-25-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Future PlansFuture Plans• Remainder of FY2004:
• Lithium amide materials research and development
• Optimize capacity and kinetics via experiments and modeling
• Measure mechanical and heat transfer properties
• Evaluate safety and contamination effects
• Develop new synthesis route for nano-materials productions
• Other new complex hydrides
• Synthesize new hydride materials using high T & P facilities
• Evaluate properties and performance of new materials
• Understand mechanisms of Ti doped alanates via modeling andcharacterizations, especially of surface reactivity aspects
• Study safety and contamination effects on alanates
• FY2005 and beyond:
• Lead the DOE Center of Excellence on Metal Hydrides focusing onoptimizing present materials and developing new hydrogen storagematerials to meet/exceed DOE FreedomCAR 2010 targets
-26-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
Proposed DOE Metal Hydride virtual Center of Excellence (MHvCE)
MHvCE
Management Team
(Jim Wang, Jay Keller, Karl Gross)
Scientific
Advisory
Committee
DOEOffice of Hydrogen, Fuel Cells &
Infrastructure Technologies
8 Universities(Hawaii, Pittsburgh, Carnegie
Mellon, Illinois, Caltech,
Stanford, Utah, UN-Reno)
3 Industrial Companies(GE, HRL, Intematix)
4 Other National Labs(BNL, ORNL, JPL, NIST)
Sandia as MHvCE
Lead Lab12 Tasks including new
hydrides synthesis,
characterization,
performance testing,
fundamental modeling,
engineering properties, and
Center management
Management
Advisory
Committee
-27-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
DOE
MHvCE
Management
Team
Scientific Advisory
Committee
Mechanism
- Hawaii
- SNL
- UIUC
- NIST
- JPL
- UNR
- Stanford
Advanced
Complex
Hydrides
- SNL
- BNL
- Hawaii
- U. Utah
Rapid
Screening
Intermettalic
Hydrides
- GE
Complex
Hydrides
- Intematix
Destabilized
Binary
Hydrides
- HRL
- Caltech
- JPL
- Stanford
- Hawaii
New Materials
Modeling
- U. Pitts
- CMU
- UIUC
- SNL
- NIST
- U. Utah
Synthesis
- SNL
- ORNL
- U. Utah
- Caltech
- HRL
- Hawaii
Hydrogen
Storage
Properties
- SNL
- BNL
- JPL
- GE
- Caltech
- UNR
- Hawaii
Engineering Science
Phase II
SNL , JPL , GE….
Topic Groups
Management Advisory
Committee
-28-
Materials & EngineeringSciences CenterAtoms to Continuum
2004 DOE Hydrogen, Fuel Cells &Infrastructure Technologies
Program Review, Philadelphia, PA
AcknowledgementAcknowledgementMark Mark AllendorfAllendorf
Tim BoyleTim Boyle
Daniel DedrickDaniel Dedrick
Karl GrossKarl Gross
Jay KellerJay Keller
WeifangWeifang LuoLuo
Eric Eric MajzoubMajzoub
Tony McDanielTony McDaniel
Tina NenoffTina Nenoff
Gary Gary SandrockSandrock
Roland Roland StumpfStumpf
KonradKonrad ThuermerThuermer
Jim VoigtJim Voigt
Ken WilsonKen Wilson