Development of Metal Hydrides at Sandia National Laboratories

Development of Metal Hydrides at Sandia National Laboratories Presented by Jim Wang Sandia National Laboratories Livermore, California May 23, 2005 This presentation does not contain any proprietary information Physical & Engineering Sciences Center Atoms to Continuum Project ID# ST2 -1DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Overview Timeline • • • • Project started in the early 1990s’ Reviewed and renewed every FY through Annual Operation Plans Incorporated into MHCoE January 2005 Percent complete ~ 50% for FY05 Barriers MYPP Section 3.3.4.2.1 On-Board Storage Barriers • A. – G. Cost, Weight & Volume, Efficiency, Durability, Refueling Time, Codes & Standards, Life Cycle & Efficiency Analyses • M. Hydrogen Capacity and Reversibility • N. Lack of Understanding of Hydrogen Physisorption and Chemisorption • O. Test Protocols and Evaluation Facilities • P. Dispensing Technology Budget 11% 11% 17% 8% FY2005 Budget ~ $1.85 M New Materials R&D Fundamental Modeling & Mechanisms Synthesis Development 53% Engineering Sciences Safety & Contamination Studies Partners • MHCoE collaborators include Caltech, ORNL, JPL, UNR, Stanford U, U of Utah, U Hawaii, U of PITT, SRNL, HRL, UIUC, CMU, GE, NIST, BNL, Intematix • Gary Sandrock operates IEA/Task-17, maintains the Hydride Information Center databases and collaborates with BNL • Singapore U., Tohoku U., UCLA, U. Geneva, LLNL -2DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Total Materials R&D ~ 70% Physical & Engineering Sciences Center Atoms to Continuum Objectives • Develop new reversible hydrogen storage materials that meet or exceed DOE FreedomCAR 2010 and 2015 goals, • Identify reversible hydrides that exceed the hydrogen capacity of Mg modified Li amides in FY05. Sandia Team (~ 6 FTEs) Ray Baldonado Bob Bastasz Tim Boyle Yongkee Chae Paul Crooker* Sherrika Daniel* Karl Gross (consultant) Steve Karim Physical & Engineering Sciences Center Atoms to Continuum Jay Keller Weifang Luo Eric Majzoub Tony McDaniel Marcina Moreno Vidvuds Ozolins (consultant) Ewa Ronnebro* Gary Sandrock (consultant) * New Team Members Ken Stewart Roland Stumpf Konrad Thuermer Jim Voigt Karl Wally* Jim Wang Ken Wilson Nancy Yang -3- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Approach Science-based materials development High Capacity Materials Research & Development Material Compatibility, Synthesis & Contamination Studies Structure Properties Fundamental Modeling Storage System Design Delivery of Storage System ……… 2005 …..……..……………………. 2007 ……………….......... 2009 … Physical & Engineering Sciences Center Atoms to Continuum -4- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 I. New Hydrogen Storage Materials A. Low temperature Mg modified Li amides Amide : -NH2, LiNH2 11st Step: Imide : NH, Li2NH Nitride : - N, Li3N LiNH2 + LiH 2nd step: 300oC 1 atm Li2NH + H2 6.5 wt% Two steps in total: 5 wt% 11.5 wt% Li2NH + LiH 300oC 0.05 atm Li3N + H2 Major limitations: •Temperature too high • Pressure too low Chen, P. et al, Nature vol. 420, ( 2002) 302. New system: Partial Mg substitution W. Luo, J. Alloys and Comp., 381 (2004) 284-287. Y. Nakamori, S. Orimo, J. Alloys and Compounds, 370 (2004) 271-275. DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Physical & Engineering Sciences Center Atoms to Continuum -5- (A1)Thermodynamic characterization - Luo 100 220C, Abs 220C, Des 200C Abs 200C Des 80 Isotherms were measured at: • 220, 200, 180oC for absorption and desorption. • Plateau pressure much higher than the one without Mg-substitution. Pressure, bar 60 180C Abs 280C Abs 40 280C Des 20 LiNH2+LiH 0 0 1 2 3 4 5 6 7 H wt% Physical & Engineering Sciences Center Atoms to Continuum -6- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A2) Sorption profile - Luo (2LiNH2+MgH2): Absorption Profile 5 220C (2LiNH2+MgH2): Desorption Profile 120 5 2.5 4 200C 110 4 220C 2 Pressure, Bar 3 100 180C 170C 200C 180C 3 Hwt% 2 90 Hwt% 200C 1.5 2 180C 1 1 220C 80 1 0.5 0 0 1 2 3 4 70 0 0 0.5 1 1.5 2 0 Time, hours Time, hours • 85% of desorption completed in 0.5h at 220oC • Sorption rate decreases with decreasing temperature Physical & Engineering Sciences Center Atoms to Continuum -7- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Pressure, Bar (A3) XRD characterization - Luo & Majzoub * (2LiNH2+MgH2) absorbed, Comparison 4500 4000 3500 3000 4000 LiNH2 MgH2 Mg(NH2)2 LiH (2LiNH2+1.1MgH2), desorbed * Li2NH MgNH 3500 3000 2500 mylar mylar Intensity Intensity 2500 2000 1500 1000 500 0 10 20 30 2Θ 40 50 60 re-absorb 2000 1 500 1 000 500 0 1 0 20 30 40 50 60 heated milled 2Θ * Mylar was used to protect sample from being contaminated during XRD scanning A new reaction path was proposed based on the material characterization results: 2LiNH2 + MgH2 Physical & Engineering Sciences Center Atoms to Continuum Li2Mg(NH)2 + 2H2 -8- 2LiH + Mg(NH2)2 DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A4) TPD-MS measurements – McDaniel & Chae • • First desorption cycle material “as milled” Second desorption cycle followed H2 adsorption – 8 MPa – 473 K – 120 minutes H2 desorption – 130 KPa – 5 K min-1 ramp Cycle #1 500 temperature (K) 450 400 350 300 8.0 6.0 4.0 2.0 0.0 0 40 80 time (min) 120 H2 NH3(x10) Tpeak = 468 K temperature (K) 500 450 400 350 300 8.0 6.0 4.0 2.0 0.0 0 40 80 time (min) 120 Tpeak = 457 K H2 NH3(x10) Cycle #2 A) -10 ion signal (10 • NH3 desorption on first heating indicates chemical instability of milled material. Absent of low temperature “shoulder” on H2 desorption peak in second cycle indicates structural changes in heated material. Physical & Engineering Sciences Center Atoms to Continuum -9- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 ion signal (10 -10 A) (A5) Diffuse Reflectance Infrared Spectroscopy Measurements– McDaniel & Chae • • First desorption cycle material “as milled” Second desorption cycle followed H2 adsorption – 8 MPa – 473 K – 120 minutes H2 desorption – 130 KPa – 5 K min-1 ramp Cycle #1 313 K 398K 418 K 453 K 473 K Repeat Cycles 453 K transmittance (AU) transmittance (AU) 1 TPD st 1 H2 ADS 2 TPD nd 2 H2 ADS 3000 wavenumber (cm ) -1 nd st • 3500 3000 2500 -1 3500 2500 wavenumber (cm ) N-H vibrational features appeared upon first heating of freshly milled sample. Structural changes in material stabilized on subsequent ads-des cycles. Physical & Engineering Sciences Center Atoms to Continuum -10- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A6) Desorbed gas analysis– Luo Desorbed gas analysis 3.0E-05 2.5E-05 Desorbed Blank Intensity 120 100 80 60 H2O NH3 Residual Gas Analysis Intensity 2.0E-05 1.5E-05 1.0E-05 5.0E-06 1.0E-10 Desorbed gas analysis 40 20 Desorbed Blank 1 5 9 AMU 13 17 2.6E-09 2.1E-09 0 1.6E-09 AMU 1.1E-09 6.0E-10 8.1E-09 1.0E-10 Intensity Intensity 0 10 20 30 40 Delta (Desorbed-background) 0 10 20 6.1E-09 30 4.1E-09 2.1E-09 1.0E-10 0 40 AMU NH3 in desorbed gas was found to be < 40 ppm Physical & Engineering Sciences Center Atoms to Continuum 10 20 30 40 AMU -11- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A7) Ammonia Issues - Luo • Ammonia formation: – Is possible from self-decomposition of amide at higher temperatures than hydrogen formation – Could be inhibited by thorough mixing with sufficient amount of hydrides • Potential methods to eliminate ammonia formation: – Optimize operational temperature – Optimize amide/hydride ratio • Potential methods to remove ammonia in H2 stream: – Add ammonia filter or trap before enter fuel cell system Ammonia desorption can be controlled by engineering design Physical & Engineering Sciences Center Atoms to Continuum -12- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A8) Cycle test to 101 cycles - Gross Capacity loss: 0.005wt% per cycle Physical & Engineering Sciences Center Atoms to Continuum -13- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (A9) Thermal Properties Measurements Hardware configuration – Crooker & Dedrick Loaded with ~ 130 grams ball-milled LiNH2-MgH2 Sample Volume Optimized to measure Kth up to ~5 W/m-K Solid model Physical & Engineering Sciences Center Atoms to Continuum Probe design DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 -14- (A10) Preliminary Kth results – Crooker 2LiNH2 + MgH2 1.2 As-milled condition After first desorption After first absorption Fully absorbed NaAlH4 Fully desorbed NaAlH4 Li2Mg(NH)2 + 2H2 2LiH + Mg(NH2)2 1 Kth (W/m-K) 0.8 0.6 0.4 0.2 0 0.01 0.1 1 10 100 1000 Pressure (atm) Thermal conductivity of LiNH2+MgH2 material increases with gas pressure and similar to those of sodium alanates. Physical & Engineering Sciences Center Atoms to Continuum -15- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 B. Modified Complex Hydrides Investigation of bi-alkali alanates • Pressed pellets of hand mixed or ball milled samples were tested at high pressures up to 136 MPa and temperatures up to 450C facility. • bi-alkali alanates of various molar ratios were tested: – Li-K, Li-Mg, Li-Ca, Li-Ti, Mg-Ti, etc…. – New bi-alkali Li-K alanate formed @ 68 MPa and 330C • Starting mixture of LiAlH4 + 2KH or LiH + 2KH + Al • Pellets expanded and showed in white color • Investigation of Li(Al1-xBx)H4, Na(Al1-xBx)H4, etc…systems are in progress Physical & Engineering Sciences Center Atoms to Continuum -16- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Properties of new Li-K alanates - Ronnebro Raman spectra Powder X-ray diffraction pattern New phase Monoclinic symmetry FTIR 0.9 0.8 0.7 Intensity (a.u.) 0.6 0.5 0.4 0.3 0.2 0.1 0 0 1000 2000 3000 4000 5000 6000 7000 Wave number Structural, kinetic and thermodynamic properties are under investigation Physical & Engineering Sciences Center Atoms to Continuum -17- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 C. Modified Borohydrides (collaboration between Sandrock & BNL) Can Hydrogen Driven Metallurgical Reactions be used to make nanocomposites for “stimulating” the Borohydrides? LiBH4 ⇔ LiH + B +3/2 H2 (13.9 wt. % H) NaBH4 ⇔ NaH + B + 3/2 H2 (8.0 wt. % H) Possible Oxide Precursor Reactions (schematic): NaBH4 + MoO3 ⇒ NaBH4 + Mo + (Na2O or B2O3 or H2O) NaBH4 + Mo ⇔ NaH + MoBx + H2 Physical & Engineering Sciences Center Atoms to Continuum -18- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Effect of Mo & MoO3 on NaBH4 - Sandrock Effect of Mo & MoO3 Additions on NaBH4 TPD NaBH4 NaBH4+5%MoO3 NaBH4+5%Mo NaBH4+10%MoO3 TPD Scan @ 4ÞC/min 3.0 2.5 10% MoO3 H2 wt% 2.0 1.5 1.0 0.5 0.0 0 50 100 150 200 250 300 350 400 5% MoO3 5% Mo 0% Mo 450 Temperature, oC Mo is not the best addition for NaBH4 reversibility because the Mo-borides are too stable. Physical & Engineering Sciences Center Atoms to Continuum -19- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 D. Destabilized Mg hydride – Gross (in collaboration with HRL) MgH2 Has 7.6 wt.% hydrogen - but too stable for FCV applications Much more favorable thermodynamics: 2MgH2 + Si ⇒ Mg2Si + 2H2 • Reversibility being tested using High-pressure station • 4.5 wt% hydrogen was release on desorption at 360oC • XRD after desorption showed 100% conversion to Mg2Si Physical & Engineering Sciences Center Atoms to Continuum -20- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 E. Aluminum hydrides (AlH3) (collaboration of Sandrock & BNL) AlH 3 α-AlH3 Al + 3/2 H2 H-capacity (g) = 10.1 wt% H-capacity (v) = 149 kg/m3 ∆Hdes = 7.6 kJ/mol H2 Depleted Al Physical & Engineering Sciences Center Atoms to Continuum -21- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Effect of LiH doping via TPD – Sandrock TPD Heating Rate = 2˚C/min 8 7 6 10% LiH H2 wt% 5 4 3 2 1 0 25 50 75 100 125 150 175 50% LiH 20% LiH 0% LiH 200 225 Temperature, oC Desorption temperature can be reduced by adding more LiH Physical & Engineering Sciences Center Atoms to Continuum -22- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 II. Fundamental Mechanisms & Modeling (1) Surface alloy catalytic model of NaAlH4 - Stumpf dissociation/ recombination H2-gas Al transport AlHx NaAlH4 NaH Al H Ti (sub)-surface segregation AlHx H-chemi Ti Al with Ti dopant H • • • • • H2 chemistry is autocatalytic: H promotes (sub-) surface Ti Sub-surface Ti creates “activated” sp3-like Al surface atoms with stronger H affinity and reduced H2 sorption barriers Exposed Ti offers chemisorbed H2 binding site and vanishing barriers AlHx provides long range Al transport Results for Sc are similar to those for Ti Surface alloys of simple and transition metals are promising new catalysts for H chemistry Physical & Engineering Sciences Center Atoms to Continuum Ti Ti -23- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (2) Effect of H2 or H ? - Majzoub & Stumpf Experimental support for surface mechanism: dosing of Al+NaH with “atomic” H Idea: use Pd surface to crack H2 • X-ray diffraction after 10 day exposure of Al+NaH to H2 in contact with Pd foil shows 10% of Al+NaH converts to Na3AlH6 and NaAlH4 Control experiment without Pd shows < 1% alanate formation X-ray Diffraction angle (2Θ) • H2 cracking ability of Pd helps hydride formation Physical & Engineering Sciences Center Atoms to Continuum -24- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (3A) Where is Ti ? - Bastasz Energy (eV) barrier H2 gas Al H Ti Ti without Ti Al H chemisorbed reaction path with Ti H2 chemisorption well Al H Ti Al Ti Reaction coordinate (Å) H may stabilize Ti on Al surfaces – Predictions: • H on surface promotes Ti segregation to near-surface sites • Ti reduces H2 adsorption barriers on Al to a fraction of an eV. • Ti facilitates both uptake and release of H2. Is there experimental evidence for this? Physical & Engineering Sciences Center Atoms to Continuum -25- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (3B) Model validation - Bastasz Ti/(Ti+Al) signal ratio changes indicating that Ti concentration on the surface appears to increase upon exposing sample to D2. Physical & Engineering Sciences Center Atoms to Continuum -26- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 (4) In-Situ Raman spectra observations - Majzoub • • • Crystal modes soften up to 6-7% at Tm AlH4 anion modes soften less than 1.5% AlH4 anion is also stable in the melt! Data shows a very stable AlH4 anion. Physical & Engineering Sciences Center Atoms to Continuum -27- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 III. Synthesis of Nanostructured Materials Wet chemistry synthesis using NH3 – Daniel & Boyle Fig. 1 Fig. 2 Scanning Electron Microscopy (SEM) images of Mg(NH2)2 show the particle size to be ~1-2 mm. The morphology appears coarse and brittle which can be easily broken or ground. However, poor performance was observed due to contamination of residue solvents from wet chemistry processing. Physical & Engineering Sciences Center Atoms to Continuum -28- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Responses to Previous Year Reviewers’ Comments 1.Overall Project Score: 3:32 – positive feedbacks validated our approach and accomplishments in FY2004. 2.Not enough progress made toward development of onboard storage module – we will start the storage module development later this FY and gradually increase its efforts as the program progresses toward Phase II. 3.Primary empirical approach to new material discovery – we selected our tested materials based on thermodynamics, atomistic modeling and experiences (teaming between modeling and experimentation). 4.Cost estimation is not covered – we will initiate cost study as one of system studies in parallel to the materials discovery efforts. 5.Difficulty of geographic separation – we established on-line, instant communication system and regular teleconferences and face-toface meetings for all Center partners. Physical & Engineering Sciences Center Atoms to Continuum DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 -29- Responses to Previous Year Reviewers’ Comments (continued) 6. System-based studies are needed – we started the Center (in Jan) with engineering system as a central focus, with a ramp up of the engineering design in phase II. 7. Make sure the performance metrics include considerations of (1) “whole storage system” weights and volumes and (2) “net” energy delivered to the vehicle – we used this to screen our material candidates as a part of our Center system-based approach. 8. Schedule down select of materials – yes, we have go/no-go decision points in our AOP milestones as well as our MHCoE plan. 9. Investment in Na-alanates? – we stopped most tests on Naalanates except some experiments to validate our 1st principle model. Physical & Engineering Sciences Center Atoms to Continuum -30- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Future Work Remainder of FY2005 • New Storage Materials Development – Explore new complex hydrides via HP/HT process – Optimize Li-Mg-H based materials for faster kinetics and lower temperatures – Search for storage materials with optimal properties • Fundamental Mechanisms – Conclude the modeling validation experiments on alanates – Initiate modeling and mechanisms studies on Li-Mg-H, B-Li-H and Al-H based materials • Chemical Synthesis Development – Improve the wet chemistry process to produce pure storage materials with nano-size particles Physical & Engineering Sciences Center Atoms to Continuum -31- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Future Work Remainder of FY05 (continued) • Engineering Science of Complex Hydrides – Continue to measure engineering properties of hydrogen storage materials, e.g., thermal conductivities, volume expansion, tap density,…..etc. – Continue to study performance degradation and reliability of candidate storage materials – Initiate investigation on reactions related to safety • Collaboration with MHCoE Partners – Lead the Metal Hydride Center of Excellence. Physical & Engineering Sciences Center Atoms to Continuum -32- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Future Work FY2006 and beyond • New Storage Materials Development – Continue to search for materials with optimal storage properties • Fundamental Mechanisms – Continue to model newly discovered materials – Develop models to predict new materials and to guide experiments • Chemical Synthesis Development – Continue to develop processes to produce storage materials with nano-size particles. • Engineering Science of newly developed Hydrides – Continue to build engineering property database of hydrides. Physical & Engineering Sciences Center Atoms to Continuum -33- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Presentation end Physical & Engineering Sciences Center Atoms to Continuum -34- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Publications 1. 2. 3. 4. W. Luo, “(LiNH2-MgH2): a viable hydrogen storage system”, J. Alloys and Compounds, 381, 284-287 (2004) W. Luo, K. Gross, “A kinetics model of hydrogen absorption and desorption in Ti-doped NaAlH4”, J. Alloys and Compounds, 385, 224-231 (2004) Z. Xiong, J. Hu, G. Wu, P. Chen, W. Luo, K. Gross, J. Wang, “Thermodynamic and kinetic investigation on the ternary imide of Li2MgN2H2”, J. Alloys and Compounds, in press. E. H. Majzoub, K. F. McCarty, and V. Ozolins, “Lattice dynamics of NaAlH4 from high-temperature single-crystal Raman scattering and ab initio calculations: Evidence of highly stable AlH-4 anions,” Phys. Rev. B 71, 024118 (2005) R. Bastasz, J.W. Medlin, J.A. Whaley, R. Beikler, and E. Taglauer, "Deuterium adsorption on W(100) studied by LEIS and DRS,” Surface Science, volume 571 (2004) pp 31-40. J. Wang and E. Ronnebro, “Hydride Developments for Hydrogen Storage,” Proceedings of the 2005 Spring TMS conference, p. 19, (2005) E. H. Majzoub, J. L. Herberg, R. Stumpf, S. Spangler, R.S. Maxwell, “XRD and NMR investigation of Ti-compound formation in solution-doping of sodium aluminum hydrides: solubility of Ti in NaAlH4crystals grown in THF,” J. of Alloys and Compounds 388, 81 (2004) V. Ozolins, E. H. Majzoub, T. J. Udovic, “Electronic structure and Rietveld refinement parameters of Ti-doped sodium alanates,” J. of Alloys and Compounds 375, 1-10 (2004) E. H. Majzoub, R. Stumpf, S. Spangler, J. Herberg, and R. Maxwell, “Compound Formation in Tidoped Sodium Aluminum Hydrides,” MRS Proceedings 801, 153-158 (2004) R. Stumpf, “H-Induced Reconstruction and Faceting of Al surfaces,” Phys. Rev. Lett. 78, 4454 (1997) G. Sandrock, J. Reilly, J. Graetz, W. Zhou, J. Johnson, and J. Wegrzyn, “Accelerated thermal decomposition of AlH3 for hydrogen-fueled vehicles,” Applied Physics A – Materials Science and Processing, 80, 687–690 (2005) . Physical & Engineering DOE 2005 Hydrogen Program Annual Sciences Center Review, Washington, D.C., May 23, 2005 -35Atoms to Continuum 5. 6. 7. 8. 9. 10. 11. Presentations 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. R. Bastasz and J.A. Whaley, "LEIS and DRS: Diagnostic tools for studying hydrogen on surfaces,” MRS Spring Meeting, Symposium on Materials and Technology for Hydrogen Storage and Generation, San Francisco, March 30, 2005. K. Gross, W. Luo, “Sorption Properties of novel hydrogen storage materials”, International Symposium on Matel Hydrogen Systems, Krakow, Poland, Sept. 6-9, 2004, K. Gross and G. Thomas, “Hydrogen Storage Where We Are Now and Where We Need to Go” , American Physical Society Annual Meeting, Montréal Canada March 20-26, 2004. K. Gross and D. Dedrick, “Advances in Hydrices for Hydrogen Storage” , American Physical Society Annual Meeting, Montréal Canada March 20-26, 2004. K. Gross, “Advances in Alanates for Hydrogen Storage,” NHA Annual Meeting 2004 K. Gross, W. Luo, “Properties of advanced hydrogen storage materials”, Material Research Society Annual Meeting, Boston, MA, Nov. 29-Dec.2, 2004. W. Luo, “Towards a viable hydrogen storage system for transportation application”, International Symposium on Matel Hydrogen Systems, Krakow, Poland, Sept. 6-9, 2004, W. Luo “Towards A Viable Hydrogen Storage System For Transportation application”, Material Solution Conference and Exposition”, Columbus, OH, Oct. 18-21, 2004. W. Luo, K. Gross, E. Ronnebro, J. Wang, “Destabilization of metal hydrides by forming nitrogen-containing compounds”, American Physical Society Annual Meeting, Los Angeles, CA, March 21-25, 2005. W. Luo, K. Gross, E. Ronnebro, J. Wang, “Metal-N-H: new promising hydrogen storage materials”, NHA Meeting, Washington DC, March 28-Apr.1, 2005 E. Majzoub, “X-ray Diffraction and Raman Spectroscopy Investigation of Titanium Substitution in Sodium Aluminum Hydride,” TMS Annual Meeting 2004 E. Majzoub, “In-situ Raman Spectra of NaAlH4 : Evidence of Highly Stable AlH4 Anions,” MRS 2004 E. Majzoub. “In-situ Raman Spectra of NaAlH4 : Evidence of Highly Stable AlH4 Anions,” International Conference on Metal-Hydrogen Systems, Krakow, Poland, 2004 G. Sandrock, J. Reilly, J. Graetz, W. Zhou, J. Johnson, J. Wegrzyn, “Doping of AlH3 with alkali metal hydrides for enhanced decomposition kinetics,” presented at the APS March meeting, March 21-25, 2005. DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Physical & Engineering Sciences Center Atoms to Continuum -36- Presentations (Continued) 15. 16. 17. 18. 19. R. Stumpf, Promotion of H2 Sorption at Al-Ti Alloy Surfaces in Alanate H Storage Materials, MRS Spring Meeting, GG2.5 (2005) R. Stumpf, Basic Mechanisms of H Uptake/Release in Ti-Doped Alanate H-Storage Materials, MS&T review, Sandia (2005) R. Stumpf, K. Thürmer, R. Bastasz, Atomistic View of the H Uptake/Release Mechanisms in the TiDoped Na-Al-H System, ASM materials solutions conference, Ohio, invited talk (2004) J. Wang, “ Hydride Development for Hydrogen Storage Applications,” TMS Spring Conference, (2005) J. Wang, “Hydrogen Storage Materials Research at Sandia National Laboratories,” Materials Solutions Conference and Exposition, ASM Annual Meeting, Columbus, OH (2004) Physical & Engineering Sciences Center Atoms to Continuum -37- DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 Hydrogen/Material Safety The most significant hydrogen hazard associated with this project is that we are developing hydrogen storage materials with unknown properties which potentially can be very energetic. Specifically, – A rapid pressure rise resulting in containment failure, – An unexpected increase in temperature of an object resulting in a burn and/or fire hazard. Either of these could occur if some of our current materials are exposed to 1) an oxidizing atmosphere and/or 2) moisture Physical & Engineering Sciences Center Atoms to Continuum DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 -38- Hydrogen/Material Safety Our approach to deal with these hazards are: – Only well trained knowledgeable personnel have access to the project/laboratory and are authorized to operate the laboratory equipment, – The quantities of material (fuel or oxidizer) are limited such that in the event of a catastrophic containment failure resulting in a rapid energy release, the resulting pressure and/or temperature rise for the system is kept well below any hazardous condition, – Material preparation, installation and removal is performed an inert gas environment. – All materials, when not in use, are sealed in secondary containment within the glove box and within sealed experimental vessels at 1 bar overpressure of inert dry gas. – Sandia’s well established and documented Integrated Safety Management System (ISMS) which addresses the safety aspects of new projects or changes in an existing one is fully implemented and enforced throughout all aspects of our hydrogen storage materials R&D project. Physical & Engineering Sciences Center Atoms to Continuum DOE 2005 Hydrogen Program Annual Review, Washington, D.C., May 23, 2005 -39-