1. Institute for Micromanufacturing Louisiana Tech University Synchrotron Studies for Tackling Technical Challenges in the Hydrogen Economy { } { Research into Novel Materials for Emerging Energy Applications } Tabbetha A. Dobbins 1,2 1. Institute for Micromanufacturing, Louisiana Tech University, Ruston, LA 2. Dept. of Physics, Grambling State University, Grambling, LA Institute for Micromanufacturing Louisiana Tech University November 5, 2009

2. Institute for Micromanufacturing Louisiana Tech University 2 -The Fossil Fuel-based economy has limitations; -An alternative fuel cell energy infrastructure (PEM Fuel Cells and Solid Oxide Fuel Cells) will penetrate energy markets; -Technical challenges facing the PEM fuel cell are nevertheless substantial; -Creative solutions are needed to tackle our societal need for “cleaner and greener” energy. Animation courtesy of: http://www.humboldt.edu ? H 2 Fuel??? “A (n) Inconvenient Truth” (about Energy Production)

3. Institute for Micromanufacturing Louisiana Tech University 3 Storage Weight % (System)63.4 Energy Efficiency %9788 Energy Density (W-h/L)11001300 Specific Energy (W-h/kg)20001080 Cost ($/Kw-h)518 Operating Temperature ( o C)Up to 50 o C Start-up Time (sec)15<15 Hydrogen Loss (scc/hr/L)1.0 Cycle Life (#)50020-50 Refueling Time (min)<5undetermined Recoverable Usable Amt90%>90% TargetPerformance Targets Table Reproduction from Millikan and Rossmeissl Aug. 14, 2002 Workshop Image from Satyapal, Petrovic, Thomas (Scientific American, April 2007)

4. Institute for Micromanufacturing Louisiana Tech University 4 DoE Targets for Hydrogen Storage Materials

5. Institute for Micromanufacturing Louisiana Tech University Synchrotron (High Flux) X-rays Source at CAMD (LSU in Baton Rouge, LA) 1.3Mile, 7GeV ring of electrons in storage ring. 38 experimental sectors Small-Angle X-ray Scattering (SAXS), 3D Imaging Collaborators: Jan Ilavsky and Francesco DeCarlo Advanced Photon Source (APS) at Argonne National Laboratory 0.3 Mile, 1-2GeV ring of electrons in storage ring. 15 experimental sectors X-ray Absorption Spectroscopy, 3D Imaging, and SAXS Collaborators: Amitava Roy Synchrotron Accelerators

6. Institute for Micromanufacturing Louisiana Tech University CAMD SSRL ALS APS CHESS NSLS SRC SURF Is the only SR source in the South! Synchrotron Radiation Facilities in the US

7. Institute for Micromanufacturing Louisiana Tech University 7 Catalysis: What is role of transition catalysts in the hydrogen discharge and recharge reaction? How are non- reversible products formed and what are their roles in catalysis? Kinetics: What fundamental limits hydrogen desorption kinetics? What are mass transport limitations in hydrogen storage materials? Improved Research Tools: What instrumentation developments are needed for improved examination of atomic local structure (0.1 – 2nm) and microstructure (2nm – 1000  m)? Some Grand Challenge Areas in H 2 Storage Research

8. Institute for Micromanufacturing Louisiana Tech University 8 Research Highlights Fundamental Materials Research Problems– (1) Role of Catalyst still not well understood; (2) Slow diffusion and reaction rates should be addressed. –3D Imaging of Interphase Boundary Area between LiBH 4 /MgH 2 and TiN/NaAlH 4 Dobbins T.A., Decarlo F., Ziao, X., Ukpai W., Narase Gowda S. (To be published) –Formation of TiAl x Alloys during introduction of TiCl 3 catalyst to NaAlH 4 Dobbins T.A., Abrecht M., Uprety Y., Moore K., ”An X-ray Photoemission Electron Microscopy Study of the Formation of Ti-Al Phases in 4 mol % TiCl 3 Catalyzed NaAlH 4 During High Energy Ball Milling”, Nanotechnology, 20, 204014 (2009). –Microwave irradiation for desorption of H 2 from NaAlH 4 Krishnan R., Agrawal D., Dobbins T.A.,“Microwave Irradiation Effects on Reversible Hydrogen Desorption in Sodium Aluminum Hydrides (NaAlH4)”, Journal of Alloys and Compounds, 470 [1-2] 250 (2009). –TiCl 3 dopant mitigating Na + and Al 3+ diffusion rates in NaAlH 4 Dobbins, T.A., Bruster E.B., Oteri, E.U., Ilavsky J., ”Ultrasmall-Angle X-ray Scattering (USAXS) Studies of Morphological Trends in High Energy Milled NaAlH 4 Powders”, Journal of Alloys and Compounds 446-447 pp 248-254 (2007). –Thin polymer films containing Ti 3+ overlayed onto NaAlH 4 Kamineni V., Lvov Y.M., Dobbins T.A. “Layer-by-Layer Nanoassembly Using Formamide as a Working Solvent”, Langmuir 23 pp 7423-27 (2007).

9. Institute for Micromanufacturing Louisiana Tech University 9 Tomography can guide this work by yielding interfacial contact area. Tomography also Offers a means to define active crystallographic surfaces (coupled with Wulff construction of images and by DFT). 3D Imaging (Computed X-ray Tomography) 50 mol % TiN in NaAlH4 (17 keV) (imaged at CAMD) 2 NaAlH 4 + 2TiN  2TiAl + 2 NaN + 4 H 2 (g)

10. Institute for Micromanufacturing Louisiana Tech University 10 0 minute mill time (blended) 1 minute mill time 5 minute mill time 25 minute mill time 125 minute mill time TiAl TiAl 3 EXAFS: TiAl and TiAl 3 formation during introduction of TiCl 3 catalyst to NaAlH 4 TiAl 3 Normalized Absorption Radial Distribution Function

11. Institute for Micromanufacturing Louisiana Tech University 11 NaAlH 4 +4 mol % TiCl 3 after high energy milled for 25 minutes. XPEEM data were collected at the VLS PGM beamline at the Synchrotron Radiation Center (SRC), Madison, WI. (Collaborator: Michael Abrecht) Ti Al Na Cl 5m5m5m5m 5m5m 5m5m X-ray Photoemission Electron Microscopy (XPEEM): TiAl x formation during high energy milling Al K-edge Spectra Ti L-edge Spectra 25 Minute Mill

12. Institute for Micromanufacturing Louisiana Tech University 12 0 min mill time1 min mill time 25 min mill time SEM images of undoped NaAlH 4 powders blended for 2 minutes in dry N 2 glovebox and milled for (a) 0 minutes; (b) 1 minute; (c) 5 minutes; and (d) 25 minutes. (a)(b) (c) 5 min mill time (d) Quantitative Parameter to describe microstructure (in terms of surface area) Small-Angle X-ray Scattering (SAXS) SAXS Data p~-3 for High surface area. p~-4 smoother colloidal particle (lowest surface area) SA~r Ds ~r p r 6 In Collaboration with Jan Ilavsky (Advanced Photon Source) Dobbins, T.A., Bruster E.B., Oteri, E.U., Ilavsky J., JALCOM 446-447 p 248 (2007).

13. Institute for Micromanufacturing Louisiana Tech University Summary and Future Plans: Dept. of Energy: Energy Frontier Research Center o The Center for Atomic-Level Catalyst Design. (Lead: James Spivey @ LSU) o Center involves 8 institutions in the U.S. (LaTech, GSU, GaTech, UFl, Penn State, Tulane and abroad (Univ. of Utrecht). o The overall objective of LaTech/GSU work is to explore catalyst structure-property relationships which dictate fuel conversion reaction mechanisms and reaction rates using synchrotron x-ray scattering and x-ray absorption spectroscopy. NSF Faculty Early Career Development Award o The objective of this proposal is to understand the influence of catalytic additives in enhancing atomic mobility and desorption rates in metal hydrides (specifically, NaAlH 4 and LiBH 4 ) by incorporating x-ray and neutron studies. o Two new courses cross-listed at LaTech, LSU and GSU.  (1) Synchrotron Studies and (2) Alternative Energy o High school design challenge: Design H 2 tank for Fuel Cell Vehicle. X-ray Data for unique Insight into structure of materials Synchrotron Courses for training new generation of students in formal setting Undergraduate Student Mentoring High School Fuel Cell Workshops C C

14. Institute for Micromanufacturing Louisiana Tech University 14 Graduate Students: Corisma Robinson (XANES); Vimal Kamineni (EXAFS/XANES) Shathabish Narase Godwa (Neutron Studies) Collaborators: CAMD (EXAFS/XANES): Amitava Roy and Greg Merchan CAMD (Tomography): Kyunming Ham and Les Butler SRC (XPEEM): Michael Abrecht APS (USAXS): Jan Ilavsky APS (Tomography): Francesco Decarlo and Xianghui Xiao LaTech IfM: Daniela Mainardi, Phani Krisha Dathara, Yuri Lvov Acknowledgments Funding Sources: Department of Energy, Office of Basic Energy Sciences (Contract No.: DE-FG02-05ER46246). National Science Foundation, Division of Materials Research (Contract No.: DMR-0508560). National Science Foundation, CAREER Award Program (Contract No.: DMR-0847464). Louisiana State Board of Regents Support Fund, RCS Program Louisiana State Board of Regents Support Fund, PFUND Program Undergraduate Students: Youaraj Uprety (XPEEM Analysis); Kristan Moore (X-ray Diffraction); Whitney Fisher (Tomography); www2.latech.edu/~tdobbins

15. Institute for Micromanufacturing Louisiana Tech University 15 Thank You. www2.latech.edu/~tdobbins