Mobility and dynamics in the complex hydrides LiAlH4 and LiBH4
作者： A. Borgschulte , A. Jain , A. J. Ramirez-Cuesta , P. Martelli , A. Remhof
DOI: 10.1039/C0FD00011F
关键词: Deuterium 、 Ion 、 Kinetic isotope effect 、 Hydrogen 、 Borohydride 、 Infrared spectroscopy 、 Chemistry 、 Raman spectroscopy 、 Inelastic neutron scattering 、 Analytical chemistry
摘要: The dynamics and bonding of the complex hydrides LiBH4 LiAlH4 have been investigated by vibrational spectroscopy. combination infrared, Raman, inelastic neutron scattering (INS) spectroscopies on hydrided deuterided samples reveals a complete picture BH−4 AlH−4 anions respectively as well lattice. straightforward interpretation isotope effects facilitates tracer diffusion experiments revealing coefficients hydrogen containing species in LiBH4, LiAlH4. exchanges atomic starting at 200 °C. Despite having an iso-electronic structure, mobility is different from that LiBH4. Upon ball-milling LiAlD4, exchanged with deuterium even room temperature. However, exchange reaction competes decomposition compound. alanate borohydride found to be D ≃ 7 × 10−14 m2s−1 473 K 5 10−16 348 K, respectively. ion easily other ions such I− or NH−2. This opens possibility tailoring physical properties temperature phase transition linked Li-ion conductivity measured nuclear magnetic resonance Raman Temperature dependent measurements gradient Li(BH4)1−cIc demonstrate increasing has similar impact iodide concentration c: system driven towards high-temperature influence anion sorption limited, though. For example, Li4(BH4)(NH2)3 does not melt.
rsc.org
harvard.edu
core.ac.uk 
sci-hub.se 参考文章(63)
John Crank, The mathematics of diffusion ,(1956)
H. Oguchi, M. Matsuo, T. Sato, H. Takamura, H. Maekawa, H. Kuwano, S. Orimo, Lithium-ion conduction in complex hydrides LiAlH4 and Li3AlH6 Journal of Applied Physics. ,vol. 107, pp. 096104- ,(2010) , 10.1063/1.3356981
Hui Wu, Wei Zhou, Terrence J. Udovic, John J. Rush, Taner Yildirim, Structures and Crystal Chemistry of Li2BNH6 and Li4BN3H10 Chemistry of Materials. ,vol. 20, pp. 1245- 1247 ,(2008) , 10.1021/CM703315E
Aline Léon, Oleg Zabara, Sabrina Sartori, Nico Eigen, Martin Dornheim, Thomas Klassen, Jiri Muller, Bjørn Hauback, Maximilian Fichtner, Investigation of (Mg, Al, Li, H)-based hydride and alanate mixtures produced by reactive ball milling Journal of Alloys and Compounds. ,vol. 476, pp. 425- 428 ,(2009) , 10.1016/J.JALLCOM.2008.09.023
A.-M. Racu, J. Schoenes, Z. Lodziana, A. Borgschulte, A. Züttel, High-resolution Raman spectroscopy study of phonon modes in LiBH4 and LiBD4. Journal of Physical Chemistry A. ,vol. 112, pp. 9716- 9722 ,(2008) , 10.1021/JP803005F
R. Miyazaki, T. Karahashi, N. Kumatani, Y. Noda, M. Ando, H. Takamura, M. Matsuo, S. Orimo, H. Maekawa, Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH4 Solid State Ionics. ,vol. 192, pp. 143- 147 ,(2011) , 10.1016/J.SSI.2010.05.017
Andrew R. Barron, Geoffrey Wilkinson, Transition-metal aluminohydride complexes Polyhedron. ,vol. 5, pp. 1897- 1915 ,(1986) , 10.1016/S0277-5387(00)87113-2
Gerhard Herzberg, Bryce L. Crawford, Infrared and Raman spectra of polyatomic molecules The Journal of Physical Chemistry. ,vol. 50, pp. 288- 288 ,(1946) , 10.1021/J150447A021
Juan C. Fallas, Wen-Ming Chien, Dhanesh Chandra, Vamsi K. Kamisetty, Erik D. Emmons, Aaron M. Covington, Raja Chellappa, Stephen A. Gramsch, Russell J. Hemley, Hans Hagemann, Raman Spectroscopy Measurements of the Pressure−Temperature Behavior of LiAlH4 Journal of Physical Chemistry C. ,vol. 114, pp. 11991- 11997 ,(2010) , 10.1021/JP1015017
Yuko Nakamori, Kazutoshi Miwa, Akihito Ninomiya, Haiwen Li, Nobuko Ohba, Shin-ichi Towata, Andreas Züttel, Shin-ichi Orimo, Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativites: First-principles calculations and experiments Physical Review B. ,vol. 74, pp. 045126- ,(2006) , 10.1103/PHYSREVB.74.045126