Fast Li diffusion in crystalline LiBH4 due to reduced dimensionality: Frequency-dependent NMR spectroscopy

被引:86
作者
Epp, V. [1 ]
Wilkening, M. [1 ]
机构
[1] Leibniz Univ Hannover, Inst Phys Chem & Electrochem, D-30167 Hannover, Germany
关键词
NUCLEAR-MAGNETIC-RESONANCE; LITHIUM BATTERIES; CONDUCTOR LI3N; RELAXATION; TRANSPORT; HYDROGEN; PHASE;
D O I
10.1103/PhysRevB.82.020301
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
The hexagonal and orthorhombic form of lithium borohydride, LiBH4, are investigated by temperature and frequency-dependent nuclear magnetic resonance (NMR) spectroscopy. The local electronic structure and microscopic diffusion parameters are determined by recording both Li-6,Li-7 NMR spectra and spin-lattice relaxation (SLR) rates. The rates of the high-temperature flank of the SLR-NMR peaks of hexagonal LiBH4 clearly depend on resonance frequency which unequivocally reveals a low-dimensional diffusion process. Due to the very limited number of suitable model substances this makes lithium borohydride an extremely attractive material to study the effect of reduced dimensionality on Li dynamics. Most likely, the spatial confinement of Li hopping is also responsible for the very high ionic conductivity found for the hexagonal polymorph, recently.
引用
收藏
页数:4
相关论文
共 35 条
[11]   FAST IONIC TRANSPORT IN SOLIDS [J].
FARRINGTON, GC ;
BRIANT, JL .
SCIENCE, 1979, 204 (4400) :1371-1379
[12]   JUMP RELAXATION IN SOLID ELECTROLYTES [J].
FUNKE, K .
PROGRESS IN SOLID STATE CHEMISTRY, 1993, 22 (02) :111-195
[13]   TRANSPORT-PROPERTIES OF LITHIUM-INTERCALATED MOO(3) [J].
JULIEN, C ;
NAZRI, GA .
SOLID STATE IONICS, 1994, 68 (1-2) :111-116
[14]   LI-7 NMR RELAXATION BY DIFFUSION IN HEXAGONAL AND CUBIC LIXTIS2 [J].
KUCHLER, W ;
HEITJANS, P ;
PAYER, A ;
SCHOLLHORN, R .
SOLID STATE IONICS, 1994, 70 :434-438
[15]   Nuclear magnetic resonance magnetic dipolar spectral density functions for two-dimensional lattice diffusion: hexagonal systems [J].
MacDonald, DH ;
Sholl, CA ;
Stephenson, PCL .
JOURNAL OF PHYSICS-CONDENSED MATTER, 1998, 10 (02) :417-428
[16]   Halide-Stabilized LiBH4, a Room-Temperature Lithium Fast-Ion Conductor [J].
Maekawa, Hideki ;
Matsuo, Motoaki ;
Takamura, Hitoshi ;
Ando, Mariko ;
Noda, Yasuto ;
Karahashi, Taiki ;
Orimo, Shin-ichi .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (03) :894-+
[17]   Lithium superionic conduction in lithium borohydride accompanied by structural transition [J].
Matsuo, Motoaki ;
Nakamori, Yuko ;
Orimo, Shin-ichi ;
Maekawa, Hideki ;
Takamura, Hitoshi .
APPLIED PHYSICS LETTERS, 2007, 91 (22)
[18]   Complex Hydrides with (BH4)- and (NH2)- Anions as New Lithium Fast-Ion Conductors [J].
Matsuo, Motoaki ;
Remhof, Arndt ;
Martelli, Pascal ;
Caputo, Riccarda ;
Ernst, Matthias ;
Miura, Yohei ;
Sato, Toyoto ;
Oguchi, Hiroyuki ;
Maekawa, Hideki ;
Takamura, Hitoshi ;
Borgschulte, Andreas ;
Zuettel, Andreas ;
Orimo, Shin-ichi .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (45) :16389-+
[19]   2-DIMENSIONAL DIFFUSION OF HYDROGEN IN ZRBE2H1.4 [J].
MCDOWELL, AF ;
MENDELSOHN, CF ;
CONRADI, MS ;
BOWMAN, RC ;
MAELAND, AJ .
PHYSICAL REVIEW B, 1995, 51 (10) :6336-6342
[20]   NMR-STUDIES OF HYDROGEN DIFFUSION IN HYDROGEN URANYL PHOSPHATE TETRAHYDRATE (HUP) [J].
METCALFE, K ;
HALSTEAD, TK ;
SLADE, RCT .
SOLID STATE IONICS, 1988, 26 (03) :209-215