Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH4

Miyazaki, Reona; Karahashi, Taiki; Kumatani, N.; Noda, Yasuto; Ando, Mariko; Takamura, Hitoshi; Matsuo, Motoaki; Orimo, Shin Ichi; Maekawa, Hideki

doi:10.1016/j.ssi.2010.05.017

Cited by 59 publications

(60 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[74] For reference, the data for LiNH 2 [73] and LiI [35] as host materials are also shown. [15] 2) Li(BH 4 ) 0.75 I 0.25 (LiBH 4 -LiI system), [54,58] 3),4) Li 2 (BH 4 ) (NH 2 ) and Li 4 (BH 4 )(NH 2 ) 3 (LiBH 4 -LiNH 2 system), [73] 5),6) LiNH 2 and Li 3 (NH 2 ) 2 I (LiNH 2 -based complex hydrides), [74] and 7),8) LiAlH 4 and Li 3 AlH 6 (LiAlH 4 -based complex hydrides). [80] For reference, the data of related compounds are also shown: 9) Li 2 NH [38] and 10) Li 3 N.…”

Section: Possible Application Of Complex Hydrides As Solid Electrolytesmentioning

confidence: 99%

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Matsuo¹,

Orimo²

2011

Advanced Energy Materials

241

261

View full text Add to dashboard Cite

Complex hydrides exhibit various energy-related functions such as hydrogen storage, microwave absorption, and neutron shielding. Furthermore, another novel energy-related function was recently reported by the authors; lithium fast-ionic conduction, which suggests that complex hydrides may be a potential candidate for solid electrolytes in lithium-ion batteries. This review presents the recent progress in the development of lithium fast-ionic conductors of complex hydrides. First, the fast-ionic conduction in LiBH 4 as a result of clarifying the mechanism of microwave absorption is presented, and then the conceptual development of complex hydrides as a new type of solid-state lithium fast-ionic conductors in LiBH 4 -, LiNH 2 -, and LiAlH 4 -based complex hydrides is discussed. Finally, the future prospects of this study from both application and fundamental viewpoints are described: possible use as solid electrolytes for batteries, formation of ionic liquids in complex hydrides, and similarity between complex hydrides and Laves-phase metal hydrides.Motoaki Matsuo and Shin-ichi Orimo* Figure 1 . Crystal structures of the a) LT and b) HT phases of LiBH 4 . [7][8][9]

show abstract

Section: Possible Application Of Complex Hydrides As Solid Electrolytesmentioning

confidence: 99%

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Matsuo¹,

Orimo²

2011

Advanced Energy Materials

241

261

View full text Add to dashboard Cite

show abstract

Section: ■ Introductionmentioning

confidence: 96%

“…The temperature of the hexagonal-to-orthorhombic phase transition for Li(BH 4 ) 1−y I y solid solutions is found to decrease with increasing iodine content, from 351 K for y = 0.067 to 213 K for y = 0.25. 12 For y = 0.33, no signs of the phase transition have been found down to 173 K. 12 Thus, the hexagonal Li(BH 4 ) 1−y I y solid solutions with y ≥ 0.33 appear to be stable down to low temperatures. In practice, these solid solutions are prepared by ball milling the LiBH 4 −LiI mixtures with subsequent annealing.…”

Section: ■ Introductionmentioning

confidence: 99%

Nuclear Magnetic Resonance Studies of Reorientational Motion and Li Diffusion in LiBH₄–LiI Solid Solutions

et al. 2012

View full text Add to dashboard Cite

To study the reorientational motion of the BH 4 groups and the translational diffusion of Li + ions in LiBH 4 −LiI solid solutions with 2:1, 1:1, and 1:2 molar ratios, we have measured the 1 H, 11 B, and 7 Li NMR spectra and spin−lattice relaxation rates in these compounds over the temperature range 18−520 K. It is found that, at low temperatures, the reorientational motion of the BH 4 groups in LiBH 4 −LiI solid solutions is considerably faster than in all other borohydridebased systems studied so far. Our results are consistent with a coexistence of at least two types of reorientational processes with different characteristic rates. For the faster reorientational process, the average activation energies derived from our data are 53 ± 4, 39 ± 4, and 33 ± 4 meV for the LiBH 4 −LiI solid solutions with 2:1, 1:1, and 1:2 molar ratios, respectively. In the studied range of iodine concentrations, the Li + jump rates are found to decrease with increasing I − content. The activation energies for Li diffusion obtained from our data are 0.63 ± 0.01, 0.65 ± 0.01, and 0.68 ± 0.01 eV for the samples with 2:1, 1:1, and 1:2 molar ratios, respectively. ■ INTRODUCTIONLithium borohydride, LiBH 4 , containing 18.4 mass % of hydrogen is considered as a promising material for hydrogen storage 1 and a prospective superionic conductor. 2 This compound is an ionic crystal consisting of Li + cations and tetrahedral [BH 4 ] − anions. At low temperatures LiBH 4 has the orthorhombic structure (space group Pnma).3−5 At T 0 ≈ 380 K it undergoes a first-order phase transition to the hexagonal structure (space group P6 3 mc).3−5 The transition from the lowtemperature (LT) orthorhombic to the high-temperature (HT) hexagonal phase is accompanied by the 3 orders of magnitude increase in the electrical conductivity, 2 so that the HT phase of LiBH 4 can be considered as a lithium superionic conductor. The HT phase of LiBH 4 is also characterized by the fast reorientational motion of BH 4 tetrahedra 6,7 with the jump rates exceeding 10 12 s −1 . Recently, it has been found 8−11 that the HT phase of LiBH 4 can be stabilized down to low temperatures by a partial halide ion substitution of [BH 4 ] − anions. Such a substitution results in the formation of Li(BH 4 ) 1−y X y solid solutions (X = Cl, Br, or I) with the hexagonal structure. The stabilizing effect increases with increasing size of the halide ion; thus, the strongest effect is observed for I − substitution. The temperature of the hexagonal-to-orthorhombic phase transition for Li(BH 4 ) 1−y I y solid solutions is found to decrease with increasing iodine content, from 351 K for y = 0.067 to 213 K for y = 0.25. 12 For y = 0.33, no signs of the phase transition have been found down to 173 K.12 Thus, the hexagonal Li(BH 4 ) 1−y I y solid solutions with y ≥ 0.33 appear to be stable down to low temperatures. In practice, these solid solutions are prepared by ball milling the LiBH 4 −LiI mixtures with subsequent annealing. It is interesting to note that while the room-temperature p...

show abstract

“…Such addition has been found to result in an even higher Li + conductivity than seen in hexagonal LiBH 4 . Studies on the structural and Li + conduction properties of the LiBH 4 -LiI solid solution have recently been published [31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Ionic conductivity and the formation of cubic CaH2 in the LiBH4–Ca(BH4)2 composite

Sveinbjörnsson

Blanchard

Mýrdal

et al. 2014

Journal of Solid State Chemistry

View full text Add to dashboard Cite

Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH4

Cited by 59 publications

References 21 publications

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Nuclear Magnetic Resonance Studies of Reorientational Motion and Li Diffusion in LiBH₄–LiI Solid Solutions

Ionic conductivity and the formation of cubic CaH2 in the LiBH4–Ca(BH4)2 composite

Contact Info

Product

Resources

About

Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH4

Cited by 59 publications

References 21 publications

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Lithium Fast‐Ionic Conduction in Complex Hydrides: Review and Prospects

Nuclear Magnetic Resonance Studies of Reorientational Motion and Li Diffusion in LiBH4–LiI Solid Solutions

Ionic conductivity and the formation of cubic CaH2 in the LiBH4–Ca(BH4)2 composite

Contact Info

Product

Resources

About

Nuclear Magnetic Resonance Studies of Reorientational Motion and Li Diffusion in LiBH₄–LiI Solid Solutions