Stabilization of lithium superionic conduction phase and enhancement of conductivity of LiBH4 by LiCl addition

Matsuo, Motoaki; Takamura, Hitoshi; Maekawa, Hideki; Li, Haiwen; Orimo, Shin Ichi

doi:10.1063/1.3088857

Cited by 97 publications

(91 citation statements)

References 26 publications

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“…We experimentally and computationally confirmed the stabilization of the high-temperature ͓hexagonal, lithium super͑fast-͒ionic conduction͔ phase of LiBH 4 Lithium borohydride ͑LiBH 4 ͒ exhibits lithium super͑fast-͒ionic conductivity accompanied by a structural transition from low-temperature ͑LT, orthorhombic͒ to hightemperature ͑HT, hexagonal͒ phases by heating to approximately 390 K. 1 Since the structural transition is reversible, the HT phase with super͑fast-͒ionic conductivity transforms into the LT phase with lower conductivity by cooling to around 380 K. It would thus be highly desirable to stabilize the HT phase ͑or to prohibit the formation of the LT phase by cooling in͒ of LiBH 4 as a potential candidate of solid-state electrolytes at room temperature ͑RT͒.…”

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confidence: 50%

“…3 Accordingly, the value of the conductivity at RT increases from the order of 10 −8 S / cm for LiBH 4 to that of 10 −5 S / cm for LiBH 4 + 0.33LiI. Systematic studies about the structural transition of LiBH 4 with and without LiI are highly required for further developments of LiBH 4 and the derived hydrides as solid-state electrolytes.…”

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confidence: 99%

“…So far, a number of the crystalline structures of LiBH 4 have been proposed and studied. 7,[16][17][18][19][20][21][22][23] In the LiBH 4 + xLiI pseudobinary system, possible intermediate ͑IM͒ phases are predicted to be stable at low x-values and a crystalline structure of the IM phase with x = 0.14 is shown in Fig.…”

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confidence: 99%

“…The samples examined were synthesized from the powders of LiBH 4 and LiI ͑both from Aldrich Co. Ltd.͒. Approximately 500 mg of the powder mixture with nominal compositions of LiBH 4 + xLiI ͑x = 0, 0.07, 0.14, 0.20, 0.33, and 1.00͒ were mechanically milled for 5 h under Ar atmosphere.…”

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confidence: 99%

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Experimental and computational studies on structural transitions in the LiBH4–LiI pseudobinary system

Oguchi

Matsuo

Hummelshøj

et al. 2009

Applied Physics Letters

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confidence: 99%

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confidence: 99%

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Experimental and computational studies on structural transitions in the LiBH4–LiI pseudobinary system

Oguchi

Matsuo

Hummelshøj

et al. 2009

Applied Physics Letters

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“…Room-temperature superionic behaviour of lithium has recently been observed in Li 10 GeP 2 S 12 and can be stabilized close to room temperature in LiBH 4 , sparking increased interest in superionic materials for practical electrochemical devices [13][14][15][16] . Despite the long history of investigations into superionic materials, the mechanism of the structural reorganization and how that gives rise to high ionic conductivity remains largely unknown, especially at the nanoscale.…”

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confidence: 99%

The mechanism of ultrafast structural switching in superionic copper (I) sulphide nanocrystals

et al. 2013

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Superionic materials are multi-component solids with simultaneous characteristics of both a solid and a liquid. Above a critical temperature associated with a structural phase transition, they exhibit liquid-like ionic conductivities and dynamic disorder within a rigid crystalline structure. Broad applications as electrochemical storage materials and resistive switching devices follow from this abrupt change in ionic mobility, but the microscopic pathways and speed limits associated with this switching process are largely unknown. Here we use ultrafast X-ray spectroscopy and scattering techniques to obtain an atomic-level, real-time view of the transition state in copper sulphide nanocrystals. We observe the transformation to occur on a twenty picosecond timescale and show that this is determined by the ionic hopping time.

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Complex Hydrides for Electrochemical Energy Storage

Unemoto

Matsuo

Orimo

2014

Adv Funct Materials

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197

226

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Complex hydrides have energy storage-related functions such as i) solid-state hydrogen storage, ii) electrochemical Li storage, and iii) fast Li-and Naionic conductions. Here, recent progress on the development of fast Li-ionic conductors based on the complex hydrides is reported. The validity of using them as electrolytes in all-solid-state lithium rechargeable batteries is also examined. Not only coated oxides but also bare sulfi des are found to be applicable as positive electrode active materials. Results related to fast Na-ionic conductivity in the complex hydrides are presented. In the last section, the future prospects for battery assemblies with high-energy densities, and Mg ion batteries with the liquid and the solid-state electrolytes are discussed. Figure 1. Crystal structures of a) LT phase and b) HT phase of LiBH 4 . [ 16 ]Adv. FEATURE ARTICLEto fast Li-ionic conduction, the advantages of the use of complex hydrides as rechargeable battery electrolytes are as follows, iii) Fast Li-and Na-ionic conductions: One of the important challenges in the fi eld of battery research is the development of fast ionic conductors because this class of materials enables the assembly from micro- [ 24 ] to bulk-type [25][26][27] all-solid-state rechargeable cells, which allows the broader applications. With this background, various solid-state electrolytes have been developed so far, however, the materials showing suffi cient ionic conductivity as well as good stability in the voltage ranges for battery operation are limited to a few cases. [ 28 ] Therefore, novel solid-state electrolytes are urgently required for the development of future generation batteries. Since the discovery of fast Li-ionic conduction in the HT phase of LiBH 4 , [ 29 ] we have developed numerous solid-state electrolytes based on the complex hydrides that exhibit fast Li-and Na-ionic conductions. [ 30 ] Herein, we briefl y report recent progress in the development of the complex hydrides that exhibit fast Li-ionic conduction. All-solid-state Li rechargeable batteries were subsequently assembled using coated-LiCoO 2 and TiS 2 positive electrodes, and LiBH 4 -based electrolytes. The validity of the use of the complex hydrides as electrolytes in a rechargeable battery was examined on the basis of charge-discharge measurements. In the following section, our recent development of fast Na-ionic conductors based on the complex hydrides is summarized. We discuss the future prospects for the development of high energy density rechargeable batteries, and Mg-ion batteries that use nonaqueous and solid-state electrolytes based on the complex hydrides. FEATURE ARTICLEhexagonal phase of LiBH 4 (fast Li-ion conduction phase) even at room temperature when x exceeds 0.25. And then, the solid-solution, Li 4 (BH 4 ) 3 I, exhibits fast Li-ionic conductivity of 2 × 10 −5 S cm −1 at 300 K. [ 34,[51][52][53] This phenomenon might be due to increased neighboring distance of [BH 4 ] − [ 54 ] and induced lattice anharmonicity by the partial substitution of I − instead of ...

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Stabilization of lithium superionic conduction phase and enhancement of conductivity of LiBH4 by LiCl addition

Cited by 97 publications

References 26 publications

Experimental and computational studies on structural transitions in the LiBH4–LiI pseudobinary system

Experimental and computational studies on structural transitions in the LiBH4–LiI pseudobinary system

The mechanism of ultrafast structural switching in superionic copper (I) sulphide nanocrystals

Complex Hydrides for Electrochemical Energy Storage

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