Lithium ion conduction in lithium borohydrides under high pressure

Takamura, Hitoshi; Kuronuma, Yu; Maekawa, Hideki; Matsuo, Motoaki; Orimo, Shin Ichi

doi:10.1016/j.ssi.2010.02.011

Cited by 18 publications

(31 citation statements)

References 14 publications

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“…In this work we present new data, complementary to those presented in earlier studies [9,13]. We have carried out measurements in the pressure range 0.1 to 2 GPa on all three phases existing in this pressure range, closing the gap between existing zero-pressure and high-pressure data in the high temperature phase I, adding data in the range 0.7 -2 GPa for the high pressure phase III and providing the first data for the ambient phase I under pressure.…”

Section: Introductionsupporting

confidence: 69%

“…Hydrides usually have a wide band gap which rules out electronic conduction, and the very high observed conductivities of order 10 -2 S cm -1 are thus entirely due to ionic transport. The conductivity and other properties of LiBH 4 have already been extensively investigated by many methods [10], and the conductivity was also recently investigated under high pressures between 2 and 6 GPa by Takamura et al [13] in three of the four solid phases existing below 6 GPa and 500 K [2][3][4]7].…”

Section: Introductionmentioning

confidence: 99%

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Ionic conductivity in three crystalline phases of LiBH₄under pressure

Sundqvist¹,

Yao²,

Andersson³

2013

High Pressure Research

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The AC electrical conductivity of LiBH 4 was investigated below 2 GPa between 1 Hz and 1.6 MHz. The high temperature phase has an ionic conductivity of up to 0.01 S cm -1 while the low temperature phases have conductivities two orders of magnitude lower. All phases show an Arrhenius behaviour with activation energies E a between 0.5 and 0.7 eV, in good agreement with earlier data except for phase III, which is found to have the highest activation energy of the phases studied. The high temperature phase has a minimum in E a near 1 GPa, close to the triple point, correlated with a sudden change in activation volume. These features may indicate an isostructural phase transition. The conductivities of the ambient temperature phases increase temporarily by an order of magnitude after transitions between these phases, probably due to new diffusion channels via structural defects. The phase diagram agrees well with earlier results.

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Section: Introductionsupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Ionic conductivity in three crystalline phases of LiBH₄under pressure

Sundqvist¹,

Yao²,

Andersson³

2013

High Pressure Research

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“…This is slightly larger than the reported value of other pure rock-salt type Li + ion conductors such as the H.P. form of LiBH 4 (0.56 eV) 16 and LiI (0.43 eV). 18 We would like to propose two possibilities to explain these results.…”

Section: -4contrasting

confidence: 61%

“…phase. 16 The most interesting point is that almost the same activation energy for Li + ion conduction is obtained despite the completely different crystal structure (wurtzite and a rock-salt type structure for the H.T. 7 and H.P.…”

mentioning

confidence: 90%

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Synthesis of rock-salt type lithium borohydride and its peculiar Li+ ion conduction properties

2014

Self Cite

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The high energy density and excellent cycle performance of lithium ion batteries makes them superior to all other secondary batteries and explains why they are widely used in portable devices. However, because organic liquid electrolytes have a higher operating voltage than aqueous solution, they are used in lithium ion batteries. This comes with the risk of fire due to their flammability. Solid electrolytes are being investigated to find an alternative to organic liquid. However, the nature of the solid-solid point contact at the interface between the electrolyte and electrode or between the electrolyte grains is such that high power density has proven difficult to attain. We develop a new method for the fabrication of a solid electrolyte using LiBH4, known for its super Li+ ion conduction without any grain boundary contribution. The modifications to the conduction pathway achieved by stabilizing the high pressure form of this material provided a new structure with some LiBH4, more suitable to the high rate condition. We synthesized the H.P. form of LiBH4 under ambient pressure by doping LiBH4 with the KI lattice by sintering. The formation of a KI - LiBH4 solid solution was confirmed both macroscopically and microscopically. The obtained sample was shown to be a pure Li+ conductor despite its small Li+ content. This conduction mechanism, where the light doping cation played a major role in ion conduction, was termed the “Parasitic Conduction Mechanism.” This mechanism made it possible to synthesize a new ion conductor and is expected to have enormous potential in the search for new battery materials.

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Complex Hydrides for Electrochemical Energy Storage

Unemoto

Matsuo

Orimo

2014

Adv Funct Materials

201

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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Lithium ion conduction in lithium borohydrides under high pressure

Cited by 18 publications

References 14 publications

Ionic conductivity in three crystalline phases of LiBH₄under pressure

Ionic conductivity in three crystalline phases of LiBH₄under pressure

Synthesis of rock-salt type lithium borohydride and its peculiar Li+ ion conduction properties

Complex Hydrides for Electrochemical Energy Storage

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Lithium ion conduction in lithium borohydrides under high pressure

Cited by 18 publications

References 14 publications

Ionic conductivity in three crystalline phases of LiBH4under pressure

Ionic conductivity in three crystalline phases of LiBH4under pressure

Synthesis of rock-salt type lithium borohydride and its peculiar Li+ ion conduction properties

Complex Hydrides for Electrochemical Energy Storage

Contact Info

Product

Resources

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Ionic conductivity in three crystalline phases of LiBH₄under pressure

Ionic conductivity in three crystalline phases of LiBH₄under pressure