XAS investigations on nanocrystalline Mg2FeH6 used as a negative electrode of Li-ion batteries

Zhang, Junxian; Zaïdi, Warda; Paul‐Boncour, V.; Provost, Karine; Michalowicz, Alain; Cuevas, Fermín; Latroche, M.; Belin, Stéphanie; Bonnet, Jean-Pierre; Aymard, L.

doi:10.1039/c3ta01482g

Cited by 39 publications

(46 citation statements)

References 40 publications

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“…[13][14][15] A percolation of lithium sites in its crystal lattice enables the formation of lithium ion conduction paths. These result in high lithium ionic conductivity that exceeds log(σ/S cm −1 ) = −3 in the HT phase of LiBH 4 . 5) Since our discovery of the fast lithium ionic conduction in the HT phase of LiBH 4 , we explored complex hydrides that exhibit high ionic conductivities with the hope of incorporating them into the solid-state batteries.…”

Section: Introductionmentioning

confidence: 99%

“…These result in high lithium ionic conductivity that exceeds log(σ/S cm −1 ) = −3 in the HT phase of LiBH 4 . 5) Since our discovery of the fast lithium ionic conduction in the HT phase of LiBH 4 , we explored complex hydrides that exhibit high ionic conductivities with the hope of incorporating them into the solid-state batteries. As a result, we found a variety of the complex hydride-based fast lithium and sodium ionic conductors with various crystal structures and compositions.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7] Owing to their high hydrogen densities, we have devoted our signi cant research and development efforts to investigate complex hydrides as potential hydrogen storage materials. LiBH 4 , a typical complex hydride, experiences a phase transition from an orthorhombic structure (low-temperature phase, LT phase) to a hexagonal one (high-temperature phase, HT phase) at elevated temperatures and around 390 K. 8) Following a further increase in temperature, this material releases hydrogen according to the following pyrolysis reaction: 2,[9][10][11][12] LiBH 4 → (1/12)Li 2 B 12 H 12 + (5/6)LiH + (13/12)H 2 → LiH + B + (3/2)H 2 (1) This pyrolysis enables the release of hydrogen from LiBH 4 with a gravimetric hydrogen density of 13.8 mass%. In the HT phase of LiBH 4 , a nearly free rotation of the complex anion [BH 4 ] − occurs.…”

Section: Introductionmentioning

confidence: 99%

“…Complex hydrides possess energy-storage-and conversion-related functions including hydrogen storage, 1,2) lithium storage, 3,4) and fast ionic conductions. [5][6][7] Owing to their high hydrogen densities, we have devoted our signi cant research and development efforts to investigate complex hydrides as potential hydrogen storage materials.…”

Section: Introductionmentioning

confidence: 99%

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Bulk-Type All-Solid-State Lithium Batteries Using Complex Hydrides Containing Cluster-Anions

et al. 2016

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In this study, we incorporated fast lithium ion conducting complex hydrides containing cluster anions, namely icosahedral dodecahydro-closo-dodecaborate anions, [B 12 H 12 ] 2− , into a bulk-type all-solid-state battery. Li 2 B 12 H 12 , TiS 2 and Li were used as an electrolyte, a positive electrode active material and a negative electrolyte, respectively, for a battery assembly to investigate its battery performance. Bulk-type battery contains high quantity of electrode active materials in the electrode layer, and thereby the enhanced energy-storage density is expected. In addition, non ammable solid-state electrolyte would ensure the safety, which is currently problematic for the conventional lithium rechargeable battery that uses organic liquid electrolyte. Li 2 B 12 H 12 has a high lithium ionic conductivity of log(σ/S cm −1 ) = −2.6 at 393 K. It exhibits a relatively higher conductivity of log(σ/S cm −1 ) = −3.5 at reduced temperatures such as 333 K. These high lithium ionic conductivity allows for the repeated operation of the bulk-type all-solid-state TiS 2 /Li battery for at least 10 cycles at not only 393 K but also 333 K with the discharge capacities higher than 190 mAh g −1 . Li 2 B 12 H 12 exhibits higher oxidative stability. Thus, our battery realized high coulombic ef ciencies of over 92% during the battery operation. This information will be bene cial for the further development of novel complex hydride-based electrolyte to have high-performance bulk-type all-solid-state batteries.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Bulk-Type All-Solid-State Lithium Batteries Using Complex Hydrides Containing Cluster-Anions

et al. 2016

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“…The ultimate dream is a cathode reaction of Li with O 2 /H 2 O (lithium-air batteries), with energy densities close to that of gasoline theoretically possible, but for which achieving full reversibility is a major issue to solve [7]. On the anode site, using conversion metal hydrides could lead to higher gravimetric densities [8][9][10][11][12][13][14]. Also, metallic lithium anodes have theoretical energy densities even ten times higher than current carbon-intercalation anodes.…”

Section: Introduction: the Relevance Of Solid-state Electrolytesmentioning

confidence: 99%

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

et al. 2016

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Complex Hydrides for Electrochemical Energy Storage

Unemoto

Matsuo

Orimo

2014

Adv Funct Materials

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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XAS investigations on nanocrystalline Mg2FeH6 used as a negative electrode of Li-ion batteries

Cited by 39 publications

References 40 publications

Bulk-Type All-Solid-State Lithium Batteries Using Complex Hydrides Containing Cluster-Anions

Bulk-Type All-Solid-State Lithium Batteries Using Complex Hydrides Containing Cluster-Anions

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

Complex Hydrides for Electrochemical Energy Storage

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