An alternative approach to the synthesis of NaB3H8 and Na2B12H12 for solid electrolyte applications

Moury, Romain; Gigante, Angelina; Hagemann, Hans‐Rudolf

doi:10.1016/j.ijhydene.2017.02.044

Cited by 36 publications

(39 citation statements)

References 30 publications

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“…As closo-Na 2 B 12 H 12 can also be synthesized cost-effectively from NaBH 4 , 25,26 our results show that hydroborate electrolytes can be made economically viable for all-solid-state batteries.…”

Section: Introductionmentioning

confidence: 75%

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

et al. 2020

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Closo-borates and carba-closo-borates recently emerged as a promising class of solid electrolytes for all-solid-state batteries, but are too expensive. Here we introduce NaB 11 H 14 nido-borates as a new building block for solid electrolytes that can be synthesized via a costeffective low-temperature method using cheap NaBH 4 as a chemical feedstock. We employ 2D nuclear magnetic resonance techniques to analyze the structure of this new building block. High ionic conductivity of up to 4 mS/cm at 20 C is achieved by combining nido-NaB 11 H 14 with closo-Na 2 B 12 H 12 into cubic unit cells. Importantly, Na 2 B 12 H 12 can also be synthesized costeffectively from NaBH 4. Crystal structures are solved and refined by synchrotron X-ray diffraction and density functional theory. Cyclic voltammetry reveals electrochemical stability from 0.15 to 2.6 V vs Na/Na +. Galvanostatic cycling in symmetrical cells with sodium metal electrodes shows only a small overpotential increase from 2 mV to 2.5 mV after 400 cycles at 50 A/cm 2. We also discuss how our results can be translated to render lithium solid electrolytes economically viable.

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Section: Introductionmentioning

confidence: 75%

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

et al. 2020

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“…Herein, we report a facile method for the synthesis of the heavier alkali metal salts of B 3 H 8 − , MB 3 H 8 (M=K, Rb, and Cs), which is based on directly reacting the respective alkali metals with THF⋅BH 3 in THF at room temperature. In the current method, no electron carriers, such as naphthalene or triphenylboron, or other reaction media, such as mercury, silica gel, or inert salts, were used, as done in previous works . The simplified synthetic method enables the convenient preparation of the heavier MB 3 H 8 alkali salts on large scale in very high yields.…”

Section: Figurementioning

confidence: 99%

Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB₃H₈ (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB₃H₈

Chen

Liu

et al. 2019

Angew Chem Int Ed

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A facile synthesis of heavy alkali metal octahydrotriborates (MB3H8; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH3, does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or inert salts as for previous procedures, and delivers the desired products at room temperature in very high yields. However, no reactions were observed when pure Li or Na was used. The reaction mechanisms for the heavy alkali metals were investigated both experimentally and computationally. The low sublimation energies of K, Rb, and Cs were found to be key for initiation of the reactions. The syntheses can be carried out at room temperature because all of the elementary reaction steps have low energy barriers, whereas reactions of LiBH4/NaBH4 with THF⋅BH3 have to be carried out under reflux. The high stability and solubility of KB3H8 were examined, and a crystal structure thereof was obtained for the first time.

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“…23,24 Na 4 (B 12 H 12 )(B 10 H 10 ) was prepared by a solution-based method. 41 An equimolar mixture of as- Super C65 was chosen as it has similar material specifications to Super P at a lower impurity level. For Na-ion conductors, a Li metal foil was replaced by a surface-scratched Na metal foil which was rolled out from a Na metal cube (99.9%, Sigma-Aldrich).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Oxidative Stability of Hydroborate-Based Solid-State Electrolytes

Asakura

Duchêne

Kühnel

et al. 2019

ACS Appl. Energy Mater.

107

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We report a robust methodology based on linear sweep voltammetry to determine experimentally the electrochemical oxidative stability of hydroborate-based solid-state electrolytes for all-solid-state batteries. To accelerate kinetics and improve the sensitivity to decomposition, we explore different solid-state electrolyte/carbon composites and employ a low scan rate of 10 μV s −1. Using LiBH 4 as a model system, we show that proper selection of the conductive carbon and its ratio in the composite are important for an accurate determination of the intrinsic oxidative stability. This method is robust with respect to the choice of the current collector material and the ionic conductivity of the solid-state

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An alternative approach to the synthesis of NaB3H8 and Na2B12H12 for solid electrolyte applications

Cited by 36 publications

References 30 publications

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB₃H₈ (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB₃H₈

Electrochemical Oxidative Stability of Hydroborate-Based Solid-State Electrolytes

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An alternative approach to the synthesis of NaB3H8 and Na2B12H12 for solid electrolyte applications

Cited by 36 publications

References 30 publications

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

Nido-Borate/Closo-Borate Mixed-Anion Electrolytes for All-Solid-State Batteries

Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB3H8 (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB3H8

Electrochemical Oxidative Stability of Hydroborate-Based Solid-State Electrolytes

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Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB₃H₈ (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB₃H₈