Issue 46, 2022

Fast divalent conduction in MB12H12·12H2O (M = Zn, Mg) complex hydrides: effects of rapid crystal water exchange and application for solid-state electrolytes

Abstract

This work investigates the divalent conduction of Zn2+ and Mg2+ in hydrated closo-type complex hydrides MB12H12·nH2O (M = Zn, Mg) and the effects of crystal water exchange in the structure for enhancing divalent ionic conduction. MB12H12·nH2O (M = Zn, Mg), which exhibited different hydrous phases, was synthesised as a single phase and characterised using X-ray diffraction and Raman spectroscopy for determining the number of crystal water molecules and the cationic water coordination environment. Among the anhydrous and hydrated MB12H12·nH2O (n = 0–12 and M = Zn, Mg), ZnB12H12·12H2O and MgB12H12·12H2O exhibited exceptional ionic conductivities of 3.8 × 10−5 and 6.1 × 10−5 S cm−1 at 50 °C, respectively, thereby being of greater significance than less-hydrated MB12H12·nH2O (n ≤ 6), and a few of the highest solid-state Zn2+ and Mg2+ conductivities reported so far. 1H, 11B, and 67Zn NMR measurements show narrow peaks indicating rapid crystal water exchange, fast [B12H12]2− anion rotation, and rapid Zn2+ isotropic motion in ZnB12H12·12H2O. Electrochemical cells fabricated using the ZnB12H12·12H2O solid electrolyte exhibited reversible Zn2+ migration through the material, indicating that ZnB12H12·12H2O shows favourable potential for application as a Zn2+ conductor in all-solid-state Zn batteries.

Graphical abstract: Fast divalent conduction in MB12H12·12H2O (M = Zn, Mg) complex hydrides: effects of rapid crystal water exchange and application for solid-state electrolytes

Supplementary files

Article information

Article type
Paper
Submitted
31 Jul 2022
Accepted
02 Nov 2022
First published
18 Nov 2022

J. Mater. Chem. A, 2022,10, 24877-24887

Fast divalent conduction in MB12H12·12H2O (M = Zn, Mg) complex hydrides: effects of rapid crystal water exchange and application for solid-state electrolytes

K. Kisu, A. Dorai, S. Kim, R. Hamada, A. Kumatani, Y. Horiguchi, R. Sato, K. Sau, S. Takagi and S. Orimo, J. Mater. Chem. A, 2022, 10, 24877 DOI: 10.1039/D2TA06060D

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