American Chemical Society
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Investigation of Structure, Ionic Conductivity, and Electrochemical Stability of Halogen Substitution in Solid-State Ion Conductor Li3YBrxCl6–x

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journal contribution
posted on 2022-12-16, 13:43 authored by Eveline van der Maas, Wenxuan Zhao, Zhu Cheng, Theodosios Famprikis, Michel Thijs, Steven R. Parnell, Swapna Ganapathy, Marnix Wagemaker
Li3YX6 (X = Cl, Br) materials are Li-ion conductors that can be used as solid electrolytes in all solid-state batteries. Solid electrolytes ideally have high ionic conductivity and (electro)chemical compatibility with the electrodes. It was proven that introducing Br to Li3YCl6 increases ionic conductivity but, according to thermodynamic calculations, should also reduce oxidative stability. In this paper, the trade-off between ionic conductivity and electrochemical stability in Li3YBrxCl6–x halogen-substituted compounds is investigated. The compositions of Li3YBr1.5Cl4.5 and Li3YBr4.5Cl1.5 are reported for the first time, along with a consistent analysis of the whole Li3YBrxCl6–x (x = 0–6) tie-line. The results show that, while Br-rich materials are more conductive (5.36 × 10–3 S/cm at 30 °C for x = 4.5), the oxidative stability is lower (∼3 V compared to ∼3.5 V). Small Br content (x = 1.5) does not affect oxidative stability but substantially increases ionic conductivity compared to pristine Li3YCl6 (2.1 compared to 0.049 × 10–3 S/cm at 30 °C). This work highlights that optimization of substitutions in the anion framework provide prolific and rational avenues for tailoring the properties of solid electrolytes.