Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations

• DOI: 10.1021/acs.chemmater.7b04096
• Publication Date: 2017-12-13T00:31:21Z
• Authors: Hanmei Tang; Zhi Deng; Zhuonan Lin; Zhenbin Wang; Iek-Heng Chu; Chi Chen; Zhuoying Zhu; Chen Zheng; Shyue Ping Ong
• Keywords: Fast ion conductor; Thiophosphate; Electrochemical window

We present an exposition of first-principles approaches to elucidating interfacial reactions in all-solid-state sodium-ion batteries. will demonstrate how thermodynamic approximations based on assumptions fast alkali diffusion and multispecies equilibrium can be used effectively screen combinations Na-ion electrodes, solid electrolytes, buffer oxides for electrochemical chemical compatibility. find that exchange reactions, especially between simple thiophosphate groups form PO43–, are the main cause large driving forces cathode/solid electrolyte reactions. A high reactivity with volume changes is also predicted at Na anode/solid interface, while Na2Ti3O7 anode much more stable against a broad range electrolytes. identify several promising binary oxides, Sc2O3, SiO2, TiO2, ZrO2, HfO2, similarly or chemically compatible most electrodes electrolytes than commonly Al2O3 is. Finally, we show ab initio molecular dynamics simulations NaCoO2/Na3PS4 interface model predict formation SO42–-containing compounds Na3P kinetically favored over PO43–-containing compounds, contrast predictions models. This work provides useful insights into materials selection strategies enabling electrode/solid interfaces, critical bottleneck designing batteries, outlines testable future experimental validation.