Combined Effect of High Voltage and Large Li-ion Flux on Decomposition of Li6PS5Cl

High voltage has been considered the culprit causing electrolyte decomposition in all-solid-state lithium batteries. However, whether high voltage is the only decisive factor in sulfide electrolyte decomposition is an open question. Herein, we redefined the decomposition conditions of sulfide electrolytes under the combined effect of high voltage (≥ 5 V vs. Li⁺/Li) and large Li⁺ flux by recording the decomposition process of Li₆PS₅Cl via in-situ Raman spectroscopy during cyclic voltammetry measurement. The result shows that under the combined action of high voltage and large Li⁺ flux, PS₄^3- anions of Li₆PS₅Cl undergo much more severe deformation and decomposition than they do only under high voltage or large Li⁺ flux. At the same time, it also suggests that the much severer decomposition of Li₆PS₅Cl located near the surface of cathode particles than that in the bulk region of Li₆PS₅Cl may be a combination result of electrochemical/chemical reactions and high voltage/large Li⁺ flux. Furthermore, theThe effect of large Li⁺ flux on the irreversible decomposition of Li₆PS₅Cl supplements our understanding of the electrochemical stability of solid electrolytes. This work redifines the stability of sulfide electrolyte and gives directions to design high stability of both bulk and interface structure of sulfide electrolyes at high voltage and high current density.