Microstructural analyses of all-solid-state Li–S batteries using LiBH₄-based solid electrolyte for prolonged cycle performance

Complex hydride materials have been widely investigated as potential solid electrolytes because they have good compatibility with the lithium metal anodes used in all-solid-state batteries. However, the development of all-solid-state batteries utilizing complex hydrides has been difficult as these cells tend to have short cycle lives. This study investigated the capacity fading mechanism of all-solid-state lithium–sulfur (Li–S) batteries using Li₄(BH₄)₃I solid electrolytes by analyzing the cathode microstructure. Cross-sectional scanning electron microscopy observations after 100 discharge–charge cycles revealed crack formation in the Li₄(BH₄)₃I electrolyte and an increased cathode thickness. Raman spectroscopy indicated that decomposition of the Li₄(BH₄)₃I solid electrolyte occurred at a constant rate during the cycling tests. To combat these effects, the cycle life of Li–S batteries was improved by increasing the amount of solid electrolyte in the cathode.