The Detrimental Effects of Carbon Additives in Li₁₀GeP₂S₁₂-Based Solid-State Batteries

All-solid-state batteries (SSBs) have recently attracted much attention due to their potential application in electric vehicles. One key issue that is central to improve the function of SSBs is to gain a better understanding of the interfaces between the material components toward enhancing the electrochemical performance. In this work, the interfacial properties of a carbon-containing cathode composite, employing Li₁₀GeP₂S₁₂ as the solid electrolyte, are investigated. A large interfacial charge-transfer resistance builds up upon the inclusion of carbon in the composite, which is detrimental to the resulting cycle life. Analysis by X-ray photoelectron spectroscopy reveals that carbon facilitates faster electrochemical decomposition of the thiophosphate solid electrolyte at the cathode/solid electrolyte interface-by transferring the low chemical potential of lithium in the charged state deeper into the solid electrolyte and extending the decomposition region. The occurring accumulation of highly oxidized sulfur species at the interface is likely responsible for the large interfacial resistances and aggravated capacity fading observed.