A Critical Review for an Accurate Electrochemical Stability Window Measurement of Solid Polymer and Composite Electrolytes

All-solid-state lithium batteries (ASSLB) are very promising for the future development of next generation lithium battery systems due to their increased energy density and improved safety. ASSLB employing Solid Polymer Electrolytes (SPE) and Solid Composite Electrolytes (SCE) in particular have attracted significant attention. Among the several expected requirements for a battery system (high ionic conductivity, safety, mechanical stability), increasing the energy density and the cycle life relies on the electrochemical stability window of the SPE or SCE. Most published works target the importance of ionic conductivity (undoubtedly a crucial parameter) and often identify the Electrochemical Stability Window (ESW) of the electrolyte as a secondary parameter. In this review, we first present a summary of recent publications on SPE and SCE with a particular focus on the analysis of their electrochemical stability. The goal of the second part is to propose a review of optimized and improved electrochemical methods, leading to a better understanding and a better evaluation of the ESW of the SPE and the SCE which is, once again, a critical parameter for high stability and high performance ASSLB applications.