Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal–Sulfur and Selenium Batteries
Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal–sulfur batteries remain challenged by several factors, including polysulfides’ (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li–S and the emerging Na–S and K–S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li–S are relatively mature, less progress has been made with Na–S and K–S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal–selenium and the metal–selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal–sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li–S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure–battery electrochemical performance interrelations. Finally, throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.