Before the debut of lithium-ion batteries (LIBs) in the commodity market, solid-state lithium metal batteries (SSLMBs) were considered promising high-energy electrochemical energy storage systems before being almost abandoned in the late 1980s because of safety concerns. However, after three decades of development, LIB technologies are now approaching their energy content and safety limits imposed by the rocking chair chemistry. These aspects are prompting the revival of research activities in SSLMB technologies at both academic and industrial levels. In this perspective article, we present a personal reflection on solid polymer electrolytes (SPEs), spanning from early development to their implementation in SSLMBs, highlighting key milestones. In particular, we discuss the SPEs’ characteristics taking into account the concept of coupled and decoupled SPEs proposed by C. Austen Angell in the early 1990s. Possible remedies to improve the physicochemical and electrochemical properties of SPEs are also examined. With this article, we also aim to highlight the missing blocks in building ideal SSLMBs and stimulate research towards innovative electrolyte materials for future rechargeable high-energy batteries.

Rechargeable batteries are becoming increasingly important for our daily life due to their strong capability of efficiently storing electric energy under chemical form. The replacement of conventional liquid electrolytes with polymer electrolytes (PEs) has been deemed as one of the most viable solutions towards safer and higher energy density electrochemical energy storage systems which are coveted for e-mobility applications (e.g., electric vehicles, EVs). In recent years, the introduction of inorganic materials into PEs has captured escalating interest, aiming at harmonizing advantages from both organic and inorganic phases. In this review, we present the progress and recent advances in PEs containing nano-sized inorganic materials, with due attention paid to the role of inorganic phases on the physical and chemical properties of the electrolytes. The paradigm shift from composite polymer electrolytes (CPEs, obtained by physical blending) to hybrid polymer electrolytes (HPEs, obtained by chemical grafting) is highlighted and the possible improvement and future directions in CPEs and HPEs are discussed.