Elucidating Ion Transport Phenomena in Sulfide/Polymer Composite Electrolytes for Practical Solid-State Batteries

Despite the enormous interest in inorganic/polymer composite solid-state electrolytes (CSEs) for solid-state batteries (SSBs), the underlying ion transport phenomena in CSEs have not yet been elucidated. Here, we address this issue by formulating a mechanistic understanding of bi-percolating ion channels formation and ion conduction across inorganic-polymer electrolyte interfaces in CSEs. A model CSE is composed of argyrodite-type Li(6)PS(5)Cl (LPSCl) and gel polymer electrolyte (GPE, including Li(+)-glyme complex as an ion-conducting medium). The percolation threshold of the LPSCl phase in the CSE strongly depends on the elasticity of the GPE phase. Additionally, manipulating the solvation/desolvation behavior of the Li(+)-glyme complex in the GPE facilitates ion conduction across the LPSCl-GPE interface. The resulting scalable CSE (area = 8 × 6 (cm × cm), thickness ~ 40 μm) can be assembled with a high-mass-loading LiNi(0.7)Co(0.15)Mn(0.15)O(2) cathode (areal-mass-loading = 39 mg cm(–2)) and a graphite anode (negative (N)/positive (P) capacity ratio = 1.1) in order to fabricate an SSB full cell with bi-cell configuration. Under this constrained cell condition, the SSB full cell exhibits high volumetric energy density (480 Wh L(cell)(−1)) and stable cyclability at 25 °C, far exceeding the values reported by previous CSE-based SSBs. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-023-01139-w.