Synthesis of Li6.4La3Zr1.4Ta0.6O12-Incorporated Composite Gel Electrolytes via Competitive Anion Anchoring for Dual-Interface Stabilization in Lithium Metal Batteries

The demand for high-energy-density and fast-charging solid-state lithium metal batteries (SSLMBs) often subjects practical devices to internal thermal loads, making high-temperature operation a common operational condition rather than an isolated scenario. To address the interfacial degradation and dendrite growth accelerated by such thermomechanical stresses, we developed a composite gel electrolyte (CGE) by incorporating an optimal concentration of active Li6.4La3Zr1.4Ta0.6O12 (LLZTO) into a fluoropolymer network. The abundant Lewis acidic sites on the LLZTO surfaces promote competitive solvation decoupling by interacting with anions, thereby modulating the primary solvation sheath of Li+. This localized modulation lowers the lithium-ion migration activation energy to 0.248 eV and facilitates a dual-interfacial passivation mechanism. Specifically, a rigid, inorganic-rich solid electrolyte interphase (SEI) forms to suppress morphological instability at the lithium anode, while an organic-dominated cathode electrolyte interphase (CEI) enhances the oxidative stability up to 4.3 V. As a result, symmetric cells demonstrate stable electrodeposition for over 450 h at 80 °C and 0.5 mA cm−2. Furthermore, NCM811/Li full cells utilizing this CGEs exhibit significantly improved thermal resilience and cycling stability.