Lithium metal batteries based on solid electrolytes are considered as promising candidates with high energy density and safety. However, the weak solid-solid contact between electrolyte and electrode can easily lead to interface instability and lithium ions discontinuous migration, which seriously reduces the electrochemical performance of the battery. Herein, we construct a soft gel interfacial layer to improve the stability of the solid-solid interface between electrolyte and electrode by means of polyester-based monomers and imidazole-based ionic liquids. Based on this, garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) particles as inorganic ceramic filler were introduced in the layer to obtain composite electrolytes with high ionic conductivity (up to 1.1 × 10⁻³ S/cm at 25 ℃). As a result, the assembled lithium symmetric battery of Li|THCE-15%LLZTO|Li suggests excellent cycling stability with 700 h at 0.1 mA/cm² at 50 ℃, and the lithium metal batteries of LFP|THCE-15%LLZTO|Li delivers high initial discharge capacity of 128.2 mA ·h/g with capacity retain of 75.48% after 150 cycles at 2 C. This work paves a new route to build safe and stable lithium metal batteries with synergistic introduction of composite electrolytes between electrolyte and electrode using soft gel interfacial layer and inorganic filler.

Due to the high reactivity between the lithium metal and traditional organic liquid electrolyte, the reaction of lithium metal electrode is usually uneven and there are also unexpected side reactions. Therefore, construction of a stable solid electrolyte interface (SEI) is highly essential to improve the performance of lithium metal anode. Herein, a sandwich-like gel polymer electrolyte (GPE) is accurately prepared by in-situ polymerization of Polyacrylonitrile (PAN) nanofiber membrane with trihydroxymethylpropyl trimethylacrylate (TMPTMA) and 1, 6-hexanediol diacrylate (HDDA). The resulting GPE with a tightly cross-linked gel skeleton exhibits high ionic conductivity and electrochemical window of 5.6 V versus Li/Li⁺. In particular, the pretreatment of Li metal anode can improve the interfacial wettability, and the synergy of the chemically pretreated Li metal anode surface and the GPE can electrochemically in situ generate SEI with compositionally stable and fluorine-rich inorganic components. Owing to these unique advantages, the interfacial compatibility between the GPE and lithium metal is greatly improved. Meanwhile, the formed SEI can inhibit the formation of lithium dendrites, and decomposition of GPE would be alleviated. The assembled Li-FEC|GPE|LiFePO₄ full cell shows a high initial discharge capacity of 157.1 mA h g⁻¹, and maintains a capacity retention of 92.3% after 100 cycles at 0.2C.