Using all-solid-state electrolytes to replace flammable liquid electrolytes can effectively improve the energy density and safety of lithium metal batteries. However, low room temperature ionic conductivity and small Li transference number of these electrolytes have caused the increase in the growth of lithium dendrites and battery internal resistance. In this work, a novel polyvinylidene fluoride (PVDF)-poly(ethylene oxide) (PEO) composite lithium ions conductor nanofiber membrane with core-shell structure and the low-cost Gd-doped CeO₂ (GDC) ceramic nanowires with oxygen vacancies are simultaneously introduced into the polymer electrolyte to obtain composite electrolytes. The core layer PVDF and the shell layer PEO in the composite nanofibers can enhance the mechanical strength and provide a three-dimensional (3D) ordered transmission channel for lithium ions, respectively. Moreover, the GDC nanowires can further provide long-range and orderly transport channels for Li-ions. The optimized composite electrolyte has a high ionic conductivity of 2.3 × 10⁻⁴ S cm⁻¹ at 30 °C, a fast Li⁺ transference number of 0.64 and a high mechanical strength up to 10.8 MPa. In addition, the composite electrolyte shows excellent compatibility with lithium metal anode, LiFePO₄ cathode and high-voltage LiNi_0.8Mn_0.1Co_0.1O₂ (NMC) cathode. The assembled lithium symmetric battery can be cycled stably under large current densities at different capacities of 0.1, 0.2, and 0.4 mAh cm⁻², and the Coulombic efficiency of the Li/NMC battery can always be maintained at around 99.2% during 250 cycles at 0.5 C. This work demonstrates that the novel electrolyte has excellent application prospects in the next generation all-solid-state lithium metal cells.

使用全固态电解质替代易燃液体电解质，可以有效提高锂金属电池的能量密度和安全性。然而，这些电解质的室温离子电导率低和锂迁移数小，导致锂枝晶生长和电池内阻增加。在这项工作中，一种新型的聚偏二氟乙烯（PVDF）-聚（环氧乙烷）（PEO）复合锂离子导体纳米纤维膜具有核壳结构和低成本的掺钆CeO ₂将具有氧空位的 (GDC) 陶瓷纳米线同时引入聚合物电解质中以获得复合电解质。复合纳米纤维中的芯层 PVDF 和壳层 PEO 可以增强机械强度，并分别为锂离子提供三维（3D）有序传输通道。此外，GDC纳米线可以进一步为锂离子提供长距离有序的传输通道。优化后的复合电解质在 30°C 下具有 2.3 × 10 ^-4 S cm ^-1的高离子电导率、0.64的快速 Li ⁺迁移数和高达 10.8 MPa 的高机械强度。此外，该复合电解质与锂金属负极 LiFePO ₄表现出优异的相容性阴极和高压 LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC) 阴极。组装的锂对称电池可以在0.1、0.2和0.4 mAh cm ^-2不同容量的大电流密度下稳定循环，并且Li/NMC电池在250次循环期间的库仑效率始终保持在99.2%左右。 0.5 C。这项工作表明，该新型电解质在下一代全固态锂金属电池中具有良好的应用前景。