All-solid-state lithium batteries (ASSLBs) employ high-capacity lithium (Li) metal as the anode and exhibit a higher energy density than that of conventional Li-ion batteries. However, the problems arose from the Li dendrites induce severely parasitic reaction between Li and electrolytes, leading to low coulombic efficiency (CE) and poor cyclic stability. Herein, a poly(vinylidene-co-hexafluoropropylene)/lithium nitrate (PVDF-HFP/LiNO₃, marked as PFH/LN) artificial layer is employed to modified Li and achieve high CE ASSLBs with polyethylene oxide-Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (PEO-LLZTO) electrolyte. LN serves as a functionalized additive to facilitate the formation of a robust solid electrolyte interface (SEI), efficiently suppressing the formation of Li dendrites. Additionally, LN as a “binder” effectively links PFH with Li, providing good contact. PFH possesses high mechanical strength and moderate flexibility, which can not only physically inhibit the growth of Li dendrites, but also maintain the structural integrity of artificial layer over long-term cycles. Finally, Li/Li cells with such artificial layer demonstrate ultralong cycle life of 1800 and 1000 h under 0.2 and 0.4 mA cm⁻¹, respectively. Furtherly, high CE can be achieved when applied in both LiFePO₄ full cells and Li-Cu half cells. This work offers a facile and efficient strategy to greatly promote CE in PEO-based ASSLBs.

全固态锂电池 (ASSLBs) 采用高容量锂 (Li) 金属作为阳极，比传统锂离子电池具有更高的能量密度。然而，锂枝晶引发的问题会导致锂与电解质之间发生严重的寄生反应，导致库仑效率（CE）低和循环稳定性差。在此，采用聚（亚乙烯基-co-六氟丙烯）/硝酸锂（PVDF-HFP/LiNO ₃，标记为PFH/LN）人工层对Li进行改性，并通过聚环氧乙烷-Li _6.4 La ₃ Zr _1.4实现高CE ASSLBs Ta _0.6 O ₁₂(PEO-LLZTO) 电解液。LN 作为一种功能化添加剂，可促进坚固的固体电解质界面 (SEI) 的形成，有效抑制锂枝晶的形成。此外，LN 作为“粘合剂”有效地将 PFH 与 Li 连接起来，提供良好的接触。PFH具有较高的机械强度和适度的柔韧性，不仅可以在物理上抑制锂枝晶的生长，而且可以在长期循环中保持人工层的结构完整性。^{最后，具有这种人工层的Li/Li电池在0.2和0.4 mA cm -1}下分别表现出1800和1000 h的超长循环寿命。此外，当应用于 LiFePO _{4时，可以实现高 CE}全电池和 Li-Cu 半电池。这项工作提供了一种简便有效的策略，以极大地促进基于 PEO 的 ASSLB 中的 CE。