Solid polymer electrolytes (SPEs) are regarded as one of the most promising substitutes for liquid electrolytes to construct highly safe electrochemical energy storage. While liquid plasticizers are frequently employed in SPEs to enhance ionic conductivity, it is inevitably accompanied by a deficiency in safety. Herein, we report plasticizer-free composite block copolymer electrolytes (BCEs) with conductive nanodomains for ultralong lifespan all-solid-state Li-metal batteries (ASSLBs). The composite BCEs with poly(ether-block-amide) (Pebax) block copolymer as a conductive framework and polyethylene glycol dimethyl ether (PEGDE) as a regulator, can connect and manipulate the highly conductive nanodomains. Compared with homopolymer poly(ethylene oxide) (PEO), the conductive nanodomains in composite BCEs with tunable size can manipulate the Li⁺ transport channel, effectively enhancing the Li⁺ conductivity and homogenizing the Li⁺ deposition. In addition, the thin and dense hybrid solid electrolyte interface (SEI) layer, as well as the potent mechanical strength of composite BCEs, can synergistically suppress the dendrite growth. Therefore, the all-solid-state LiFePO₄/Li cells achieve impressive electrochemical performance with a tiny capacity reduction of 0.0127% per cycle for more than 1350 cycles at 0.5 C. This work aims to give impetus to the development of practical ASSLBs which meet the demands for high safety, long lifespan, and mass production.

固体聚合物电解质（SPEs）被认为是最有前途的液体电解质替代品之一，可用于构建高度安全的电化学储能。虽然液体增塑剂经常用于 SPE 以提高离子电导率，但不可避免地伴随着安全性不足。在此，我们报告了具有导电纳米域的无增塑剂复合嵌段共聚物电解质（BCEs），用于超长寿命全固态锂金属电池（ASSLBs）。以聚（醚-嵌段-酰胺）（Pebax）嵌段共聚物为导电框架，聚乙二醇二甲醚（PEGDE）为调节剂的复合BCE可以连接和操纵高导电纳米域。与均聚物聚（环氧乙烷）（PEO）相比，具有可调尺寸的复合 BCE 中的导电纳米域可以控制 Li⁺传输通道，有效提高 Li ⁺电导率，使 Li ⁺沉积均匀化。此外，薄而致密的混合固体电解质界面 (SEI) 层，以及复合 BCE 的强大机械强度，可以协同抑制枝晶生长。因此，全固态 LiFePO ₄ /Li 电池实现了令人印象深刻的电化学性能，在 0.5 C 下循环超过 1350 次后，每个循环的容量降低了 0.0127%  。这项工作旨在推动开发符合要求的实用 ASSLBs高安全性、长寿命、大批量生产的需求。