As a result of the increasing need for highly efficient energy storage systems, Li-solid-state batteries emerge as the next-generation energy storage devices to satisfy high energy density and safety requirements. Particularly, solid polymer-based electrolytes have attracted attention as a promising alternative due to their high mechanical flexibility, suitably interfacial compatibility with electrodes, and easy processability, procuring safe, miniaturized and flexible storage devices. Despite the progress made, it is still a challenge to develop low-cost, industrially scalable solid-state batteries with high energy density and stable cycling life. In this context, a review and discussion of recent approaches to polymeric-based electrolyte design for high-performance all-solid-state Li-battery applications are presented. Herein, the latest different design approaches are shown considering: additives incorporation into the polymer matrix, structural modification of the polymer matrix, and lithium salt molecular design. Furthermore, for understanding structure-conduction property relationships in polymer-based electrolytes, the fundamental bearings related to ion transport mechanism, critical parameters involved in the conduction process, and physicochemical aspects related to solid electrolytes performance and stability were analysed. Likewise, significant attention is paid to electrode/ electrolyte interface behaviour and their significance in advanced solid electrolyte designing.

由于对高效储能系统的需求日益增加，锂固态电池作为下一代储能设备应运而生，以满足高能量密度和安全性要求。特别是，基于固体聚合物的电解质因其高机械柔韧性、与电极适当的界面相容性、易于加工、获得安全、小型化和灵活的存储设备而作为一种有前途的替代品引起了人们的关注。尽管取得了进展，但开发具有高能量密度和稳定循环寿命的低成本、工业上可扩展的固态电池仍然是一个挑战。在此背景下，对用于高性能全固态锂电池应用的聚合物基电解质设计的最新方法进行了回顾和讨论。在此处，展示了最新的不同设计方法，考虑到：将添加剂掺入聚合物基体、聚合物基体的结构改性和锂盐分子设计。此外，为了了解聚合物基电解质中的结构-传导特性关系，分析了与离子传输机制相关的基本轴承、传导过程中涉及的关键参数以及与固体电解质性能和稳定性相关的物理化学方面。同样，电极/电解质界面行为及其在先进固体电解质设计中的意义也受到了极大的关注。为了了解聚合物基电解质中的结构-传导特性关系，分析了与离子传输机制相关的基本轴承、传导过程中涉及的关键参数以及与固体电解质性能和稳定性相关的物理化学方面。同样，电极/电解质界面行为及其在先进固体电解质设计中的意义也受到了极大的关注。为了了解聚合物基电解质中的结构-传导特性关系，分析了与离子传输机制相关的基本轴承、传导过程中涉及的关键参数以及与固体电解质性能和稳定性相关的物理化学方面。同样，电极/电解质界面行为及其在先进固体电解质设计中的意义也受到了极大的关注。