Sodium batteries are considered as promising candidates for large-scale energy-storage systems owing to the abundant and low-cost sodium resources. However, many reported sodium batteries are based on conventional organic liquid electrolyte, which would lead to potential safety issues. Developing solid-state electrolyte (SSE) for sodium batteries is an effective way to solve such problems. Nevertheless, how to develop high-performance SSE and compatible interface for constructing solid-state sodium batteries is still challenging. In this review, we mainly focus on the development and recent advances of SSE (including all-solid-state and quasi-solid-state electrolyte) and interface engineering for sodium batteries. The structure-property correlations and design principles of different inorganic and organic SSE are discussed in depth. The comprehensive performance of SSE depends on the structural characteristics such as defects, crystallinity, and stability of bonds. The design principles mainly include increasing the density of mobile Na⁺ ions, reducing the energy barrier, immobilizing anions, adjusting the stability of bonds, adding specific buffer layers, and increasing interfacial contact area. Moreover, we discuss the interface between SSE and electrode because a suitable interface is the key prerequisite for high-performance solid-state sodium batteries. This review provides fundamental insights and future perspectives to design advanced SSE and concomitant interface for next-generation rechargeable solid-state sodium batteries.

由于钠资源丰富且成本低廉，钠电池被认为是大规模储能系统的有前途的候选者。然而，许多报道的钠电池基于常规的有机液体电解质，这将导致潜在的安全问题。开发用于钠电池的固态电解质（SSE）是解决此类问题的有效方法。然而，如何开发高性能的SSE和兼容的接口来构造固态钠电池仍然是一个挑战。在这篇综述中，我们主要关注SSE（包括全固态和准固态电解质）和钠电池接口工程的发展和最新进展。深入讨论了不同无机和有机SSE的结构性质相关性和设计原理。SSE的综合性能取决于缺陷，结晶度和键稳定性等结构特征。设计原理主要包括增加移动Na的密度⁺离子，减少能垒，固定阴离子，调节键的稳定性，添加特定的缓冲层并增加界面接触面积。此外，我们讨论了SSE和电极之间的接口，因为合适的接口是高性能固态钠电池的关键前提。这篇综述为设计下一代下一代可充电固态钠电池的高级SSE和随之而来的界面提供了基本见识和未来展望。