All solid-state sodium metal batteries (ASSSMBs) have emerged as promising candidates to be a key technology in large-scale energy storage systems relative to mature Li/Na-ion batteries using flammable liquid electrolytes, owing to their abundant sodium resources, robust safety performance, desirable energy density, and favorable reliability and stability. A series of solid-state electrolytes (SSEs), regarded as an essential component of ASSSMBs, have been extensively developed in recent years. Among them, the Na superionic conductor (NASICON)-structure Na_1+xZr₂Si_xP_3−xO₁₂ (0 ≤ x ≤ 3, defined as NZSP) materials have attracted overwhelming attention as the most appropriate SSEs for the next-generation high energy density ASSSMBs. Herein, this review seeks to provide a comprehensive and in-depth understanding of NZSP SSEs, by first investigating their fundamentals, including composition, crystal structure, Na⁺-ion conduction mechanism, synthetic methods, and the key challenges associated with the NZSP-based ASSSMBs. Subsequently, comprehensive constructive modification strategies are proposed to optimize integrated NZSP SSE-based ASSSMBs. Finally, informed and strategic perspectives from various angles are summarized, providing potential guidance and possible avenues for further research aimed at achieving exceptional NZSP SSE-based ASSSMBs for practical applications.

中文翻译：

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全面了解先进钠金属电池中 Na1+xZr2SixP3−xO12 固态电解质：批判性综述


相对于使用易燃液体电解质的成熟 Li/Na 离子电池，全固态钠金属电池 （ASSSMB） 因其丰富的钠资源、稳健的安全性能、理想的能量密度以及良好的可靠性和稳定性，已成为相对于使用易燃液体电解质的成熟 Li/Na 离子电池的大规模储能系统的关键技术。近年来，一系列固态电解质 （SSE） 被视为 ASSSMB 的重要组成部分，已得到广泛开发。其中，Na 超离子导体 （NASICON） 结构的 Na_1+xZr₂Si_xP_3−xO₁₂ （0 ≤ x ≤ 3，定义为 NZSP）材料作为最适合下一代高能量密度 ASSSMB 的 SSE 而引起了压倒性的关注。在此，本文旨在通过首先研究其基本原理，包括组成、晶体结构、Na ⁺ 离子传导机制、合成方法以及与基于 NZSP 的 ASSSMB 相关的关键挑战，对 NZSP SSE 提供全面和深入的了解。随后，提出了全面的建设性修饰策略来优化基于 NZSP SSE 的综合 ASSSMBs。最后，从各个角度总结了明智的战略观点，为进一步研究提供了潜在的指导和可能的途径，旨在实现基于 NZSP SSE 的 ASSSMB 用于实际应用的卓越表现。