Dong Zhi Liang, Gan Yi, Martins Vinicius, Wang Xuchun, Fu Bolin, Jin Enzhong, Gao Yingjie, Hu Yang, Lin Xiaoting, Yuan Yi, Turner Colin, Pang Xin, Abdolvand Hamidreza, Huang Yining, Sham Tsun-Kong, Zhao Yang
Department of Mechanical and Materials Engineering, University of Western Ontario, London, ON, N6A 5B9, Canada.
Department of Chemistry, University of Western Ontario, London, ON, N6G 2V4, Canada.
Adv Mater. 2025 Jul;37(30):e2503107. doi: 10.1002/adma.202503107. Epub 2025 May 19.
Solid-state Na batteries (SSNBs) are among the most promising next-generation energy storage devices due to their high energy density, enhanced safety, and cost-efficiency. Achieving high-performance SSNBs depends on the development of solid-state electrolytes (SSEs) with excellent ionic conductivity, wide electrochemical windows, and robust mechanical properties. Sulfide and halide-based Na SSEs have been widely studied in recent years with their respective strengths and limitations. Herein for the first time, a new family of Na-Zr-S-Cl sulfide-chloride Na SSEs with tailored anion compositions is explored. A high ionic conductivity of 4.89 × 10 S cm is realized with a Cl-rich structure, attributed to the unique chloride bridging structure and low Na-ion migration barrier. Furthermore, by tuning the ratio between sulfur and chloride anions, two different unique structures are obtained with different surface morphology, thermal stability, mechanical properties, and electrochemical stability. The Cl-deficient structure of NaS-1.3ZrCl SSEs demonstrates excellent stability for solid-state Na-ion batteries, maintaining a high reversible capacity of over 90 mAh g after 600 cycles at 0.1 C. This study offers insights into the design of new Na SSEs, advancing the development of safer and high-performance SSNBs.
固态钠电池（SSNBs）因其高能量密度、更高的安全性和成本效益，成为最具前景的下一代储能设备之一。实现高性能的固态钠电池取决于开发具有优异离子导电性、宽电化学窗口和强大机械性能的固态电解质（SSEs）。近年来，基于硫化物和卤化物的钠固态电解质因其各自的优缺点而受到广泛研究。在此，首次探索了一种具有定制阴离子组成的新型Na-Zr-S-Cl硫化物-氯化物钠固态电解质。通过富含氯的结构实现了4.89×10 S cm的高离子电导率，这归因于独特的氯化物桥接结构和低钠离子迁移势垒。此外，通过调整硫和氯阴离子之间的比例，获得了两种具有不同表面形态、热稳定性、机械性能和电化学稳定性的独特结构。NaS-1.3ZrCl固态电解质的贫氯结构对固态钠离子电池表现出优异的稳定性，在0.1 C下循环600次后仍保持超过90 mAh g的高可逆容量。这项研究为新型钠固态电解质的设计提供了见解，推动了更安全、高性能固态钠电池的发展。
