Lin Xiaoting, Zhao Yang, Wang Changhong, Luo Jing, Fu Jiamin, Xiao Biwei, Gao Yingjie, Li Weihan, Zhang Shumin, Xu Jiabin, Yang Feipeng, Hao Xiaoge, Duan Hui, Sun Yipeng, Guo Jinghua, Huang Yining, Sun Xueliang
Department of Mechanical and Materials Engineering, University of Western Ontario, 1151 Richmond St, London, Ontario, N6A 3K7, Canada.
Eastern Institute for Advanced Study, Eastern Institute of Technology, Ningbo, Zhejiang, 315200, P. R. China.
Angew Chem Int Ed Engl. 2024 Jan 8;63(2):e202314181. doi: 10.1002/anie.202314181. Epub 2023 Dec 11.
Glassy Na-ion solid-state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state-of-the-art GNSSEs at room temperature lessens their promise in the development of all-solid-state Na-ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na O -TaCl (NTOC), based on dual-anion sublattice of oxychlorides. The unique local structures with abundant bridging and non-bridging oxygen atoms contributes to a highly disordered Na-ion distribution as well as low Na migration barrier within NTOC, enabling an ultrahigh ionic conductivity of 4.62 mS cm at 25 °C (more than 20 times higher than those of previously reported GNSSEs). Moreover, the excellent formability of glassy NTOC electrolyte and its high electrochemical oxidative stability ensure a favourable electrolyte-electrode interface, contributing to superior cycling stability of ASSNIBs for over 500 cycles at room temperature. The discovery of glassy NTOC electrolyte would reignite research enthusiasm in superionic glassy SSEs based on multi-anion chemistry.
玻璃态钠离子固态电解质（GNSSEs）是一类重要的非晶态固态电解质。然而，目前最先进的GNSSEs在室温下离子电导率不足，这降低了它们在开发具有高能量密度和更高安全性的全固态钠离子电池（ASSNIBs）方面的前景。在此，我们报告基于氧氯化物双阴离子亚晶格发现了一种新型钠超离子玻璃，即0.5Na₂O -TaCl₅（NTOC）。NTOC中丰富的桥连和非桥连氧原子构成的独特局部结构，导致钠离子分布高度无序且钠迁移势垒较低，使得在25℃时离子电导率高达4.62 mS cm⁻¹（比此前报道的GNSSEs高出20多倍）。此外，玻璃态NTOC电解质优异的可成型性及其高电化学氧化稳定性确保了良好的电解质 - 电极界面，有助于ASSNIBs在室温下实现超过500次循环的卓越循环稳定性。玻璃态NTOC电解质的发现将重新点燃基于多阴离子化学的超离子玻璃态固态电解质的研究热情。
