- Lin, Xiaoting;
- Zhang, Shumin;
- Yang, Menghao;
- Xiao, Biwei;
- Zhao, Yang;
- Luo, Jing;
- Fu, Jiamin;
- Wang, Changhong;
- Li, Xiaona;
- Li, Weihan;
- Yang, Feipeng;
- Duan, Hui;
- Liang, Jianwen;
- Fu, Bolin;
- Abdolvand, Hamidreza;
- Guo, Jinghua;
- King, Graham;
- Sun, Xueliang
The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na2O2-MCly, M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na2O2-MCly electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm-1, wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na2O2-HfCl4 electrolyte and a Na0.85Mn0.5Ni0.4Fe0.1O2 cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g-1) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.