A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries

Xiaoting Lin; Shumin Zhang; Menghao Yang; Biwei Xiao; Yang Zhao; Jing Luo; Jiamin Fu; Changhong Wang; Xiaona Li; Weihan Li; Feipeng Yang; Hui Duan; Jianwen Liang; Bolin Fu; Hamidreza Abdolvand; Jinghua Guo; Graham King; Xueliang Sun

doi:10.1038/s41563-024-02011-x

A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries

Nat Mater. 2025 Jan;24(1):83-91. doi: 10.1038/s41563-024-02011-x. Epub 2024 Oct 1.

Authors

Xiaoting Lin^#¹, Shumin Zhang^#^{1

2}, Menghao Yang^#³, Biwei Xiao⁴, Yang Zhao¹, Jing Luo¹, Jiamin Fu^{1

2}, Changhong Wang^{1

5}, Xiaona Li^{1

5}, Weihan Li¹, Feipeng Yang^{6

7}, Hui Duan¹, Jianwen Liang¹, Bolin Fu¹, Hamidreza Abdolvand¹, Jinghua Guo⁶, Graham King⁸, Xueliang Sun^{9

10}

Affiliations

¹ Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario, Canada.
² Department of Chemistry, University of Western Ontario, London, Ontario, Canada.
³ Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, P.R. China.
⁴ GRINM (Guangdong) Research Institute for Advanced Materials and Technology, Foshan, P.R. China.
⁵ Ningbo Key Laboratory of All-Solid-State Battery, Eastern Institute for Advanced Study, Eastern Institute of Technology, Ningbo, P.R. China.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁷ National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA.
⁸ Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.
⁹ Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario, Canada. [email protected].
¹⁰ Ningbo Key Laboratory of All-Solid-State Battery, Eastern Institute for Advanced Study, Eastern Institute of Technology, Ningbo, P.R. China. [email protected].

^# Contributed equally.

Abstract

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-MCl_y, 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-MCl_y 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 Na_0.85Mn_0.5Ni_0.4Fe_0.1O₂ 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.

Abstract

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