Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites

Lei Zhu; Youwei Wang; Junchao Chen; Wenlei Li; Tiantian Wang; Jie Wu; Songyi Han; Yuanhua Xia; Yongmin Wu; Mengqiang Wu; Fangwei Wang; Yi Zheng; Luming Peng; Jianjun Liu; Liquan Chen; Weiping Tang

doi:10.1126/sciadv.abj7698

Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites

Sci Adv. 2022 Mar 18;8(11):eabj7698. doi: 10.1126/sciadv.abj7698. Epub 2022 Mar 18.

Authors

Lei Zhu¹, Youwei Wang^{2

3}, Junchao Chen^{1

4}, Wenlei Li⁵, Tiantian Wang^{2

3}, Jie Wu¹, Songyi Han¹, Yuanhua Xia⁶, Yongmin Wu¹, Mengqiang Wu⁵, Fangwei Wang⁷, Yi Zheng¹, Luming Peng⁴, Jianjun Liu^{2

3

8}, Liquan Chen⁷, Weiping Tang^{1

9}

Affiliations

¹ State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China.
² State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China.
³ Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China.
⁴ Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
⁵ Center for Advanced Electric Energy Technologies, School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China.
⁶ Key Laboratory of Neutron Physics, Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621999, China.
⁷ Beijing National Laboratory for Condensed Mater Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
⁸ School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Science, Hangzhou 310024, China.
⁹ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.

Abstract

Solid electrolytes are highly important materials for improving safety, energy density, and reversibility of electrochemical energy storage batteries. However, it is a challenge to modulate the coordination structure of conducting ions, which limits the improvement of ionic conductivity and hampers further development of practical solid electrolytes. Here, we present a skeleton-retained cationic exchange approach to produce a high-performance solid electrolyte of Li₃Zr₂Si₂PO₁₂ stemming from the NASICON-type superionic conductor of Na₃Zr₂Si₂PO₁₂. The introduced lithium ions stabilized in under-coordination structures are facilitated to pass through relatively large conduction bottlenecks inherited from the Na₃Zr₂Si₂PO₁₂ precursor. The synthesized Li₃Zr₂Si₂PO₁₂ achieves a low activation energy of 0.21 eV and a high ionic conductivity of 3.59 mS cm^-1 at room temperature. Li₃Zr₂Si₂PO₁₂ not only inherits the satisfactory air survivability from Na₃Zr₂Si₂PO₁₂ but also exhibits excellent cyclic stability and rate capability when applied to solid-state batteries. The present study opens an innovative avenue to regulate cationic occupancy and make new materials.