电化学（中英文）2026，Vol.32Issue(6)：1-9,9.DOI:10.61558/2993-074X.3612
超离子导体Li3-xNaxZr2Si2PO12中的Li+/Na+混合离子传导机制
Li+/Na+Hybrid Ion Conduction Mechanism in the Superionic Conductor Li3-xNaxZr2Si2PO12
摘要
Abstract
Hybrid ion conductors that transport multiple ionic conductive species provide a useful platform for understanding how mixed-ion transport governs ionic conductivity within a single phase.However,the controlled introduction of mul-tiple mobile ions into solid-state electrolytes and a mechanistic understanding of their migration within the framework remain challenging.Herein,a skeleton-retained Li+↔Na+cationic exchange was used to simultaneously induce Li+and Na+cations into the NASICON-type framework of Li3-xNaxZr2Si2PO12(0<x<3).We show that the interpenetration of NaO6 and NaO8 coordination polyhedra significantly influences the ionic conductivity of hybrid ion conductors.Computational anal-ysis indicates that Na+transfer from octahedral NaO6 sites to octa-coordinated NaO8 sites is thermodynamically favorable,accompanied by Li+relocation from NaO8 to tetrahedral LiO4 environments at former NaO6 sites,thereby promoting Li+/Na+site segregation.The increased occupation of Na+at NaO8 sites not only suppresses Na+mobility due to bottleneck lim-itations but also hinders the formation of a continuous Li+migration network,thereby reducing the room-temperature ionic conductivity from 1.78 to 0.50 mS·cm-1.Upon re-exchange,Na+in the NaO8 sites is replaced by Li+in penta-coordinated LiO5,which re-establish percolating ion-transport pathways for Li+and enable reversible recovery of the overall conduc-tivity.These results reveal a fast dual-ion conduction mechanism enabled by the interpenetrating occupation of Li+and Na+across the available sites.This work opens a new avenue for the development of hybrid ion conductors.关键词
混合离子导体/锂/钠阳离子交换/双离子传导机制/渗透占据Key words
Hybrid ion conductor/Li+/Na+cationic exchange/Dual-ion transport mechanism/Interpenetrating occupation引用本文复制引用
吴艺弘,谢霞,朱蕾,于沐冉,张果泰,陈俊超,孙淑英,王有伟,汤卫平..超离子导体Li3-xNaxZr2Si2PO12中的Li+/Na+混合离子传导机制[J].电化学（中英文）,2026,32(6):1-9,9.基金项目
This work was financially supported by the Na-tional Natural Science Foundation of China,NSFC(22402119,22509129,92372103 and U25A20243),Puji-ang Project of the Shanghai Baiyulan Talent Program(24PJD049),Natural Science Foundation of Shang-hai(25ZR1402376),Open Foundation of Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(JDSX2023011),and Opening Project of State Key Laboratory of Space-Power Sources(24-1533). （22402119,22509129,92372103 and U25A20243）
