超离子导体Li3-xNaxZr2Si2PO12中的Li+/Na+混合离子传导机制

doi:10.61558/2993-074X.3612

电化学（中英文） ›› 2026, Vol. 32 ›› Issue (6): 2613001. doi: 10.61558/2993-074X.3612

超离子导体Li_3-_xNa_xZr₂Si₂PO₁₂中的Li⁺/Na⁺混合离子传导机制

吴艺弘^a, 谢霞^b^,^c, 朱蕾^d, 于沐冉^e, 张果泰^e, 陈俊超^e^,^*()(), 孙淑英^a^,^*()(), 王有伟^b^,^c^,^*()(), 汤卫平^e^,^*()()

^a 华东理工大学资源与环境工程学院，上海 200237
^b 中国科学院上海硅酸盐研究所高性能陶瓷和超微结构国家重点实验室，上海 200050
^c 中国科学院大学材料科学与光电技术学院，北京 100049
^d 上海空间电源研究所，上海 200245
^e 上海交通大学化学化工学院，上海 200240

收稿日期:2026-02-07 修回日期:2026-04-01 接受日期:2026-04-22 发布日期:2026-04-22 出版日期:2026-06-28

Li⁺/Na⁺ Hybrid Ion Conduction Mechanism in the Superionic Conductor Li_3-_xNa_xZr₂Si₂PO₁₂

Yi-Hong Wu^a, Xia Xie^b^,^c, Lei Zhu^d, Mu-Ran Yu^e, Guo-Tai Zhang^e, Jun-Chao Chen^e^,^*()(), Shu-Ying Sun^a^,^*()(), You-Wei Wang^b^,^c^,^*()(), Wei-Ping Tang^e^,^*()()

^a School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, China
^b State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China
^c Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, China
^d State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai, 200245, China
^e School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

Received:2026-02-07 Revised:2026-04-01 Accepted:2026-04-22 Online:2026-04-22 Published:2026-06-28
Contact: *E-mail: junchaochen@sjtu.edu.cn(J.-C. Chen), shysun@ecust.edu.cn(S.-Y. Sun), ywwang@mail.sic.ac.cn(Y.-W. Wang) tangweiping@sjtu.edu.cn(W.-P. Tang)
About author:Author contributions
Yi-Hong Wu, Xia Xie, Lei Zhu, Mu-Ran Yu, Guo-Tai Zhang, Jun-Chao Chen, Shu-Ying Sun, You-Wei Wang, and Wei-Ping Tang jointly conceived the work. Yi-Hong Wu performed material synthesis and characterisation. Xia Xie conducted the DFT calculations. Jun-Chao Chen collected and analysed the NMR spectra. Yi-Hong Wu, Xia Xie, Lei Zhu, MuRan Yu, Guo-Tai Zhang, Jun-Chao Chen, Shu-Ying Sun, You-Wei Wang, and Wei-Ping Tang jointly drafted the manuscript. All authors discussed the experimental content and the final manuscript.

1. JOE2613001SI.pdf(1147KB)

摘要/Abstract

摘要：

混合离子导体能够同时传导多种离子，为探究单一相中混合离子传输对离子电导调控机制提供了重要支持。然而，多种可迁移离子在固态电解质中的可控引入及其在晶体骨架内的迁移机理仍面临挑战。本文采用一种骨架保持的Li⁺↔Na⁺阳离子交换策略，在NASICON型Li_3-_xNa_xZr₂Si₂PO₁₂ (0 < x < 3)的骨架中同时引入Li⁺和Na⁺。研究表明，NaO₆和NaO₈配位多面体的相互贯通对混合离子导体的离子电导率具有显著影响。计算分析显示，Na⁺更倾向于从八面体配位的NaO₆位点迁移至八配位的NaO₈位点，同时伴随Li⁺从NaO₈位点向原NaO₆位点处的四面体LiO₄环境迁移，从而促进Li⁺/Na⁺位点分离。随着Na⁺在NaO₈位点占据比例的增加，瓶颈效应限制了Na⁺的迁移，同时阻碍了连续Li⁺迁移网络的形成，导致离子电导率由1.78 mS·cm^-1降低至0.50 mS·cm^-1。经再次离子交换后，NaO₈环境中的Na⁺被Li⁺所取代，形成五配位的LiO₅，从而重建Li⁺的渗透传输通道，实现体电导的可逆恢复。该研究揭示了基于Li⁺与Na⁺在可用位点间分散占据的快速双离子传导机制，为进一步发展固态混合离子导体开辟了新途径。

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

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 multiple 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 Li_3-_xNa_xZr₂Si₂PO₁₂ (0 < x < 3). We show that the interpenetration of NaO₆ and NaO₈ coordination polyhedra significantly influences the ionic conductivity of hybrid ion conductors. Computational analysis 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 limitations 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 conductivity. 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.

Key words: Hybrid ion conductor, Li⁺/Na⁺ cationic exchange, Dual-ion transport mechanism, Interpenetrating occupation

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Li_3-_xNa_xZr₂Si₂PO₁₂中的Li⁺/Na⁺混合离子传导机制[J]. 电化学（中英文）, 2026, 32(6): 2613001.

Yi-Hong Wu, Xia Xie, Lei Zhu, Mu-Ran Yu, Guo-Tai Zhang, Jun-Chao Chen, Shu-Ying Sun, You-Wei Wang, Wei-Ping Tang. Li⁺/Na⁺ Hybrid Ion Conduction Mechanism in the Superionic Conductor Li_3-_xNa_xZr₂Si₂PO₁₂[J]. Journal of Electrochemistry, 2026, 32(6): 2613001.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3612

https://electrochem.xmu.edu.cn/CN/Y2026/V32/I6/2613001

图/表 3

参考文献 29

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超离子导体Li_3-_xNa_xZr₂Si₂PO₁₂中的Li⁺/Na⁺混合离子传导机制

Li⁺/Na⁺ Hybrid Ion Conduction Mechanism in the Superionic Conductor Li_3-_xNa_xZr₂Si₂PO₁₂

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