TY  - JOUR
AU  - Wu, Yi-Hong
AU  - Xie, Xia
AU  - Zhu, Lei
AU  - Yu, Mu-Ran
AU  - Zhang, Guo-Tai
AU  - Chen, Jun-Chao
AU  - Sun, Shu-Ying
AU  - Wang, You-Wei
AU  - Tang, Wei-Ping
PY  - 2026
TI  - Li+/Na+ Hybrid Ion Conduction Mechanism in the Superionic Conductor Li3–xNaxZr2Si2PO12
JO  - Journal of Electrochemistry
SN  - 1006-3471
VL  - 32
IS  - 6
AB  - 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 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 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.
UR  - https://doi.org/10.61558/2993-074X.3612
DO  - 10.61558/2993-074X.3612