Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte NaxZn2TeO6

doi:10.1007/s40242-025-4224-8

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (2): 296-304.doi: 10.1007/s40242-025-4224-8

Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte Na_xZn₂TeO₆

SUN Huangyijia¹, LI Xiaohui¹, ZENG Xiaoling¹, LIU Jian¹, RAKHMATULLIN Aydar², LOU Chenjie³, TANG Mingxue⁴, FERNáNDEZ-CARRIóN Alberto Jose¹, KUANG Xiaojun¹

1. Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. China;
2. Conditions Extremes et Materiaux:Haute Temperature et Irradiation (CNRS), CEMHTI, UPR 3079, Université Orléans, Orléans F-45071, France;
3. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, P. R. China;
4. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China

收稿日期:2024-11-17 接受日期:2024-12-24 出版日期:2025-04-01 发布日期:2025-03-31
通讯作者: LI Xiaohui,xiaohuili@glut.edu.cn;KUANG Xiaojun,kuangxj@glut.edu.cn E-mail:xiaohuili@glut.edu.cn;kuangxj@glut.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos. 22205017, 22090043), the Guangxi Natural Science Foundation, China (No. 2019GXNSFGA245006), and the Guilin University of Technology Research Startup Project, China (No. RD2400002912).

Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte Na_xZn₂TeO₆

SUN Huangyijia¹, LI Xiaohui¹, ZENG Xiaoling¹, LIU Jian¹, RAKHMATULLIN Aydar², LOU Chenjie³, TANG Mingxue⁴, FERNáNDEZ-CARRIóN Alberto Jose¹, KUANG Xiaojun¹

1. Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. China;
2. Conditions Extremes et Materiaux:Haute Temperature et Irradiation (CNRS), CEMHTI, UPR 3079, Université Orléans, Orléans F-45071, France;
3. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, P. R. China;
4. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China

Received:2024-11-17 Accepted:2024-12-24 Online:2025-04-01 Published:2025-03-31
Contact: LI Xiaohui,xiaohuili@glut.edu.cn;KUANG Xiaojun,kuangxj@glut.edu.cn E-mail:xiaohuili@glut.edu.cn;kuangxj@glut.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 22205017, 22090043), the Guangxi Natural Science Foundation, China (No. 2019GXNSFGA245006), and the Guilin University of Technology Research Startup Project, China (No. RD2400002912).

摘要/Abstract

摘要： Sodium-ion conducting materials in sodium-ion battery have drawn widespread attention in energy storage technologies due to the advantages of low cost, high performance, and efficient environmental adaptability. Herein, bond valence site energy (BVSE) calculations were used to predict the sodium ion electrical performances by the Na nonstoichiometric modifications, and we have carried out fine experiments to modulate the sodium ion conductivity of Na_xZn₂TeO₆ guided by BVSE calculations. The optimized composition Na_2.1Zn₂TeO₆ shows the superior sodium ionic conductivity of 5.3×10^-3 S/cm at 190 ℃, with a low activation energy of 0.28 eV. The excess Na preferentially occupies the Na1 site with tetrahedral voids, which has a higher capacity for sodium ion migration, as revealed by the combined neutron powder diffraction technique with the 1D and 2D ²³Na solid-state NMR technique, which is responsible for the variations in sodium ion conductivity. In addition, it is worth noting that the resulting Na_2.1Zn₂TeO₆ material maintains superior thermal and phase stability, as well as approximately the same thermal expansion coefficient values even during the temperature rise and fall cycles in the temperature range of 25—800 ℃. Furthermore, molecular dynamics simulations revealed that the sodium ions exhibit long-range anisotropic migration within the Na⁺ interlayers of Na_2.1Zn₂TeO₆.

关键词: Sodium solid electrolyte, Bond valence site energy, Nonstoichiometric modification

Abstract: Sodium-ion conducting materials in sodium-ion battery have drawn widespread attention in energy storage technologies due to the advantages of low cost, high performance, and efficient environmental adaptability. Herein, bond valence site energy (BVSE) calculations were used to predict the sodium ion electrical performances by the Na nonstoichiometric modifications, and we have carried out fine experiments to modulate the sodium ion conductivity of Na_xZn₂TeO₆ guided by BVSE calculations. The optimized composition Na_2.1Zn₂TeO₆ shows the superior sodium ionic conductivity of 5.3×10^-3 S/cm at 190 ℃, with a low activation energy of 0.28 eV. The excess Na preferentially occupies the Na1 site with tetrahedral voids, which has a higher capacity for sodium ion migration, as revealed by the combined neutron powder diffraction technique with the 1D and 2D ²³Na solid-state NMR technique, which is responsible for the variations in sodium ion conductivity. In addition, it is worth noting that the resulting Na_2.1Zn₂TeO₆ material maintains superior thermal and phase stability, as well as approximately the same thermal expansion coefficient values even during the temperature rise and fall cycles in the temperature range of 25—800 ℃. Furthermore, molecular dynamics simulations revealed that the sodium ions exhibit long-range anisotropic migration within the Na⁺ interlayers of Na_2.1Zn₂TeO₆.

Key words: Sodium solid electrolyte, Bond valence site energy, Nonstoichiometric modification

SUN Huangyijia, LI Xiaohui, ZENG Xiaoling, LIU Jian, RAKHMATULLIN Aydar, LOU Chenjie, TANG Mingxue, FERNáNDEZ-CARRIóN Alberto Jose, KUANG Xiaojun. Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte Na_xZn₂TeO₆[J]. 高等学校化学研究, 2025, 41(2): 296-304.

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Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte Na_xZn₂TeO₆

Na Nonstoichiometric Modifications Unraveling the Sodium Ion Mobility and Transport Mechanism in Sodium Solid Electrolyte Na_xZn₂TeO₆

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