固态钠电池中Y3+掺杂Na3Zr2Si2PO12固态电解质性能分析

doi:10.16552/j.cnki.issn1001-1625.2025.0432

硅酸盐通报 ›› 2025, Vol. 44 ›› Issue (10): 3853-3863.DOI: 10.16552/j.cnki.issn1001-1625.2025.0432

固态钠电池中Y³⁺掺杂Na₃Zr₂Si₂PO₁₂固态电解质性能分析

王媛媛¹, 李妍¹, 王歧², 李海晨¹, 韩双双¹

1.北京石油化工学院新材料与化工学院,北京 102617;
2.北京石油化工学院机械工程学院,北京 102617

收稿日期:2025-04-24 修订日期:2025-07-07 出版日期:2025-10-15 发布日期:2025-11-03
通信作者: 李妍,博士,副教授。E-mail:yanli@bipt.edu.cn
作者简介:王媛媛(1998—),女,硕士研究生。主要从事新能源材料方面的研究。E-mail:1258784585@qq.com

Performance Analysis of Y³⁺-Doped Na₃Zr₂Si₂PO₁₂ Solid-State Electrolytes for Solid-State Sodium Batteries

WANG Yuanyuan¹, LI Yan¹, WANG Qi², LI Haichen¹, HAN Shuangshuang¹

1. College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China;
2. School of Mechanical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Received:2025-04-24 Revised:2025-07-07 Published:2025-10-15 Online:2025-11-03

摘要/Abstract

摘要： 钠离子电池因低成本和较高的能量密度,成为储能领域的研究热点。然而,传统的液态电解质存在易泄漏、易燃等安全隐患,亟需开发稳定可靠的固态电解质。本研究通过Y³⁺异价掺杂Na₃Zr₂Si₂PO₁₂,制备Na_3+xZr_2-xY_xSi₂PO₁₂(x=0、0.05、0.10、0.15)系列固态电解质,以提升其致密性、离子电导率与界面稳定性。采用X射线衍射(XRD)和扫描电子显微镜(SEM)进行分析。结果表明,适量Y³⁺掺杂(x=0.10)在不破坏NASICON型Na₃Zr₂Si₂PO₁₂晶体结构基础上,显著提高了其致密度(91.93%)和室温离子电导率(8.91×10^-4 S·cm^-1)。Y³⁺掺杂样品具有更小的界面极化电压与阻抗增长率,表现出优异的界面稳定性。基于Na_3.10Zr_1.90Y_0.10Si₂PO₁₂组装的固态钠电池,在室温0.1 C倍率下,100次循环后容量保持率达到98.55%。本研究揭示了Y³⁺掺杂对晶体结构与界面行为的协同调控作用,为钠离子固态电解质材料的设计与界面优化提供了重要参考。

关键词: NASICON型固态电解质, Na₃Zr₂Si₂PO₁₂, Y³⁺掺杂, 钠离子电导率, 晶体结构调控, 界面稳定性, 固态钠电池

Abstract: Sodium ion batteries have become a research hotspot in the field of energy storage due to their low cost and relatively high energy density. However, traditional liquid-state electrolytes have potential safety hazards such as leakage and flammability, and it is urgent to develop stable and reliable solid-state electrolytes. In this study, a series of Na_3+xZr_2-xY_xSi₂PO₁₂ (x=0, 0.05, 0.10, 0.15) solid-state electrolytes were prepared by Y³⁺ heterovalent doping Na₃Zr₂Si₂PO₁₂ to improve its compactness, ionic conductivity, and interface stability. The samples were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the appropriate amount of Y³⁺-doping (x=0.10) significantly improves the density (91.93%) and room temperature ionic conductivity (8.91×10^-4 S·cm^-1) of NASICON-type Na₃Zr₂Si₂PO₁₂ without destroying the crystal structure. The Y³⁺-doped samples have smaller interface polarization voltage and impedance growth rate, showing excellent interface stability. The solid-state sodium battery assembled based on Na_3.10Zr_1.90Y_0.10Si₂PO₁₂ has a capacity retention rate of 98.55% after 100 cycles at 0.1 C at room temperature. This study reveals the synergistic regulation of Y³⁺-doping on crystal structure and interface behavior, which provides an important reference for the design and interface optimization of sodium ion solid-state electrolyte materials.

Key words: NASICON-type solid-state electrolyte, Na₃Zr₂Si₂PO₁₂, Y³⁺-doping, sodium-ion conductivity, crystal structure regulation, interface stability, solid-state sodium battery

中图分类号:

TM911.3

王媛媛, 李妍, 王歧, 李海晨, 韩双双. 固态钠电池中Y³⁺掺杂Na₃Zr₂Si₂PO₁₂固态电解质性能分析[J]. 硅酸盐通报, 2025, 44(10): 3853-3863.

WANG Yuanyuan, LI Yan, WANG Qi, LI Haichen, HAN Shuangshuang. Performance Analysis of Y³⁺-Doped Na₃Zr₂Si₂PO₁₂ Solid-State Electrolytes for Solid-State Sodium Batteries[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(10): 3853-3863.

参考文献

[1] MANTHIRAM A, GOODENOUGH J B. Layered lithium cobalt oxide cathodes[J]. Nature Energy, 2021, 6(3): 323.
[2] WANG X H, LU J Y, WU Y H, et al. Building stable anodes for high-rate Na-metal batteries[J]. Advanced Materials, 2024, 36(16): 2311256.
[3] WANG X H, WU Y H, ZHOU Y H, et al. Interface engineering with an organic aluminum additive for high-rate sodium metal batteries[J]. Advanced Functional Materials, 2025, 35(4): 2414041.
[4] HU W, LI X Y, HUANG J B, et al. NASICON Li_1.3Al_0.3Ti_1.7(PO₄)₃ electrolyte coating enables stable cycling of Li-rich manganese-based cathode[J]. Tungsten, 2024: 1-7.
[5] JIN Y, XU Y B, LE P M L, et al. Highly reversible sodium ion batteries enabled by stable electrolyte-electrode interphases[J]. ACS Energy Letters, 2020, 5(10): 3212-3220.
[6] LI T, XIONG L Y. Carbon-coated sodium vanadium phosphate for high-performance sodium-ion batteries[J]. Fullerenes, Nanotubes and Carbon Nanostructures, 2022, 30(11): 1142-1147.
[7] HIRONO T, USUI H, DOMI Y, et al. Effect of Sn addition on anode properties of SiO_x in sodium-ion batteries[J]. Electrochemistry, 2023, 91(1): 017001.
[8] LIU Q, ZHAO X H, YANG Q, et al. The progress in the electrolytes for solid state sodium-ion battery[J]. Advanced Materials Technologies, 2023, 8(7): 2200822.
[9] LI C, LI R, LIU K N, et al. NaSICON: a promising solid electrolyte for solid-state sodium batteries[J]. Interdisciplinary Materials, 2022, 1(3): 396-416.
[10] KOU Z Y, MIAO C, WANG Z Y, et al. Novel NASICON-type structural Li_1.3Al_0.3Ti_1.7Si_xP₅(3-0.8x)O₁₂ solid electrolytes with improved ionic conductivity for lithium ion batteries[J]. Solid State Ionics, 2019, 343: 115090.
[11] SHEN L, YANG J, LIU G, et al. High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries[J]. Materials Today Energy, 2021, 20: 100691.
[12] ZHAO S, CHE H, CHEN S, et al. Research progress on the solid electrolyte of solid-state sodium-ion batteries[J]. Electrochemical Energy Reviews, 2024, 7(1): 3.
[13] FUENTES R O, FIGUEIREDO F M, MARQUES F M B, et al. Influence of microstructure on the electrical properties of NASICON materials[J]. Solid State Ionics, 2001, 140(1/2): 173-179.
[14] CHEN D, LUO F, ZHOU W C, et al. Influence of Nb⁵⁺, Ti⁴⁺, Y³⁺ and Zn²⁺ doped Na₃Zr₂Si₂PO₁₂ solid electrolyte on its conductivity[J]. Journal of Alloys and Compounds, 2018, 757: 348-355.
[15] JOLLEY A G, TAYLOR D D, SCHREIBER N J, et al. Structural investigation of monoclinic-rhombohedral phase transition in Na₃Zr₂Si₂PO₁₂ and doped NASICON[J]. Journal of the American Ceramic Society, 2015, 98(9): 2902-2907.
[16] ZHANG Q, LIANG F, OU T, et al. Effect on ionic conductivity of Na_3+xZr_2-xM_xSi₂PO₁₂ (M=Y, La) by doping rare-earth elements[J]. IOP Conference Series: Materials Science and Engineering, 2018, 423: 012122.
[17] RUAN Y L, SONG S D, LIU J J, et al. Improved structural stability and ionic conductivity of Na₃Zr₂Si₂PO₁₂ solid electrolyte by rare earth metal substitutions[J]. Ceramics International, 2017, 43(10): 7810-7815.
[18] WANG X X, LIU Z H, TANG Y H, et al. Low temperature and rapid microwave sintering of Na₃Zr₂Si₂PO₁₂ solid electrolytes for Na-Ion batteries[J]. Journal of Power Sources, 2021, 481: 228924.

固态钠电池中Y³⁺掺杂Na₃Zr₂Si₂PO₁₂固态电解质性能分析

Performance Analysis of Y³⁺-Doped Na₃Zr₂Si₂PO₁₂ Solid-State Electrolytes for Solid-State Sodium Batteries

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