铌酸锂/PVDF基复合固态电解质设计构筑及其电化学性能

doi:10.15541/jim20260317

无机材料学报

• 研究论文 • 下一篇

铌酸锂/PVDF基复合固态电解质设计构筑及其电化学性能

邓婷, 王龙, 杨海俊, 方如意, 张俊, 夏阳, 黄辉, 张文魁, 夏新辉

浙江工业大学先进分离膜材料全国重点实验室,材料科学与工程学院, 浙江杭州 310014

收稿日期:2026-07-26 修回日期:2026-08-27
通讯作者: 夏新辉, 教授. E-mail: helloxxh@zju.edu.cn
作者简介:邓婷(2002–), 女, 硕士研究生. E-mail: 211125250080@zjut.edu.cn
基金资助:
浙江省自然科学基金(LD25E020003); 国家自然科学基金(52372235、22379020、U20A20253、22279116); 浙江省创新团队项目(2025R01023)

Design and Fabrication of LiNbO₃/PVDF Composite Solid Electrolytes and Their Electrochemical Properties

DENG Ting, WANG Long, YANG Haijun, FANG Ruyi, ZHANG Jun, XIA Yang, HUANG Hui, ZHANG Wenkui, XIA Xinhui

State Key Laboratory of Advanced Separation Membrane Materials, School of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Received:2026-07-26 Revised:2026-08-27
Contact: XIA Xinhui, professor. E-mail: helloxxh@zju.edu.cn
About author:DENG Ting(2002-), female, Master candidate. E-mail: 211125250080@zjut.edu.cn
Supported by:
Natural Science Foundation of Zhejiang Province (LD25E020003); National Natural Science Foundation of China (52372235, 22379020, U20A20253, 22279116); Zhejiang Provincial Innovation Team Project (2025R01023).

摘要/Abstract

摘要： 复合固态电解质是提升固态锂金属电池安全性与能量密度的关键材料,但其室温离子电导率低及界面稳定性差等问题亟待解决。本研究选取兼具高介电常数与锂离子传导能力的铌酸锂(LiNbO₃,LN)作为功能填料,分别引入聚偏氟乙烯(PVDF)和聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)两种聚合物基体中,通过溶液浇铸法制备复合固态电解质膜,系统对比了LiNbO₃含量及基体类型对离子传输行为、电化学稳定窗口及锂负极界面稳定性的影响。结果表明,LiNbO₃的最佳添加量均为30%(质量分数),其中PVDF/30LN的室温离子电导率达9.0×10^-4 S∙cm^-1,电化学窗口拓宽至4.6 V,而PVDF-HFP/30LN因HFP单元显著降低聚合物结晶度、增大非晶区比例,离子电导率进一步提升至14.8×10^-4 S∙cm^-1,电化学窗口达到5.1 V,展现出更优的锂盐解离与高压耐受能力。然而,PVDF-HFP基体因非晶链段固有的高蠕变性,其在临界电流密度(0.52 mA∙cm^-2)及长循环稳定性方面略逊于PVDF基复合电解质。本研究揭示了同一铁电活性填料在化学结构相近但结晶度不同的聚合物基体中的性能响应差异,为复合固态电解质基体材料的选型与界面工程优化提供了实验依据。

关键词: 复合固态电解质, 锂金属电池, 铌酸锂, PVDF, PVDF-HFP

Abstract: Composite solid electrolytes are key materials for enhancing the safety and energy density of solid-state lithium metal batteries, yet their low room-temperature ionic conductivity and poor interfacial stability remain critical challenges. In this study, lithium niobate(LiNbO₃, LN), a functional filler with both high dielectric constant and lithium-ion conduction capability, was introduced into poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer matrices. Composite solid electrolyte membranes were prepared via solution casting, and the effects of LiNbO₃, content and matrix type on ion transport behavior, electrochemical stability window, and lithium anode interface stability were systematically compared. The optimal LiNbO₃, loading was found to be 30%(in mass) for both matrices. The PVDF/30LN electrolyte exhibited a room-temperature ionic conductivity of 9.0×10^-4 S∙cm^-1 and an electrochemical window extended to 4.6 V. In contrast, the PVDF-HFP/30LN electrolyte, benefited from the reduced polymer crystallinity and enlarged amorphous fraction imparted by the HFP units, achieved a higher ionic conductivity of 14.8×10^-4 S∙cm^-1 and a wider electrochemical window of 5.1 V, demonstrating superior lithium salt dissociation and high-voltage tolerance. However, due to the inherent high creep compliance of the amorphous chain segments in the PVDF-HFP matrix, this electrolyte showed slightly inferior performance in critical current density (0.52 mA∙cm^-2) and long-term cycling stability compared with its PVDF-based counterpart. This study reveals the distinct performance responses of the same ferroelectric active filler in polymer matrices with similar chemical structures but different crystallinity, providing experimental evidence for matrix material selection and interface engineering optimization in composite solid electrolytes.

Key words: composite solid electrolyte, lithium metal battery, LiNbO₃, PVDF, PVDF-HFP

中图分类号:

TM912

邓婷, 王龙, 杨海俊, 方如意, 张俊, 夏阳, 黄辉, 张文魁, 夏新辉. 铌酸锂/PVDF基复合固态电解质设计构筑及其电化学性能[J]. 无机材料学报, DOI: 10.15541/jim20260317.

DENG Ting, WANG Long, YANG Haijun, FANG Ruyi, ZHANG Jun, XIA Yang, HUANG Hui, ZHANG Wenkui, XIA Xinhui. Design and Fabrication of LiNbO₃/PVDF Composite Solid Electrolytes and Their Electrochemical Properties[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260317.

参考文献

[1] SHEN W, LIU P, WANG L,et al. Research progress on halide solid-state electrolytes: synthesis, mechanism, and modification. Carbon Energy, 2026, 8(4): e70170.
[2] TARASCON J M, ARMAND M.Issues and challenges facing rechargeable lithium batteries.Nature, 2001, 414(6861): 359.
[3] SUN C, LIU J, GONG Y, WILKINSON D P, ZHANG J.Recent advances in all-solid-state rechargeable lithium batteries.Nano Energy, 2017, 33: 363.
[4] QIU Z, YANG T, LIU P,et al. Multi‐dimensional interphase modulation by plasma for construction of advanced lithium metal batteries. Advanced Functional Materials, 2025, 35(42): 2501761.
[5] MA J, YANG T, LIU P,et al. Organosilane plasma enhanced interfacial engineering to boost inorganic-rich hybrid solid electrolyte interface for advanced lithium metal batteries. Small, 2026, 22(2): e10297.
[6] LIANG X, YANG T, SHEN S,et al. Plasma design of alloy‐based gradient solid electrolyte interphase on lithium metal anodes for energy storage. Advanced Materials, 2026, 38(10): e21029.
[7] ZHANG Z, SHAO Y, LOTSCH B,et al. New horizons for inorganic solid state ion conductors. Energy & Environmental Science, 2018, 11(8): 1945.
[8] KAMAYA N, HOMMA K, YAMAKAWA Y,et al. A lithium superionic conductor. Nature Materials, 2011, 10(9): 682.
[9] MURAMATSU H, HAYASHI A, OHTOMO T, HAMA S, TATSUMISAGO M.Structural change of Li₂S-P₂S₅ sulfide solid electrolytes in the atmosphere.Solid State Ionics, 2011, 182(1): 116.
[10] ZHU Y, HE X, MO Y.Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations.ACS Applied Materials & Interfaces, 2015, 7(42): 23685.
[11] TANG G, LIN G, DENG Y,et al. Solid-polymer-electrolyte interphase inductively formed by surface chemistry to stabilize the high Ni cathode in sulfide-based all-solid-state lithium batteries. Carbon Energy, 2026, 8(1): e70076.
[12] ZHAO Q, STALIN S, ZHAO C Z, ARCHER L A.Designing solid-state electrolytes for safe, energy-dense batteries.Nature Reviews Materials, 2020, 5(3): 229.
[13] ZHOU D, SHANMUKARAJ D, TKACHEVA A, ARMAND M, WANG G.Polymer electrolytes for lithium-based batteries: advances and prospects.Chem, 2019, 5(9): 2326.
[14] LI H, QU X, PAN Y,et al. Customized design of LiF-rich SEI layer on lithium metal anode for high flame retardant electrolyte. Carbon Energy, 2025, 7(11): e70077.
[15] PENG S, CHEN J, LI Y,et al. Vertically aligned ion pathways for fast conduction and uniform lithium deposition in solid-state batteries. Carbon Energy, 2026, 8(3): e70152.
[16] LI C, ZHANG T, QIU Z,et al. Plasma-assisted fabrication of multiscale materials for electrochemical energy conversion and storage. Carbon Energy, 2025, 7(2): e641.
[17] WANG S H, LA MONACA A, DEMOPOULOS G P.Composite solid-state electrolytes for all solid-state lithium batteries: progress, challenges and outlook.Energy Advances, 2024, 4(1): 11.
[18] HUANG Y F, GU T, RUI G,et al. A relaxor ferroelectric polymer with an ultrahigh dielectric constant largely promotes the dissociation of lithium salts to achieve high ionic conductivity. Energy & Environmental Science, 2021, 14(11): 6021.
[19] WU Y, ZHANG H, LIU L, LI Z.Poly(vinylidene fluoride) based composite electrolytes enhanced with asymmetrically distributed multiferroic BiFeO₃ fillers for lithium metal batteries.Journal of Energy Storage, 2026, 171: 122930.
[20] LIU X, WEN B, ZHONG G,et al. Dielectric LiNbO₃ electrolyte regulating internal electric field in composite solid-state electrolyte to fundamentally boost Li-ion transport. Science China Materials, 2024, 67(6): 1947.
[21] WANG Z, FAN S, LI L, YANG H, LI S.LiNbO₃-mediated dielectric polarization tailoring at polymer electrolyte interfaces for dendrite-free lithium metal batteries.ACS Applied Materials & Interfaces, 2026, 18(5): 8190.
[22] WU F, FENG T, BAI Y, WU C, YE L, FENG Z.Preparation and characterization of solid polymer electrolytes based on PHEMO and PVDF-HFP.Solid State Ionics, 2009, 180(9): 677.
[23] XIE H, TANG Z, LI Z, HE Y, LIU Y, WANG H.PVDF-HFP composite polymer electrolyte with excellent electrochemical properties for Li-ion batteries.Journal of Solid State Electrochemistry, 2008, 12(11): 1497.
[24] LIU W, YI C, LI L,et al. Designing polymer-in-salt electrolyte and fully infiltrated 3D electrode for integrated solid-state lithium batteries. Angewandte Chemie International Edition, 2021, 133(23): 13041.
[25] CHAKKORIA J J, DUBEY A, MITCHELL A, BOES A.Ferroelectric domain engineering of lithium niobate.Opto-Electronic Advances, 2025, 8(2): 240139.
[26] MARTINS P, LOPES A C, LANCEROS-MENDEZ S.Electroactive phases of poly(vinylidene fluoride): determination, processing and applications.Progress in Polymer Science, 2014, 39(4): 683.
[27] LIU S, ZHOU L, LI H, NEYTS K.Novel insights into solid-state batteries through phase modulations: dielectric phase and liquid crystal phase.Advanced Materials, 2026, 38(5): e17122.
[28] HUANG Z X, WANG M M, FENG Y H, QU J P.β-phase formation of polyvinylidene fluoridevia hot pressing under cyclic pulsating pressure. Macromolecules, 2020, 53(19): 8494.
[29] MONROE C, NEWMAN J.The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces.Journal of the Electrochemical Society, 2005, 152(2): A396.
[30] DONG T, ZHANG J, XU G, et al.A multifunctional polymer electrolyte enables ultra-long cycle-life in a high-voltage lithium metal battery.Energy & Environmental Science, 2018, 11(5): 1197.
[31] YANG C, WOOTTAPANIT P, GENG S, et al.A multifunctional quasi-solid-state polymer electrolyte with highly selective ion highways for practical zinc ion batteries.Nature Communications, 2025, 16(1): 183.

铌酸锂/PVDF基复合固态电解质设计构筑及其电化学性能

Design and Fabrication of LiNbO₃/PVDF Composite Solid Electrolytes and Their Electrochemical Properties

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 11

编辑推荐

Metrics

本文评价

[1]	郝永鑫, 孙军, 杨金凤, 赵晨成, 刘子琦, 李清连, 许京军. 近化学计量比铌酸锂晶体的孪晶缺陷研究[J]. 无机材料学报, 2025, 40(2): 196-204.
[2]	田甜, 方辰恺, 张杰, 王维维, 伍霆锋, 徐家跃. 高价态离子掺杂铌酸锂晶体光折变性能的研究进展[J]. 无机材料学报, 2025, 40(10): 1079-1096.
[3]	郝永鑫, 秦娟, 孙军, 杨金凤, 李清连, 黄贵军, 许京军. 坩埚底角形状对提拉法生长同成分铌酸锂晶体的影响[J]. 无机材料学报, 2024, 39(10): 1167-1174.
[4]	秦娟, 梁丹丹, 孙军, 杨金凤, 郝永鑫, 李清连, 张玲, 许京军. 提拉法生长平肩同成分铌酸锂晶体的研究[J]. 无机材料学报, 2023, 38(8): 978-986.
[5]	蔡佳, 黄高旭, 金晓盼, 魏驰, 毛嘉毅, 李永生. 金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积[J]. 无机材料学报, 2022, 37(12): 1337-1343.
[6]	梁凤青, 温兆银. 固态锂电池用MOF/聚氧化乙烯复合聚合物电解质[J]. 无机材料学报, 2021, 36(3): 332-336.
[7]	李锐,王浩,付强,田子玉,王建旭,马小健,杨剑,钱逸泰. 构建亲锂铜基3D集流体实现金属锂的均匀沉积[J]. 无机材料学报, 2020, 35(8): 882-888.
[8]	张裕卿, 赵丽丽, 许世龙, 张超, 陈笑迎, 宋力昕. 宽带隙、高折射率聚偏四氟乙烯/TiO₂-ZrO₂光学膜的制备和表征[J]. 无机材料学报, 2013, 28(06): 671-676.
[9]	赵琰, 孙康宁, 刘鹏. 铌酸锂增韧碳纳米管/羟基磷灰石生物复合材料的低温烧结和力学性能研究[J]. 无机材料学报, 2011, 26(8): 863-868.
[10]	涂小牛, 郑燕青, 陈辉, 孔海宽, 忻隽, 曾一明, 施尔畏. 高均匀性高掺镁铌酸锂晶体的生长与表征[J]. 无机材料学报, 2010, 25(12): 1257-1262.
[11]	冯少新,李宝会,杨智,金庆华,郭振亚,丁大同. LiNbO₃晶体点缺陷形成能的经验途径计算[J]. 无机材料学报, 2003, 18(2): 283-288.

铌酸锂/PVDF基复合固态电解质设计构筑及其电化学性能

Design and Fabrication of LiNbO3/PVDF Composite Solid Electrolytes and Their Electrochemical Properties

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 11

编辑推荐

Metrics

本文评价

Design and Fabrication of LiNbO₃/PVDF Composite Solid Electrolytes and Their Electrochemical Properties