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Dielectric LiNbO3 electrolyte regulating internal electric field in composite solid-state electrolyte to fundamentally boost Li-ion transport

铌酸锂调控固态电解质电场结构促进锂离子高效传输

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Abstract

The composite solid-state electrolytes (CSEs) are one of the most promising electrolytes for advanced solid-state Li metal batteries. However, it is unclear for the effect of the induced electric field inside CSEs on the Li-ion transport. Herein, we design a compact CSE by imbedding the lithium niobate (LiNbO3) with both high ionic conductivity and dielectric constant into poly(vinylidene fluoride) matrix (NPC). The LiNbO3 significantly enhances the internal electric field of NPC along the LiNbO3 particles and establishes uniform interfacial electric field between NPC and electrodes, which fundamentally facilitates the Li-ion transport, weakens the space-charge layer and inhibits the growth of Li dendrites. Continuous fast ion-conducting channels with high concentration of Li-ions are constructed inside NPC, which contributes to a quite high ionic conductivity (7.39×10−4 S cm−1, 25°C) and ultra-low activation energy (0.112 eV). The LiNi0.8Co0.1Mn0.1O2/NPC/Li solid-state batteries exhibit quite stable cycling performance at 25°C.

摘要

聚合物基固态电解质得益于其易加工性, 最有希望应用于下一代固态锂金属电池. 目前, 聚合物基态电解质的离子电导率提升策略多为加入导锂陶瓷以构建离子传输通道, 其提升程度有限. 电场在锂离子输运过程中存在重要影响, 目前研究中有关电场对锂离子传输的影响机制尚不明确. 本文将兼具高离子电导率和高介电常数的铌酸锂嵌入聚偏氟乙烯基体中, 设计了一种新型复合固态电解质. 铌酸锂颗粒有效调节电解质内部电场结构, 增强了离子输运方向电场强度, 实现了离子电导率的大幅提升(7.39×10−4 S cm−1, 25°C). 该电解质匹配高镍正极和锂金属负极的固态电池可稳定循环1000 次以上, 容量保持率为72%. 该研究为设计下一代固态锂电池用高离子电导复合固态电解质提供了新的策略.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2021YFF0500600), National Natural Science Foundation of China (No. U2001220), Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center (XMHT20200203006), and Shenzhen Technical Plan Project (RCJC20200714114436091, JCYJ20220818101003007, and JCYJ20220818101003008).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center, Institute of Materials Research (IMR), Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, China

    Xiaotong Liu  (刘晓潼), Bohua Wen  (温博华), Xing Cheng  (程醒), Jiabin Ma  (马家宾), Peiran Shi  (史沛然), Likun Chen  (陈立坤), Danfeng Zhang  (张丹丰), Ming Liu  (柳明), Wei Lv  (吕伟), Yan-Bing He  (贺艳兵) & Feiyu Kang  (康飞宇)

  2. School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China

    Xiaotong Liu  (刘晓潼), Xing Cheng  (程醒), Jiabin Ma  (马家宾), Peiran Shi  (史沛然), Likun Chen  (陈立坤) & Danfeng Zhang  (张丹丰)

  3. Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics Chinese Academy of Sciences, Dalian, 116023, China

    Guiming Zhong  (钟贵明)

  4. Department of Mechanical Engineering, York University, Toronto, ON M3J 1P3, Canada

    Cuiying Jian  (简翠英)

  5. Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China

    Yong Guo  (郭勇) & Shichao Wu  (吴士超)

  6. College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518055, China

    Yanfei Huang  (黄妍斐)

Authors
  1. Xiaotong Liu  (刘晓潼)
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  2. Bohua Wen  (温博华)
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  5. Cuiying Jian  (简翠英)
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  6. Yong Guo  (郭勇)
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Contributions

Author contributions He YB, Lv W and Kang F conceived the idea and supervised the project. He YB, Liu XT, Wen BH and Lv W designed the experiments. Liu XT, Cheng X, Guo Y, Huang YF, Ma JB, Shi PR, Chen LK, Zhang DF and Wu SC carried out the experimental work, data collection and analysis. Zhong GM, and Jian CY performed the ssNMR measurement, simulation and data analysis. He YB, Liu XT, Wen BH, Liu M, Lv W, and Kang FY prepared and revised this manuscript with contributions from all other authors.

Corresponding authors

Correspondence to Wei Lv  (吕伟), Yan-Bing He  (贺艳兵) or Feiyu Kang  (康飞宇).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Xiaotong Liu is currently a PhD candidate at Tsinghua Shenzhen International Graduate School, Tsinghua University. He obtained his BS degree (2019) in University of Science and Technology Beijing. His research mainly focuses on the high-performance polymer-based solid-state electrolytes for high-energy density lithium batteries, as well as the interface issues between the electrolyte and electrodes.

Bohua Wen is currently an associate professor of Tsinghua Shenzhen International Graduate School, Tsinghua University. She received his PhD degree from State University of New York at Binghamton. She worked as a postdoctoral associate at the Massachusetts Institute of Technology. Her research interests mainly focus on the high-energy density and high-power density battery cathode materials and their ion transport processes.

Wei Lv is currently a tenured associate professor of Tsinghua Shenzhen International Graduate School, Tsinghua University. He received his PhD degree from Tianjin University in 2012. His research interests mainly focus on novel carbon materials, such as graphene and porous carbons, and their applications in electrochemical sensing and energy storage.

Yan-Bing He is currently a tenured associate professor of Tsinghua Shenzhen International Graduate School, Tsinghua University. He received his PhD degree from Tianjin University in 2010. He worked as a post-doctoral fellow at the Graduate School at Shenzhen, Tsinghua University from 2010 to 2012 and a visiting scholar at Hong Kong University of Science and Technology from 2012 to 2013. His research interests mainly focus on lithium-ion power batteries and materials, solid-state electrolytes and lithium metal anodes.

Feiyu Kang is currently a full professor in the Department of Materials Science and Engineering, Tsinghua University. He received his PhD degree from Hong Kong University of Science and Technology. His research interests mainly focus on nanocarbon materials, graphite, thermal conductive materials, lithium-ion batteries, supercapacitors, electric vehicles, porous carbon and adsorption, indoor air clearing and water purification.

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Dielectric LiNbO3 electrolyte regulating internal electric field in composite solid-state electrolyte to fundamentally boost Li-ion transport

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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. Sci. China Mater. 67, 1947–1955 (2024). https://doi.org/10.1007/s40843-024-2915-3

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