ACS Publications. Most Trusted. Most Cited. Most Read
Tunneling Interpenetrative Lithium Ion Conduction Channels in Polymer-in-Ceramic Composite Solid Electrolytes

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2024, 146, 10, 6591-6603
    Article

    Tunneling Interpenetrative Lithium Ion Conduction Channels in Polymer-in-Ceramic Composite Solid Electrolytes
    Click to copy article linkArticle link copied!

    • Lei Zhu
      Lei Zhu
      Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, China
      State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China
      More by Lei Zhu
    • Junchao Chen*
      Junchao Chen
      School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
      Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen AJ 6525, The Netherlands
      *Email: [email protected]
      More by Junchao Chen
    • Youwei Wang
      Youwei Wang
      State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
      More by Youwei Wang
      Orcidhttps://orcid.org/0000-0001-8498-6548
    • Wuliang Feng
      Wuliang Feng
      Institute of Sustainable Energy & College of Science, Shanghai University, Shanghai 200444, China
      More by Wuliang Feng
    • Yanzhe Zhu
      Yanzhe Zhu
      School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
      More by Yanzhe Zhu
    • Sander F. H. Lambregts
      Sander F. H. Lambregts
      Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen AJ 6525, The Netherlands
      More by Sander F. H. Lambregts
    • Yongmin Wu
      Yongmin Wu
      State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China
      More by Yongmin Wu
    • Cheng Yang
      Cheng Yang
      State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China
      More by Cheng Yang
    • Ernst R. H. van Eck
      Ernst R. H. van Eck
      Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen AJ 6525, The Netherlands
      More by Ernst R. H. van Eck
    • Luming Peng
      Luming Peng
      Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Road, Nanjing 210023, China
      More by Luming Peng
      Orcidhttps://orcid.org/0000-0003-1935-1620
    • Arno P. M. Kentgens
      Arno P. M. Kentgens
      Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen AJ 6525, The Netherlands
      More by Arno P. M. Kentgens
      Orcidhttps://orcid.org/0000-0001-5893-4488
    • Weiping Tang*
      Weiping Tang
      State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China
      School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
      Key Laboratory of Green and High-end Utilization of Salt Lake Resources, Chinese Academy of Sciences, Xining 810008, China
      *Email: [email protected]
      More by Weiping Tang
    • Yongyao Xia*
      Yongyao Xia
      Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, China
      Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, China
      *Email: [email protected]
      More by Yongyao Xia
      Orcidhttps://orcid.org/0000-0001-6379-9655
    Other Access OptionsSupporting Information (4)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 10, 6591–6603
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c11988
    Published February 29, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Polymer-in-ceramic composite solid electrolytes (PIC–CSEs) provide important advantages over individual organic or inorganic solid electrolytes. In conventional PIC–CSEs, the ion conduction pathway is primarily confined to the ceramics, while the faster routes associated with the ceramic–polymer interface remain blocked. This challenge is associated with two key factors: (i) the difficulty in establishing extensive and uninterrupted ceramic–polymer interfaces due to ceramic aggregation; (ii) the ceramic–polymer interfaces are unresponsive to conducting ions because of their inherent incompatibility. Here, we propose a strategy by introducing polymer-compatible ionic liquids (PCILs) to mediate between ceramics and the polymer matrix. This mediation involves the polar groups of PCILs interacting with Li+ ions on the ceramic surfaces as well as the interactions between the polar components of PCILs and the polymer chains. This strategy addresses the ceramic aggregation issue, resulting in uniform PIC–CSEs. Simultaneously, it activates the ceramic–polymer interfaces by establishing interpenetrating channels that promote the efficient transport of Li+ ions across the ceramic phase, the ceramic–polymer interfaces, and the intervening pathways. Consequently, the obtained PIC–CSEs exhibit high ionic conductivity, exceptional flexibility, and robust mechanical strength. A PIC–CSE comprising poly(vinylidene fluoride) (PVDF) and 60 wt % PCIL-coated Li3Zr2Si2PO12 (LZSP) fillers showcasing an ionic conductivity of 0.83 mS cm–1, a superior Li+ ion transference number of 0.81, and an elongation of ∼300% at 25 °C could be produced on meter-scale. Its lithium metal pouch cells show high energy densities of 424.9 Wh kg–1 (excluding packing films) and puncture safety. This work paves the way for designing PIC–CSEs with commercial viability.

    Copyright © 2024 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c11988.

    • Supporting figures and tables including synthesis and characterization (PDF)

    • 3D reconstruction of PELL60 obtained from XCT (MPG)

    • 3D reconstruction of PLL60 conducted from XCT (MPG)

    • Nail penetration test of the NCM811/PELL60/Li pouch cell (MP4)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 34 publications.

    1. Shilei Chang, Jialong Cao, Aonan Wang, Mochun Zhang, Fan Yang, Jing Xu, Yanqing Lai, Faping Zhong, Mengran Wang, Zhian Zhang. In Situ Reconstruction of the Ceramic Particle Surface Boosting High-Performance and Ultrathin Hybrid Solid-State Electrolyte. ACS Nano 2025, 19 (9) , 8621-8631. https://doi.org/10.1021/acsnano.4c14459
    2. Liying Wei, Yan Feng, Shuhui Ge, Shujie Liu, Yanyan Ma, Jianhua Yan. Three-Dimensionally Printed Ionogel-Coated Ceramic Electrolytes for Solid-State Lithium Batteries. ACS Nano 2025, 19 (5) , 5789-5800. https://doi.org/10.1021/acsnano.4c17761
    3. Wankai Wang, Yanfei Yang, Junping Zhang. Regulating Lithium-Ion Transport in PEO-Based Solid-State Electrolytes through Microstructures of Clay Minerals. ACS Applied Materials & Interfaces 2025, 17 (3) , 5307-5315. https://doi.org/10.1021/acsami.4c16874
    4. Huayu Huang, Shishi Liu, Yuxiang Xie, Junke Liu, Chenguang Shi, Miaolan Sun, Hao Peng, Jian Lan, Ya-Ping Deng, Ling Huang, Shi-Gang Sun. Constructing an Artificial Interface as a Bifunctional Promoter for the Li Anode and the NCM Cathode in Lithium Metal Batteries. Journal of the American Chemical Society 2024, 146 (45) , 31137-31149. https://doi.org/10.1021/jacs.4c11012
    5. Pan Mei, Yuan Zhang, Bing Ai, Luxi Hong, Chenhuan Zhou, Wei Zhang. Versatile Peroxide Route-Based Kinetics-Controlled Coating Method to Construct Uniform Alkali Metal-Containing Fast Ionic Conductor Nanoshells. Journal of the American Chemical Society 2024, 146 (42) , 28677-28684. https://doi.org/10.1021/jacs.4c04519
    6. Jian-Cang Wang, Wei-Jian Zhou, Nan Zhang, Peng-Fei Wang, Ting-Feng Yi. Review on Poly(ethylene oxide)-Based Solid Electrolytes: Key Issues, Potential Solutions, and Outlook. Energy & Fuels 2024, 38 (19) , 18395-18412. https://doi.org/10.1021/acs.energyfuels.4c03846
    7. Nan Meng, Fang Lian, Luetao Wu, Yue Wang, Jingyi Qiu. Across Interfacial Li+ Conduction Accelerated by a Single-Ion Conducting Polymer in Ceramic-Rich Composite Electrolytes for Solid-State Batteries. ACS Applied Materials & Interfaces 2024, 16 (31) , 41487-41494. https://doi.org/10.1021/acsami.4c06551
    8. Bing Cheng, Peng Du, Jin Xiao, Xiaowen Zhan, Lingyun Zhu. Improving the Ionic Conductivity and Anode Interface Compatibility of LLZO/PVDF Composite Polymer Electrolytes by Compositional Tuning. ACS Applied Materials & Interfaces 2024, 16 (24) , 31648-31656. https://doi.org/10.1021/acsami.4c06803
    9. Xiong Xiong Liu, Long Pan, Haotian Zhang, Pengcheng Yuan, Mufan Cao, Yaping Wang, Zeyuan Xu, Min Gao, Zheng Ming Sun. Host–Guest Inversion Engineering Induced Superionic Composite Solid Electrolytes for High-Rate Solid-State Alkali Metal Batteries. Nano-Micro Letters 2025, 17 (1) https://doi.org/10.1007/s40820-025-01691-7
    10. Zixuan Wang, Jialong Fu, Xin Guo. Conduction of lithium ions in polymer-based electrolytes. Solid State Ionics 2025, 424 , 116858. https://doi.org/10.1016/j.ssi.2025.116858
    11. Lingguang Yi, Xiaoyi Chen, Jiajia Huang, Jiali Liu, Honghui Hu, Huahui Zhao, Tianjing Wu, Li Liu, Xianyou Wang. Organic-inorganic composite electrolyte with in-situ polymerization poly(1,3-dioxolane) toward high-performance quasi-solid-state lithium metal batteries. Journal of Energy Storage 2025, 120 , 116459. https://doi.org/10.1016/j.est.2025.116459
    12. Aoxuan Wang, Runze Zhang, Dehua Xu, Hao Chen, Zhenglin Hu, Jiayan Luo. Amide Induced Fast‐Ion Transport in Bulk Phases and Interfaces for Polymer‐In‐Ceramic Electrolytes. Advanced Functional Materials 2025, 14 https://doi.org/10.1002/adfm.202503649
    13. Yuzhuo Ding, Longbin Li, Shuo Xu, Binghua Zhou, Jing Wang, Yiwang Chen. In situ preparation of composite gel electrolytes with high room-temperature ionic conductivity and homogeneous Na+ flux for sodium metal batteries. Science China Chemistry 2025, 68 (4) , 1522-1532. https://doi.org/10.1007/s11426-024-2491-9
    14. Qiyue Chen, Haitao Lv, Jun Peng, Qi Zhou, Wenzhuo Wu, Jing Wang, Lili Liu, Lijun Fu, Yuhui Chen, Yuping Wu. A Solid Electrolyte Based on Sodium‐Doped Li 4‐x Na x Ti 5 O 12 with PVDF for Solid State Lithium Metal Battery. ChemSusChem 2025, 18 (7) https://doi.org/10.1002/cssc.202401755
    15. Hyun Woo Kim, Seung-Min You, Jong Su Han, Ying Liu, Jae-Kwang Kim. A scalable and flexible hybrid solid electrolyte based on NASICON-structure Li3Zr2Si2PO12 for high-voltage hybrid batteries. Journal of Power Sources 2025, 635 , 236415. https://doi.org/10.1016/j.jpowsour.2025.236415
    16. Shanshan Lv, Guojiang Wen, Wenrui Cai, Sifan Yang, Jiarui Yang, Yuanming Zhai, Xuewei Fu, Wei Yang, Yu Wang. Building slippy ion-conduction highways in polymer electrolyte by electrostatic adsorption enabled asymmetric solvation structure. Journal of Energy Chemistry 2025, 103 , 48-58. https://doi.org/10.1016/j.jechem.2024.11.050
    17. Xiaoping Yi, Yang Yang, Junjie Song, Luyu Gan, Bitong Wang, Guoliang Jiang, Kaishan Xiao, Xuening Song, Nan Wu, Liquan Chen, Hong Li. Strategically tailored polyethylene separator parameters enable cost-effective, facile, and scalable development of ultra-stable liquid and all-solid-state lithium batteries. Energy Storage Materials 2025, 77 , 104191. https://doi.org/10.1016/j.ensm.2025.104191
    18. Li Yang, Lilian Wang, Qingxia Hu, Mou Yang, Guiquan Zhao, Yunchun Zha, Qi An, Qing Liu, Haijiao Xie, Yongjiang Sun, Lingyan Duan, Xiaoxiao Zou, Genfu Zhao, Hong Guo. Creating electrostatic shielding effects through dual-salt strategy to regulate coordination environment of Li⁺ and realize high-performance all-solid-state lithium metal batteries. Energy Storage Materials 2025, 77 , 104210. https://doi.org/10.1016/j.ensm.2025.104210
    19. Feng Tao, Kaijian Yan, Chenxu Dong, Jiajing Wang, Qianmu Pan, Minjian Gong, Jiapei Gu, Chunli Shen, Ruohan Yu, Yuanzhi Jiang, Mingjian Yuan, Cheng Zhou, Meng Huang, Xu Xu, Liqiang Mai. Electric‐Dipole Coupling Ion‐Dipole Engineering Induced Rational Solvation‐Desolvation Behavior for Constructing Stable Solid‐State Lithium Metal Batteries. Angewandte Chemie 2025, 22 https://doi.org/10.1002/ange.202503037
    20. Feng Tao, Kaijian Yan, Chenxu Dong, Jiajing Wang, Qianmu Pan, Minjian Gong, Jiapei Gu, Chunli Shen, Ruohan Yu, Yuanzhi Jiang, Mingjian Yuan, Cheng Zhou, Meng Huang, Xu Xu, Liqiang Mai. Electric‐Dipole Coupling Ion‐Dipole Engineering Induced Rational Solvation‐Desolvation Behavior for Constructing Stable Solid‐State Lithium Metal Batteries. Angewandte Chemie International Edition 2025, 22 https://doi.org/10.1002/anie.202503037
    21. Zhian Zhang, Meng Ye, Jianhua Chen, Xiaopeng Fu, Xunzhu Zhou, Limin Zheng, Liqing He, Zhenguo Wu, Amit Kumar, Lin Li, Fang Wan, Xiaodong Guo. Regulating cation–solvent interactions in PVDF-based solid-state electrolytes for advanced Li metal batteries. Chemical Science 2025, 16 (12) , 5028-5035. https://doi.org/10.1039/D5SC00071H
    22. An-Chun Tang, Er-Hai Hu, Bei-Er Jia, Chu-Bin Wan, Zi-Yue Wen, Shuen Tso, Xin Ju, Qing-Yu Yan. Recent fluorination strategies in solid electrolytes for high-voltage solid-state lithium-ion batteries. Rare Metals 2025, 1 https://doi.org/10.1007/s12598-025-03244-8
    23. Xiaoping Yi, Yang Yang, Kaishan Xiao, Sidong Zhang, Bitong Wang, Nan Wu, Bowei Cao, Kun Zhou, Xiaolong Zhao, Kee Wah Leong, Xuelong Wang, Wending Pan, Hong Li. Achieving Balanced Performance and Safety for Manufacturing All‐Solid‐State Lithium Metal Batteries by Polymer Base Adjustment. Advanced Energy Materials 2025, 15 (10) https://doi.org/10.1002/aenm.202404973
    24. Xiaoming Zhou, Zejian Ouyang, Jin Liu, Fangyang Liu, Zongliang Zhang, Yanqing Lai, Jie Li, Liangxing Jiang. Compatible Interfaces Constructed by Surficial Indiumization on Garnet Solid Electrolyte for Long‐Cycling All‐Solid‐State Lithium Metal Battery. Small 2025, 21 (9) https://doi.org/10.1002/smll.202411062
    25. Yu‐Long Liao, Xi‐Long Wang, Hong Yuan, Yong‐Jian Li, Chun‐Ming Xu, Shuai Li, Jiang‐Kui Hu, Shi‐Jie Yang, Fang Deng, Jia Liu, Jia‐Qi Huang. Ultrafast Li‐Rich Transport in Composite Solid‐State Electrolytes. Advanced Materials 2025, 37 (10) https://doi.org/10.1002/adma.202419782
    26. Yueshan Li, Weihao Yuan, Zhen Hu, Yibo Shen, Guoshuai Wu, Fei Cong, Xinzhe Fu, Fei Lu, Yunling Li, Pengxiang Liu, Yudong Huang, Jun Li. Constructing PVDF‐Based Polymer Electrolyte for Lithium Metal Batteries by Polymer‐Induced Phase Structure Adjustment Strategy. Advanced Functional Materials 2025, 146 https://doi.org/10.1002/adfm.202424763
    27. Weiting Ma, Xiurui Cui, Yong Chen, Shuang Wan, Shunshun Zhao, Jiajun Gong, Guoxiu Wang, Shimou Chen. Designing a Refined Multi‐Structural Polymer Electrolyte Framework for Highly Stable Lithium‐Metal Batteries. Angewandte Chemie 2025, 137 (3) https://doi.org/10.1002/ange.202415617
    28. Weiting Ma, Xiurui Cui, Yong Chen, Shuang Wan, Shunshun Zhao, Jiajun Gong, Guoxiu Wang, Shimou Chen. Designing a Refined Multi‐Structural Polymer Electrolyte Framework for Highly Stable Lithium‐Metal Batteries. Angewandte Chemie International Edition 2025, 64 (3) https://doi.org/10.1002/anie.202415617
    29. Yuchen Li, Qi Wang, Xuetong Zhao, Binlang He, Yongjian Xiao, Jing Guo, Lijun Yang, Ruijin Liao. High ionic conductive sodium β-alumina (SBA) and SBA-NaPF6 composite solid electrolytes prepared by cold sintering process. Ceramics International 2025, 51 (1) , 1318-1325. https://doi.org/10.1016/j.ceramint.2024.11.111
    30. Jing Yu, Yuhao Wang, Longyun Shen, Jiapeng Liu, Zilong Wang, Shengjun Xu, Ho Mei Law, Francesco Ciucci. Fast‐Charging Solid‐State Li Batteries: Materials, Strategies, and Prospects. Advanced Materials 2024, 2022 https://doi.org/10.1002/adma.202417796
    31. Haifeng Tu, Keyang Peng, Jiangyan Xue, Jingjing Xu, Jiawei Zhao, Yuyue Guo, Suwan Lu, Zhicheng Wang, Liquan Chen, Hong Li, Xiaodong Wu. Solvation and interfacial chemistry in ionic liquid based electrolytes toward rechargeable lithium-metal batteries. Journal of Materials Chemistry A 2024, 12 (48) , 33362-33391. https://doi.org/10.1039/D4TA05906A
    32. Xianhai Qi, Dapeng Liu, Haohan Yu, Zerui Fu, Yu Zhang. Solid‐State Electrolytes for Lithium‐Air Batteries. Batteries & Supercaps 2024, 31 https://doi.org/10.1002/batt.202400625
    33. Dheeraj Kumar Maurya, Behrouz Bazri, Pavitra Srivastava, Jheng‐Yi Huang, Yuan‐Ting Hung, Wen‐Tse Huang, Da‐Hua Wei, Ru‐Shi Liu. Ceramic Rich Composite Electrolytes: An Overview of Paradigm Shift toward Solid Electrolytes for High‐Performance Lithium‐Metal Batteries. Advanced Energy Materials 2024, 14 (43) https://doi.org/10.1002/aenm.202402402
    34. Fuyao Deng, Lin Zhang, Yi Dong, Guodong Cui. The synergistic interaction of polymer electrolyte in solid state lithium batteries: A perspective from simulations at electrical level. Journal of Energy Storage 2024, 102 , 114259. https://doi.org/10.1016/j.est.2024.114259
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 10, 6591–6603
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c11988
    Published February 29, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

    Article Views

    4325

    Altmetric

    -

    Citations

    34
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.