Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries

Abstract Poly(vinylidene fluoride) (PVDF)‐based polymer electrolytes have attracted widespread attention due to their unique Li+ transport mechanism. However, their low ionic conductivity and porous structure, as well as residual solvent limit their application at high current densities. Here, a com...

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Main Authors: Ziyang Liang, Chang Liu, Xiang Bai, Jiahui Zhang, Xinyue Chang, Bo Zhang, Mengxue Xia, Huayun Du, Hao Huang, Bing Wu, Chengkai Yang, Shi Wang, Wen Liu, Qian Wang
Format: Article
Language:English
Published: Wiley 2025-04-01
Series:Advanced Science
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Online Access:https://doi.org/10.1002/advs.202413875
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author Ziyang Liang
Chang Liu
Xiang Bai
Jiahui Zhang
Xinyue Chang
Bo Zhang
Mengxue Xia
Huayun Du
Hao Huang
Bing Wu
Chengkai Yang
Shi Wang
Wen Liu
Qian Wang
author_facet Ziyang Liang
Chang Liu
Xiang Bai
Jiahui Zhang
Xinyue Chang
Bo Zhang
Mengxue Xia
Huayun Du
Hao Huang
Bing Wu
Chengkai Yang
Shi Wang
Wen Liu
Qian Wang
author_sort Ziyang Liang
collection DOAJ
description Abstract Poly(vinylidene fluoride) (PVDF)‐based polymer electrolytes have attracted widespread attention due to their unique Li+ transport mechanism. However, their low ionic conductivity and porous structure, as well as residual solvent limit their application at high current densities. Here, a composite solid electrolyte (CSE) is developed by integrating poly(vinylidene‐co‐trifluoroethylene) [P(VDF‐TrFE)] in its all‐trans conformation with aminofunctionalized metal–organic framework (ZIF‐90‐NH2). In such a CSE, all F atoms located on one side of the polymer chain, providing fast Li+ transport channels. Concurrently, the functionalized ZIF‐90‐NH2 can effectively anchor the residual N, N‐dimethylformamide (DMF) in CSEs while weakening Li+‐DMF solvent coordination, inducing the rearrangement of Li+ solvation structure and inhibiting the decomposition of DMF at the interface. Synergistically, ZIF‐90‐NH2 can immobilize anions in Li salts, promoting their dissociation. Based on integrating competitive Li+ coordination with immobilized anions, the obtained CSEs exhibit a high Li+ transference number (0.77). The full cells with LiFePO4 cathode can run stably over 400 cycles at 5 C, while the Li || LiNi0.7Co0.1Mn0.2O2 full cells deliver a high capacity retention (>85%) after 200 cycles at a charge cutoff voltage of 4.5 V. This work opens up a new path for building CSEs with high interfacial stability and fast Li+ transport.
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spelling doaj-art-dd3dbcd8406c46bc84052e82a0d67e1e2025-08-20T02:16:22ZengWileyAdvanced Science2198-38442025-04-011214n/an/a10.1002/advs.202413875Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal BatteriesZiyang Liang0Chang Liu1Xiang Bai2Jiahui Zhang3Xinyue Chang4Bo Zhang5Mengxue Xia6Huayun Du7Hao Huang8Bing Wu9Chengkai Yang10Shi Wang11Wen Liu12Qian Wang13College of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaShanxi Energy Internet Research Institute Taiyuan Shanxi 030024 ChinaShanxi Energy Internet Research Institute Taiyuan Shanxi 030024 ChinaShanxi Energy Internet Research Institute Taiyuan Shanxi 030024 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaEmergency Research Institute Chinese Institute of Coal Science (CICS) Beijing 100013 ChinaKey Laboratory of Advanced Materials Technology College of Materials Science and Engineering Fuzhou University Fuzhou 350108 ChinaState Key Laboratory of Organic Electronics & Information Displays (SKLOEID) Institute of Advanced Materials (IAM) Nanjing University of Posts & Telecommunications Nanjing 210023 ChinaState Key Lab of Chemical Resource Engineering College of Science and College of Energy Beijing University of Chemical Technology Beijing 100092 ChinaCollege of Materials Science and Engineering Taiyuan University of Technology Taiyuan Shanxi 030024 ChinaAbstract Poly(vinylidene fluoride) (PVDF)‐based polymer electrolytes have attracted widespread attention due to their unique Li+ transport mechanism. However, their low ionic conductivity and porous structure, as well as residual solvent limit their application at high current densities. Here, a composite solid electrolyte (CSE) is developed by integrating poly(vinylidene‐co‐trifluoroethylene) [P(VDF‐TrFE)] in its all‐trans conformation with aminofunctionalized metal–organic framework (ZIF‐90‐NH2). In such a CSE, all F atoms located on one side of the polymer chain, providing fast Li+ transport channels. Concurrently, the functionalized ZIF‐90‐NH2 can effectively anchor the residual N, N‐dimethylformamide (DMF) in CSEs while weakening Li+‐DMF solvent coordination, inducing the rearrangement of Li+ solvation structure and inhibiting the decomposition of DMF at the interface. Synergistically, ZIF‐90‐NH2 can immobilize anions in Li salts, promoting their dissociation. Based on integrating competitive Li+ coordination with immobilized anions, the obtained CSEs exhibit a high Li+ transference number (0.77). The full cells with LiFePO4 cathode can run stably over 400 cycles at 5 C, while the Li || LiNi0.7Co0.1Mn0.2O2 full cells deliver a high capacity retention (>85%) after 200 cycles at a charge cutoff voltage of 4.5 V. This work opens up a new path for building CSEs with high interfacial stability and fast Li+ transport.https://doi.org/10.1002/advs.202413875composite solid electrolytesimmobilized anionsLi metal batteriesLi+ coordinationZIF‐90‐NH2
spellingShingle Ziyang Liang
Chang Liu
Xiang Bai
Jiahui Zhang
Xinyue Chang
Bo Zhang
Mengxue Xia
Huayun Du
Hao Huang
Bing Wu
Chengkai Yang
Shi Wang
Wen Liu
Qian Wang
Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
Advanced Science
composite solid electrolytes
immobilized anions
Li metal batteries
Li+ coordination
ZIF‐90‐NH2
title Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
title_full Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
title_fullStr Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
title_full_unstemmed Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
title_short Integrating Competitive Li+ Coordination with Immobilized Anions in Composite Solid Electrolyte for High‐Performance Li Metal Batteries
title_sort integrating competitive li coordination with immobilized anions in composite solid electrolyte for high performance li metal batteries
topic composite solid electrolytes
immobilized anions
Li metal batteries
Li+ coordination
ZIF‐90‐NH2
url https://doi.org/10.1002/advs.202413875
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