<italic style="font-style: italic">In situ</italic> Construction of Fluorinated Polyester-based Block Copolymer Electrolytes <italic style="font-style: italic">via</italic> Orthogonal Polymerization

Kai-Rui Guo; Mu-Yao Lv; Zhi-Gang Xue

doi:10.1007/s10118-025-3542-0

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In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization

RESEARCH ARTICLE | Updated：2026-02-13

- In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization
- In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization
- Chinese Journal of Polymer Science 2026年44卷第3期页码：623-631
- Affiliations：
  
  Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
- Author bio：
  
  zgxue@mail.hust.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52573079), the Innovation and Talent Recruitment Base of New Energy Chemistry and Device (No. B21003), and the technical assistance from the HUST Analytical & Testing Center.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3542-0.
- DOI：10.1007/s10118-025-3542-0
  中图分类号：
- 收稿：2025-11-27，
  
  录用：2025-12-16，
  
  网络首发：2026-02-04，
  
  纸质出版：2026-03-15
- Accepted：
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Guo, K. R.; Lv, M. Y.; Xue, Z. G. In situ construction of fluorinated polyester-based block copolymer electrolytes via orthogonal polymerization. Chinese J. Polym. Sci. 2026, 44, 623–631

Kai-Rui Guo, Mu-Yao Lv, Zhi-Gang Xue. In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(3): 623-631.
Guo, K. R.; Lv, M. Y.; Xue, Z. G. In situ construction of fluorinated polyester-based block copolymer electrolytes via orthogonal polymerization. Chinese J. Polym. Sci. 2026, 44, 623–631 DOI： 10.1007/s10118-025-3542-0.

Kai-Rui Guo, Mu-Yao Lv, Zhi-Gang Xue. In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(3): 623-631. DOI： 10.1007/s10118-025-3542-0.

摘要

This work develops a fluorinated block copolymer electrolyte that disrupts poly(

-caprolactone) (PCL) crystallinity to enhance ion transport and

in situ

forms a LiF-rich solid electrolyte interphase (SEI) for stable lithium metal cycling.

Abstract

The practical deployment of polyester-based solid electrolytes such as poly(

-caprolactone) (PCL) is hindered by two inherent material-level constraints: the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity

whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling. Based on orthogonal polymerization technology combined with electrolyte structural design concepts

this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte (BCPE) system comprising fluorinated segments (PTFEA) and poly(

-caprolactone) (PCL). Structurally

this design enables a dual breakthrough in electrochemical performance: on one hand

the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain

reduce the crystallinity of PCL within the polymer electrolyte

and significantly enhance the segmental mobility of the polymer matrix; on the other hand

during the charge/discharge cycles of lithium batteries

fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase (SEI) through

in situ

decomposition reactions

achieving interface stabilization and homogeneous lithium-ion deposition regulation.

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references

Sångeland, C.; Younesi, R.; Mindemark, J.; Brandell, D. Towards room temperature operation of all-solid-state Na-ion batteries through polyester–polycarbonate-based polymer electrolytes. Energy Storage Mater. 2019 , 19 , 31−38..

Xie, X.; Zhang, P.; Li, X.; Wang, Z.; Qin, X.; Shao, M.; Zhang, L.; Zhou, W. Rational design of F-modified polyester electrolytes for sustainable all-solid-state lithium metal batteries. J. Am. Chem. Soc. 2024 , 146 , 5940−5951..

Eriksson, T.; Gudla, H.; Manabe, Y.; Yoneda, T.; Friesen, D.; Zhang, C.; Inokuma, Y.; Brandell, D.; Mindemark, J. Carbonyl-containing solid polymer electrolyte host materials: conduction and coordination in polyketone, polyester, and polycarbonate systems. Macromolecules 2022 , 55 , 10940−10949..

Xue, Z.; He, D.; Xie, X. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J. Mater. Chem. A 2015 , 3 , 19218−19253..

Mindemark, J.; Lacey, M. J.; Bowden, T.; Brandell, D. Beyond PEO—alternative host materials for Li + -conducting solid polymer electrolytes. Prog. Polym. Sci. 2018 , 81 , 114−143..

Huang, L.; Wu, Y.; Luo, P.; Su, K.; Song, X.; Liu, M.; Li, M.; Song, H.; Cui, Z. Multi-dimensional optimization of polymer-involved Li + solvation enabling stable polymer plastic crystal electrolyte for long-cycle lithium metal batteries. J. Energy Chem. 2026 , 112 , 656−665..

Xu, D.; Zhao, D.; Niu, X.; Wang, T.; Yang, Z. Polyester-enhanced poly (cyclic carbonate-fluoride)-based polymer electrolyte for stable circulating solid lithium batteries. Chem. Eng. J. 2024 , 490 , 151780..

Zhang, Q.; Bian, T.; Wang, X.; Shi, R.; Zhao, Y. Unlocking mechanism of anion and cation interaction on ion conduction of polymer based electrolyte in metal batteries. Angew. Chem. Int. Ed. 2025 , 64 , e202415343..

Yang, Z.; Cai, J.; Shen, Z.; Bian, J.; Chen, J.; Xu, Y.; Fang, Z.; Du, C.; Xiang, X.; Wang, J.; Yu, P.; Cui, R.; Bi, S. Effect of LiTFSI solvation on ionic conductivity of polyester-based solid electrolytes. Macromolecules 2024 , 57 , 4460−4470..

[Dai, X.; Ye, H.-M.; Huang, G.; Li, G. Structure-tunable fluorinated polyester electrolytes with enhanced interfacial stability for recyclable solid-state lithium metal batteries. Adv. Mater . 2025 , e11556..

Wang, Q.; Xu, H.; Fan, Y.; Chi, S.-S.; Han, B.; Ke, R.; Wang, R.; Wang, J.; Wang, C.; Xu, X.; Zheng, Z.; Deng, Y.; Chang, J. Insight into multiple intermolecular coordination of composite solid electrolytes via cryo-electron microscopy for high-voltage all-solid-state lithium metal batteries. Adv. Mater. 2024 , 36 , 2314063..

Aktas Eken, G.; Ober, C. K. Strong polyelectrolyte brushes via alternating copolymers of styrene an d maleimides: synthesis, properties, and stability. Macromolecules 2022 , 55 , 5291−5300..

[Patel, S. N. 100th anniversary of macromolecular science viewpoint: solid polymer electrolytes in cathode electrodes for lithium batteries. current challenges and future opportunities. ACS Macro Lett . 2021 , 10 , 141−153..

Wang, J.; Li, S.; Zhao, Q.; Song, C.; Xue, Z. Structure code for advanced polymer electrolyte in lithium-ion batteries. Adv. Funct. Mater. 2021 , 31 , 2008208..

Guo, K.; Li, S.; Chen, G.; Wang, J.; Wang, Y.; Xie, X.; Xue, Z. One-pot synthesis of polyester-based linear and graft copolymers for solid polymer electrolytes. CCS Chem. 2021 , 4 , 3134−3149..

Guo, K.; Wang, J.; Shi, Z.; Wang, Y.; Xie, X.; Xue, Z. One-step in situ polymerization: a facile design strategy for block copolymer electrolytes. Angew. Chem. Int. Ed. 2023 , 62 , e2022−13606..

Guo, K.; Li, S.; Wang, J.; Shi, Z.; Wang, Y.; Xue, Z. In situ orthogonal polymeriz ation for constructing fast-charging and long-lifespan Li metal batteries with topological copolymer electrolytes. ACS Energy Lett. 2024 , 9 , 843−852..

Zhang, B.; Liu, Y.; Pan, X.; Liu, J.; Doyle-Davis, K.; Sun, L.; Liu, J.; Jiao, X.; Jie, J.; Xie, H.; Sun, X. Dendrite-free lithium metal solid battery with a novel polyester based triblock copolymer solid-state electrolyte. Nano Energy 2020 , 72 , 104690..

Wang, T.; Zhong, L.; Xiao, M.; Han, D.; Wang, S.; Huang, Z.; Huang, S.; Sun, L.; Meng, Y. Block copolymer electrolytes for lithium metal batteries: strategies to boost both ionic conductivity and mechanical strength. Prog. Polym. Sci. 2023 , 146 , 101743..

Yoo, D.-J.; Liu, Q.; Cohen, O.; Kim, M.; Persson, K. A.; Zhang, Z. Rational design of fluorinated electrolytes for low temperature lithium-ion batteries. Adv. Energy Mater. 2023 , 13 , 2204182..

Zhang, B.; Zhang, Y.; Zhang, N.; Liu, J.; Cong, L.; Liu, J.; Sun, L.; Mauger, A.; Julien, C. M.; Xie, H.; Pan, X. Synthesis and interface stability of polystyrene-poly(ethylene glycol)-polystyrene triblock copolymer as solid-state electrolyte for lithium-metal batteries. J. Power Sources 2019 , 428 , 93−104..

Gregory, G. L.; Gao, H.; Liu, B.; Gao, X.; Rees, G. J.; Pasta, M.; Bruce, P. G.; Williams, C. K. Buffering volume change in solid-state battery composite cathodes with CO 2 -derived block polycarbonate ethers. J. Am. Chem. Soc. 2022 , 144 , 17477−17486..

Zhao, C.; He, G.; Chen, T.; Li, H.; Zhao, J. Precision organocatalytic synthesis of fluoropolyesters with enhanced degradability and ionic conductivity. Macromolecules 2025 , 58 , 1630−1641..

Shen, Z.; Liu, X.; Guo, J.; Zhang, C.; Zhang, X. Tunable fluorinated polyether-based solid electrolytes. Macromolecules 2025 , 58 , 7481−7488..

Wang, X.; Zhang, C.; Sawczyk, M.; Sun, J.; Yuan, Q.; Chen, F.; Mendes, T. C.; Howlett, P. C.; Fu, C.; Wang, Y.; Tan, X.; Searles, D. J.; Král, P.; Hawker, C. J.; Whittaker, A. K.; Forsyth, M. Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes. Nat. Mater. 2022 , 21 , 1057−1065..

Xia, X.; Gao, T.; Li, F.; Suzuki, R.; Isono, T.; Satoh, T. Multidimensional control of repeati ng unit/sequence/topology for one-step synthesis of block polymers from monomer mixtures. J. Am. Chem. Soc. 2022 , 144 , 17905−17915..

Dau, H.; Jones, G. R.; Tsogtgerel, E.; Nguyen, D.; Keyes, A.; Liu, Y.-S.; Rauf, H.; Ordonez, E.; Puchelle, V.; Basbug Alhan, H.; Zhao, C.; Harth, E. Linear block copolymer synthesis. Chem. Rev. 2022 , 122 , 14471−14553..

Schmitt, A.; Kazerouni, N.; Castillo, G. E.; Thompson, B. C. Synthesis of block copolymers containing stereoregular pendant electroactive blocks. ACS Macro Lett. 2023 , 12 , 159−164..

Yan, T.; Walsh, D. J.; Qiu, C.; Guironnet, D. One-pot synthesis of block copolymers containing a polyolefin block. Macromolecules 2018 , 51 , 10167−10173..

Huang, S.-L.; Ye, C.-C.; Pan, Y.-N.; Liu, Q.-Y.; Wang, C.; Xu, L. Living direct arylation polymerization via C–H activation for the precision synthesis of polythiophenes and their block copolymers. Macromolecules 2025 , 58 , 2357−2365..

Xia, X.; Suzuki, R.; Gao, T.; Isono, T.; Satoh, T. One-step synthesis of sequence-controlled multiblock polymers with up to 11 segments from monomer mixture. Nat. Commun. 2022 , 13 , 163..

Li, H.; Zeng, W.; Li, Z.; Zhao, J.; Zhang, G. One-step hybrid block copolymerization by organocatalysis. Prog. Polym. Sci. 2025 , 163 , 101955..

Ladelta, V.; Zapsas, G.; Abou-hamad, E.; Gnanou, Y.; Hadjichristidis, N. Tetracrystalline tetrablock quarterpolymers: four different crystallites under the same roof. Angew. Chem. Int. Ed. 2019 , 58 , 16267−16274..

Zhao, Y.; Jung, J.; Nozaki, K. One-pot synthesis of polyethylene-based block copolymers via a dual polymerization pathway. J. Am. Chem. Soc. 2021 , 143 , 18832−18837..

Chen, Y.; Zhang, S.; Chung-Yen Jung, J.; Zhang, J. Carbons as low-platinum catalyst supports and non-noble catalysts for polymer electrolyte fuel cells. Prog. Energy Combust. Sci. 2023 , 98 , 101101..

Zou, J.; Wang, L.; Zhang, J.; Sun, Q.; Wang, Y.; Zheng, M.; Xiao, Y.; Hu, H.; Liu, Y.; Liang, Y. Construction of covalent electrode/sol id electrolyte interface for stable flexible solid-state lithium batteries. Chem. Eng. J. 2024 , 500 , 157382..

Yin, X.; Guo, Y.; Chi, S.; Jia, Y.; Li, F.; Qi, J.; Yi, X.; Wu, S.; Yang, Q.-H. Beyond polymerization: in situ coupled fluorination enables more stable interfaces for solid-state lithium batteries. J. Am. Chem. Soc. 2025 , 147 , 4393−4402..

Luo, L.; Sun, Z.; Gao, H.; Lan, C.; Huang, X.; Han, X.; Su, P.; Zhang, Z.; Li, C.; Huang, W.; Wei, Q.; Zhang, Q.; Wang, M.-S.; Chen, S. Insights into the enhanced interfacial stability enabled by electronic conductor layers in solid-state Li batteries. Adv. Energy Mater. 2023 , 13 , 2203517..

Dechy-Cabaret, O.; Martin-Vaca, B.; Bourissou, D. Controlled ring-opening polymerization of lactide and glycolide. Chem. Rev. 2004 , 104 , 6147−6176..

Rasines Mazo, A.; Allison-Logan, S.; Karimi, F.; Chan, N. J. A.; Qiu, W.; Duan, W.; O’Brien-Simpson, N. M.; Qiao, G. G. Ring openingpolymerization of α-amino acids: advances in synthesis, architecture and applications of polypeptides and their hybrids. Chem. Soc. Rev. 2020 , 49 , 4737−4834..

Zhou, L.; Wang, Z.; Xu, G.; Lv, C.; Wang, Q. Structure and activity relationship studies of N-heterocyclic olefin and thiourea/urea catalytic systems: application in ring-opening polymerization of lactones. Polym. Chem. 2021 , 12 , 1806−1815..

Zhang, X.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M. Fast and selective ring-opening polymerizations by alkoxides and thioureas. Nat. Chem. 2016 , 8 , 1047−1053..

Halama, K.; Lin, M. T. Y.; Schaffer, A.; Foith, M.; Adams, F.; Rieger, B. Cytocompatible triblock copolymers with controlled microstructure enabling orthogonally functionalized bio-polymer conjugates. Macromolecules 2024 , 57 , 1438−1447..

Corbin, D. A.; Miyake, G. M. Making block copolymers with the flip of a switch. Chem 2020 , 6 , 1508−1510..

Pedretti, B. J.; Czarnecki, N. J.; Zhu, C.; Imbrogno, J.; Rivers, F.; Freeman, B. D.; Ganesan, V.; Lynd, N. A. Structure–property relationships for polyether-based electrolytes in the high-dielectric-constant regime. Macromolecules 2022 , 55 , 6730−6738..

Wang, T.; Zhang, Y.; Huang, X.; Su, P.; Xiao, M.; Wang, S.; Huang, S.; Han, D.; Meng, Y. Designing weakly and strongly solvating polymer electrolytes: systematically boosting high-voltage lithium metal batteries. SusMat 2024 , 4 , e219..

Bai, L.; Han, Y.; Wei, Q.; Sun, L.; Sun, N.; Wei, C.; An, X.; Ni, M.; Cai, J.; Zhuo, Z.; Zheng, Y.; Wang, S.; He, L.; Yang, J.; Liu, B.; Lin, Z.; Xu, M.; Lin, J.; Huang, W. A molecular design principle for pure-blue light-emitting polydiaryl fluorenes with suppressed defect emission by the side-chain steric hindrance effect. Macromolecules 2022 , 55 , 3335−3343..

Rosenwinkel, M. P.; Andersson, R.; Mindemark, J.; Schönhoff, M. Coordination effects in polymer electrolytes: fast Li + transport by weak ion binding. J. Phys. Chem. C 2020 , 124 , 23588−23596..

Olson, K. R.; Wong, D. H. C.; Chintapalli, M.; Timachova, K.; Janusziewicz, R.; Daniel, W. F. M.; Mecham, S.; Sheiko, S.; Balsara, N. P.; DeSimone, J. M. Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications. Polymer 2016 , 100 , 126−133..

Mu, J.; Liao, S.; Shi, L.; Su, B.; Xu, F.; Guo, Z.; Li, H.; Wei, F. Solid-state polymer electrolytes in lithium batteries: latest progress and perspective. Polym. Chem. 2024 , 15 , 473−499..

Hu, L.; Gao, X.; Wang, H.; Song, Y.; Zhu, Y.; Tao, Z.; Yuan, B.; Hu, R. Progress of polymer electrolytes worked in solid-state lithium batteries for wide-temperature application. Small 2024 , 20 , 2312251..

Xu, H.; Yang, J.; Niu, Y.; Hou, X.; Sun, Z.; Jiang, C.; Xiao, Y.; He, C.; Yang, S.; Li, B.; Chen, W. Deciphering and integrating functionalized side chains for high ion-conductive elastic ternary copolymer solid-state electrolytes for safe lithium metal batteries. Angew. Chem. Int. Ed. 2024 , 63 , e202406637..

Amanchukwu, C. V.; Yu, Z.; Kong, X.; Qin, J.; Cui, Y.; Bao, Z. A new class of ionically conducting fluorinated ether electrolytes with high electrochemical stability. J. Am. Chem. Soc. 2020 , 142 , 7393−7403..

Jia, M.; Wen, P.; Wang, Z.; Zhao, Y.; Liu, Y.; Lin, J.; Chen, M.; Lin, X. Fluorinated bifunctional solid polymer electrolyte synthesized under visible light for stable lithium deposition and dendrite-free all-solid-state batteries. Adv. Funct. Mater. 2021 , 31 , 2101736..

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In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization

In situ Construction of Fluorinated Polyester-based Block Copolymer Electrolytes via Orthogonal Polymerization

DOI：10.1007/s10118-025-3542-0

摘要

Abstract

关键词

Keywords

references