{"title":"线性-组合嵌段共聚物电解质的微相分离:静电效应与构象不对称","authors":"Lei Shen, Rui Liu, Yue Zhou, Tiantian Song, Yu Guan, Xiaoxue Wu, Zizhen Wei, Xiaotong Chen, Wangqing Zhang and Weichao Shi*, ","doi":"10.1021/acs.macromol.4c00444","DOIUrl":null,"url":null,"abstract":"<p >In this work, we synthesize a series of linear-comb block copolymers, polystyrene-<i>b</i>-poly(polyethylene glycol methyl ether acrylate) (PS–PPEGMEA), and study the microphase separation mechanism by LiTFSI-doping. The increasing salt concentration promotes the microphase separation of PS–PPEGMEA and also deflects the phase transition boundaries to the lower PPEGMEA volume fraction. We reveal that the effective interaction parameter exhibits a linear to nonlinear dependence on increasing salt concentration and is eventually weakened by the formation of ion clusters at high salt concentration. We further quantify the conformational asymmetry of PS–PPEGMEA by theoretical analysis and point out that the limit of the order–order transition boundaries is defined by strong segregation theory. Therefore, electrostatic interaction and conformational asymmetry jointly determine the microphase separation of PS–PPEGMEA block copolymer electrolytes. This study provides a fundamental understanding of the phase behaviors of salt-doped linear-comb block copolymers and suggests experimental strategies to modulate their nanostructures, which could be very useful for developing novel solid polymer electrolytes.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Microphase Separation of Linear-Comb Block Copolymer Electrolyte: Electrostatic Effect and Conformational Asymmetry\",\"authors\":\"Lei Shen, Rui Liu, Yue Zhou, Tiantian Song, Yu Guan, Xiaoxue Wu, Zizhen Wei, Xiaotong Chen, Wangqing Zhang and Weichao Shi*, \",\"doi\":\"10.1021/acs.macromol.4c00444\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this work, we synthesize a series of linear-comb block copolymers, polystyrene-<i>b</i>-poly(polyethylene glycol methyl ether acrylate) (PS–PPEGMEA), and study the microphase separation mechanism by LiTFSI-doping. The increasing salt concentration promotes the microphase separation of PS–PPEGMEA and also deflects the phase transition boundaries to the lower PPEGMEA volume fraction. We reveal that the effective interaction parameter exhibits a linear to nonlinear dependence on increasing salt concentration and is eventually weakened by the formation of ion clusters at high salt concentration. We further quantify the conformational asymmetry of PS–PPEGMEA by theoretical analysis and point out that the limit of the order–order transition boundaries is defined by strong segregation theory. Therefore, electrostatic interaction and conformational asymmetry jointly determine the microphase separation of PS–PPEGMEA block copolymer electrolytes. This study provides a fundamental understanding of the phase behaviors of salt-doped linear-comb block copolymers and suggests experimental strategies to modulate their nanostructures, which could be very useful for developing novel solid polymer electrolytes.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-05-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00444\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00444","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Microphase Separation of Linear-Comb Block Copolymer Electrolyte: Electrostatic Effect and Conformational Asymmetry
In this work, we synthesize a series of linear-comb block copolymers, polystyrene-b-poly(polyethylene glycol methyl ether acrylate) (PS–PPEGMEA), and study the microphase separation mechanism by LiTFSI-doping. The increasing salt concentration promotes the microphase separation of PS–PPEGMEA and also deflects the phase transition boundaries to the lower PPEGMEA volume fraction. We reveal that the effective interaction parameter exhibits a linear to nonlinear dependence on increasing salt concentration and is eventually weakened by the formation of ion clusters at high salt concentration. We further quantify the conformational asymmetry of PS–PPEGMEA by theoretical analysis and point out that the limit of the order–order transition boundaries is defined by strong segregation theory. Therefore, electrostatic interaction and conformational asymmetry jointly determine the microphase separation of PS–PPEGMEA block copolymer electrolytes. This study provides a fundamental understanding of the phase behaviors of salt-doped linear-comb block copolymers and suggests experimental strategies to modulate their nanostructures, which could be very useful for developing novel solid polymer electrolytes.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.