{"title":"自由体积介导的离子传导与节段弛豫解耦导致聚合物电解质在低温下的离子传导性增强。","authors":"S K Sharma, J Mor","doi":"10.1021/acsmacrolett.4c00467","DOIUrl":null,"url":null,"abstract":"<p><p>Coupling between segmental relaxation and ionic conduction has limited the ionic conductivity of flexible polymers like poly(ethylene oxide), PEO, based electrolytes especially at low temperatures where segmental relaxation becomes extremely slow. In the present study, we show that ionic conduction becomes decoupled from segmental relaxation in PEO-based electrolytes simply by loading succinonitrile (SN). As a result of SN interactions induced rigid chain packing of PEO, the semicrystalline morphology of PEO is completely altered along with the enhancement in number density of free volumes having smaller size and narrower size distribution. These free volumes provide additional pathways for ionic diffusion independent of segmental relaxations of PEO leading to decoupling of ionic diffusion from the segmental relaxation process. The decoupling finally leads to nearly two orders higher ionic conductivity (∼10<sup>-11</sup> Scm<sup>-1</sup>)at glass transition temperature (<i>T</i><sub>g</sub> ∼ 210 K), than what is expected in the case of complete coupling.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"1211-1217"},"PeriodicalIF":5.2000,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Free Volume Mediated Decoupling of Ionic Conduction from Segmental Relaxation Leading to Enhancement in Ionic Conductivity of Polymer Electrolytes at Low Temperatures.\",\"authors\":\"S K Sharma, J Mor\",\"doi\":\"10.1021/acsmacrolett.4c00467\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Coupling between segmental relaxation and ionic conduction has limited the ionic conductivity of flexible polymers like poly(ethylene oxide), PEO, based electrolytes especially at low temperatures where segmental relaxation becomes extremely slow. In the present study, we show that ionic conduction becomes decoupled from segmental relaxation in PEO-based electrolytes simply by loading succinonitrile (SN). As a result of SN interactions induced rigid chain packing of PEO, the semicrystalline morphology of PEO is completely altered along with the enhancement in number density of free volumes having smaller size and narrower size distribution. These free volumes provide additional pathways for ionic diffusion independent of segmental relaxations of PEO leading to decoupling of ionic diffusion from the segmental relaxation process. The decoupling finally leads to nearly two orders higher ionic conductivity (∼10<sup>-11</sup> Scm<sup>-1</sup>)at glass transition temperature (<i>T</i><sub>g</sub> ∼ 210 K), than what is expected in the case of complete coupling.</p>\",\"PeriodicalId\":18,\"journal\":{\"name\":\"ACS Macro Letters\",\"volume\":\" \",\"pages\":\"1211-1217\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2024-09-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Macro Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acsmacrolett.4c00467\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/9/3 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Macro Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acsmacrolett.4c00467","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/9/3 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Free Volume Mediated Decoupling of Ionic Conduction from Segmental Relaxation Leading to Enhancement in Ionic Conductivity of Polymer Electrolytes at Low Temperatures.
Coupling between segmental relaxation and ionic conduction has limited the ionic conductivity of flexible polymers like poly(ethylene oxide), PEO, based electrolytes especially at low temperatures where segmental relaxation becomes extremely slow. In the present study, we show that ionic conduction becomes decoupled from segmental relaxation in PEO-based electrolytes simply by loading succinonitrile (SN). As a result of SN interactions induced rigid chain packing of PEO, the semicrystalline morphology of PEO is completely altered along with the enhancement in number density of free volumes having smaller size and narrower size distribution. These free volumes provide additional pathways for ionic diffusion independent of segmental relaxations of PEO leading to decoupling of ionic diffusion from the segmental relaxation process. The decoupling finally leads to nearly two orders higher ionic conductivity (∼10-11 Scm-1)at glass transition temperature (Tg ∼ 210 K), than what is expected in the case of complete coupling.
期刊介绍：
ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science.
With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.
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