{"title":"聚酰亚胺正极内偶极子的多重增强效应促进锂离子电池的高效储能","authors":"","doi":"10.1016/j.ensm.2024.103779","DOIUrl":null,"url":null,"abstract":"<div><p>Polyimide (PI) has been recognized as a potential organic cathode for Li-ion batteries (LIBs) due to its programmable structural design, high theoretical capacity, and resource availability. However, the poor intrinsic electrical conductivity of PI means that PI-based cathodes of LIBs have inefficient energy storage performance, especially at high current densities. In this work, the molecular structure of PI is optimized to obtain a layer-stacked crystalline PI with significantly enhanced dipoles, denoted NT-B for the first time. The dipoles in this PI are induced by the electronegative carbonyl groups from the monomer biuret and further enhanced via a π-π layer stacking effect. This work is the first to verify that the co-directional dipole enhancement effect of biuret is surprisingly different from that of monomer urea. A series of ex-situ/in-situ and theoretical DFT simulations are carried out to understand the functional mechanism of such effects. The multiple enhancement effects of the dipoles synergistically promoting the generation of a strong built-in electric field (BIEF) within NT-B are proposed based on the results obtained. It is confirmed that this BIEF plays a significant role in accelerating electron transport, which enhances the electrochemical activity of LIB cathodes. This work provides a new idea for the structural design of high-performance PI cathodes for LIBs.</p></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":null,"pages":null},"PeriodicalIF":18.9000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Multiple enhancement effects of dipoles within polyimide cathode promoting highly efficient energy storage of lithium-ion batteries\",\"authors\":\"\",\"doi\":\"10.1016/j.ensm.2024.103779\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Polyimide (PI) has been recognized as a potential organic cathode for Li-ion batteries (LIBs) due to its programmable structural design, high theoretical capacity, and resource availability. However, the poor intrinsic electrical conductivity of PI means that PI-based cathodes of LIBs have inefficient energy storage performance, especially at high current densities. In this work, the molecular structure of PI is optimized to obtain a layer-stacked crystalline PI with significantly enhanced dipoles, denoted NT-B for the first time. The dipoles in this PI are induced by the electronegative carbonyl groups from the monomer biuret and further enhanced via a π-π layer stacking effect. This work is the first to verify that the co-directional dipole enhancement effect of biuret is surprisingly different from that of monomer urea. A series of ex-situ/in-situ and theoretical DFT simulations are carried out to understand the functional mechanism of such effects. The multiple enhancement effects of the dipoles synergistically promoting the generation of a strong built-in electric field (BIEF) within NT-B are proposed based on the results obtained. It is confirmed that this BIEF plays a significant role in accelerating electron transport, which enhances the electrochemical activity of LIB cathodes. This work provides a new idea for the structural design of high-performance PI cathodes for LIBs.</p></div>\",\"PeriodicalId\":306,\"journal\":{\"name\":\"Energy Storage Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":18.9000,\"publicationDate\":\"2024-09-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy Storage Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2405829724006056\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy Storage Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2405829724006056","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
聚酰亚胺(PI)因其可编程的结构设计、高理论容量和资源可用性,已被视为锂离子电池(LIB)的潜在有机阴极。然而,聚酰亚胺的固有导电性较差,这意味着基于聚酰亚胺的锂离子电池阴极储能效率较低,尤其是在高电流密度下。本研究优化了 PI 的分子结构,首次获得了偶极子显著增强的层堆叠结晶 PI,命名为 NT-B。这种 PI 中的偶极子由来自单体双缩脲的电负性羰基引起,并通过 π-π 层堆叠效应进一步增强。这项研究首次验证了双缩脲的共向偶极增强效应与单体脲的共向偶极增强效应有着惊人的不同。为了理解这种效应的功能机制,我们进行了一系列原位/原位和理论 DFT 模拟。根据所得结果,提出了偶极子协同促进在 NT-B 中产生强内置电场(BIEF)的多重增强效应。研究证实,这种内置电场在加速电子传输方面发挥了重要作用,从而增强了 LIB 阴极的电化学活性。这项工作为锂电池用高性能 PI 阴极的结构设计提供了新思路。
Multiple enhancement effects of dipoles within polyimide cathode promoting highly efficient energy storage of lithium-ion batteries
Polyimide (PI) has been recognized as a potential organic cathode for Li-ion batteries (LIBs) due to its programmable structural design, high theoretical capacity, and resource availability. However, the poor intrinsic electrical conductivity of PI means that PI-based cathodes of LIBs have inefficient energy storage performance, especially at high current densities. In this work, the molecular structure of PI is optimized to obtain a layer-stacked crystalline PI with significantly enhanced dipoles, denoted NT-B for the first time. The dipoles in this PI are induced by the electronegative carbonyl groups from the monomer biuret and further enhanced via a π-π layer stacking effect. This work is the first to verify that the co-directional dipole enhancement effect of biuret is surprisingly different from that of monomer urea. A series of ex-situ/in-situ and theoretical DFT simulations are carried out to understand the functional mechanism of such effects. The multiple enhancement effects of the dipoles synergistically promoting the generation of a strong built-in electric field (BIEF) within NT-B are proposed based on the results obtained. It is confirmed that this BIEF plays a significant role in accelerating electron transport, which enhances the electrochemical activity of LIB cathodes. This work provides a new idea for the structural design of high-performance PI cathodes for LIBs.
期刊介绍:
Energy Storage Materials is a global interdisciplinary journal dedicated to sharing scientific and technological advancements in materials and devices for advanced energy storage and related energy conversion, such as in metal-O2 batteries. The journal features comprehensive research articles, including full papers and short communications, as well as authoritative feature articles and reviews by leading experts in the field.
Energy Storage Materials covers a wide range of topics, including the synthesis, fabrication, structure, properties, performance, and technological applications of energy storage materials. Additionally, the journal explores strategies, policies, and developments in the field of energy storage materials and devices for sustainable energy.
Published papers are selected based on their scientific and technological significance, their ability to provide valuable new knowledge, and their relevance to the international research community.