{"title":"通过液相环化合成用于先进阴极材料的高环化聚丙烯腈","authors":"Zhenpu Shi, Yujiao Wang, Miaomiao Liu, Jiongxiang Ma, Hongyun Yue, Zhiguo Hu, Shu-Ting Yang, Yanhong Yin","doi":"10.1021/acssuschemeng.4c07155","DOIUrl":null,"url":null,"abstract":"Sulfurized polyacrylonitrile (SPAN) based on a solid–solid reaction has attracted wide attention due to its advantages of no shuttle effect. However, the solid-state polyacrylonitrile raw material is used during the preparation of SPAN and results in a low vulcanization efficiency. Meanwhile, a series of side reactions such as the formation of cyclic polyamines and conjugated polyenes, cross-linking side reactions, and polymer degradation prevent an ideal trapezoidal conjugated main-chain structure. In this work, a liquid-phase cyclization method is proposed to prepare SPAN materials (SPAN-L). The reaction temperature is significantly lowered by leveraging the high reactivity characteristics under liquid-phase conditions, thereby inhibiting a series of side reactions caused by high temperature and improving the structural regularity of SPAN. The SPAN-L cathode has good structural regularity and a uniform sulfur distribution, which contribute to its enhanced electrical conductivity and high sulfur utilization ratio. Additionally, ex situ Raman and XPS analyses reveal stable C–S bonds in SPAN-L during cycling, indicating enhanced electrode stability. This study synthesizes SPAN cathode materials with enhanced performance by adjusting the reaction environment, showing better electronic conductivity, sulfur utilization, and cycle stability than the solid-phase methods.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"42 1","pages":""},"PeriodicalIF":7.3000,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of Highly Cyclized Polyacrylonitrile via Liquid-Phase Cyclization for Advanced Cathode Materials\",\"authors\":\"Zhenpu Shi, Yujiao Wang, Miaomiao Liu, Jiongxiang Ma, Hongyun Yue, Zhiguo Hu, Shu-Ting Yang, Yanhong Yin\",\"doi\":\"10.1021/acssuschemeng.4c07155\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Sulfurized polyacrylonitrile (SPAN) based on a solid–solid reaction has attracted wide attention due to its advantages of no shuttle effect. However, the solid-state polyacrylonitrile raw material is used during the preparation of SPAN and results in a low vulcanization efficiency. Meanwhile, a series of side reactions such as the formation of cyclic polyamines and conjugated polyenes, cross-linking side reactions, and polymer degradation prevent an ideal trapezoidal conjugated main-chain structure. In this work, a liquid-phase cyclization method is proposed to prepare SPAN materials (SPAN-L). The reaction temperature is significantly lowered by leveraging the high reactivity characteristics under liquid-phase conditions, thereby inhibiting a series of side reactions caused by high temperature and improving the structural regularity of SPAN. The SPAN-L cathode has good structural regularity and a uniform sulfur distribution, which contribute to its enhanced electrical conductivity and high sulfur utilization ratio. Additionally, ex situ Raman and XPS analyses reveal stable C–S bonds in SPAN-L during cycling, indicating enhanced electrode stability. This study synthesizes SPAN cathode materials with enhanced performance by adjusting the reaction environment, showing better electronic conductivity, sulfur utilization, and cycle stability than the solid-phase methods.\",\"PeriodicalId\":25,\"journal\":{\"name\":\"ACS Sustainable Chemistry & Engineering\",\"volume\":\"42 1\",\"pages\":\"\"},\"PeriodicalIF\":7.3000,\"publicationDate\":\"2024-11-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Sustainable Chemistry & Engineering\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acssuschemeng.4c07155\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acssuschemeng.4c07155","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Synthesis of Highly Cyclized Polyacrylonitrile via Liquid-Phase Cyclization for Advanced Cathode Materials
Sulfurized polyacrylonitrile (SPAN) based on a solid–solid reaction has attracted wide attention due to its advantages of no shuttle effect. However, the solid-state polyacrylonitrile raw material is used during the preparation of SPAN and results in a low vulcanization efficiency. Meanwhile, a series of side reactions such as the formation of cyclic polyamines and conjugated polyenes, cross-linking side reactions, and polymer degradation prevent an ideal trapezoidal conjugated main-chain structure. In this work, a liquid-phase cyclization method is proposed to prepare SPAN materials (SPAN-L). The reaction temperature is significantly lowered by leveraging the high reactivity characteristics under liquid-phase conditions, thereby inhibiting a series of side reactions caused by high temperature and improving the structural regularity of SPAN. The SPAN-L cathode has good structural regularity and a uniform sulfur distribution, which contribute to its enhanced electrical conductivity and high sulfur utilization ratio. Additionally, ex situ Raman and XPS analyses reveal stable C–S bonds in SPAN-L during cycling, indicating enhanced electrode stability. This study synthesizes SPAN cathode materials with enhanced performance by adjusting the reaction environment, showing better electronic conductivity, sulfur utilization, and cycle stability than the solid-phase methods.
期刊介绍:
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.