{"title":"用于化学锂化的有机锂的降解机制和稳定性增强","authors":"Shiwei Xu, Yue Liu, Yejing Li, Mengyan Cao, QingLi Wu, Bingyun Ma, Jiayi Zhang, Qiu Fang, Liquan Chen, Zhaoxiang Wang, Tao Cheng, Xuefeng Wang","doi":"10.1002/aenm.202402941","DOIUrl":null,"url":null,"abstract":"Organolithium solutions, especially Li-arene solutions (LASs) with high reactivity and controllable redox potentials, have gained significant attention because of their wide applications in chemical lithiation, liquid anodes, and battery recycling. However, the sudden loss of reactivity when stored or applied at room temperature is still puzzling and inhibits the application of LASs. In this work, the degradation mechanism of LASs is fully investigated and revealed by combining various experimental characterization and computational simulations. A hierarchical reaction mechanism for lithium biphenyl/2-methyl tetrahydrofuran (Li-Bp-2MT), a lithiation solution used for most anodes, explains degradation and side product formation. Specifically, the dimerization of the active component Li<sub>1</sub>Bp[2MT]<sub>1</sub> forms an inactive dimer that is irreversibly reduced in the presence of locally accumulated highly reductive Li<sup>0</sup>. This reaction mechanism reveals the atomic origins of lithiation solution deactivation and accounts for all solid and gaseous byproducts. LiH is identified as the dominating solid byproduct, indicating irreversible destruction of the active components and facilitating side reactions producing H<sub>2</sub> and CH<sub>4.</sub> Based on reaction mechanism insights, modifying molecular interactions and reaction kinetics are experimentally shown to inhibit Li<sup>0</sup> aggregation kinetics, enhancing long-term prelithiation performance. This research provides comprehensive guidelines for practical applications of LASs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":24.4000,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Degradation Mechanism and Enhanced Stability of Organolithium for Chemical Lithiation\",\"authors\":\"Shiwei Xu, Yue Liu, Yejing Li, Mengyan Cao, QingLi Wu, Bingyun Ma, Jiayi Zhang, Qiu Fang, Liquan Chen, Zhaoxiang Wang, Tao Cheng, Xuefeng Wang\",\"doi\":\"10.1002/aenm.202402941\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Organolithium solutions, especially Li-arene solutions (LASs) with high reactivity and controllable redox potentials, have gained significant attention because of their wide applications in chemical lithiation, liquid anodes, and battery recycling. However, the sudden loss of reactivity when stored or applied at room temperature is still puzzling and inhibits the application of LASs. In this work, the degradation mechanism of LASs is fully investigated and revealed by combining various experimental characterization and computational simulations. A hierarchical reaction mechanism for lithium biphenyl/2-methyl tetrahydrofuran (Li-Bp-2MT), a lithiation solution used for most anodes, explains degradation and side product formation. Specifically, the dimerization of the active component Li<sub>1</sub>Bp[2MT]<sub>1</sub> forms an inactive dimer that is irreversibly reduced in the presence of locally accumulated highly reductive Li<sup>0</sup>. This reaction mechanism reveals the atomic origins of lithiation solution deactivation and accounts for all solid and gaseous byproducts. LiH is identified as the dominating solid byproduct, indicating irreversible destruction of the active components and facilitating side reactions producing H<sub>2</sub> and CH<sub>4.</sub> Based on reaction mechanism insights, modifying molecular interactions and reaction kinetics are experimentally shown to inhibit Li<sup>0</sup> aggregation kinetics, enhancing long-term prelithiation performance. This research provides comprehensive guidelines for practical applications of LASs.\",\"PeriodicalId\":111,\"journal\":{\"name\":\"Advanced Energy Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":24.4000,\"publicationDate\":\"2024-10-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Energy Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1002/aenm.202402941\",\"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":"Advanced Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/aenm.202402941","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}
Degradation Mechanism and Enhanced Stability of Organolithium for Chemical Lithiation
Organolithium solutions, especially Li-arene solutions (LASs) with high reactivity and controllable redox potentials, have gained significant attention because of their wide applications in chemical lithiation, liquid anodes, and battery recycling. However, the sudden loss of reactivity when stored or applied at room temperature is still puzzling and inhibits the application of LASs. In this work, the degradation mechanism of LASs is fully investigated and revealed by combining various experimental characterization and computational simulations. A hierarchical reaction mechanism for lithium biphenyl/2-methyl tetrahydrofuran (Li-Bp-2MT), a lithiation solution used for most anodes, explains degradation and side product formation. Specifically, the dimerization of the active component Li1Bp[2MT]1 forms an inactive dimer that is irreversibly reduced in the presence of locally accumulated highly reductive Li0. This reaction mechanism reveals the atomic origins of lithiation solution deactivation and accounts for all solid and gaseous byproducts. LiH is identified as the dominating solid byproduct, indicating irreversible destruction of the active components and facilitating side reactions producing H2 and CH4. Based on reaction mechanism insights, modifying molecular interactions and reaction kinetics are experimentally shown to inhibit Li0 aggregation kinetics, enhancing long-term prelithiation performance. This research provides comprehensive guidelines for practical applications of LASs.
期刊介绍:
Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small.
With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics.
The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.