Lijin An, Ruomu Zhang, Pravin N. Didwal, Michael W. Fraser, Leanne A. H. Jones, Conor M. E. Phelan, Namrata Ramesh, Grant Harris, Robert S Weatherup, Jack E. N. Swallow, Peixi Cong, Andrey Poletayev, Erik Björklund, Christophe Sahle, Pilar Ferrer, David C. Grinter, Peter Bencok, Shusaku Hayama, Saiful Islam, Robert House, Peter D Nellist, Robert J. Green, Rebecca J Nicholls
{"title":"区分氧化镍锂阴极中的大量氧化还原与近表面降解","authors":"Lijin An, Ruomu Zhang, Pravin N. Didwal, Michael W. Fraser, Leanne A. H. Jones, Conor M. E. Phelan, Namrata Ramesh, Grant Harris, Robert S Weatherup, Jack E. N. Swallow, Peixi Cong, Andrey Poletayev, Erik Björklund, Christophe Sahle, Pilar Ferrer, David C. Grinter, Peter Bencok, Shusaku Hayama, Saiful Islam, Robert House, Peter D Nellist, Robert J. Green, Rebecca J Nicholls","doi":"10.1039/d4ee02398f","DOIUrl":null,"url":null,"abstract":"Ni-rich layered oxide cathodes can deliver higher energy density batteries, but uncertainties remain over their charge compensation mechanisms and the degradation processes that limit cycle life. Trapped molecular O2 has been identified within LiNiO2 at high states of charge, as seen for Li-rich cathodes where excess capacity is associated with reversible O-redox. Here we show that bulk redox in LiNiO2 occurs by Ni-O rehybridization, lowering the electron density on O sites, but importantly without the involvement of molecular O2. Instead, trapped O2 is related to degradation at surfaces in contact with the electrolyte, and is accompanied by Ni reduction. O2 is removed on discharge, but excess Ni2+ persists forming a reduced surface layer, associated with impeded Li transport. This implicates the instability of delithiated LiNiO2 in contact with the electrolyte in surface degradation through O2 formation and Ni reduction, highlighting the importance of surface stabilisation strategies in suppressing LNO degradation.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.4000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Distinguishing Bulk Redox from Near-Surface Degradation in Lithium Nickel Oxide Cathodes\",\"authors\":\"Lijin An, Ruomu Zhang, Pravin N. Didwal, Michael W. Fraser, Leanne A. H. Jones, Conor M. E. Phelan, Namrata Ramesh, Grant Harris, Robert S Weatherup, Jack E. N. Swallow, Peixi Cong, Andrey Poletayev, Erik Björklund, Christophe Sahle, Pilar Ferrer, David C. Grinter, Peter Bencok, Shusaku Hayama, Saiful Islam, Robert House, Peter D Nellist, Robert J. Green, Rebecca J Nicholls\",\"doi\":\"10.1039/d4ee02398f\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Ni-rich layered oxide cathodes can deliver higher energy density batteries, but uncertainties remain over their charge compensation mechanisms and the degradation processes that limit cycle life. Trapped molecular O2 has been identified within LiNiO2 at high states of charge, as seen for Li-rich cathodes where excess capacity is associated with reversible O-redox. Here we show that bulk redox in LiNiO2 occurs by Ni-O rehybridization, lowering the electron density on O sites, but importantly without the involvement of molecular O2. Instead, trapped O2 is related to degradation at surfaces in contact with the electrolyte, and is accompanied by Ni reduction. O2 is removed on discharge, but excess Ni2+ persists forming a reduced surface layer, associated with impeded Li transport. This implicates the instability of delithiated LiNiO2 in contact with the electrolyte in surface degradation through O2 formation and Ni reduction, highlighting the importance of surface stabilisation strategies in suppressing LNO degradation.\",\"PeriodicalId\":72,\"journal\":{\"name\":\"Energy & Environmental Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":32.4000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Environmental Science\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ee02398f\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Science","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ee02398f","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Distinguishing Bulk Redox from Near-Surface Degradation in Lithium Nickel Oxide Cathodes
Ni-rich layered oxide cathodes can deliver higher energy density batteries, but uncertainties remain over their charge compensation mechanisms and the degradation processes that limit cycle life. Trapped molecular O2 has been identified within LiNiO2 at high states of charge, as seen for Li-rich cathodes where excess capacity is associated with reversible O-redox. Here we show that bulk redox in LiNiO2 occurs by Ni-O rehybridization, lowering the electron density on O sites, but importantly without the involvement of molecular O2. Instead, trapped O2 is related to degradation at surfaces in contact with the electrolyte, and is accompanied by Ni reduction. O2 is removed on discharge, but excess Ni2+ persists forming a reduced surface layer, associated with impeded Li transport. This implicates the instability of delithiated LiNiO2 in contact with the electrolyte in surface degradation through O2 formation and Ni reduction, highlighting the importance of surface stabilisation strategies in suppressing LNO degradation.
期刊介绍:
Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences."
Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).