{"title":"面向 5C 快速充电 4.6 V 钴酸锂的表层到块体调谐深度脱锂策略","authors":"Zhihong Bi, Zonglin Yi, Anping Zhang, Cong Dong, Gongrui Wang, Lijing Xie, Shihao Liao, Hanqing Liu, Chengmeng Chen and Zhong-Shuai Wu","doi":"10.1039/D4EE01674B","DOIUrl":null,"url":null,"abstract":"<p >Achieving highly reversible anionic redox reactions (ARR) in high-voltage LiCoO<small><sub>2</sub></small> (LCO) is critical for increasing its power/energy density but still lacks a reliable tuning strategy. Herein, we report a comprehensive surface-to-bulk tuning deep delithiation strategy by coupling trace Mg–Nb–Al Li-layer co-doping with ultrathin interfacial hierarchical fluorination, featured by a unique ultra-thin double-layer cathode electrolyte interphase structure consisting of an inner1 nm-thick LiF-rich layer and an outer 2 nm-thick Li<small><sub><em>x</em></sub></small>PO<small><sub><em>y</em></sub></small>F<small><sub><em>z</em></sub></small> layer, to extremely stabilize fast charging of 4.6 V-LCO. The slight cation disorder induced by Li-layer co-doping and synergistically confined interfacial hierarchical fluorination enhances the bulk-to-surface anion/cation redox process of LCO and suppresses interfacial side reactions during fast-charging cycles, and the Mg–Nb–Al pillars strengthen the layered lithium diffusion channels. Consequently, our LCO achieves a record reversible capacity of 198 mA h g<small><sup>−1</sup></small> and a 77.8% capacity retention at 5C fast-charging after 500 cycles. The assembled graphite‖LCO pouch cell demonstrates the state-of-the-art cyclability with virtually no capacity decay after 1400 cycles at 5C charge and 10C discharge. It is theoretically unraveled that suppressing oxygen electronic hole generation through an Nb<small><sup>5+</sup></small>-induced high spin-polarized weak Co–O octahedral crystal field is the key to highly reversible ARR in 4.6 V-LCO. This work provides a design guidance for achieving reversible deep delithiation of high-voltage LCO.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.4000,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A surface-to-bulk tuning deep delithiation strategy for 5C fast-charging 4.6 V LiCoO2†\",\"authors\":\"Zhihong Bi, Zonglin Yi, Anping Zhang, Cong Dong, Gongrui Wang, Lijing Xie, Shihao Liao, Hanqing Liu, Chengmeng Chen and Zhong-Shuai Wu\",\"doi\":\"10.1039/D4EE01674B\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Achieving highly reversible anionic redox reactions (ARR) in high-voltage LiCoO<small><sub>2</sub></small> (LCO) is critical for increasing its power/energy density but still lacks a reliable tuning strategy. Herein, we report a comprehensive surface-to-bulk tuning deep delithiation strategy by coupling trace Mg–Nb–Al Li-layer co-doping with ultrathin interfacial hierarchical fluorination, featured by a unique ultra-thin double-layer cathode electrolyte interphase structure consisting of an inner1 nm-thick LiF-rich layer and an outer 2 nm-thick Li<small><sub><em>x</em></sub></small>PO<small><sub><em>y</em></sub></small>F<small><sub><em>z</em></sub></small> layer, to extremely stabilize fast charging of 4.6 V-LCO. The slight cation disorder induced by Li-layer co-doping and synergistically confined interfacial hierarchical fluorination enhances the bulk-to-surface anion/cation redox process of LCO and suppresses interfacial side reactions during fast-charging cycles, and the Mg–Nb–Al pillars strengthen the layered lithium diffusion channels. Consequently, our LCO achieves a record reversible capacity of 198 mA h g<small><sup>−1</sup></small> and a 77.8% capacity retention at 5C fast-charging after 500 cycles. The assembled graphite‖LCO pouch cell demonstrates the state-of-the-art cyclability with virtually no capacity decay after 1400 cycles at 5C charge and 10C discharge. It is theoretically unraveled that suppressing oxygen electronic hole generation through an Nb<small><sup>5+</sup></small>-induced high spin-polarized weak Co–O octahedral crystal field is the key to highly reversible ARR in 4.6 V-LCO. This work provides a design guidance for achieving reversible deep delithiation of high-voltage LCO.</p>\",\"PeriodicalId\":72,\"journal\":{\"name\":\"Energy & Environmental Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":32.4000,\"publicationDate\":\"2024-06-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Environmental Science\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/ee/d4ee01674b\",\"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://pubs.rsc.org/en/content/articlelanding/2024/ee/d4ee01674b","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}
A surface-to-bulk tuning deep delithiation strategy for 5C fast-charging 4.6 V LiCoO2†
Achieving highly reversible anionic redox reactions (ARR) in high-voltage LiCoO2 (LCO) is critical for increasing its power/energy density but still lacks a reliable tuning strategy. Herein, we report a comprehensive surface-to-bulk tuning deep delithiation strategy by coupling trace Mg–Nb–Al Li-layer co-doping with ultrathin interfacial hierarchical fluorination, featured by a unique ultra-thin double-layer cathode electrolyte interphase structure consisting of an inner1 nm-thick LiF-rich layer and an outer 2 nm-thick LixPOyFz layer, to extremely stabilize fast charging of 4.6 V-LCO. The slight cation disorder induced by Li-layer co-doping and synergistically confined interfacial hierarchical fluorination enhances the bulk-to-surface anion/cation redox process of LCO and suppresses interfacial side reactions during fast-charging cycles, and the Mg–Nb–Al pillars strengthen the layered lithium diffusion channels. Consequently, our LCO achieves a record reversible capacity of 198 mA h g−1 and a 77.8% capacity retention at 5C fast-charging after 500 cycles. The assembled graphite‖LCO pouch cell demonstrates the state-of-the-art cyclability with virtually no capacity decay after 1400 cycles at 5C charge and 10C discharge. It is theoretically unraveled that suppressing oxygen electronic hole generation through an Nb5+-induced high spin-polarized weak Co–O octahedral crystal field is the key to highly reversible ARR in 4.6 V-LCO. This work provides a design guidance for achieving reversible deep delithiation of high-voltage LCO.
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).