Xu Xue , Yaru Zhao , Zhi Wang , Yufei Zhang , Chenchen Li
{"title":"通过结合块体和表面重新配置,消除钴酸锂在 4.6 V 电压下的电压衰减","authors":"Xu Xue , Yaru Zhao , Zhi Wang , Yufei Zhang , Chenchen Li","doi":"10.1016/j.electacta.2024.145540","DOIUrl":null,"url":null,"abstract":"<div><div>LiCoO<sub>2</sub> is an imperative cathode material for lithium-ion batteries due to its high discharge voltage and volumetric energy density. However, the practical application of LiCoO<sub>2</sub> at high voltage is greatly limited by the detrimental phase transition and interfacial side reactions. Herein, a combined bulk and surface reconfiguration via <em>K</em><sup>+</sup>–Mg<sup>2+</sup>–Al<sup>3+</sup>–Ti<sup>4+</sup> multi-ion doping and AlPO<sub>4</sub> coating is proposed to design high-voltage LiCoO<sub>2</sub> single crystals. This strategy can significantly change the morphology and microstructure of LiCoO<sub>2</sub>, resulting in obviously increased Li<sup>+</sup> diffusion kinetics and improved structural stability when charged to 4.6 V. In addition, the AlPO<sub>4</sub> coating layer can mitigate the cathode/electrolyte side reactions and contribute to form a robust Li<sub>3</sub>PO<sub>4</sub>- and LiF-rich cathode/electrolyte interphase during long-term cycling. As a result, voltage decay, particle cracks and the detrimental phase transition up to 4.6 V are effectively inhibited. The modified LiCoO<sub>2</sub> delivers a high discharge capacity of 136 mAh g<sup>–1</sup> at 10 C with outstanding capacity retention of 85.4 % and negligible voltage decay after 1000 cycles. This work can be enlightening for designing stable high-voltage cathode materials for lithium-ion batteries with long lifespan.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"512 ","pages":"Article 145540"},"PeriodicalIF":5.5000,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Eliminate voltage decay of LiCoO2 at 4.6 V through a combined bulk and surface reconfiguration\",\"authors\":\"Xu Xue , Yaru Zhao , Zhi Wang , Yufei Zhang , Chenchen Li\",\"doi\":\"10.1016/j.electacta.2024.145540\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>LiCoO<sub>2</sub> is an imperative cathode material for lithium-ion batteries due to its high discharge voltage and volumetric energy density. However, the practical application of LiCoO<sub>2</sub> at high voltage is greatly limited by the detrimental phase transition and interfacial side reactions. Herein, a combined bulk and surface reconfiguration via <em>K</em><sup>+</sup>–Mg<sup>2+</sup>–Al<sup>3+</sup>–Ti<sup>4+</sup> multi-ion doping and AlPO<sub>4</sub> coating is proposed to design high-voltage LiCoO<sub>2</sub> single crystals. This strategy can significantly change the morphology and microstructure of LiCoO<sub>2</sub>, resulting in obviously increased Li<sup>+</sup> diffusion kinetics and improved structural stability when charged to 4.6 V. In addition, the AlPO<sub>4</sub> coating layer can mitigate the cathode/electrolyte side reactions and contribute to form a robust Li<sub>3</sub>PO<sub>4</sub>- and LiF-rich cathode/electrolyte interphase during long-term cycling. As a result, voltage decay, particle cracks and the detrimental phase transition up to 4.6 V are effectively inhibited. The modified LiCoO<sub>2</sub> delivers a high discharge capacity of 136 mAh g<sup>–1</sup> at 10 C with outstanding capacity retention of 85.4 % and negligible voltage decay after 1000 cycles. This work can be enlightening for designing stable high-voltage cathode materials for lithium-ion batteries with long lifespan.</div></div>\",\"PeriodicalId\":305,\"journal\":{\"name\":\"Electrochimica Acta\",\"volume\":\"512 \",\"pages\":\"Article 145540\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-02-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Electrochimica Acta\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0013468624017766\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ELECTROCHEMISTRY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Electrochimica Acta","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0013468624017766","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ELECTROCHEMISTRY","Score":null,"Total":0}
引用次数: 0
摘要
钴酸锂具有较高的放电电压和体积能量密度,是锂离子电池必不可少的正极材料。然而,由于有害的相变和界面副反应,钴酸锂在高电压下的实际应用受到很大限制。本文提出了一种通过 K+-Mg2+-Al3+-Ti4+ 多离子掺杂和 AlPO4 镀膜进行体质和表面组合重构的方法来设计高压钴酸锂单晶。此外,AlPO4 涂层还能缓解阴极/电解质副反应,有助于在长期循环过程中形成稳健的富含 LiF 和 Li3PO4 的阴极/电解质相。因此,电压衰减、微粒裂纹和高达 4.6 V 的有害相变都得到了有效抑制。改性后的钴酸锂在 10 C 时放电容量高达 136 mAh g-1,容量保持率高达 85.4%,1000 次循环后的电压衰减可忽略不计。这项研究对设计稳定、高电压、长寿命的锂离子电池正极材料具有启发意义。
Eliminate voltage decay of LiCoO2 at 4.6 V through a combined bulk and surface reconfiguration
LiCoO2 is an imperative cathode material for lithium-ion batteries due to its high discharge voltage and volumetric energy density. However, the practical application of LiCoO2 at high voltage is greatly limited by the detrimental phase transition and interfacial side reactions. Herein, a combined bulk and surface reconfiguration via K+–Mg2+–Al3+–Ti4+ multi-ion doping and AlPO4 coating is proposed to design high-voltage LiCoO2 single crystals. This strategy can significantly change the morphology and microstructure of LiCoO2, resulting in obviously increased Li+ diffusion kinetics and improved structural stability when charged to 4.6 V. In addition, the AlPO4 coating layer can mitigate the cathode/electrolyte side reactions and contribute to form a robust Li3PO4- and LiF-rich cathode/electrolyte interphase during long-term cycling. As a result, voltage decay, particle cracks and the detrimental phase transition up to 4.6 V are effectively inhibited. The modified LiCoO2 delivers a high discharge capacity of 136 mAh g–1 at 10 C with outstanding capacity retention of 85.4 % and negligible voltage decay after 1000 cycles. This work can be enlightening for designing stable high-voltage cathode materials for lithium-ion batteries with long lifespan.
期刊介绍:
Electrochimica Acta is an international journal. It is intended for the publication of both original work and reviews in the field of electrochemistry. Electrochemistry should be interpreted to mean any of the research fields covered by the Divisions of the International Society of Electrochemistry listed below, as well as emerging scientific domains covered by ISE New Topics Committee.