Xuerui Yang , Ying Lin , Shijun Tang , Yuqi Zhou , Xuan Huang , Wen Song , Wen Yang , Yong Yang
{"title":"颗粒级高电压LiCoO2阴极界面与结构裂纹退化模式的相互作用","authors":"Xuerui Yang , Ying Lin , Shijun Tang , Yuqi Zhou , Xuan Huang , Wen Song , Wen Yang , Yong Yang","doi":"10.1016/j.ensm.2025.104473","DOIUrl":null,"url":null,"abstract":"<div><div>Elevating the cut-off voltage is a promising strategy to enhance the energy density of LiCoO<sub>2</sub> (LCO), as demonstrated by a ∼22 % increase in discharge capacity at 4.6 V compared to 4.5 V. However, severe structural degradation and interfacial instability above 4.5 V hinder its practical application, with limited research focusing on decoupling these mechanisms to mitigate performance decay. Herein, LCO samples with distinct particle sizes are systematically investigated by using electrochemical techniques and numerical modeling to elucidate complex failure modes. Larger-sized LCO particles exhibit structural cracking and fracture, particularly at high current density, due to prolonged Li<sup>+</sup> diffusion pathways, inhomogeneous lithium distribution, and stress accumulation. Conversely, smaller-sized LCO particles suffer from intensified interfacial side reactions attributed to their higher surface area, especially at low current density. These results highlight that LCO degradation arises from the interplay of size- and rate-dependent mechanisms rather than a single dominant factor. To address this complexity, we develop a multivariate nonlinear equation to fully decouple different degradation mechanisms and successfully determine the optimal mass mixing ratios of larger- and smaller-sized LCO particles under various current density conditions to maximize cycling stability. This work provides valuable mechanistic insights into degradation pathways and effectively bridges the gap between empirical optimization and a deeper understanding of LCO degradation.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"81 ","pages":"Article 104473"},"PeriodicalIF":20.2000,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Interplay of interfacial and structural cracking degradation modes for the high-voltage LiCoO2 cathode at particle’s level\",\"authors\":\"Xuerui Yang , Ying Lin , Shijun Tang , Yuqi Zhou , Xuan Huang , Wen Song , Wen Yang , Yong Yang\",\"doi\":\"10.1016/j.ensm.2025.104473\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Elevating the cut-off voltage is a promising strategy to enhance the energy density of LiCoO<sub>2</sub> (LCO), as demonstrated by a ∼22 % increase in discharge capacity at 4.6 V compared to 4.5 V. However, severe structural degradation and interfacial instability above 4.5 V hinder its practical application, with limited research focusing on decoupling these mechanisms to mitigate performance decay. Herein, LCO samples with distinct particle sizes are systematically investigated by using electrochemical techniques and numerical modeling to elucidate complex failure modes. Larger-sized LCO particles exhibit structural cracking and fracture, particularly at high current density, due to prolonged Li<sup>+</sup> diffusion pathways, inhomogeneous lithium distribution, and stress accumulation. Conversely, smaller-sized LCO particles suffer from intensified interfacial side reactions attributed to their higher surface area, especially at low current density. These results highlight that LCO degradation arises from the interplay of size- and rate-dependent mechanisms rather than a single dominant factor. To address this complexity, we develop a multivariate nonlinear equation to fully decouple different degradation mechanisms and successfully determine the optimal mass mixing ratios of larger- and smaller-sized LCO particles under various current density conditions to maximize cycling stability. This work provides valuable mechanistic insights into degradation pathways and effectively bridges the gap between empirical optimization and a deeper understanding of LCO degradation.</div></div>\",\"PeriodicalId\":306,\"journal\":{\"name\":\"Energy Storage Materials\",\"volume\":\"81 \",\"pages\":\"Article 104473\"},\"PeriodicalIF\":20.2000,\"publicationDate\":\"2025-07-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy Storage Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2405829725004702\",\"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":"Energy Storage Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2405829725004702","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}
Interplay of interfacial and structural cracking degradation modes for the high-voltage LiCoO2 cathode at particle’s level
Elevating the cut-off voltage is a promising strategy to enhance the energy density of LiCoO2 (LCO), as demonstrated by a ∼22 % increase in discharge capacity at 4.6 V compared to 4.5 V. However, severe structural degradation and interfacial instability above 4.5 V hinder its practical application, with limited research focusing on decoupling these mechanisms to mitigate performance decay. Herein, LCO samples with distinct particle sizes are systematically investigated by using electrochemical techniques and numerical modeling to elucidate complex failure modes. Larger-sized LCO particles exhibit structural cracking and fracture, particularly at high current density, due to prolonged Li+ diffusion pathways, inhomogeneous lithium distribution, and stress accumulation. Conversely, smaller-sized LCO particles suffer from intensified interfacial side reactions attributed to their higher surface area, especially at low current density. These results highlight that LCO degradation arises from the interplay of size- and rate-dependent mechanisms rather than a single dominant factor. To address this complexity, we develop a multivariate nonlinear equation to fully decouple different degradation mechanisms and successfully determine the optimal mass mixing ratios of larger- and smaller-sized LCO particles under various current density conditions to maximize cycling stability. This work provides valuable mechanistic insights into degradation pathways and effectively bridges the gap between empirical optimization and a deeper understanding of LCO degradation.
期刊介绍:
Energy Storage Materials is a global interdisciplinary journal dedicated to sharing scientific and technological advancements in materials and devices for advanced energy storage and related energy conversion, such as in metal-O2 batteries. The journal features comprehensive research articles, including full papers and short communications, as well as authoritative feature articles and reviews by leading experts in the field.
Energy Storage Materials covers a wide range of topics, including the synthesis, fabrication, structure, properties, performance, and technological applications of energy storage materials. Additionally, the journal explores strategies, policies, and developments in the field of energy storage materials and devices for sustainable energy.
Published papers are selected based on their scientific and technological significance, their ability to provide valuable new knowledge, and their relevance to the international research community.