Kai Zhang , Zeyu Wang , Zhenming Xu , Xing Zhou , Guodong Li , Zhe Mei , Yi Yu , Yonggang Wang , Congxiao Wang , Guannan Zhu , Yong-Ning Zhou , Yongyao Xia
{"title":"在LiCoO2上构建晶格匹配应变缓冲层用于稳定高压循环","authors":"Kai Zhang , Zeyu Wang , Zhenming Xu , Xing Zhou , Guodong Li , Zhe Mei , Yi Yu , Yonggang Wang , Congxiao Wang , Guannan Zhu , Yong-Ning Zhou , Yongyao Xia","doi":"10.1016/j.ensm.2025.104081","DOIUrl":null,"url":null,"abstract":"<div><div>Lithium cobalt oxide (LCO) has received considerable attention due to its high volumetric energy density, particularly at elevated cut-off voltages up to 4.7 V. However, the poor cyclic stability of high-voltage LCO limits its practical application, primarily due to detrimental phase transitions above 4.55 V, oxygen loss upon deep delithiation, and the interfacial side reactions. In this study, we introduce an <em>in-situ</em> formed strain buffer layer on LCO particles by CePO<sub>4</sub> coating to improve its high-voltage performance. The coated CePO<sub>4</sub> layer reacts with LCO particles spontaneously to generate a lattice-matched Li<sub>8</sub>CeO<sub>6</sub> phase, which can facilitate Li<sup>+</sup> transportation and relieve near-surface intrinsic stress. With less lattice strain, the undesirable phase transition and notorious surface degradation are suppressed significantly. Moreover, strong covalence of Ce 4f and O 2p bonds, and delocalized electrons in Ce-O<sub>6</sub> octahedral configuration help to suppress oxygen redox at 4.6 V. A high capacity retention of 93.3% after 300 cycles at 4.6 V and 88% after 100 cycles at 4.7 V is harvested. This strategy of constructing a strain buffer layer near the particle surface provides a novel insight for stabilizing the high-voltage LCO and paves the way for further modification of other cathode materials.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104081"},"PeriodicalIF":20.2000,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Constructing lattice-matched strain buffer layer on LiCoO2 for stable high-voltage cycling\",\"authors\":\"Kai Zhang , Zeyu Wang , Zhenming Xu , Xing Zhou , Guodong Li , Zhe Mei , Yi Yu , Yonggang Wang , Congxiao Wang , Guannan Zhu , Yong-Ning Zhou , Yongyao Xia\",\"doi\":\"10.1016/j.ensm.2025.104081\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Lithium cobalt oxide (LCO) has received considerable attention due to its high volumetric energy density, particularly at elevated cut-off voltages up to 4.7 V. However, the poor cyclic stability of high-voltage LCO limits its practical application, primarily due to detrimental phase transitions above 4.55 V, oxygen loss upon deep delithiation, and the interfacial side reactions. In this study, we introduce an <em>in-situ</em> formed strain buffer layer on LCO particles by CePO<sub>4</sub> coating to improve its high-voltage performance. The coated CePO<sub>4</sub> layer reacts with LCO particles spontaneously to generate a lattice-matched Li<sub>8</sub>CeO<sub>6</sub> phase, which can facilitate Li<sup>+</sup> transportation and relieve near-surface intrinsic stress. With less lattice strain, the undesirable phase transition and notorious surface degradation are suppressed significantly. Moreover, strong covalence of Ce 4f and O 2p bonds, and delocalized electrons in Ce-O<sub>6</sub> octahedral configuration help to suppress oxygen redox at 4.6 V. A high capacity retention of 93.3% after 300 cycles at 4.6 V and 88% after 100 cycles at 4.7 V is harvested. This strategy of constructing a strain buffer layer near the particle surface provides a novel insight for stabilizing the high-voltage LCO and paves the way for further modification of other cathode materials.</div></div>\",\"PeriodicalId\":306,\"journal\":{\"name\":\"Energy Storage Materials\",\"volume\":\"75 \",\"pages\":\"Article 104081\"},\"PeriodicalIF\":20.2000,\"publicationDate\":\"2025-02-01\",\"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/S2405829725000820\",\"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/S2405829725000820","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}
Constructing lattice-matched strain buffer layer on LiCoO2 for stable high-voltage cycling
Lithium cobalt oxide (LCO) has received considerable attention due to its high volumetric energy density, particularly at elevated cut-off voltages up to 4.7 V. However, the poor cyclic stability of high-voltage LCO limits its practical application, primarily due to detrimental phase transitions above 4.55 V, oxygen loss upon deep delithiation, and the interfacial side reactions. In this study, we introduce an in-situ formed strain buffer layer on LCO particles by CePO4 coating to improve its high-voltage performance. The coated CePO4 layer reacts with LCO particles spontaneously to generate a lattice-matched Li8CeO6 phase, which can facilitate Li+ transportation and relieve near-surface intrinsic stress. With less lattice strain, the undesirable phase transition and notorious surface degradation are suppressed significantly. Moreover, strong covalence of Ce 4f and O 2p bonds, and delocalized electrons in Ce-O6 octahedral configuration help to suppress oxygen redox at 4.6 V. A high capacity retention of 93.3% after 300 cycles at 4.6 V and 88% after 100 cycles at 4.7 V is harvested. This strategy of constructing a strain buffer layer near the particle surface provides a novel insight for stabilizing the high-voltage LCO and paves the way for further modification of other cathode materials.
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.