{"title":"Engineering the diphasic Li-rich Mn-based composite with alleviated Jahn–Teller effect for high-energy Li-ion batteries","authors":"Feng Li, Jia-Cheng Li, Mao-Sheng Gong, Ze-Zhou Lin, Xuan-Ming Chang, Mo-Han Dong, Pei-Yu Hou","doi":"10.1007/s12598-024-03092-y","DOIUrl":null,"url":null,"abstract":"<div><p>The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides (LLOs) and maintains outstanding voltage stability. However, the ion-exchange synthesis promotes the Mn-ion valence reduction and aggravates the Jahn–Teller (J–T) distortion alongside disproportionation. Since the main oxidation state of the Mn ions is +4 in the traditional O3-type LLOs, synergistic effects of the O2-type and O3-type structures are expected in the O2/O3 diphasic Li-rich material. Herein, O2/O3 biphasic intergrowth LLOs were rationally designed, and the synergic optimization of the biphasic structure was planned to retard the J–T effect. The O2/O3 intergrowth nature was confirmed, and the percentages of the O2 and O3 phases were 56% and 44%, respectively. Density functional theory calculations demonstrated that the Mn<sup>2+</sup>(EC) sheath had a remarkably lower energy barrier than the Li<sup>+</sup>(EC) sheath. This finding suggests that Mn<sup>2+</sup> ions that are dissolved into the electrolyte accelerate the electrolyte oxidization, so the deposition of the cathode electrolyte interface for pristine O2-LLOs causes a high electrochemical impedance. The designed O2/O3 biphasic LLOs boost the capacity stability and suppress the voltage drop upon repeated Li<sup>+</sup> de-intercalation. The phase regulation strategy offers great potential for developing low-cost LLOs with enhanced structural stability for advanced Li-ion batteries.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 5","pages":"2945 - 2957"},"PeriodicalIF":9.6000,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rare Metals","FirstCategoryId":"88","ListUrlMain":"https://link.springer.com/article/10.1007/s12598-024-03092-y","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides (LLOs) and maintains outstanding voltage stability. However, the ion-exchange synthesis promotes the Mn-ion valence reduction and aggravates the Jahn–Teller (J–T) distortion alongside disproportionation. Since the main oxidation state of the Mn ions is +4 in the traditional O3-type LLOs, synergistic effects of the O2-type and O3-type structures are expected in the O2/O3 diphasic Li-rich material. Herein, O2/O3 biphasic intergrowth LLOs were rationally designed, and the synergic optimization of the biphasic structure was planned to retard the J–T effect. The O2/O3 intergrowth nature was confirmed, and the percentages of the O2 and O3 phases were 56% and 44%, respectively. Density functional theory calculations demonstrated that the Mn2+(EC) sheath had a remarkably lower energy barrier than the Li+(EC) sheath. This finding suggests that Mn2+ ions that are dissolved into the electrolyte accelerate the electrolyte oxidization, so the deposition of the cathode electrolyte interface for pristine O2-LLOs causes a high electrochemical impedance. The designed O2/O3 biphasic LLOs boost the capacity stability and suppress the voltage drop upon repeated Li+ de-intercalation. The phase regulation strategy offers great potential for developing low-cost LLOs with enhanced structural stability for advanced Li-ion batteries.
期刊介绍:
Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.