Yurong Wu, Ziyun Zhang, Jiangshan Huo, Runguo Zheng, Zhishuang Song, Zhiyuan Wang, Yanguo Liu and Dan Wang
{"title":"用于高性能钾离子电池的阴离子掺杂 P2 型层状阴极材料工程学","authors":"Yurong Wu, Ziyun Zhang, Jiangshan Huo, Runguo Zheng, Zhishuang Song, Zhiyuan Wang, Yanguo Liu and Dan Wang","doi":"10.1039/D5QI00385G","DOIUrl":null,"url":null,"abstract":"<p >P2-type layered oxides have emerged as promising cathode candidate materials for potassium-ion batteries. Nevertheless, unsatisfactory cycling stability hinders their practical application, chiefly arising from deleterious phase transitions and the Jahn–Teller distortion of Mn<small><sup>3+</sup></small>. Herein, an anion-doping strategy where F<small><sup>−</sup></small> is incorporated into P2-K<small><sub>0.6</sub></small>Zn<small><sub>0.1</sub></small>Ti<small><sub>0.05</sub></small>Al<small><sub>0.05</sub></small>Mn<small><sub>0.8</sub></small>O<small><sub>2</sub></small> (KTMO) cathode materials is proposed. Raman spectroscopy was employed to investigate the local chemical environment of these materials. The results revealed a slight shift to higher wavenumbers in the E<small><sub>g</sub></small> and A<small><sub>1g</sub></small> peaks, which was ascribed to the shortening of the average TM–O bond length triggered by the addition of F. <em>Ex situ</em> XRD analysis revealed that the material K<small><sub>0.6</sub></small>Zn<small><sub>0.1</sub></small>Ti<small><sub>0.05</sub></small>Al<small><sub>0.05</sub></small>Mn<small><sub>0.8</sub></small>O<small><sub>1.93</sub></small>F<small><sub>0.07</sub></small> effectively suppresses undesirable phase transitions. Moreover, the maximum variation in the lattice parameter <em>c</em> is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. This strategy brings about excellent cycling stability with a reversible capacity of 131.8 mA h g<small><sup>−1</sup></small> and capacity retention of 76.8% after 100 cycles, within a voltage range of 2.0–4.0 V. These findings offer novel insights into the design of cathode materials possessing optimized structures and enhanced performance for potassium-ion batteries.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 13","pages":" 4237-4246"},"PeriodicalIF":6.4000,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Anionic F-doping-induced engineering of P2-type layered cathode materials for high-performance potassium-ion batteries†\",\"authors\":\"Yurong Wu, Ziyun Zhang, Jiangshan Huo, Runguo Zheng, Zhishuang Song, Zhiyuan Wang, Yanguo Liu and Dan Wang\",\"doi\":\"10.1039/D5QI00385G\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >P2-type layered oxides have emerged as promising cathode candidate materials for potassium-ion batteries. Nevertheless, unsatisfactory cycling stability hinders their practical application, chiefly arising from deleterious phase transitions and the Jahn–Teller distortion of Mn<small><sup>3+</sup></small>. Herein, an anion-doping strategy where F<small><sup>−</sup></small> is incorporated into P2-K<small><sub>0.6</sub></small>Zn<small><sub>0.1</sub></small>Ti<small><sub>0.05</sub></small>Al<small><sub>0.05</sub></small>Mn<small><sub>0.8</sub></small>O<small><sub>2</sub></small> (KTMO) cathode materials is proposed. Raman spectroscopy was employed to investigate the local chemical environment of these materials. The results revealed a slight shift to higher wavenumbers in the E<small><sub>g</sub></small> and A<small><sub>1g</sub></small> peaks, which was ascribed to the shortening of the average TM–O bond length triggered by the addition of F. <em>Ex situ</em> XRD analysis revealed that the material K<small><sub>0.6</sub></small>Zn<small><sub>0.1</sub></small>Ti<small><sub>0.05</sub></small>Al<small><sub>0.05</sub></small>Mn<small><sub>0.8</sub></small>O<small><sub>1.93</sub></small>F<small><sub>0.07</sub></small> effectively suppresses undesirable phase transitions. Moreover, the maximum variation in the lattice parameter <em>c</em> is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. This strategy brings about excellent cycling stability with a reversible capacity of 131.8 mA h g<small><sup>−1</sup></small> and capacity retention of 76.8% after 100 cycles, within a voltage range of 2.0–4.0 V. These findings offer novel insights into the design of cathode materials possessing optimized structures and enhanced performance for potassium-ion batteries.</p>\",\"PeriodicalId\":79,\"journal\":{\"name\":\"Inorganic Chemistry Frontiers\",\"volume\":\" 13\",\"pages\":\" 4237-4246\"},\"PeriodicalIF\":6.4000,\"publicationDate\":\"2025-03-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/qi/d5qi00385g\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/qi/d5qi00385g","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
P2- 型层状氧化物是很有前途的钾离子电池阴极候选材料。然而,令人不满意的循环稳定性阻碍了它的实际应用,主要原因是有害的相变和 Mn3+ 的 Jahn-Teller 畸变。本文提出了一种阴离子掺杂策略,即在 P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) 阴极材料中加入 F-。拉曼测试用于研究材料的局部化学环境。原位 XRD 分析表明,K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 材料有效地抑制了不良相变。此外,在钾插入/提取过程中,晶格参数 c 的最大变化仅为 2.2%,这充分证明了该材料在结构稳定性方面的出色表现。该策略带来了出色的循环稳定性,在 4.0 V 下循环 100 次后,可逆容量为 131.8 mAh g-1,容量保持率为 76.8%。这些发现为设计具有最佳结构和更高性能的钾离子电池阴极材料提供了新的见解。
Anionic F-doping-induced engineering of P2-type layered cathode materials for high-performance potassium-ion batteries†
P2-type layered oxides have emerged as promising cathode candidate materials for potassium-ion batteries. Nevertheless, unsatisfactory cycling stability hinders their practical application, chiefly arising from deleterious phase transitions and the Jahn–Teller distortion of Mn3+. Herein, an anion-doping strategy where F− is incorporated into P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) cathode materials is proposed. Raman spectroscopy was employed to investigate the local chemical environment of these materials. The results revealed a slight shift to higher wavenumbers in the Eg and A1g peaks, which was ascribed to the shortening of the average TM–O bond length triggered by the addition of F. Ex situ XRD analysis revealed that the material K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 effectively suppresses undesirable phase transitions. Moreover, the maximum variation in the lattice parameter c is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. This strategy brings about excellent cycling stability with a reversible capacity of 131.8 mA h g−1 and capacity retention of 76.8% after 100 cycles, within a voltage range of 2.0–4.0 V. These findings offer novel insights into the design of cathode materials possessing optimized structures and enhanced performance for potassium-ion batteries.