{"title":"二茂铁作为 p 型氧化还原媒介可直接再生废旧磷酸铁锂阴极的潜在调节策略","authors":"Mingli Xu , Chen Wu , Fengxue Zhang , Yanhui Zhang , Jiaxin Ren , Chengyi Zhang , Xuanze Wang , Li Xiao , Olivier Fontaine , Jiangfeng Qian","doi":"10.1016/j.ensm.2024.103611","DOIUrl":null,"url":null,"abstract":"<div><p>Conventional metallurgical technologies for recycling cathode materials from retired Li-ion batteries go against carbon neutrality owing to massive material input and energy consumption. Although featuring with simplified process, direct regeneration technology still fails to bypass high-temperature driving forces for Li<sup>+</sup> compensation of degraded cathodes. Herein, chemical re-lithiation strategy mediated by ferrocene is proposed to directly regenerate the Li-deficient spent cathodes. Ferrocene and its derivatives, the so-called p-type redox mediators, can be oxidized spontaneously from neutral molecules to stable cations under ambient conditions, allowing them to function as electron donors. Meanwhile, lithium salts serve as Li<sup>+</sup> donors to ensure charge neutrality of the cathode lattice. The effects of solvation and substituent are thoroughly investigated to precisely regulate the potential of a series of ferrocene-based reductants. Chemical re-lithiation is driven thermodynamically by the intrinsic potential gap between ferrocene and degraded cathodes, thus fundamentally realizing a rapid lithiation reaction (taking less than 20 min at 25 °C), while avoiding the involvement of high-temperature operation. Diverse characterizations have been performed to explore the Li<sup>+</sup>-electron concerted re-lithiation mechanism. The regenerated LiFePO<sub>4</sub> cathode demonstrated comparable Li<sup>+</sup> storage capability to commercial cathode. Life-cycle analysis verifies the economical and environmental superiority of our chemical re-lithiation strategy to metallurgy in practical industry. The thermodynamically spontaneous chemical re-lithiation provides competitive options for greener recycling of retired batteries in the future.</p></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":null,"pages":null},"PeriodicalIF":18.9000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Potential regulation strategy enables ferrocene as p-type redox mediator for direct regeneration of spent LiFePO4 cathode\",\"authors\":\"Mingli Xu , Chen Wu , Fengxue Zhang , Yanhui Zhang , Jiaxin Ren , Chengyi Zhang , Xuanze Wang , Li Xiao , Olivier Fontaine , Jiangfeng Qian\",\"doi\":\"10.1016/j.ensm.2024.103611\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Conventional metallurgical technologies for recycling cathode materials from retired Li-ion batteries go against carbon neutrality owing to massive material input and energy consumption. Although featuring with simplified process, direct regeneration technology still fails to bypass high-temperature driving forces for Li<sup>+</sup> compensation of degraded cathodes. Herein, chemical re-lithiation strategy mediated by ferrocene is proposed to directly regenerate the Li-deficient spent cathodes. Ferrocene and its derivatives, the so-called p-type redox mediators, can be oxidized spontaneously from neutral molecules to stable cations under ambient conditions, allowing them to function as electron donors. Meanwhile, lithium salts serve as Li<sup>+</sup> donors to ensure charge neutrality of the cathode lattice. The effects of solvation and substituent are thoroughly investigated to precisely regulate the potential of a series of ferrocene-based reductants. Chemical re-lithiation is driven thermodynamically by the intrinsic potential gap between ferrocene and degraded cathodes, thus fundamentally realizing a rapid lithiation reaction (taking less than 20 min at 25 °C), while avoiding the involvement of high-temperature operation. Diverse characterizations have been performed to explore the Li<sup>+</sup>-electron concerted re-lithiation mechanism. The regenerated LiFePO<sub>4</sub> cathode demonstrated comparable Li<sup>+</sup> storage capability to commercial cathode. Life-cycle analysis verifies the economical and environmental superiority of our chemical re-lithiation strategy to metallurgy in practical industry. The thermodynamically spontaneous chemical re-lithiation provides competitive options for greener recycling of retired batteries in the future.</p></div>\",\"PeriodicalId\":306,\"journal\":{\"name\":\"Energy Storage Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":18.9000,\"publicationDate\":\"2024-07-03\",\"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/S2405829724004379\",\"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/S2405829724004379","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}
Potential regulation strategy enables ferrocene as p-type redox mediator for direct regeneration of spent LiFePO4 cathode
Conventional metallurgical technologies for recycling cathode materials from retired Li-ion batteries go against carbon neutrality owing to massive material input and energy consumption. Although featuring with simplified process, direct regeneration technology still fails to bypass high-temperature driving forces for Li+ compensation of degraded cathodes. Herein, chemical re-lithiation strategy mediated by ferrocene is proposed to directly regenerate the Li-deficient spent cathodes. Ferrocene and its derivatives, the so-called p-type redox mediators, can be oxidized spontaneously from neutral molecules to stable cations under ambient conditions, allowing them to function as electron donors. Meanwhile, lithium salts serve as Li+ donors to ensure charge neutrality of the cathode lattice. The effects of solvation and substituent are thoroughly investigated to precisely regulate the potential of a series of ferrocene-based reductants. Chemical re-lithiation is driven thermodynamically by the intrinsic potential gap between ferrocene and degraded cathodes, thus fundamentally realizing a rapid lithiation reaction (taking less than 20 min at 25 °C), while avoiding the involvement of high-temperature operation. Diverse characterizations have been performed to explore the Li+-electron concerted re-lithiation mechanism. The regenerated LiFePO4 cathode demonstrated comparable Li+ storage capability to commercial cathode. Life-cycle analysis verifies the economical and environmental superiority of our chemical re-lithiation strategy to metallurgy in practical industry. The thermodynamically spontaneous chemical re-lithiation provides competitive options for greener recycling of retired batteries in the future.
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.