Arturo Gutierrez, Subhadip Mallick, Chun Yuen Kwok, Yulin Lin, Fulya Dogan, Jianguo Wen, Mahalingam Balasubramanian, Jason R. Croy
{"title":"结合内在复杂性提高富锂氧化物的性能:领域选择性替代","authors":"Arturo Gutierrez, Subhadip Mallick, Chun Yuen Kwok, Yulin Lin, Fulya Dogan, Jianguo Wen, Mahalingam Balasubramanian, Jason R. Croy","doi":"10.1021/acs.chemmater.4c00415","DOIUrl":null,"url":null,"abstract":"Historically, modifications to Li- and Mn-rich (LMR) cathodes have been studied in relation to their efficacy in solving challenges such as oxygen loss and voltage fade, which are inherent to the activation process of these electrodes. However, even in the presence of these phenomena, well-optimized LMR cathodes show considerable promise as earth-abundant options, particularly if other barriers to implementation can be overcome or mitigated. As the complex mechanisms of LMR electrodes are known to stem from the local, chemical inhomogeneities that define the nanocomposite domain nature of these oxides, strategies aimed at manipulating the performance of activated electrodes, irrespective of voltage fade, through domain-selective modifications, could prove instructive. Herein, we use a novel synthesis process aimed at influencing the site occupancy of substituted Sn<sup>4+</sup>, as an example 4+ cation, into a Co-free Li<sub>1.13</sub>Mn<sub>0.57(1–<i>x</i>)</sub>Sn<sub>0.57<i>x</i></sub>Ni<sub>0.3</sub>O<sub>2</sub> LMR oxide. We show that Sn<sup>4+</sup> can be selectively substituted into Li-rich environments. The consequences are revealed to be both chemical and morphological, and the domain-selective doping strategy provides a knob for directed control of the low state-of-charge impedance behavior. These results reveal new clues and insights with respect to further advancing the practical relevance of LMR cathode particles and electrodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Advancing the Performance of Lithium-Rich Oxides in Concert with Inherent Complexities: Domain-Selective Substitutions\",\"authors\":\"Arturo Gutierrez, Subhadip Mallick, Chun Yuen Kwok, Yulin Lin, Fulya Dogan, Jianguo Wen, Mahalingam Balasubramanian, Jason R. Croy\",\"doi\":\"10.1021/acs.chemmater.4c00415\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Historically, modifications to Li- and Mn-rich (LMR) cathodes have been studied in relation to their efficacy in solving challenges such as oxygen loss and voltage fade, which are inherent to the activation process of these electrodes. However, even in the presence of these phenomena, well-optimized LMR cathodes show considerable promise as earth-abundant options, particularly if other barriers to implementation can be overcome or mitigated. As the complex mechanisms of LMR electrodes are known to stem from the local, chemical inhomogeneities that define the nanocomposite domain nature of these oxides, strategies aimed at manipulating the performance of activated electrodes, irrespective of voltage fade, through domain-selective modifications, could prove instructive. Herein, we use a novel synthesis process aimed at influencing the site occupancy of substituted Sn<sup>4+</sup>, as an example 4+ cation, into a Co-free Li<sub>1.13</sub>Mn<sub>0.57(1–<i>x</i>)</sub>Sn<sub>0.57<i>x</i></sub>Ni<sub>0.3</sub>O<sub>2</sub> LMR oxide. We show that Sn<sup>4+</sup> can be selectively substituted into Li-rich environments. The consequences are revealed to be both chemical and morphological, and the domain-selective doping strategy provides a knob for directed control of the low state-of-charge impedance behavior. These results reveal new clues and insights with respect to further advancing the practical relevance of LMR cathode particles and electrodes.\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-07-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.chemmater.4c00415\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acs.chemmater.4c00415","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Advancing the Performance of Lithium-Rich Oxides in Concert with Inherent Complexities: Domain-Selective Substitutions
Historically, modifications to Li- and Mn-rich (LMR) cathodes have been studied in relation to their efficacy in solving challenges such as oxygen loss and voltage fade, which are inherent to the activation process of these electrodes. However, even in the presence of these phenomena, well-optimized LMR cathodes show considerable promise as earth-abundant options, particularly if other barriers to implementation can be overcome or mitigated. As the complex mechanisms of LMR electrodes are known to stem from the local, chemical inhomogeneities that define the nanocomposite domain nature of these oxides, strategies aimed at manipulating the performance of activated electrodes, irrespective of voltage fade, through domain-selective modifications, could prove instructive. Herein, we use a novel synthesis process aimed at influencing the site occupancy of substituted Sn4+, as an example 4+ cation, into a Co-free Li1.13Mn0.57(1–x)Sn0.57xNi0.3O2 LMR oxide. We show that Sn4+ can be selectively substituted into Li-rich environments. The consequences are revealed to be both chemical and morphological, and the domain-selective doping strategy provides a knob for directed control of the low state-of-charge impedance behavior. These results reveal new clues and insights with respect to further advancing the practical relevance of LMR cathode particles and electrodes.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.