{"title":"铜配位金属共价有机框架作为锂离子电池负极材料的出色储锂性能","authors":"Derong Luo, Huizi Zhao, Feng Liu, Hai Xu, Xiaoyu Dong, Bing Ding, Hui Dou, Xiaogang Zhang","doi":"10.1002/eem2.12732","DOIUrl":null,"url":null,"abstract":"<p>Metal-covalent organic frameworks (MCOF) as a bridge between covalent organic framework (COF) and metal organic framework (MOF) possess the characteristics of open metal sites, structure stability, crystallinity, tunability as well as porosity, but still in its infancy. In this work, a covalent organic framework DT-COF with a keto-enamine structure synthesized from the condensation of 3,3′-dihydroxybiphenyl diamine (DHBD) and triformylphloroglucinol (TFP) was coordinated with Cu<sup>2+</sup> by a simple post-modification method to a obtain a copper-coordinated metal-covalent organic framework of Cu-DT COF. The isomerization from a keto-enamine structure of DT-COF to a enol-imine structure of Cu-DT COF is induced due to the coordination interaction of Cu<sup>2+</sup>. The structure change of Cu-DT COF induces the change of the electron distribution in the Cu-DT COF, which greatly promotes the activation and deep Li-storage behavior of the COF skeleton. As anode material for lithium-ion batteries (LIBs), Cu-DT COF exhibits greatly improved electrochemical performance, retaining the specific capacities of 760 mAh g<sup>−1</sup> after 200 cycles and 505 mAh g<sup>−1</sup> after 500 cycles at a current density of 0.5 A g<sup>−1</sup>. The preliminary lithium storage mechanism studies indicate that Cu<sup>2+</sup> is also involved in the lithium storage process. A possible mechanism for Cu-DT COF was proposed on the basis of FT-IR, XPS, EPR characterization and electrochemical analysis. This work enlightens a novel strategy to improve the energy storage performance of COF and promotes the application of COF and MCOF in LIBs.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12732","citationCount":"0","resultStr":"{\"title\":\"Outstanding Lithium Storage Performance of a Copper-Coordinated Metal-Covalent Organic Framework as Anode Material for Lithium-Ion Batteries\",\"authors\":\"Derong Luo, Huizi Zhao, Feng Liu, Hai Xu, Xiaoyu Dong, Bing Ding, Hui Dou, Xiaogang Zhang\",\"doi\":\"10.1002/eem2.12732\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Metal-covalent organic frameworks (MCOF) as a bridge between covalent organic framework (COF) and metal organic framework (MOF) possess the characteristics of open metal sites, structure stability, crystallinity, tunability as well as porosity, but still in its infancy. In this work, a covalent organic framework DT-COF with a keto-enamine structure synthesized from the condensation of 3,3′-dihydroxybiphenyl diamine (DHBD) and triformylphloroglucinol (TFP) was coordinated with Cu<sup>2+</sup> by a simple post-modification method to a obtain a copper-coordinated metal-covalent organic framework of Cu-DT COF. The isomerization from a keto-enamine structure of DT-COF to a enol-imine structure of Cu-DT COF is induced due to the coordination interaction of Cu<sup>2+</sup>. The structure change of Cu-DT COF induces the change of the electron distribution in the Cu-DT COF, which greatly promotes the activation and deep Li-storage behavior of the COF skeleton. As anode material for lithium-ion batteries (LIBs), Cu-DT COF exhibits greatly improved electrochemical performance, retaining the specific capacities of 760 mAh g<sup>−1</sup> after 200 cycles and 505 mAh g<sup>−1</sup> after 500 cycles at a current density of 0.5 A g<sup>−1</sup>. The preliminary lithium storage mechanism studies indicate that Cu<sup>2+</sup> is also involved in the lithium storage process. A possible mechanism for Cu-DT COF was proposed on the basis of FT-IR, XPS, EPR characterization and electrochemical analysis. This work enlightens a novel strategy to improve the energy storage performance of COF and promotes the application of COF and MCOF in LIBs.</p>\",\"PeriodicalId\":11554,\"journal\":{\"name\":\"Energy & Environmental Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.0000,\"publicationDate\":\"2024-05-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12732\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Environmental Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/eem2.12732\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/eem2.12732","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Outstanding Lithium Storage Performance of a Copper-Coordinated Metal-Covalent Organic Framework as Anode Material for Lithium-Ion Batteries
Metal-covalent organic frameworks (MCOF) as a bridge between covalent organic framework (COF) and metal organic framework (MOF) possess the characteristics of open metal sites, structure stability, crystallinity, tunability as well as porosity, but still in its infancy. In this work, a covalent organic framework DT-COF with a keto-enamine structure synthesized from the condensation of 3,3′-dihydroxybiphenyl diamine (DHBD) and triformylphloroglucinol (TFP) was coordinated with Cu2+ by a simple post-modification method to a obtain a copper-coordinated metal-covalent organic framework of Cu-DT COF. The isomerization from a keto-enamine structure of DT-COF to a enol-imine structure of Cu-DT COF is induced due to the coordination interaction of Cu2+. The structure change of Cu-DT COF induces the change of the electron distribution in the Cu-DT COF, which greatly promotes the activation and deep Li-storage behavior of the COF skeleton. As anode material for lithium-ion batteries (LIBs), Cu-DT COF exhibits greatly improved electrochemical performance, retaining the specific capacities of 760 mAh g−1 after 200 cycles and 505 mAh g−1 after 500 cycles at a current density of 0.5 A g−1. The preliminary lithium storage mechanism studies indicate that Cu2+ is also involved in the lithium storage process. A possible mechanism for Cu-DT COF was proposed on the basis of FT-IR, XPS, EPR characterization and electrochemical analysis. This work enlightens a novel strategy to improve the energy storage performance of COF and promotes the application of COF and MCOF in LIBs.
期刊介绍:
Energy & Environmental Materials (EEM) is an international journal published by Zhengzhou University in collaboration with John Wiley & Sons, Inc. The journal aims to publish high quality research related to materials for energy harvesting, conversion, storage, and transport, as well as for creating a cleaner environment. EEM welcomes research work of significant general interest that has a high impact on society-relevant technological advances. The scope of the journal is intentionally broad, recognizing the complexity of issues and challenges related to energy and environmental materials. Therefore, interdisciplinary work across basic science and engineering disciplines is particularly encouraged. The areas covered by the journal include, but are not limited to, materials and composites for photovoltaics and photoelectrochemistry, bioprocessing, batteries, fuel cells, supercapacitors, clean air, and devices with multifunctionality. The readership of the journal includes chemical, physical, biological, materials, and environmental scientists and engineers from academia, industry, and policy-making.