Nan Jiang, Mengpei Qi, Yalong Jiang, Yin Fan, Shiwei Jin, Yingkui Yang
{"title":"Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff-Base Covalent Organic Frameworks","authors":"Nan Jiang, Mengpei Qi, Yalong Jiang, Yin Fan, Shiwei Jin, Yingkui Yang","doi":"10.1002/eem2.12797","DOIUrl":null,"url":null,"abstract":"<p>Covalent organic frameworks (COFs) after undergoing the superlithiation process promise high-capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox-active sites. Herein, integrating carbon nanotubes (CNTs) with imine-linked covalent organic frameworks (COFs) was rationally executed by in-situ Schiff-base condensation between 1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde and 1,4-diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites (CNT@COF). Accordingly, the redox-active shell of COF nanoparticles around one-dimensional conductive CNTs synergistically creates robust three-dimensional hybrid architectures with high specific surface area, thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode. Remarkably, upon the full activation with a superlithiation process, the as-fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g<sup>−1</sup>, which is the highest specific capacity among organic electrode materials reported so far. Meanwhile, the superior rate capability and excellent cycling stability are also obtained. The redox reaction mechanisms for the COF moiety were further revealed by Fourier-transform infrared spectroscopy in conjunction with X-ray photoelectron spectroscopy, involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12797","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/eem2.12797","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}
引用次数: 0
Abstract
Covalent organic frameworks (COFs) after undergoing the superlithiation process promise high-capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox-active sites. Herein, integrating carbon nanotubes (CNTs) with imine-linked covalent organic frameworks (COFs) was rationally executed by in-situ Schiff-base condensation between 1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde and 1,4-diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites (CNT@COF). Accordingly, the redox-active shell of COF nanoparticles around one-dimensional conductive CNTs synergistically creates robust three-dimensional hybrid architectures with high specific surface area, thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode. Remarkably, upon the full activation with a superlithiation process, the as-fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g−1, which is the highest specific capacity among organic electrode materials reported so far. Meanwhile, the superior rate capability and excellent cycling stability are also obtained. The redox reaction mechanisms for the COF moiety were further revealed by Fourier-transform infrared spectroscopy in conjunction with X-ray photoelectron spectroscopy, involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.
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.