Regulating the radical intermediates by conjugated units in covalent organic frameworks for optimized lithium ion storage

Gu，Shuai1,2; Ma，Xiaoxia2; Chen，Jingjing1; Hao，Rui1; Wang，Zhiqiang1; Qin，Ning1,2; Zheng，Wei1; Gan，Qingmeng1; Luo，Wen1; Li，Muqing1; Li，Zhiqiang1; Liao，Kemeng1; Guo，Hao1; Liu，Guiyu1; Zhang，Kaili2; Lu，Zhouguang1

2022-06-01

10.1016/j.jechem.2022.01.005

Journal of Energy Chemistry   影响因子和分区

2095-4956

Organic active units often transform into radical intermediates during the redox processes but exhibit poor cycling stability due to the uncontrollable redox of the radicals. Herein, we report a facile and efficient strategy to modulate the molecular orbital energies, charge transport capacities, and spin electron densities of the active units in covalent organic frameworks (COFs) via regulating the conjugated unit size to optimize the redox activity and stability of the organic radicals. COFs based on different imide conjugated units exhibit tunable discharge voltages, rate performance and cycling stabilities. Detailed characterizations and theoretical calculation reveal that imide radicals are the important active intermediates during the redox processes of these COFs. Specifically, increasing the size of the imide conjugated units could effectively delocalize the radical electrons and improve the stability of the COFs electrodes. This study offers a very effective strategy to modulate the redox chemistry of organic materials for electrochemical energy storage.

Covalent organic frameworks Organic electrodes Radical intermediates

SCI ; EI

英语

第一

Basic Research Project of the Science and Technology Innovation Commission of Shenzhen[JCYJ20200109141640095] ; Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials[ZDSYS20200421111401738] ; Leading Talents of Guangdong Province Program[2016LJ06C536] ; National Natural Science Foundation of China[21875097] ; Guangdong-Hong Kong-Macao Joint Laboratory[2019B121205001] ; Hong Kong Research Grants Council[CityU 11218420]

Chemistry ; Energy & Fuels ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Energy & Fuels ; Engineering, Chemical

WOS:000813929300005

ELSEVIER

20221011745641

Electric discharges ; Electrodes ; Lithium ; Molecular orbitals ; Organic polymers

Lithium and Alloys:542.4 ; Alkali Metals:549.1 ; Electricity: Basic Concepts and Phenomena:701.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Polymers:815.1.1 ; Atomic and Molecular Physics:931.3

2-s2.0-85125557294

Scopus

1.Department of Materials Science and Engineering,Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials,Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.Department of Mechanical Engineering,City University of Hong Kong,Hong Kong,Kowloon,999077,Hong Kong

Gu，Shuai,Ma，Xiaoxia,Chen，Jingjing,et al. Regulating the radical intermediates by conjugated units in covalent organic frameworks for optimized lithium ion storage[J]. Journal of Energy Chemistry,2022,69:428-433.

Gu，Shuai.,Ma，Xiaoxia.,Chen，Jingjing.,Hao，Rui.,Wang，Zhiqiang.,...&Lu，Zhouguang.(2022).Regulating the radical intermediates by conjugated units in covalent organic frameworks for optimized lithium ion storage.Journal of Energy Chemistry,69,428-433.

Gu，Shuai,et al."Regulating the radical intermediates by conjugated units in covalent organic frameworks for optimized lithium ion storage".Journal of Energy Chemistry 69(2022):428-433.