Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials
Dong Joo Min,
Kyunam Lee,
Hyunji Park,
Ji Eon Kwon,
Soo Young Park
Affiliations
Dong Joo Min
Lab for Supramolecular Optoelectronic Materials (LSOM), Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea
Kyunam Lee
Lab for Supramolecular Optoelectronic Materials (LSOM), Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea
Hyunji Park
Lab for Supramolecular Optoelectronic Materials (LSOM), Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea
Ji Eon Kwon
Functional Composite Materials Research Center, Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), 92 Chudong-ro, Bongdong-eup, Wanju-gun, Jeonbuk 55324, Korea
Soo Young Park
Lab for Supramolecular Optoelectronic Materials (LSOM), Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea
Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k0) of the s-tetrazine molecules and Li-ion diffusivity (DLi) in the s-tetrazine electrodes are much faster than conventional electrode active materials.
