Regulating Intramolecular Electron Transfer of Nickel‐Based Coordinations through Ligand Engineering for Aqueous Batteries

Abstract The integration of electronic effects into complexes for the construction of novel materials has not yet attracted significant attention in the field of energy storage. In the current study, eight one‐dimensional (1D) nickel‐based salicylic acid complexes (Ni‐XSAs, X = pH, pMe, pMeO, mMe, pBr, pCl, pF, and pCF₃), are prepared by ligand engineering. The coordination environments in the Ni–XSAs are explored using X‐ray absorption fine structure spectroscopy. The charge transfer of the complexes is modulated according to the difference in the electron‐donating ability of the substituents, in combination with frontier orbital theory. Furthermore, density functional theory is used to investigate the effect of the substituent position on the electronic properties of the complexes. Ni‐mMeSA exhibits better electrical conductivity than Ni‐pMeSA. The electrochemical performance of Ni‐mMeSA as an aqueous battery cathode is remarkably improved with a maximum energy density of 0.30 mWh cm⁻² (125 Wh kg⁻¹) and a peak power density of 33.72 mW cm⁻² (14.03 kW kg⁻¹). This study provides ideas for the application of new coordination chemistry in the field of energy materials science.