Binuclear Metal Phthalocyanines Catalysis for Li/SOCl2 Batteries: An Experimental and Computational Study

Four kinds of binuclear metal phthalocyanines (MPcs) complexes M2(PcTN)2Nap and M2(PcTA)2Nap (M=NiII, ZnII) are synthesized and used in Li/SOCl2 battery as electrocatalysts to enhance capacity and discharge voltage. Density functional theory (DFT) calculations are carried out to investigate the improvement in electrochemical performance by carefully observing the shape of the frontier molecular orbitals (MOs). It is confirmed that a close relationship exists between MOs and catalytic performance of MPcs. The variation in reduction potentials of electrolyte SOCl2 are also related to the MOs. Based on cyclic voltammetry measurements and the energy gap of MOs, a reaction mechanism that involves an irreversible two‐step electron transfer process can be deduced, and a better strategy for the selection of catalysts is obtained.