Heme-Based Composites as Cathode Catalysts for Lithium-Oxygen Batteries and Analysis of the Reaction Mechanism

Despite the high theoretical energy density of lithium-oxygen (Li-O 2 ) batteries, the charge/discharge efficiency is unsatisfactory. To overcome this critical problem, we synthesized heme-graphene composites (HEME-GO) as catalysts for Li-O 2 batteries. The introduction of graphene produced π - π interactions with the heme matrix, resulting in a composite with enhanced ORR/OER catalytic activity. The free energy diagram of the redox reaction was calculated using density functional theory (DFT) for HEME-GO based on the four-electron reaction pathway, and it was demonstrated that HEME-GO has the lowest ORR overpotential (0.67 V) and OER overpotential (0.53 V). The catalytic mechanism of HEME-GO was also quantitatively described by calculating the adsorption energy of intermediates in the rate determining step (RDS). In addition, the Li-O 2 batteries with the composite catalyst exhibited better cycling performance, discharge capacity (7770 mAh g −1 ), and lower overpotential due to the ability of heme to scavenge superoxide radicals and thus protect the electrode. The results in this paper contribute to the understanding of the redox process of Li-O 2 batteries for organic systems and suggest innovative ideas for the design of environmentally friendly batteries.