Highly Efficient Cu-Porphyrin-Based Metal–Organic Framework Nanosheet as Cathode for High-Rate Li-CO₂ Battery

The lithium-carbon dioxide (Li-CO₂) battery as a novel metal-air battery has a high specific energy density and unique CO₂ conversion ability. However, its further development is limited by incomplete product decomposition resulting in poor cycling and rate performance. In this work, Cu-tetra(4-carboxyphenyl) porphyrin (Cu-TCPP) nanosheets are prepared through the solvothermal method successfully. An efficient Li-CO₂ battery with Cu-TCPP as catalyst achieves a high discharge capacity of 20393 mAh g⁻¹ at 100 mA g⁻¹, a long-life cycle of 123 at 500 mA g⁻¹, and a lower overpotential of 1.8 V at 2000 mA g⁻¹. Density functional theory calculation reveals that Cu-TCPP has higher adsorption energy of CO₂ and Li₂CO₃ compared with TCPP, and a large number of electrons gather near the Cu-N₄ active sites in Cu-TCPP. Therefore, the excellent CO₂ capture ability of the porphyrin ligand and the synergic catalytic effect of Cu atom in Cu-TCPP promote the thermodynamics and kinetics of CO₂ reduction and evolution processes.