Probing the Chemical Action of M–N4 Motif in Metal Phthalocyanine‐Based Redox Mediators in Li‐O₂ Batteries

Despite the exceptionally high theoretical specific energy of Li-O₂ rechargeable batteries, their practical realization remains elusive, primarily due to the sluggish oxygen reduction/evolution kinetics and the underlying nontrivial mechanisms. This study systematically investigates, by operando spectroscopy and density functional theory calculations, the anchoring characteristics of various discharge (viz. metal-superoxide, metal-peroxide) and side products (viz. Li₂CO₃, LiOH) on the M-N₄ motif of first-row transition metal phthalocyanines redox mediators (RMs) and their impact on Li-O₂ battery performance. The unsaturated d-orbital and discharge products oriented between the two MN bonds lead to stability of the Mn-, Fe-, and Co-based RMs, low charge polarization, and superior battery performance. On the contrary, strong anchoring with the phthalocyanine ring leads to a loss of RM activity. While discharge and parasitic products coordinate more strongly with the metal center for unsaturated d-orbital RMs, for filled d-orbitals, the products coordinate with the porphyrin ring. The findings on the orientation of discharge/side products on the M-N4 motif catalyst clearly account for the polarization during the charging process. This fundamental study aid in comprehensive molecular designs for liquid-based RMs for next-generation battery systems for stationary applications.