Photo‐Assisted Charge–Discharge Behavior of NMC622 Cathode

In this study, a nitrogen (N)‐doped graphene film was synthesized on copper foil via chemical vapor deposition (CVD) and employed as a photocatalytic electrode for the photo‐assisted charging and discharging of lithium‐ion batteries (LIBs). By integrating the photocatalyst as a separate electrode and allowing the cathode to function solely in its conventional role, this configuration mitigated the long‐term degradation of light‐harvesting efficiency commonly observed in semiconductor‐based cathodes and eliminated the constraint of using only semiconductor materials in LIBs. The photo‐charging response of the LIB under 1 Sun illumination yielded a photo‐conversion efficiency (η%) of 0.152% for the N‐doped graphene. Photo‐assisted operation enhanced the discharge capacity by at least 15%, improved capacity retention to 90%, and maintained a Coulombic efficiency of 100% over 100 cycles in NMC622 half‐cells. The photo‐generated electrons effectively accelerated interfacial charge transfer kinetics, thereby facilitating redox reactions at the electrode–electrolyte interface during cycling. Overall, this photo‐assisted strategy not only improves LIB performance but also offers a promising route for integrating solar energy conversion directly into energy storage technologies.