Photoactive NIR-Absorbing Aza-BODIPY Polymer Networks for High-Performance Supercapacitors

π-Conjugated photoactive organic-semiconductor-based supercapacitor electrodes are emerging as next-generation energy storage systems that integrate light harvesting with electrochemical energy storage within a single platform. Among various photoactive materials, aza-BODIPY-based semiconductors have gained significant attention due to their strong and tunable near-infrared (NIR) absorption and versatile electronic properties, making them promising candidates for light-assisted energy storage applications. In this study, new π-conjugated polymer networks, TA-BODIPY-PN and HA-BODIPY-PN, were directly coated onto the electrode surface via a thiol–ene click reaction to fabricate supercapacitor electrodes to use in photoelectrochemical supercapacitor applications. Supercapacitor performance tests showed that both devices predominantly exhibit a pseudocapacitance charge storage mechanism. The TA-BODIPY-PN -based electrochemical cell exhibited better performance than the HA-BODIPY-PN (318.45 F/g) by exhibiting a specific capacitance of 426.06 F/g and an energy density of 59.17 Wh/kg at a current density of 1 A/g. Upon surface illumination of the TA-BODIPY-PN electrode, the specific capacitance increased by approximately 74% to 740.29 F/g. This photoassisted capacitive enhancement is attributed to the strengthened ion-electron interactions at the interface by the photoexcited charge increase in the polymer, while the stable performance of the cells above 85% after 10000 cycles indicates that these NIR-absorbing materials are strong candidates for light-assisted supercapacitors.