Layer-by-Layer Electrode Fabrication for Improved Performance of Porous Polyimide-Based Supercapacitors

Nanoporous polymers are becoming increasingly interesting materials for electrochemical applications, as their large surface areas with redox-active sites allow efficient adsorption and diffusion of ions. However, their limited electrical conductivity remains a major obstacle in practical applications. The conventional approach that alleviates this problem is the hybridisation of the polymer with carbon-based additives, but this directly prevents the utilisation of the maximum capacity of the polymers. Here, we report a layer-by-layer fabrication technique where we separated the active (porous polymer, top) layer and the conductive (carbon, bottom) layer and used these layered electrodes in a supercapacitor (SC). Through this approach, direct contact with the electrolyte and polymer material is greatly enhanced. With extensive electrochemical characterisation techniques, we show that the layered electrodes allowed a significant contribution of fast faradic surface reactions to the overall capacitance. The electrochemical performance of the layered-electrode SC outperformed other reported porous polymer-based devices with a specific gravimetric capacitance of 388 F center dot g(-1) and an outstanding energy density of 65 Wh center dot kg(-1) at a current density of 0.4 A center dot g(-1). The device also showed outstanding cyclability with 90% of capacitance retention after 5000 cycles at 1.6 A center dot g(-1), comparable to the reported porous polymer-based SCs. Thus, the introduction of a layered electrode structure would pave the way for more effective utilisation of porous organic polymers in future energy storage/harvesting and sensing devices by exploiting their nanoporous architecture and limiting the negative effects of the carbon/binder matrix.

Automated summary

Nanoporous polymers are interesting materials for electrochemical applications due to their large surface areas and redox-active sites. This study introduces a layer-by-layer fabrication technique to enhance the electrochemical performance of porous polymer-based supercapacitors. By separating the active layer and conductive layer, the direct contact with the electrolyte and polymer material is greatly enhanced, resulting in a significant contribution of fast faradic surface reactions to the overall capacitance. The layered-electrode supercapacitor outperforms other reported devices in terms of specific gravimetric capacitance and energy density, with outstanding cyclability.