Pseudocapacitive gels based on conjugated polyelectrolytes: thickness and ion diffusion limitations†
Abstract
Conjugated polymer hydrogels (CPHs) are emerging pseudocapacitive materials capable of forming redox-active hydrogels. Current efforts focus on increasing their areal capacitance (CAreal) and cycling stabilities by using binders tolerant to H2SO4-based electrolytes, while alternatives in more environmentally friendly electrolytes underperform due to low-capacity values. Herein, we demonstrate that it is possible to use conjugated polyelectrolyte (CPE), namely CPE-K, to create a single-component binder-free pseudocapacitive gel in environmentally friendly electrolytes (2 M: NaCl, MgCl2, and MgSO4), with CAreal 1.9 times larger than those reported for single-component binder-free CPHs. The resulting pseudocapacitive gel exhibited CAreal (523 mF cm−2 at 0.25 mA cm−2) scalable with its thickness in NaCl electrolytes, providing an attractive solution to improve the capacitance of devices while maintaining a minimal charge-collecting electrode surface footprint. In addition, the CPE-K gel demonstrates 86% capacitance retention after 100 000 cycles at 10 mA cm−2, which is higher than those reported for conventional state-of-the-art conjugated polymers. Electrochemical characterization revealed that CAreal at all cycling rates tested is proportional to dThk up to 750 μm, primarily due to facile ionic diffusion within the 3D conductive network of the gel. Thicker electrodes (dThk = 1250 μm) can be operated at a rate of 15 mA cm−2 with minimal capacity loss. These results demonstrate the potential applications of self-doped CPE gels in designing the next generation of multi-functional electrochemical energy storage and conversion technologies for targeting high energy and power density applications.