A Cross-linked n-Type Conjugated Polymer with Polar Side Chains Enables Ultrafast Pseudocapacitive Energy Storage.

Pseudocapacitors bridge the performance gap between batteries and electric double-layer capacitors by storing energy via a combination of fast surface/near-surface Faradaic redox processes and electrical double-layer capacitance. Organic semiconductors are an emerging class of pseudocapacitive materials that benefit from facile synthetic tunability and mixed ionic-electronic conduction. Reported examples are mostly limited to p-type (electron-donating) conjugated polymers, while n-type (electron-accepting) examples remain comparatively underexplored. This work introduces a new cross-linked n-type conjugated polymer, spiro-NDI-N, strategically designed with polar tertiary amine side chains. This molecular design aims to synergistically increase the electroactive surface area and boost ion transport for efficient ionic-electronic coupling. Spiro-NDI-N demonstrates excellent pseudocapacitive energy storage performance in pH-neutral aqueous electrolytes, with specific capacitance values of up to 532 F g at 5 A g and stable cycling over 5000 cycles. Moreover, it maintains a rate capability of 307 F g at 350 A g. The superior pseudocapacitive performance of spiro-NDI-N, compared to strategically designed structural analogues lacking either the cross-linked backbone or polar side chains, validates the essential role of its molecular design elements. More broadly, the design and performance of spiro-NDI-N provide a novel strategy for developing high-performance organic pseudocapacitors.