Bending Resistance Covalent Organic Framework Superlattice: “Nano-Hourglass”-Induced Charge Accumulation for Flexible In-Plane Micro-Supercapacitors

Covalent organic framework (COF) film with highly exposed active sites is considered as the promising flexible self-supported electrode for in-plane micro-supercapacitor (MSC). Superlattice configuration assembled alternately by different nanofilms based on van der Waals force can integrate the advantages of each isolated layer to exhibit unexpected performances as MSC film electrodes, which may be a novel option to ensure energy output. Herein, a mesoporous free-standing A-COF nanofilm (pore size is 3.9 nm, averaged thickness is 4.1 nm) with imine bond linkage and a microporous B-COF nanofilm (pore size is 1.5 nm, averaged thickness is 9.3 nm) with β-keto-enamine-linkages are prepared, and for the first time, we assembly the two lattice matching films into sandwich-type superlattices via layer-by-layer transfer, in which ABA–COF superlattice stacking into a “nano-hourglass” steric configuration that can accelerate the dynamic charge transportation/accumulation and promote the sufficient redox reactions to energy storage. The fabricated flexible MSC–ABA–COF exhibits the highest intrinsic C(V) of 927.9 F cm(−3) at 10 mV s(−1) than reported two-dimensional alloy, graphite-like carbon and undoped COF-based MSC devices so far, and shows a bending-resistant energy density of 63.2 mWh cm(−3) even after high-angle and repeat arbitrary bending from 0 to 180°. This work provides a feasible way to meet the demand for future miniaturization and wearable electronics. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-022-00997-0.