Direct Laser Scribing of All‐Solid‐State In‐Plane Proton Microsupercapacitors on Ionic Covalent Organic Framework Films

Abstract Proton microsupercapacitors (MSCs) are promising energy storage devices for cutting‐edge applications. However, all‐solid‐state designs face challenges due to the need for synergistic innovations in electrolytes, electrodes, and interface engineering. Herein, the direct laser scribing of metal‐free all‐solid‐state in‐plane proton MSCs are reported on ionic covalent organic framework (iCOF) films. The solid‐state AA‐stacked iCOF electrolytes with perfect 2D proton channels (d = 0.33 nm) are prepared by vacuum filtration, exhibiting proton conductivities from 0.23 to 4.7 mS cm⁻¹ depending on humidity. Furthermore, patterned carbon electrodes are fabricated via in situ laser carbonization of iCOFs, forming a seamless electrolyte‒electrode interface. To reveal the photophysical features of insulating iCOFs and conductive laser‐treated iCOFs, femtosecond transient absorption experiments are carried out. The multiphysics simulation indicates that the electric field is uniformly distributed at the electrode−electrolyte interface. Notably, the resulting proton MSC exhibits an ultrahigh specific capacitance (≈10.13 mF cm⁻² and 101.3 F cm⁻³), high volumetric energy density (2.52 mWh cm⁻³), a rapid scan rate (1000 mV s⁻¹), and excellent cycling stability (no capacitance degradation after 50 000 cycles). This approach provides high‐performance metal‐free all‐solid‐state in‐plane proton MSCs, revealing great potential for applications in intelligent microsystems.