Electrochemically Exfoliated Graphene Additive‐Free Inks for 3D Printing Customizable Monolithic Integrated Micro‐Supercapacitors on a Large Scale

Abstract Three‐dimensional (3D) printing technology with enhanced fidelity can achieve multiple functionalities and boost electrochemical performance of customizable planar micro‐supercapacitors (MSCs), however, precise structural control of additive‐free graphene‐based macro‐assembly electrode for monolithic integrated MSCs (MIMSCs) remains challenging. Here, the large‐scale 3D printing fabrication of customizable planar MIMSCs is reported utilizing additive‐free, high‐quality electrochemically exfoliated graphene inks, which is not required the conventional cryogenic assistance during the printing process and any post‐processing reduction. The resulting MSCs reveal an extremely small engineering footprint of 0.025 cm², exceptionally high areal capacitance of 4900 mF cm⁻², volumetric capacitance of 195.6 F cm⁻³, areal energy density of 2.1 mWh cm⁻², and unprecedented volumetric energy density of 23 mWh cm⁻³ for a single cell, surpassing most previously reported 3D printed MSCs. The 3D printed MIMSC pack is further demonstrated, with the maximum areal cell count density of 16 cell cm⁻², the highest output voltage of 192.5 V and the largest output voltage per unit area of 56 V cm⁻² up to date are achieved. This work presents an innovative solution for processing high‐performance additive‐free graphene ink and realizing the large‐scale production of 3D printed MIMSCs for planar energy storage.