LAUSR

Abstract MXene films are attractive for advanced supercapacitor electrodes requiring high volumetric energy density due to their high redox capacitance combined with extremely high packing density. However, the self‐restacking of MXene flakes unavoidably decreases the volumetric performance, mass loading, and rate capability. Herein, a simple strategy is developed to prepare a flexible and free‐standing modified MXene/holey graphene film by filtration of the alkalized MXene and holey graphene oxide dispersions, followed by a mild annealing treatment. After terminal groups (—F/—OH) are removed, the increased proportion of Ti atoms enables more pseudocapacitive reaction. Meanwhile, the embedded holey graphene effectively prevents the self‐restacking of MXene and forms a high nanopore connectivity network, which is able to immensely accelerate the ion transport and shorten transport pathways for both ion and electron. When applied as electrode materials for supercapacitors, it can deliver an ultrahigh volumetric capacitance (1445 F cm−3) at 2 mV s−1, excellent rate capability, and high mass loading. In addition, the assembled symmetric supercapacitor demonstrates a fantastic volumetric energy density (38.6 Wh L−1), which is the highest value reported for MXene‐based electrodes in aqueous electrolytes. This work opens a new avenue for the further exploration of MXene materials in energy storage devices.