Abstract MXene is a promising energy storage material for miniaturized microbatteries and microsupercapacitors (MSCs). Despite its superior electrochemical performance, only a few studies have reported MXene‐based ultrahigh‐rate (>1000 mV s−1) on‐paper MSCs, mainly due to the reduced electrical conductance of MXene films deposited on paper. Herein, ultrahigh‐rate metal‐free on‐paper MSCs based on heterogeneous MXene/poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS)‐stack electrodes are fabricated through the combination of direct ink writing and femtosecond laser scribing. With a footprint area of only 20 mm2, the on‐paper MSCs exhibit excellent high‐rate capacitive behavior with an areal capacitance of 5.7 mF cm−2 and long cycle life (>95% capacitance retention after 10,000 cycles) at a high scan rate of 1000 mV s−1, outperforming most of the present on‐paper MSCs. Furthermore, the heterogeneous MXene/PEDOT:PSS electrodes can interconnect individual MSCs into metal‐free on‐paper MSC arrays, which can also be simultaneously charged/discharged at 1000 mV s−1, showing scalable capacitive performance. The heterogeneous MXene/PEDOT:PSS stacks are a promising electrode structure for on‐paper MSCs to serve as ultrafast miniaturized energy storage components for emerging paper electronics.
