Multifunctional electronic textiles hold great potential applications in the wearable electronics field. However, it remains challenging to seamlessly integrate the multiple functions on the textile substrates without sacrificing their intrinsic properties. Herein, we report a novel and facile vapor phase polymerization (VPP) and spray-coating strategy towards the construction of a laminated film containing a PEDOT film and Ti₃C₂T_x MXene sheets on the fiber surface. The fabricated PEDOT/MXene decorated cotton fabrics are integrated with excellent electrochemical performance, joule heating performance, good electromagnetic interference (EMI) shielding, and strain sensing performance. The resultant multifunctional textiles have a low sheet resistance of 3.6 Ω sq⁻¹, and the assembled all-solid-state fabric supercapacitors exhibit an ultrahigh specific capacitance of 1000.2 mF cm⁻², which exceeds the state-of-the-art MXene-based fabric supercapacitors. In addition, the PEDOT/MXene modified fabrics exhibit an exceptional joule heating performance of 193.1 °C at the applied voltage of 12 V, high EMI shielding effectiveness of 36.62 dB, and high sensitivity as strain sensors for human motion detection. This work provides a novel strategy for the structure design of multifunctional textiles and will lay the foundation for the development of multifunctional wearable electronics.

Owing to their high power density, fast charge/discharge rate, ultralong cycling life and safe operating conditions, all-carbon fiber-shaped supercapacitors (FSSCs) hold great promise for powering wearable electronics. However, their low energy density hinders them from practical application, due to the absence of effective approaches for highly electrically conductive fiber electrodes with high specific capacitance. Herein, we develop a scalable and cost-effective strategy towards hierarchically porous core–sheath graphene-based fiber electrodes with a rational PSD (88–97% micropores, 0–8.3% mesopores and 1.9–4.2% macropores) and high SSA (up to 416.4 m² g⁻¹). The hierarchical architecture is achieved by simply decorating graphene fiber with carbonized phenol formaldehyde (CPF) resin containing small-size (∼156 nm in diameter) graphene (SG), wherein the incorporation of CPF and SG synergistically provides ultrahigh micro-porosity with narrowed micro-/meso-PSDs and enhanced electrical conductivity, facilitating ion storage and transport. The assembled FSSCs exhibit an ultrahigh specific areal capacitance of 391.2 mF cm⁻² in polyvinyl alcohol/H₂SO₄ electrolyte at 0.1 mA cm⁻² in a two-electrode cell, which is 17 times that of graphene fibers. The entire-device energy density E_cell,A is 8.7 μW h cm⁻² in aqueous electrolyte and 66.4 μW h cm⁻² at an areal power density of 0.54 mW cm⁻² in organic electrolyte. Moreover, the FSSCs also show ultralong cycling life (98.9% capacitance retention after 7000 cycles) and good flexibility. All these results have made it one of the best ever reported all-carbon FSSCs to date. This work may shed light on mass-manufacturing low-cost but high-performance wearable fiber-shaped energy storage devices.