3D Hierarchical Ti3C2TX@PANI-Reduced Graphene Oxide Heterostructure Hydrogel Anode and Defective Reduced Graphene Oxide Hydrogel Cathode for High-Performance Zinc Ion Capacitors

The practical application of supercapacitors (SCs) has been known to be restricted by low energy density, and zinc ion capacitors (ZICs) with a capacitive cathode and a battery-type anode have emerged as a unique technology that can effectively mitigate the issue. To this end, the design of electrodes with low electrochemical impedance, high specific capacitance, and outstanding reaction stability represents a critical first step. Herein, we report the synthesis of hierarchical Ti3C2TX@PANI heterostructures by uniform deposition of conductive polyaniline (PANI) polymer nanofibers on the exposed surface of the Ti3C2TX nanosheets, which are then assembled into a three-dimensional (3D) cross-linking framework by a graphene oxide (GO)-assisted self-convergence hydrothermal strategy. This resulting 3D Ti3C2TX@PANI-reduced graphene oxide (Ti3C2TX@PANI-RGO) heterostructure hydrogel shows a large surface area (488.75 F g-1 at 0.5 A g-1), outstanding electrical conductivity, and fast reaction kinetics, making it a promising electrode material. Separately, defective RGO (DRGO) hydrogels are prepared by a patterning process, and they exhibit a broad and uniform distribution of mesopores, which is conducive to ion transport with an excellent specific capacitance (223.52 F g-1 at 0.5 A g-1). A ZIC is subsequently constructed by utilizing Ti3C2TX@PANI-RGO as the anode and DRGO as the cathode, which displays an extensive operating voltage (0-3.0 V), prominent energy density (1060.96 Wh kg-1 at 761.32 W kg-1, 439.87 Wh kg-1 at 9786.86 W kg-1), and durable cycle stability (retaining 67.9% of the original capacitance after 4000 cycles at 6 A g-1). This study underscores the immense prospect of the Ti3C2TX-based heterostructure hydrogel and DRGO as a feasible anode and cathode for ZICs, respectively.