To achieve high‐performance wearable supercapacitors (SCs), a new class of flexible electrodes with favorable architectures allowing large porosity, high conductivity, and good mechanical stability is strongly needed. Here, this study reports the rational design and fabrication of a novel flexible electrode with nanotube‐built multitripod architectures of ternary metal sulfides' composites (FeCo2S4–NiCo2S4) on a silver‐sputtered textile cloth. Silver sputtering is applicable to almost all kinds of textiles, and S2− concentration is optimized during sulfidation process to achieve such architectures and also a complete sulfidation assuring high conductivity. New insights into concentration‐dependent sulfidation mechanism are proposed. The additive‐free FeCo2S4–NiCo2S4 electrode shows a high specific capacitance of 1519 F g−1 at 5 mA cm−2 and superior rate capability (85.1% capacitance retention at 40 mA cm−2). All‐solid‐state SCs employing these advanced electrodes deliver high energy density of 46 W h kg−1 at 1070 W kg−1 as well as achieve remarkable cycling stability retaining 92% of initial capacitance after 3000 cycles at 10 mA cm−2, and outstanding reliability with no capacitance degradation under large twisting. These are attributed to the components' synergy assuring rich redox reactions, high conductivity as well as highly porous but robust architectures. An almost linear increase in capacitance with devices' area indicates possibility to meet various energy output requirements. This work provides a general, low‐cost route to wearable power sources.

A significant advance toward the design and fabrication of a novel hierarchical supercapacitor electrode consisting of FeCo2S4‐tubes with well‐defined square cross‐section and intersecting nanosheets built porous shells on a 3D porous Ni backbone via controlled sulfidation is reported. This general method allows template‐free synthesis of metal sulfides tubular structures with polygonal cross‐sections and also fine control over the nanostructure leading to both maximized porosity and saturation sulfidation. New insights into concentration and time dependent sulfidation reaction kinetics are proposed. The FeCo2S4 electrode achieves a specific capacitance reaching 2411 F g‐1 at 5 mA cm‐2 and good rate capability, which are superior over those for nanotube arrays of other ternary transition metal sulfides. This is attributed to rich redox reactions, the highly porous but robust architecture as well as high electrical conductivity. Especially such porous shells effectively avoid “dead volume”, thus improve the utilization ratio of the electrode material. Asymmetric solid‐state device applying the FeCo2S4 as positive electrode and N‐doped graphene hydrogel film as negative electrode has a high cell voltage of 1.6 V and thus delivers considerably higher energy density of 76.1 W h kg‐1 (at 755 W kg‐1) than those reported for similar devices.

High energy density, fast recharging ability, and sustained cycle life are the primary requisite of supercapacitors (SCs); these necessities can be fulfilled by engineering a smart current collector with hierarchical combination of different active materials. This study reports a multicomponent design of hierarchical zinc cobalt sulfide (ZCS) hollow nanotube arrays wrapped with interlaced ultrathin Ni(OH)2 nanoflakes for high‐performance electrodes. The ZCS exhibits a unique pentagonal cross‐section and a rough surface that facilitates the deposition of Ni(OH)2 nanoflakes with a thickness of 7.5 nm. The ZCS/Ni(OH)2 hierarchical electrode exhibits a high specific capacitance of 2156 F g−1 and excellent cyclic stability with 94% retention over 3000 cycles. This is attributed to enhanced redox reactions, the direct growth of arrays on 3D porous foam acting as a “superhighway” for electron transport, and the increased availability of electrochemical active sites provided by the ultrathin Ni(OH)2 flakes that also sustain the stability of the electrode by sacrificing themselves during long charge/discharge cycles. Symmetric SCs are assembled to achieve high energy density of 74.93 W h kg−1 and exhibit superior cyclic stability of 78% retention with 81% coulombic efficiency over 10 000 cycles.