Hollow Nanotube Arrays Research Articles

Hollow transition metal chalcogenides derived from vanadium-based metal organic framework for hybrid supercapacitors with excellent energy-density and stability

In-situ synthesized hollow transition metal chalcogenides have gained significant attention on account of their excellent electrochemical properties. Here, Ni-doped V-MOF (V(Ni)-MOF) nanorod arrays as precursor are first grown on nickel foam (NF). Subsequently, the nanorod arrays are converted into V(NiCo)-OH hollow nanotube arrays with cross-linked nanosheets by Co2+ etching. Finally, V(NiCo)-OH/NF is converted into V(NiCo)-X/NF (X = O, S and Se) by annealing or ion exchange. Due to the unique morphology of hollow nanotube arrays with cross-linked nanosheets and synergistic effect of multi-metal components, the V(NiCo)-Se/NF achieves an outstanding specific capacity (1806.7 C g−1 at 1 A g−1), which is higher than that of V(NiCo)-O/NF (1208.3 C g−1) and V(NiCo)-S/NF (1558.4 C g−1). In addition, the capacity retention rate is 91.7 % (at 10 A g−1 after 10, 000 cycles). Utilizing V(NiCo)-Se/NF (positive) and activated carbon/NF (negative), the hybrid supercapacitor (HSC) achieves an impressive high energy density of 114.8 Wh kg−1 (at 679.5 W kg−1). Moreover, two HSCs in series can power the LED and stopwatch, and keep working for more than 60 min, displaying good practical application capabilities.

NH4Cl-Assisted Electrosynthesis of P-Doped Co(OH)2 Nanosheet on Cu2S Hollow Nanotube Arrays for Glycerol Electrooxidation.

The glycerol oxidation reaction (GOR) for producing high-value-added organic compounds is of great research interest due to its potential in alleviating the energy crisis. Herein, a facile NH4Cl-assisted electrodeposition strategy is reported to fabricate 3D nano-forest array-like hollow nanostructures. The hierarchical heterojunction by combining phosphorus doping Co(OH)2 nanosheets with Cu2S nanotube arrays (P-Co(OH)2@Cu2S NTs/CF) is developed to realize the optimization on GOR. The optimized P-Co(OH)2@Cu2S NTs/CF catalyst exhibits an exceptional activity with a formate Faradaic efficiency (FE) of 97.40% at a potential of 1.30V (vs RHE). The experimental results indicate that this unique hollow nano-forest structure, grown on a conductive support, can expose more active sites and facilitate electron transfer, thereby demonstrating excellent GOR performance. This work provides new opportunities for the design of electrocatalysts of high-activity and low-cost hollow heterostructure electrocatalysts for glycerol electrooxidation.

Reactive P and S co-doped porous hollow nanotube arrays for high performance chloride ion storage

Developing stable, high-performance chloride-ion storage electrodes is essential for energy storage and water purification application. Herein, a P, S co-doped porous hollow nanotube array, with a free ion diffusion pathway and highly active adsorption sites, on carbon felt electrodes (CoNiPS@CF) is reported. Due to the porous hollow nanotube structure and synergistic effect of P, S co-doped, the CoNiPS@CF based capacitive deionization (CDI) system exhibits high desalination capacity (76.1 mgCl– g–1), fast desalination rate (6.33 mgCl– g–1 min–1) and good cycling stability (capacity retention rate of > 90%), which compares favorably to the state-of-the-art electrodes. The porous hollow nanotube structure enables fast ion diffusion kinetics due to the swift ion transport inside the electrode and the presence of a large number of reactive sites. The introduction of S element also reduces the passivation layer on the surface of CoNiP and lowers the adsorption energy for Cl– capture, thereby improving the electrode conductivity and surface electrochemical activity, and further accelerating the adsorption kinetics. Our results offer a powerful strategy to improve the reactivity and stability of transition metal phosphides for chloride capture, and to improve the efficiency of electrochemical dechlorination technologies.

Hollow nanotube arrays of CoP@CoMoO4 as advanced electrocatalyst for overall water splitting

Developing cost-effective and high-performance bifunctional electrocatalysts for water-splitting in alkaline electrolytes is considered to be one of the prerequisites for exploring hydrogen energy technology. Herein, we present a kind of ZnO template etching strategy coupled with electrodeposition process to prepare MOF-derived CoP@CoMoO4 hollow nanotubes (CoP@CoMoO4 HNTs). The CoP@CoMoO4 HNTs exhibit outstanding electrocatalytic performances, which only require a low potential of 34 and 120 mV to deliver 10 mA cm−2 current density for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Furthermore, the assembled electrolysis system, integrated with the as-prepared CoP@CoMoO4 HNTs, just needs a quite low voltage of 1.51 V to drive 10 mA cm−2 current density and also exhibits excellent durability in alkaline electrolyte for over 24 h. These fascinating electrochemical properties are the results of the unique 3D hollow nanostructure, various heterogeneous interfaces between CoP and CoMoO4 as well as strong electronic configurations of the CoP@CoMoO4 HNTs catalyst. This work emphasizes the key roles of synergism in promoting electrocatalytic reaction kinetics and provides a new pathway for preparing non-noble-based electrocatalysts with astonishing properties.

Morphological tuning of hollow NiCo2Se4 nanotube arrays anchored on Ni/C at varied selenization duration for efficient battery-type supercapacitors

The rational design of transition bimetal selenides with porous hollow structures has attracted significant attention in supercapacitor applications. Herein, the hierarchical hollow nanotubes NiCo2Se4/NC (porous NC derived from Ni-MOF) arrays were synthesized by hydrothermal and selenide strategies. The porous NC substrate could provide additional capacitance and boost the electrochemical capacity of NiCo2Se4 nanotubes through synergistic effect. By comparing electrochemical properties, we found that the electrodes of selenization 6 h (NiCo-Se-6/NC) exhibit the highest capacity properties among other electrodes. As a result, NiCo-Se-6/NC (NiCo2Se4/NC) achieved a distinguished specific capacity performance of 306.4 mAh g−1 (1 A g−1) and maintained better rate performance (81.4 % at 20 A g−1). The assembled NiCo2Se4/NC//AC device exhibits an energy density of 69.2 Wh kg−1 at 750.0 W kg−1 and excellent cycle durability (86.6 % after 5000 cycles), indicating that the hierarchical layered hollow NiCo2Se4/NC composite has wonderful prospects for the use of energy storage applications.

Effect of oxygen vacancy on electrochemical performance of NiCo-layered double oxides as water splitting electrocatalyst

It is of importance for the design of cost-effective bifunctional electrocatalysts with good durability to decrease the energy rampart of total water decomposition. However, few electrocatalysts simultaneously exhibits excellent catalytic property and durability for both oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER). Herein, we adopt strategies toward defect engineering coupled with metal organic framework (MOF) to synthesize oxygen vacancy abundant NiCo-layered double oxides with hollow nanotube arrays structures supported on Ni foam (Ov-NiCo-LDO HNTAs/NF) via etching of ZnO template, which is considered as an efficient electrocatalyst for water splitting. The optimal Ov-NiCo-LDO HNTAs/NF reveals an ultra-low overpotential of 149 and 30 mV to afford a current density of 10 mA cm−2 for OER and HER in alkaline solution, respectively. Moreover, the catalyst also displays significant stability for 24 h with no significant decrease when a stable current density of 100 mA cm−2 is applied. A full water splitting system coupled with Ov-NiCo-LDO HNTAs/NF as both poles of hydrolysis tank can drive of 20 mA cm−2 current density at a potential of 1.68 V, along with steady operation for over 24 h, indicating that Ov-NiCo-LDO HNTAs/NF is a promising bifunctional electrocatalyst.

Crystalline-amorphous heterostructures with assortative strong-weak adsorption pairs enable extremely high water oxidation capability toward multi-scenario water electrolysis

Nano-sized crystalline-amorphous heterostructures display prominent catalytic activity toward multifarious electrochemical reactions, while no rational component selection strategy could be provided hitherto. Herein, an accurate tactic by introducing assortative strong-weak Ru-Co adsorptive atomic pair into the construction of hollow Ru-CoMoSx nanotube arrays is first proposed. Benefiting from the favorable charge density redistribution and adjusted d-band centers over the coupling strong-weak Ru-Co adsorption sites, balanced adsorption behaviors can be achieved upon potential active centers, thereby leading to the very low reaction energy barriers. Indeed, due to the anticipatory strong-weak Ru-Co adsorption pair, the as-constructed crystalline-amorphous Ru-CoMoSx heterointerface affords one of the best electrocatalytic activity toward oxygen evolution reaction (OER) in alkaline media to date, with an extremely low overpotential of 147 mV at the current density of 10 mA cm−2. Also, it exhibits an admirable Pt-like hydrogen evolution (HER) behavior (35 mV @ 10 mA cm−2). Thereout, its application prospect in practical multi-scenario water electrolysis, including freshwater/seawater electrolysis and integrated photovoltaics-hydrogen production system, is well demonstrated. This work provides instructive guidance for the rational design and in-depth structure-activity analysis of nano-sized crystalline-amorphous heterostructures.

The Hierarchical Structures of Co3S4 Hollow Nanotube Arrays Wrapped with NiCo‐Layered Double Hydroxide Nanosheets for High‐Performance Asymmetric Supercapacitors

Cobalt‐based sulfide is an excellent electrode material applied to supercapacitors (SCs) because of its good reversibility and abundant nanoforms. However, the feasibility of its practical application is reduced due to lack of stability and some difference with theoretical capacity. Herein, the hierarchical structures of Co3S4 hollow nanotube arrays wrapped with NiCo‐layered double hydroxide nanosheets (Co3S4@NiCo‐LDHs) are successfully fabricated on the nickel foam (NF) as the nonbinder electrode of SCs. Profiting from the synthetic effect of Co3S4 hollow nanotube arrays with effective diffusion channels, and NiCo‐LDH nanosheets with a stable interconnected network, the prepared Co3S4@NiCo‐LDH/NF composite electrode with a unique hierarchical structure attains an amazing areal capacity (7.45 C cm−2 at 2 mA cm−2) and impressive cycle stability (87.7% through 5000 charge and discharge cycles). In addition, the assembled asymmetric supercapacitor (Co3S4@NiCo‐LDH/NF//AC) shows pleasant energy density (0.661 mWh cm−2 under 1.359 mW cm−2). The capacity of the assembled device can still be retained at 92% after 5000 cycles, which verifies the feasibility of the device in practical application.

Hierarchical construction of hollow NiCo2S4 nanotube@NiCo2S4 nanosheet arrays on Ni foam as an efficient and durable electrocatalyst for hydrogen evolution reaction

Ternary transition metal chalcogenide (TTMC) with multicomponent, different phases and unique electronic structures have been studied in electrocatalytic hydrogen evolution reaction (HER). However, the strong interaction between adsorbed H (H∗) and sulfur leads to the unfavorable hydrogen desorption properties of considerable TTMC. Herein, we constructed the hierarchical hollow NiCo2S4 nanotube@NiCo2S4 nanosheet arrays on Ni foam substrate (NT-NiCo2S4@NS-NiCo2S4/NF) by ion-exchange method. Homogeneous anion diffusion facilitates the formation of regular ultrathin nanosheets on hollow NiCo2S4 nanotube arrays, which presents hierarchical architecture with more surface area and channels to active site exposure, electrolyte diffusion, and gas desorption for HER. As-synthesized optimal NT-NiCo2S4@NS-NiCo2S4/NF electrode demonstrates an excellent HER activity, especially an overpotential of 221 mV, a Tafel slope of 108 mV dec−1, and remarkable stability at current densities of 100 mA cm−2 in 1.0 M NaOH electrolyte.

MoS2 nanosheets vertically grown on CoSe2 hollow nanotube arrays as an efficient catalyst for the hydrogen evolution reaction.

Although the design and synthesis of efficient electrocatalysts for the hydrogen evolution reaction (HER) are highly desirable, severe challenges still need to be addressed. Herein, ultrathin MoS2 nanosheets were vertically grown on CoSe2 hollow nanotube arrays via a simple three-step hydrothermal reaction by using carbon cloth (CC) as a substrate and were subsequently used as a highly efficient HER electrocatalyst (MoS2@CoSe2-CC hybrid). The MoS2 nanosheets uniformly self-assembled on conductive CoSe2 nanotube arrays exhibited a hierarchical and well-ordered structure. Such a unique structure may not only comprise more exposed active sites, but also enable fast electrolyte penetration and facilitate H+/electron transportation to accelerate the reduction and evolution of H2 during the electrocatalytic process. As an HER electrocatalyst with a novel three-dimensional hierarchical structure, the MoS2@CoSe2-CC hybrid exhibited an outstanding catalytic HER performance with a small Tafel slope of 67 mV dec-1 in alkaline media, while only requiring a low HER overpotential of 101 mV at 10 mA cm-2. Notably, the MoS2@CoSe2-CC hybrid also demonstrated exceptional electrochemical durability and structural stability even after 1000 cycles or 48 h of continuous electrolysis. Overall, this work presents a new approach for the design and synthesis of robust, highly active, and cost-effective electrocatalysts for hydrogen generation.

Ultra-thin dark amorphous TiOx hollow nanotubes for full spectrum solar energy harvesting and conversion‡

Dark titania (TiOx) have been widely used for solar energy harvesting and conversion applications due to its excellent light absorbing performance throughout the ultraviolet to near infrared wavelength band, low cost, and non-toxic nature. However, the synthesis methods of dark TiOx are usually complicated and time-consuming. Here we report a facile and rapid method to fabricate dark amorphous TiOx (am-TiOx) hollow nanotube arrays on nanoporous anodic alumina oxide (AAO) templates using atomic layer deposition. Systematic investigation was performed to demonstrate that Ti3+ and O- species in the am-TiOx ultra-thin films, as well as the spatial distribution of these am-TiOx ultra-thin films on the vertical side walls of AAO templates are two major mechanisms of the black color. Importantly, the film deposition took ~18 min only to produce the optimized ~4‐nm‐thick am-TiOx film. Representative applications were demonstrated using photocatalytic reduction of silver nitrate and photothermal solar vapor generation, revealing the potential of these ultra-thin dark am-TiOx/AAO structures for full spectrum solar energy harvesting and conversion.

Photocorrosion of CdS nanorod arrays and fabrication of CdS@TiO2 core@shell nanorod arrays by atomic layer deposition for improved photostability

In this manuscript, an interesting phenomenon was found that partially or entirely hollow CdS nanotube arrays (PEH CdS NT) were obtained after photocorrosion of CdS nanorod arrays (NR). The forming process of PEH CdS NT was studied in detail. Afterwards, CdS@TiO2 core@shell NR with controllable TiO2 thickness onto CdS NR were preparated by atomic layer deposition (ALD), and the photostability of CdS@TiO2 core@shell NR was studied. Compared with unmodified CdS NR, the CdS@TiO2-1500 core@shell NR (the thickness of the TiO2 layer was 1500 ALD cycles) exhibited higher photostability within 300 s, which could be ascribed to the TiO2 nanolayer. TiO2 nanolayer can protect CdS NR from photocorrosion because it can effectually transfer the hole and the electron separation from photoluminescence (PL) characteristic. These results suggest that CdS@TiO2 core@shell NR fabricated by ALD are effective in protecting of CdS NR from photocorrosion.

Engineering defect-rich Fe-doped NiO coupled Ni cluster nanotube arrays with excellent oxygen evolution activity

Herein we present a novel multi-level structure of Fe-doped NiO coupled Ni cluster hollow nanotube arrays (Fe-NiO-Ni CHNAs) grown on carbon fiber cloth as an efficient catalyst for oxygen evolution reaction. In this multi-level structure, rocksalt-type Fe-doped NiO phase hybrids with Ni clusters coupled into the nanospheres anchored to the outside of nanotube, forming a unique 3D corn-like structure. This novel multi-level structure represents a large specific area for catalytic reaction. X-ray absorption fine structure indicates that the defect-rich Fe-doped NiO phase has abundant coordinative unsaturated sites as active sites, and Fe doping downshifts the d-band of metal sites, which is the main contribution to the improved oxygen evolution reaction catalytic activity. The OER of Fe-NiO-Ni CHNAs obeys the adsorbate evolution mechanism with the nonconcerted proton-electron transfer pathway as a rate-determining step. Thus Fe-doped NiO CHNAs exhibits excellent OER performance and outstanding durability that surpasses most of transition metal oxides.

LaF3 Nanosheet-induced Epitaxial Growth: Hollow (Co, Ni)2P/LaF3 Nanotube Arrays Built by Porous Heterojunction Walls Grown on Ni Foam as Active Electrocatalyst for Hydrogen Evolution Reaction

Free-standing (Co, Ni)2P/LaF3 hollow nanotube arrays are directly grown on Ni foam (NF) (denoted as (Co, Ni)2P-La4/NF, where "4" refers to 4 g L-1 of La3+ in the starting material), which exhibits efficient electrocatalytic activity for hydrogen evolution reaction (HER) with an overpotential of 94 mV at 10 mA cm2, Tafel slope of 88 mV dec-1, and superior long-term durability in alkaline electrolyte. Investigated was La dosage-induced compositional and morphological evolution of (Co, Ni)2P/LaF3, and it was found that suitable La dosage is beneficial for the epitaxial growth of (Co, Ni)2P on LaF3 nanosheets (the thickness direction of LaF3 nanosheet is along the (03i̅) facet), leading to the formation of porous (Co, Ni)2P/LaF3 nanotube walls, giving rise to hollow nanotube arrays. The binder-free (Co, Ni)2P-La4/NF electrode with unique morphology not only provides more active sites exposure to electrolyte ions and accessible ion diffusion path but also favors electron and charge transfer. Density functional theory calculation and experimental data reveal the doping of La into metal phosphide can lead to electron transfer from metal centers to P atoms, make the ΔGH on the P sites closer to zero with lower H2O adsorption energy (-0.58 eV), thus improving the HER behavior. The present work gives a novel strategy to design hollow nanotubular microstructure as non-noble-metal HER electrocatalyst.

Design of FeCo2S4@Ni(OH)2 core-shell hollow nanotube arrays on carbon paper for ultra-high capacitance in supercapacitors

In this paper, we design a novel FeCo2S4@Ni(OH)2 core-shell hollow nanotube arrays on carbon paper for superior capacitance of supercapacitors. FeCo2S4 hollow nanotube arrays vertically grow on carbon paper via hydrothermal reaction served as a “core” to shorten the ion transport path, Ni(OH)2 nanosheets modified on the hollow nanotube arrays based on constant voltage electrodeposition reveal outstanding pseudocapacitance characteristic. The ultrathin Ni(OH)2 nanosheets act as a “shell” layered to expand the specific surface area, effectively increasing the active sites of the faraday reaction. The subtle heterogeneous synergistic effects significantly improve their electrochemical performance. The unique core-shell structure of FeCo2S4@Ni(OH)2 displays a superior capacity of 239.72 mA h g−1 at 1 A g−1, even at 8 A g−1 still has a capacity of 128.0 mA h g−1, indicating the excellent rate performance. Significantly, the asymmetric supercapacitor assembled by the FeCo2S4@Ni(OH)2 nanoarrays positive electrode and activated carbon (AC) negative electrode exhibits superior electrochemical performance with ultra-high energy density (55.33 Wh Kg−1 at 800 W kg−1) and power density (8000 W kg−1 at 15.78 Wh Kg−1). After 10000 charge-discharge cycles, the device still has capacitance retention of 93.8%. Therefore, FeCo2S4@Ni(OH)2 nanoarrays can be widely used in high-performance supercapacitors as potential and promising electrode materials.

A hierarchical glucose-intercalated NiMn-G-LDH@NiCo2S4 core-shell structure as a binder-free electrode for flexible all-solid-state asymmetric supercapacitors.

Flexible, lightweight, and high-energy-density asymmetric supercapacitors (ASCs) are highly attractive for portable and wearable electronics. However, the implementation of such flexible ASCs is still hampered by the low specific capacitance and sluggish reaction kinetics of the electrode materials. Herein, a hierarchical core-shell structure of hybrid glucose intercalated NiMn-LDH (NiMn-G-LDH)@NiCo2S4 hollow nanotubes is deliberately constructed on flexible carbon fiber cloth (CFC). The highly conductive hollow NiCo2S4 nanotube arrays can not only provide high-speed pathways for ion and electrolyte transfer but also regulate the growth of NiMn-G-LDH nanosheets. The expanded interlayer distance on NiMn-G-LDH nanosheets could further facilitate ion diffusion and improve the rate retention. Benefiting from the rational engineering, the flexible NiMn-G-LDH@NiCo2S4@CFC as a free-standing electrode could deliver a superior specific capacity of 1018 C g-1 at 1 A g-1, which is almost twice higher than that of pristine NiCo2S4@CFC. In addition, the as-assembled flexible all-solid-state ASC device (NiMn-G-LDH@NiCo2S4@CFC//AC) is capable of working at various bending angles and exhibits an impressive energy density of 60.3 W h kg-1 at a power density of 375 W kg-1, as well as a superior cycling stability of 86.4% after 10 000 cycles.

CeOx-Decorated Hierarchical NiCo2S4 Hollow Nanotubes Arrays for Enhanced Oxygen Evolution Reaction Electrocatalysis.

Developing hollow self-supported nanotube arrays with hierarchical microporous and abundant multiactive sites shows great promise for oxygen evolution reaction (OER) electrocatalysis. Herein, a facile and low-cost strategy of NiCo2S4 hollow nanotubes arrays decorated with CeOx nanoparticles (NPs) assembled on a flexible support carbon cloth (CC) for enhanced OER performance is reported. The obtained hierarchical nanoarrays CeOx/NiCo2S4/CC exhibited excellent activity toward OER with an overpotential (270 mV) at 10 mA cm-2, relatively weak Tafel slope, and distinguished durability. CeOx/NiCo2S4/CC nanoarrays not only provide fast electronic transmission and well-defined connection to the substrate but also defective sites and electron transfer by the introduction of CeOx NPs. This new strategy was offered to construct low-cost and effectively hierarchical structural electrocatalysts containing rare-earth species.

Conformal dispersed cobalt nanoparticles in hollow carbon nanotube arrays for flexible Zn-air and Al-air batteries

The development of both flexible solid-state Zn-air and Al-air batteries are challenged by the efficient and stable air cathodes with high catalytic activities in both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). In this work, we report the rational design of hollow N-doped carbon nanotube arrays embedded with confined Co nanoparticles (HCA-Co) through a facile solution-reaction and annealing process. Due to the unique integration of hollow carbon nanoarray with tiny cobalt nanoparticles, the obtained flexible HCA-Co electrode shows promising catalytic properties toward both ORR and OER that achieves a current density of 10 mA cm−2 at small overpotential of 290 mV in OER, and demonstrates an onset potential of 0.92 V in ORR. The HCA-Co can be applied as a binder-free air-cathode for flexible all-solid-state zinc-air batteries, which presents a relatively high open circuit potential (1.40 V) with better cycling stability than Pt/C based battery. The HCA-Co is also utilised as cathode for solid-state Al battery, which shows a high open circuit potential (1.966 V) with better mechanical flexibility than that of Pt/C-based battery. Such flexible electrode with excellent bifunctional catalytic properties hold great promise for the application in flexible electronics.

Mn2O3 Hollow Nanotube Arrays on Ni Foam as Efficient Supercapacitors and Electrocatalysts for Oxygen Evolution Reaction

It is imperative to study the earth abundant nonprecious metal oxides with high electrocatalytic activity and excellent energy storage performance. Herein, Mn2O3 nanotube arrays (Mn2O3 NAs) have been synthesized by controllably annealing the Mn-MOFs precursors. The hollow Mn2O3 NAs exhibit high electrocatalytic activity for oxygen evolution reaction (OER), accompanied by a low overpotential of 270 mV to achieve 10 mA cm–2 in 1.0 M KOH solution. The corresponding Tafel slope is only 85 mV dec–1 and the Faradaic efficiency is nearly 100%. Besides the excellent OER performance, Mn2O3 NAs also exhibit enhanced specific capacitance of 677 F g–1 at 1 mA cm–2, which is preferable to most Mn2O3 materials. The electrocatalytic results strongly demonstrate that the three-dimensional skeleton structure and microstructure of hollow nanotube arrays in Mn2O3 NAs are the intrinsical factors for the enhanced OER performance and high specific capacitance.

Hierarchical Multicomponent Electrode with Interlaced Ni(OH)2 Nanoflakes Wrapped Zinc Cobalt Sulfide Nanotube Arrays for Sustainable High‐Performance Supercapacitors

AbstractHigh 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.