Oxygen Evolution Assisted Fabrication of Highly Loaded Carbon Nanotube/MnO2 Hybrid Films for High‐Performance Flexible Pseudosupercapacitors

To date, it has been a great challenge to design high‐performance flexible energy storage devices for sufficient loading of redox species in the electrode assemblies, with well‐maintained mechanical robustness and enhanced electron/ionic transport during charge/discharge cycles. An electrochemical activation strategy is demonstrated for the facile regeneration of carbon nanotube (CNT) film prepared via floating catalyst chemical vapor deposition strategy into a flexible, robust, and highly conductive hydrogel‐like film, which is promising as electrode matrix for efficient loading of redox species and the fabrication of high‐performance flexible pseudosupercapacitors. The strong and conductive CNT films can be effectively expanded and activated by electrochemical anodic oxygen evolution reaction, presenting greatly enhanced internal space and surface wettability with well‐maintained strength, flexibility, and conductivity. The as‐formed hydrogel‐like film is quite favorable for electrochemical deposition of manganese dioxide (MnO₂) with loading mass up to 93 wt% and electrode capacitance kept around 300 F g^?1 (areal capacitance of 1.2 F cm^?2). This hybrid film was further used to assemble a flexible symmetric pseudosupercapacitor without using any other current collectors and conductive additives. The assembled flexible supercapacitors exhibited good rate performance, with the areal capacitance of more than 300 mF cm^?2, much superior to other reported MnO₂ based flexible thin‐film supercapacitors.     

High Volumetric Energy Density Asymmetric Supercapacitors Based on Well‐Balanced Graphene and Graphene‐MnO2 Electrodes with Densely Stacked Architectures

The well‐matched electrochemical parameters of positive and negative electrodes, such as specific capacitance, rate performance, and cycling stability, are important for obtaining high‐performance asymmetric supercapacitors. Herein, a facile and cost‐effective strategy is demonstrated for the fabrication of 3D densely stacked graphene (DSG) and graphene‐MnO₂ (G‐MnO₂) architectures as the electrode materials for asymmetric supercapacitors (ASCs) by using MnO₂‐intercalated graphite oxide (GO‐MnO₂) as the precursor. DSG has a stacked graphene structure with continuous ion transport network in‐between the sheets, resulting in a high volumetric capacitance of 366 F cm^–3, almost 2.5 times than that of reduced graphene oxide, as well as long cycle life (93% capacitance retention after 10 000 cycles). More importantly, almost similar electrochemical properties, such as specific capacitance, rate performance, and cycling stability, are obtained for DSG as the negative electrode and G‐MnO₂ as the positive electrode. As a result, the assembled ASC delivers both ultrahigh gravimetric and volumetric energy densities of 62.4 Wh kg^–1 and 54.4 Wh L^–1 (based on total volume of two electrodes) in 1 m Na₂SO₄ aqueous electrolyte, respectively, much higher than most of previously reported ASCs in aqueous electrolytes.     

3D-Printed Structure Boosts the Kinetics and Intrinsic Capacitance of Pseudocapacitive Graphene Aerogels

The performance of pseudocapacitive electrodes at fast charging rates are typically limited by the slow kinetics of Faradaic reactions and sluggish ion diffusion in the bulk structure. This is particularly problematic for thick electrodes and electrodes highly loaded with active materials. Here, a surface-functionalized 3D-printed graphene aerogel (SF-3D GA) is presented that achieves not only a benchmark areal capacitance of 2195 mF cm⁻² at a high current density of 100 mA cm⁻² but also an ultrahigh intrinsic capacitance of 309.1 µF cm⁻² even at a high mass loading of 12.8 mg cm⁻². Importantly, the kinetic analysis reveals that the capacitance of SF-3D GA electrode is primarily (93.3%) contributed from fast kinetic processes. This is because the 3D-printed electrode has an open structure that ensures excellent coverage of functional groups on carbon surface and facilitates the ion accessibility of these surface functional groups even at high current densities and large mass loading/electrode thickness. An asymmetric device assembled with SF-3D GA as anode and 3D-printed GA decorated with MnO₂ as cathode achieves a remarkable energy density of 0.65 mWh cm⁻² at an ultrahigh power density of 164.5 mW cm⁻², outperforming carbon-based supercapacitors operated at the same power density.     

Facile,Room Temperature,Electroless Deposited (Fe1−x,Mnx)OOH Nanosheets as Advanced Catalysts: The Role of Mn Incorporation

Herein, bimetallic iron (Fe)–manganese (Mn) oxyhydroxide ((Fe_1−x,Mn_x)OOH, FeMnOOH) nanosheets on fluorine‐doped tin oxide conducting substrates and on semiconductor photoanodes are synthesized by a facile, room temperature, electroless deposition method as catalysts for both electrochemical and photo‐electrochemical (PEC) water splitting, respectively. Surprisingly, Mn‐doped FeOOH can significantly modulate the nanosheet morphology to increase the active surface area, boost more active sites, and augment the intrinsic activity by tuning the electronic structure of FeOOH. Due to the 2D nanosheet architecture, the optimized FeMnOOH exhibits superior electrochemical activity and outstanding durability for the oxygen evolution reaction with a low overpotential of 246 mV at 10 mA cm⁻² and 414 mV at 100 mA cm⁻², and long‐term stability for 40 h without decay, which is comparable to the best electrocatalysts for water oxidation reported in the literature. By integrating with semiconductor photoanodes (such as α‐Fe₂O₃ nanorod (NR) arrays), bimetallic FeMnOOH catalysts achieve solar‐driven water splitting with a significantly enhanced PEC performance (3.36 mA cm⁻² at 1.23 V vs reversible hydrogen electrode (RHE)) with outstanding long‐term stability (≈8 h) compared to that of the bare Fe₂O₃ NR (0.92 mA cm⁻² at 1.23 V vs RHE).     

Robust Electrodes Based on Coaxial TiC/C–MnO2 Core/Shell Nanofiber Arrays with Excellent Cycling Stability for High‐Performance Supercapacitors

A coaxial electrode structure composed of manganese oxide‐decorated TiC/C core/shell nanofiber arrays is produced hydrothermally in a KMnO₄ solution. The pristine TiC/C core/shell structure prepared on the Ti alloy substrate provides the self‐sacrificing carbon shell and highly conductive TiC core, thus greatly simplifying the fabrication process without requiring an additional reduction source and conductive additive. The as‐prepared electrode exhibits a high specific capacitance of 645 F g^?1 at a discharging current density of 1 A g^?1 attributable to the highly conductive TiC/C and amorphous MnO₂ shell with fast ion diffusion. In the charging/discharging cycling test, the as‐prepared electrode shows high stability and 99% capacity retention after 5000 cycles. Although the thermal treatment conducted on the as‐prepared electrode decreases the initial capacitance, the electrode undergoes capacitance recovery through structural transformation from the crystalline cluster to layered birnessite type MnO₂ nanosheets as a result of dissolution and further electrodeposition in the cycling. 96.5% of the initial capacitance is retained after 1000 cycles at high charging/discharging current density of 25 A g^?1. This study demonstrates a novel scaffold to construct MnO₂ based SCs with high specific capacitance as well as excellent mechanical and cycling stability boding well for future design of high‐performance MnO₂‐based SCs.     

High‐Performance 2.6 V Aqueous Asymmetric Supercapacitors based on In Situ Formed Na0.5MnO2 Nanosheet Assembled Nanowall Arrays

The voltage limit for aqueous asymmetric supercapacitors is usually 2 V, which impedes further improvement in energy density. Here, high Na content Birnessite Na_0.5MnO₂ nanosheet assembled nanowall arrays are in situ formed on carbon cloth via electrochemical oxidation. It is interesting to find that the electrode potential window for Na_0.5MnO₂ nanowall arrays can be extended to 0–1.3 V (vs Ag/AgCl) with significantly increased specific capacitance up to 366 F g^?1. The extended potential window for the Na_0.5MnO₂ electrode provides the opportunity to further increase the cell voltage of aqueous asymmetric supercapacitors beyond 2 V. To construct the asymmetric supercapacitor, carbon‐coated Fe₃O₄ nanorod arrays are synthesized as the anode and can stably work in a negative potential window of ?1.3 to 0 V (vs Ag/AgCl). For the first time, a 2.6 V aqueous asymmetric supercapacitor is demonstrated by using Na_0.5MnO₂ nanowall arrays as the cathode and carbon‐coated Fe₃O₄ nanorod arrays as the anode. In particular, the 2.6 V Na_0.5MnO₂//Fe₃O₄@C asymmetric supercapacitor exhibits a large energy density of up to 81 Wh kg^?1 as well as excellent rate capability and cycle performance, outperforming previously reported MnO₂‐based supercapacitors. This work provides new opportunities for developing high‐voltage aqueous asymmetric supercapacitors with further increased energy density.     

面向基因测序芯片应用的TiN电极薄膜制备及性能研究

基因测序技术正处于快速发展阶段,作为灵敏度极高的测序技术——纳米孔测序,对薄膜电极的电阻率和储能特性提出了更高的要求。为了降低薄膜的电阻率并提高储能特性,本文利用反应磁控溅射方法,基于原位生长原理,分别制备了TiO_xN_y和Ti/TiN/TiO_xN_y电极薄膜。采用扫描电子显微镜、X射线衍射仪和电化学工作站对薄膜的微观结构、化学成分及其电化学性能进行研究。结果表明,在TiN高导电性和TiO_xN_y高比表面积的协同作用下,Ti/TiN/TiO_xN_y电极薄膜表现出优异的电化学性能。当电流密度为0.15 mA/cm²时获得7.01 mF/cm²的比电容,是TiO_xN_y电极薄膜比电容值的1.3倍。同时,与TiO_xN_y单电极相比,Ti/TiN/TiO_xN_y...     

Advanced In Situ Electrochemical Induced Dual-Mechanism Heterointerface toward High-Energy Aqueous Zinc-Ion Batteries

In situ electrochemical activation brings unexpected electrochemical performance improvements to electrode materials, while the mechanism behind is still needed to study deeply. Herein, an in situ electrochemically approach is developed for the activation of heterointerface MnO_x/Co₃O₄ by inducing Mn-defect, wherein the Mn defects are formed through a charge process that converts the MnO_x with poor electrochemical activities toward Zn²⁺ into high electrochemically active cathode for aqueous zinc-ion batteries (ZIBs). Guided by the coupling engineering strategy, the heterointerface cathode exhibits an intercalation/conversion dual-mechanism without structural collapse during storage/release of Zn²⁺. The heterointerfaces between different phases can generate built-in electric fields, reducing the energy barrier for ion migration and facilitating electron/ion diffusion. As a consequence, the dual-mechanism MnO_x/Co₃O₄ shows an outstanding fast charging performance and maintains a capacity of 401.03 mAh g⁻¹ at 0.1 A g⁻¹. More importantly, a ZIB based on MnO_x/Co₃O₄ delivered an energy density of 166.09 Wh kg⁻¹ at an ultrahigh power density of 694.64 W kg⁻¹, which outperforms those of fast charging supercapacitors. This work provides insights for using defect chemistry to introduce novel properties in active materials for highly for high-performance aqueous ZIBs.     

Zn2+ Pre‐Intercalation Stabilizes the Tunnel Structure of MnO2 Nanowires and Enables Zinc‐Ion Hybrid Supercapacitor of Battery‐Level Energy Density

Although there has been tremendous progress in exploring new configurations of zinc‐ion hybrid supercapacitors (Zn‐HSCs) recently, the much lower energy density, especially the much lower areal energy density compared with that of the rechargeable battery, is still the bottleneck, which is impeding their wide applications in wearable devices. Herein, the pre‐intercalation of Zn²⁺ which gives rise to a highly stable tunnel structure of Zn_xMnO₂ in nanowire form that are grown on flexible carbon cloth with a disruptively large mass loading of 12 mg cm^?2 is reported. More interestingly, the Zn_xMnO₂ nanowires of tunnel structure enable an ultrahigh areal energy density and power density, when they are employed as the cathode in Zn‐HSCs. The achieved areal capacitance of up to 1745.8 mF cm^?2 at 2 mA cm^?2, and the remarkable areal energy density of 969.9 µWh cm^?2 are comparable favorably with those of Zn‐ion batteries. When integrated into a quasi‐solid‐state device, they also endow outstanding mechanical flexibility. The truly battery‐level Zn‐HSCs are timely in filling up of the battery‐supercapacitor gap, and promise applications in the new generation flexible and wearable devices.     

Cr-doped MnO<Subscript>2</Subscript> nanostructure: morphology evolution and electrochemical properties

Cr-doped MnO₂ nanostructure has been fabricated via a facile hydrothermal method and its morphology and electrochemical properties was discussed systematically. In this process, flower-like MnO₂ transforms into the self-assembled orchid structure under the influence of Cr-doped. Moreover, electrochemical behaviors of the Cr-doped MnO₂ nanostructure electrode were clarified by cyclic voltammograms, galvanostatic charge/discharge tests and electrochemical impedance spectroscopy, which shows a high specific capacitance of 202.5 F g^?1 and superior cycling stability (6.8 % capacitance decay after 1000 cycling test). These remarkable and excellent results prove it has a great potential of application in future energy storage device.     

Rutile TiO2 nanorod arrays directly grown on Ti foil substrates towards lithium-ion micro-batteries

Nanosized rutile TiO₂ is one of the most promising candidates for anode material in lithium-ion micro-batteries owing to their smaller dimension in ab-plane resulting in an enhanced performance for area capacity. However, few reports have yet emerged up to date of rutile TiO₂ nanorod arrays growing along c-axis for Li-ion battery electrode application. In this study, single-crystalline rutile TiO₂ nanorod arrays growing directly on Ti foil substrates have been fabricated using a template-free method. These nanorods can significantly improve the electrochemical performance of rutile TiO₂ in Li-ion batteries. The capacity increase is about 10 times in comparison with rutile TiO₂ compact layer.     

Photodeposition fabrication of hierarchical layered Co-doped Ni oxyhydroxide (NixCo1−xOOH) catalysts with enhanced electrocatalytic performance for oxygen evolution reaction

Highly active, durable and inexpensive oxygen evolution reaction (OER) catalysts are crucial for achieving practical and high-efficiency water splitting. Herein, hierarchical interconnected Ni_xCo_1−xOOH nanosheet arrays supported on TiO₂/Ti substrate have been fabricated through a facile photodeposition method. Compared with pristine NiOOH, the obtained Ni_xCo_1−xOOH nanosheet arrays possess larger exposed electrochemical active surface area, faster transfer and collection of electrons and stronger electronic interaction, showing a low overpotential of 350 mV at a current density of 10 mA·cm⁻² and a small Tafel slope of 41 mV·dec⁻¹ in basic solutions, with the OER performance superior to pristine NiOOH and most Ni-based catalysts. Furthermore, the Ni_xCo_1−xOOH electrode demonstrates excellent stability at the current density of 10 mA·cm⁻² for 24 hours, which is attributed to the structural maintenance caused by the good adhesion of the catalyst and the substrate. Our study provides an alternative approach for the rational design of highly active and promising OER electrocatalysts.

     

Hierarchical NiCo@NiOOH@CoMoO4 Core–Shell Heterostructure on Carbon Cloth for High-Performance Asymmetric Supercapacitors

The fabrication of low-cost, effective, and highly integrated nanostructured materials through simple and reproducible methods for high-energy-density supercapacitors is highly desirable. Herein, an activated carbon cloth (ACC) is designed as the functional scaffold for supercapacitors and treated hydrothermally to deposit NiCo nanoneedles working as internal core, followed by a dip-dry coating of NiOOH nanoflakes core–shell and uniform hydrothermal deposition of CoMoO₄ nanosheets serving as an external shell. The structured core–shell heterostructure ACC@NiCo@NiOOH@CoMoO₄ electrode resulted in exceptional specific areal capacitance of 2920 mF cm⁻² and exceptional cycling stability for 10 000 cycles. Moreover, the fabricated electrode is developed into an asymmetric supercapacitor which demonstrates excellent areal capacitance, energy density, and power density within the broad potential window of 1.7 V with a cycling life of 92.4% after 10 000 charge–discharge cycles, which reflects excellent cycle life. The distinctive core–shell structure, highly conductive substrate, and synergetic effect of coated material results in more electrochemical active sites and flanges for effective electrons and ion transportation. This unique technique provides a new perspective for cost-efficient supercapacitor applications.     

Three-dimensional heterostructured MnO2/graphene/carbon nanotube composite on Ni foam for binder-free supercapacitor electrode

In this article, three-dimensional (3D) heterostructured of MnO₂/graphene/carbon nanotube (CNT) composites were synthesized by electrochemical deposition (ELD)-electrophoretic deposition (EPD) and subsequently chemical vapour deposition (CVD) methods. MnO₂/graphene/CNT composites were directly used as binder-free electrodes to investigate the electrochemical performance. To design a novel electrode material with high specific area and excellent electrochemical property, the Ni foam was chosen as the substrate, which could provide a 3D skeleton extremely enhancing the specific surface area and limiting the huge volume change of the active materials. The experimental results indicated that the specific capacitance of MnO₂/graphene/CNT composite was up to 377.1 F g^?1 at the scan speed of 200 mV s^?1 with a measured energy density of 75.4 Wh kg^?1. The 3D hybrid structures also exhibited superior long cycling life with close to 90% specific capacitance retained after 500 cycles.     

Tungsten Oxide@Polypyrrole Core–Shell Nanowire Arrays as Novel Negative Electrodes for Asymmetric Supercapacitors

Among active pseudocapacitive materials, polypyrrole (PPy) is a promising electrode material in electrochemical capacitors. PPy‐based materials research has thus far focused on its electrochemical performance as a positive electrode rather than as a negative electrode for asymmetric supercapacitors (ASCs). Here high‐performance electrochemical supercapacitors are designed with tungsten oxide@PPy (WO₃@PPy) core–shell nanowire arrays and Co(OH)₂ nanowires grown on carbon fibers. The WO₃@PPy core–shell nanowire electrode exhibits a high capacitance (253 mF/cm²) in negative potentials (–1.0–0.0 V). The ASCs packaged with CF‐Co(OH)₂ as a positive electrode and CF‐WO₃@PPy as a negative electrode display a high volumetric capacitance up to 2.865 F/cm³ based on volume of the device, an energy density of 1.02 mWh/cm³, and very good stability performance. These findings promote the application of PPy‐based nanostructures as advanced negative electrodes for ASCs.     

A three-dimensional nanostructured PANI/MnOx porous microsphere and its capacitive performance

Three-dimensional nanostructured polyaniline (PANI) and manganese oxide (MnO _x ) composite porous microspheres were prepared by oxidizing aniline with KMnO₄ under interfacial chemical synthesis with 4-amino-thiophenol (4-ATP) as the structure-directing agent on the Au substrate. Surface morphology and chemical composition of PANI/MnO _x microsphere were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermo gravimetric-differential thermal analysis, and Fourier transform infrared spectrum. The result displayed that concentration of KMnO₄ played a key role in forming the 3D nanostructured porous microspheres. To obtain the regular shapes and uniform sizes of the porous microspheres, the optimal concentration of oxidant was 0.15 mol L⁻¹. The electrochemistry performances of PANI/MnO _x microsphere were determined by cyclic voltammograms, electrochemical impedance spectroscopy, and galvanostatic charge–discharge. The specific capacitance of the 3D nanostructured PANI–MnO _x porous microspheres exhibited a maximum value of 828 F g⁻¹ at current density of 2 mA cm⁻² over a potential range of 0.0–0.9 V versus SCE. It has improved 365 and 88 % comparing with that of PANI (178 F g⁻¹) and MnO _x (440 F g⁻¹) obtained at the similar condition. The charge–discharge tests showed the PANI/MnO _x microsphere possessed a good cycling stability. It maintained about 84.2 % of the initial capacitance after 1000 cycles at a current density of 2.0 mA cm⁻².     

Scalable Synthesis of Triple‐Core–Shell Nanostructures of TiO2@MnO2@C for High Performance Supercapacitors Using Structure‐Guided Combustion Waves

Core–shell nanostructures of metal oxides and carbon‐based materials have emerged as outstanding electrode materials for supercapacitors and batteries. However, their synthesis requires complex procedures that incur high costs and long processing times. Herein, a new route is proposed for synthesizing triple‐core–shell nanoparticles of TiO₂@MnO₂@C using structure‐guided combustion waves (SGCWs), which originate from incomplete combustion inside chemical‐fuel‐wrapped nanostructures, and their application in supercapacitor electrodes. SGCWs transform TiO₂ to TiO₂@C and TiO₂@MnO₂ to TiO₂@MnO₂@C via the incompletely combusted carbonaceous fuels under an open‐air atmosphere, in seconds. The synthesized carbon layers act as templates for MnO₂ shells in TiO₂@C and organic shells of TiO₂@MnO₂@C. The TiO₂@MnO₂@C‐based electrodes exhibit a greater specific capacitance (488 F g^?1 at 5 mV s^?1) and capacitance retention (97.4% after 10 000 cycles at 1.0 V s^?1), while the absence of MnO₂ and carbon shells reveals a severe degradation in the specific capacitance and capacitance retention. Because the core‐TiO₂ nanoparticles and carbon shell prevent the deformation of the inner and outer sides of the MnO₂ shell, the nanostructures of the TiO₂@MnO₂@C are preserved despite the long‐term cycling, giving the superior performance. This SGCW‐driven fabrication enables the scalable synthesis of multiple‐core–shell structures applicable to diverse electrochemical applications.     

Flexible Graphene‐Wrapped Carbon Nanotube/Graphene@MnO2 3D Multilevel Porous Film for High‐Performance Lithium‐Ion Batteries

The ingenious design of a freestanding flexible electrode brings the possibility for power sources in emerging wearable electronic devices. Here, reduced graphene oxide (rGO) wraps carbon nanotubes (CNTs) and rGO tightly surrounded by MnO₂ nanosheets, forming a 3D multilevel porous conductive structure via vacuum freeze‐drying. The sandwich‐like architecture possesses multiple functions as a flexible anode for lithium‐ion batteries. Micrometer‐sized pores among the continuously waved rGO layers could extraordinarily improve ion diffusion. Nano‐sized pores among the MnO₂ nanosheets and CNT/rGO@MnO₂ particles could provide vast accessible active sites and alleviate volume change. The tight connection between MnO₂ and carbon skeleton could facilitate electron transportation and enhance structural stability. Due to the special structure, the rGO‐wrapped CNT/rGO@MnO₂ porous film as an anode shows a high capacity, excellent rate performance, and superior cycling stability (1344.2 mAh g⁻¹ over 630 cycles at 2 A g⁻¹, 608.5 mAh g⁻¹ over 1000 cycles at 7.5 A g⁻¹). Furthermore, the evolutions of microstructure and chemical valence occurring inside the electrode after cycling are investigated to illuminate the structural superiority for energy storage. The excellent electrochemical performance of this freestanding flexible electrode makes it an attractive candidate for practical application in flexible energy storage.     

High‐Stability MnOx Nanowires@C@MnOx Nanosheet Core–Shell Heterostructure Pseudocapacitance Electrode Based on Reversible Phase Transition Mechanism

A stable MnO_x@C@MnO_x core–shell heterostructure consisting of vertical MnO_x nanosheets grown evenly on the surface of the MnO_x@carbon nanowires are obtained by simple liquid phase method combined with thermal treatment. The hierarchical MnO_x@C@MnO_x heterostructure electrode possesses a high specific capacitance of 350 F g^?1 and an excellent cycle performance owing to the existence of the pore structure among the ultrasmall MnO_x nanoparticles and the rapid transmission of electrons between the active material and carbon coating layer. Particularly, according to the in situ Raman spectra analysis, no characteristic peaks corresponding to MnOOH are found during charging/discharging, indicating that pseudocapacitive behavior of the MnO_x electrode have no relevance to the intercalation/deintercalation of protons (H⁺) in the electrolyte. Further combining in situ X‐ray powder diffraction analysis, the diffraction peak of α‐MnO₂ can be detected in the process of charging, while Mn₃O₄ phase is found in discharge products. Therefore, these results demonstrate that the MnO_x undergoes a reversible phase transformation reaction of Mn₃O₄?α‐MnO₂. Moreover, the assembled all‐solid‐state asymmetric supercapacitor with a MnO_x@C@MnO_x electrode delivers a high energy density of 23 Wh kg^?1, an acceptable power density of 2500 W kg^?1, and an excellent cyclic stability performance of 94% after 2000 cycles, showing the potential for practical application.     

A Solid‐State Fibriform Supercapacitor Boosted by Host–Guest Hybridization between the Carbon Nanotube Scaffold and MXene Nanosheets

Fiber‐shaped supercapacitors with improved specific capacitance and high rate capability are a promising candidate as power supply for smart textiles. However, the synergistic interaction between conductive filaments and active nanomaterials remains a crucial challenge, especially when hydrothermal or electrochemical deposition is used to produce a core (fiber)–shell (active materials) fibrous structure. On the other hand, although 2D pseudocapacitive materials, e.g., Ti₃C₂T _x (MXene), have demonstrated high volumetric capacitance, high electrical conductivity, and hydrophilic characteristics, MXene‐based electrodes normally suffer from poor rate capability owing to the sheet restacking especially when the loading level is high and solid‐state gel is used as electrolyte. Herein, by hosting MXene nanosheets (Ti₃C₂T _x ) in the corridor of a scrolled carbon nanotube (CNT) scaffold, a MXene/CNT fiber with helical structure is successfully fabricated. These features offer open spaces for rapid ion diffusion and guarantee fast electron transport. The solid‐state supercapacitor based on such hybrid fibers with gel electrolyte coating exhibits a volumetric capacitance of 22.7 F cm⁻³ at 0.1 A cm⁻³ with capacitance retention of 84% at current density of 1.0 A cm⁻³ (19.1 F cm⁻³), improved volumetric energy density of 2.55 mWh cm⁻³ at the power density of 45.9 mW cm⁻³, and excellent mechanical robustness.