High-performance Flexible Symmetric Supercapacitor Based on Heterostructured PANI@MoS2 Nanocomposite Electrode

Three-dimensional (3D) heterostructured molybdenum disulfide (MoS₂) is used as base materials for aniline monomer in situ polymerization on its surface. It is found that the aniline addition has a remarkable effect on the energy storage of the final compounds due to the improvement of the conductivity and structure stability combined with the synergistic effect between the two types of species. The optimal compound of PANI@MoS₂-150 not only shows a high capacitance value of 801.4 F ⋅ g⁻¹ at a current density of 0.5 A ⋅ g⁻¹ but also provides a high retention rate of 77.4 % after 10,000 cycles. The capacitance fading may be due to the increase of the internal resistance analyzed by EIS. Furthermore, a flexible symmetric supercapacitor based on PANI@MoS₂-150 has also been fabricated and the specific capacitance reaches 105 F ⋅ g⁻¹ at a current density of 1 A ⋅ g⁻¹. Impressively, the capacitance retention is larger than 100 % undergoing 10,000 cycles. Besides, the highest energy density of 21 Wh ⋅ kg⁻¹ was obtained. Additionally, the fabricated symmetric supercapacitor demonstrates excellent flexibility.     

Flexible Polyester Cellulose Paper Supercapacitor with a Gel Electrolyte

A low-cost polyester cellulose paper has been used as a substrate for a flexible supercapacitor device that contains aqueous carbon nanotube ink as the electrodes and a polyvinyl alcohol (PVA)-based gel as the electrolyte. Gel electrolytes have attracted much interest due to their solvent-holding capacity and good film-forming capability. The electrodes are characterized for their conductivity and morphology. Because of its high conductivity, the conductive paper is studied in supercapacitor applications as active electrodes and as separators after coating with polyvinylidene fluoride. Carbon nanotubes deposited on porous paper are more accessible to ions in the electrolyte than those on flat substrates, which results in higher power density. A simple fabrication process is achieved and paper supercapacitors are tested for their performance in both aqueous and PVA gel electrolytes by using galvanostatic and cyclic voltammetry methods. A high specific capacitance of 270 F g⁻¹ and an energy density value of 37 W h kg⁻¹ are achieved for devices with PVA gel electrolytes. Furthermore, this device can maintain excellent specific capacitance even under high currents. This is also confirmed by another counter experiment with aqueous sulfuric acid as the electrolyte. The cycle life, one of the most critical parameters in supercapacitor operations, is found to be excellent (6000 cycles) and less than 0.5 % capacitance loss is observed. Moreover, the supercapacitor device is flexible and even after twisting does not show any cracks or evidence of breakage, and shows almost the same specific capacitance of 267 F g⁻¹and energy density of 37 W h kg⁻¹. This work suggests that a paper substrate can be a highly scalable and low-cost solution for high-performance supercapacitors.     

Post-synthetic Modification of Covalent Organic Frameworks through in situ Polymerization of Aniline for Enhanced Capacitive Energy Storage

Covalent organic frameworks (COFs) having layered architecture with open nanochannels and high specific surface area are promising candidates for energy storage. However, the low electrical conductivity of two-dimensional COFs often limits their scope in energy storage applications. The conductivity of COFs can be enhanced through post-synthetic modification with conducting polymers. Herein, we developed polyaniline (PANI) modified triazine-based COFs via in situ polymerization of aniline within the porous frameworks. The composite materials showed high conductivity of 1.4–1.9×10⁻² S cm⁻¹ at room temperature with a 20-fold enhancement of the specific capacitance than the pristine frameworks. The fabricated supercapacitor exhibited a high energy density of 24.4 W h kg⁻¹ and a power density of 200 W kg⁻¹ at 0.5 A g⁻¹ current density. Moreover, the device fabricated using the conducting polymer-triazine COF composite could light up a green light-emitting diode for 1 min after being charged for 10 s.     

A High-Performance Asymmetric Supercapacitor Based on Tungsten Oxide Nanoplates and Highly Reduced Graphene Oxide Electrodes

Tungsten oxide/graphene hybrid materials are attractive semiconductors for energy-related applications. Herein, we report an asymmetric supercapacitor (ASC, HRG//m-WO₃ ASC), fabricated from monoclinic tungsten oxide (m-WO₃) nanoplates as a negative electrode and highly reduced graphene oxide (HRG) as a positive electrode material. The supercapacitor performance of the prepared electrodes was evaluated in an aqueous electrolyte (1 m H₂SO₄) using three- and two-electrode systems. The HRG//m-WO₃ ASC exhibits a maximum specific capacitance of 389 F g⁻¹ at a current density of 0.5 A g⁻¹, with an associated high energy density of 93 Wh kg⁻¹ at a power density of 500 W kg⁻¹ in a wide 1.6 V operating potential window. In addition, the HRG//m-WO₃ ASC displays long-term cycling stability, maintaining 92 % of the original specific capacitance after 5000 galvanostatic charge–discharge cycles. The m-WO₃ nanoplates were prepared hydrothermally while HRG was synthesized by a modified Hummers method.     

Mixed Cu2Se Hexagonal Nanosheets@Co3Se4 Nanospheres for High-Performance Asymmetric Supercapacitors

Rational designing and constructing multiphase hybrid electrode materials is an effective method to compensate for the performance defects of the single component. Based on this strategy, Cu₂Se hexagonal nanosheets@Co₃Se₄ nanospheres mixed structures have been fabricated by a facile two-step hydrothermal method. Under the synergistic effect of the high ionic conductivity of Cu₂Se and the remarkable cycling stability of Co₃Se₄, Cu₂Se@Co₃Se₄ can exhibit outstanding electrochemical performance as a novel electrode material. The as-prepared Cu₂Se@Co₃Se₄ electrode displays high specific capacitance of 1005 F g⁻¹ at 1 A g⁻¹ with enhanced rate capability (56 % capacitance retention at 10 A g⁻¹), and ultralong lifespan (94.2 % after 10 000 cycles at 20 A g⁻¹). An asymmetric supercapacitor is assembled applying the Cu₂Se@Co₃Se₄ as anode and graphene as cathode, which delivers a wide work potential window of 1.6 V, high energy density (30.9 Wh kg⁻¹ at 0.74 kW kg⁻¹), high power density (21.0 Wh kg⁻¹ at 7.50 kW kg⁻¹), and excellent cycling stability (85.8 % after 10 000 cycles at 10 A g⁻¹).     

Highly Flexible and Tailorable Cobalt-Doped Cross-Linked Polyacrylamide-Based Electrolytes for Use in High-Performance Supercapacitors

A novel hydrogel polymer electrolyte was prepared by incorporation of 1,4-butanediol diglycidyl ether (BG) to cross-linked polyacrylamide (PAM). The electrolyte (PAMBG) was modified with cobalt (II) sulfate with various doping ratios (PAMBGCoX) to increase the capacitance by increasing faradaic reactions. The supercapacitor device assembly was performed by using active carbon (AC) electrodes and hydrogel polymer electrolytes. The specific capacitance of the PAMBGCo5 device indicated 130 F g⁻¹, which is at least a seven-fold improvement due to the insertion of Co as a redox component. The electrolyte device, PAMBGCo5, displays superior performance having an energy density of 38 Wh kg⁻¹ at a power density of 500 W kg⁻¹. Additionally, with the same hydrogel, the device performed 10,000 galvanostatic charge-discharge cycles via retaining 91% of the initial capacitance. A cost-effective electrolyte, PAMBGCo5, was tested in a carbon-based supercapacitor under bent and twisted conditions at various angles, confirming the robustness of the device.     

In Situ Synthesis of CoCeSx Bimetallic Sulfide Nanoparticles on a Bi-Pyrene Terminated Molecular Wire Modified Graphene Surface for Supercapacitors

The excellent electrical conductivity of graphene is due to its highly-conjugated structures. Manipulation of the electronic and mechanical properties of graphene can be achieved by controlling the destruction of its in-sheet conjugation system. Herein, we report the preparation of CoCeS_x−SA@BPMW@RGO through π-π stacking interactions at the molecular level. In this study, sodium alginate was reacted with Co²⁺ and Ce³⁺, and the composite was loaded onto a graphene surface. The graphene sheets were prepared using a bi-pyrene terminated molecular wire (BPMW) to avoid re-stacking of the grapheme sheets, thereby forming nanoscale spaces between sheets. The angle between the BPMW coplanar pyrene group and the phenyl group was 33.2°, and the graphene layer is supported in an oblique direction. Finally, a three-dimensional porous composite was obtained after annealing and vulcanization. The obtained CoCeS_x−SA@BPMW@RGO exhibited excellent electrical conductivity and remarkable cycle stability. When the current density was 1 A g⁻¹, its specific capacitance was as high as 1004 F g⁻¹. BPMW modifies graphene through the synergistic effect of π-π stacking interaction and special structure to obtain excellent electrochemical performance. Moreover, a solid-state asymmetric supercapacitor device was fabricated based on the synthesized CoCeS_x−SA@BPMW@RGO hybrid, which exhibited a power density of 979 W kg⁻¹ at an energy density of 23.96 Wh kg⁻¹.     

A hexaazatriphenylene-based porous organic polymer for high performance supercapacitor

Porous organic polymers (POPs) with high physiochemical stability and pseudocapacitive activity are crucial for supercapacitors with high specific capacitance and long cycle life. We report herein a hexaazatrinaphthylene-based POP (HPOP-1) for high-performance supercapacitor by introducing redox-active hexaazatrinaphthylene (HATN) moiety through Sonogashira–Hagihara coupling reaction. HATN moiety can undergo a proton-induced electron transfer redox reaction, which endows HPOP-1 with high pseudocapacitive activity. As electrode materials for supercapacitor application, HPOP-1 exhibits high specific capacitance (667 F g⁻¹ at 0.5 A g⁻¹) and long-term cyclic stability (90% capacitance retention after 10,000 cycles at 5 A g⁻¹) in a three-electrode system with 1 M H₂SO₄ as the electrolyte. In addition, HPOP-1 also exhibits a specific capacitance of 376 F g⁻¹ at 0.5 A g⁻¹ in 1 M KOH electrolyte. An asymmetric supercapacitor was further fabricated with HPOP-1 as negative electrode and rGO as positive electrode, respectively. The device delivers a specific capacitance of 63 F g⁻¹ at 0.5 A g⁻¹ and a rate performance of 37 F g⁻¹ at 5 A g⁻¹. Our work provides a facile approach for the design and preparation of pseudocapacitive POPs with high specific capacitance and long cycle life.     

In situ polymerization and reduction to fabricate gold nanoparticle‐incorporated polyaniline as supercapacitor electrode materials

Nanocomposites of gold nanoparticles and polyaniline are synthesized by using HAuCl₄ and ammonium peroxydisulfate as the co‐oxidant involving in situ polymerization of aniline and in situ reduction of HAuCl₄. Through these in situ methods, the synthesized Au nanoparticles of ca. 20 nm embedded tightly and dispersed uniformly in polyaniline backbone. With the Au content in composite increasing from 4.20 to 24.72 wt.%, the specific capacitance of the materials first increased from 334 to 392 F g⁻¹ and then decreased to 298 F g⁻¹. Based on the real content of PANI in composite material, the highest specific capacitance is calculated to be 485 F g⁻¹ at the Au amount of 19.15 wt.%, which remains 55.6% after 5000 cycles at the current density of 2 A g⁻¹. Finally, the asymmetric supercapacitor of AuNP/PANI||AC and the symmetric supercapacitor of AuNP/PANI||AuNP/PANI are assembled. The asymmetric supercapacitor device shows a better electrochemical performance, which delivers the maximum energy density of 7.71 Wh kg⁻¹ with power density of 125 W kg⁻¹ and maximum power density of 2500 W kg⁻¹ with the energy density of 5.35 Wh kg⁻¹.     

Perovskite SrCo0.9Nb0.1O3−δ as an Anion‐Intercalated Electrode Material for Supercapacitors with Ultrahigh Volumetric Energy Density

We have synthesized and characterized perovskite‐type SrCo_0.9Nb_0.1O_3−δ (SCN) as a novel anion‐intercalated electrode material for supercapacitors in an aqueous KOH electrolyte, demonstrating a very high volumetric capacitance of about 2034.6 F cm⁻³ (and gravimetric capacitance of ca. 773.6 F g⁻¹) at a current density of 0.5 A g⁻¹ while maintaining excellent cycling stability with a capacity retention of 95.7 % after 3000 cycles. When coupled with an activated carbon (AC) electrode, the SCN/AC asymmetric supercapacitor delivered a specific energy density as high as 37.6 Wh kg⁻¹ with robust long‐term stability.     

Hierarchical FeCo2S4@FeNi2S4 Core/Shell Nanostructures on Ni Foam for High-Performance Supercapacitors

The design of electrode materials with rational core/shell structures is promising for improving the electrochemical properties of supercapacitors. Hence, hierarchical FeCo₂S₄@FeNi₂S₄ core/shell nanostructures on Ni foam were fabricated by a simple hydrothermal method. Owing to their structure and synergistic effect, they deliver an excellent specific capacitance of 2393 F g⁻¹ at 1 A g⁻¹ and long cycle lifespan as positive electrode materials. An asymmetric supercapacitor device with FeCo₂S₄@FeNi₂S₄ as positive electrode and graphene as negative electrode exhibited a specific capacitance of 133.2 F g⁻¹ at 1 A g⁻¹ and a high energy density of 47.37 W h kg⁻¹ at a power density of 800 W kg⁻¹. Moreover, the device showed remarkable cycling stability with 87.0 % specific-capacitance retention after 5000 cycles at 2 A g⁻¹. These results demonstrate that the hierarchical FeCo₂S₄@FeNi₂S₄ core/shell structures have great potential in the field of electrochemical energy storage.     

ZIFs骨架型双壳层纳米笼状CoS/NiCo2S4的制备及其电化学性能

采用离子刻蚀和化学气相沉积法制备出具有沸石咪唑酯骨架(ZIFs)型双壳层纳米笼状的CoS/NiCo_2S_4并组装成超级电容器。该结构有较大的比表面积(98 m2·g-1),合适的孔道(孔径4 nm),且保留了ZIFs骨架构型。作为电极活性材料时,具有良好的结构稳定性和电化学活性,有利于增强所组装的超级电容器的循环稳定性和比容量。在三电极体系中,在1 A·g-1的电流密度下,容量为1 230 F·g-1;在3 A·g-1电流密度下循环9 000圈后,初始电容保持率为76.6%。在以该电极、活性炭电极与KOH/聚乙烯醇(PVA)凝胶态电解质组装的器件中,当功率密度为702 W·kg-1时,能量密度达31.6 Wh·kg-1;在7 056 W·kg-1的高功率密度下,仍保持16.5 Wh·kg-1的能量密度。     

Fabrication of Cobaltosic Oxide Nanoparticle-Doped 3 D MXene/Graphene Hybrid Porous Aerogels for All-Solid-State Supercapacitors

MXenes are a new family of 2 D transition metal carbides and nitrides, which have attracted enormous attention in electrochemical energy storage, sensing technology, and catalysis owing to their good conductivity, high specific surface area, and excellent electrochemical properties. In this work, a series of Co₃O₄-doped 3 D MXene/RGO hybrid porous aerogels is designed and prepared through a facile in situ reduction and thermal annealing process, in which the reduced graphene oxide (RGO) conductive network can electrically link the separated Co₃O₄-MXene composite nanosheets, leading to enhanced electronic conductivity. It is found that upon using the Co₃O₄-MXene/RGO hybrid porous aerogel prepared with a mass ratio of Co₃O₄-MXene/RGO of 3:1 (CMR31) as an electrode for a supercapacitor, a superior specific capacitance of 345 F g⁻¹ at the current density of 1 A g⁻¹ is achieved, which is significantly higher than those of Ti₃C₂T_x MXene, RGO, and MXene/RGO electrodes. In addition, a high capacitance retention (85 % of the initial capacitance after 10 000 cycles at a high current density of 3 A g⁻¹) and a low internal resistance R_s (0.44 Ω) can be achieved. An all-solid-state asymmetric supercapacitor (ASC) device is assembled using CMR31, and it has the ability to light up a blue LED indicator for 5 min if four ASCs are connected in series. Therefore, these novel Co₃O₄-MXene/RGO hybrid porous aerogels have potential practical applications in high-energy storage devices.     

Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor

In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn_0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn_0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm⁻² (specific capacity C: 1178 C g⁻¹) at 2 mA cm⁻² in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn_0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg⁻¹ at 143.8 Wkg⁻¹ power density with a capacitance retention of 83.6 % after 5000 cycles.     

An Approach to Preparing Ni–P with Different Phases for Use as Supercapacitor Electrode Materials

Herein, we describe a simple two‐step approach to prepare nickel phosphide with different phases, such as Ni₂P and Ni₅P₄, to explain the influence of material microstructure and electrical conductivity on electrochemical performance. In this approach, we first prepared a Ni–P precursor through a ball milling process, then controlled the synthesis of either Ni₂P or Ni₅P₄ by the annealing method. The as‐prepared Ni₂P and Ni₅P₄ are investigated as supercapacitor electrode materials for potential energy storage applications. The Ni₂P exhibits a high specific capacitance of 843.25 F g^?1, whereas the specific capacitance of Ni₅P₄ is 801.5 F g^?1. Ni₂P possesses better cycle stability and rate capability than Ni₅P₄. In addition, the Fe₂O₃//Ni₂P supercapacitor displays a high energy density of 35.5 Wh kg^?1 at a power density of 400 W kg^?1 and long cycle stability with a specific capacitance retention rate of 96 % after 1000 cycles, whereas the Fe₂O₃//Ni₅P₄ supercapacitor exhibits a high energy density of 29.8 Wh kg^?1 at a power density of 400 W kg^?1 and a specific capacitance retention rate of 86 % after 1000 cycles.     

MnO2 Nanosheets Grown on Nitrogen‐Doped Hollow Carbon Shells as a High‐Performance Electrode for Asymmetric Supercapacitors

A hierarchical hollow hybrid composite, namely, MnO₂ nanosheets grown on nitrogen‐doped hollow carbon shells (NHCSs@MnO₂), was synthesized by a facile in situ growth process followed by calcination. The composite has a high surface area (251 m²g^?1) and mesopores (4.5 nm in diameter), which can efficiently facilitate transport during electrochemical cycling. Owing to the synergistic effect of NHCSs and MnO₂, the composite shows a high specific capacitance of 306 F g^?1, good rate capability, and an excellent cycling stability of 95.2 % after 5000 cycles at a high current density of 8 A g^?1. More importantly, an asymmetric supercapacitor (ASC) assembled by using NHCSs@MnO₂ and activated carbon as the positive and negative electrodes exhibits high specific capacitance (105.5 F g^?1 at 0.5 A g^?1 and 78.5 F g^?1 at 10 A g^?1) with excellent rate capability, achieves a maximum energy density of 43.9 Wh kg^?1 at a power density of 408 W kg^?1, and has high stability, whereby the ASC retains 81.4 % of its initial capacitance at a current density of 5 A g^?1 after 4000 cycles. Therefore, the NHCSs@MnO₂ electrode material is a promising candidate for future energy‐storage systems.     

High Energy Density Heteroatom (O,N and S) Enriched Activated Carbon for Rational Design of Symmetric Supercapacitors

Carbon-based symmetric supercapacitors (SCs) are known for their high power density and long cyclability, making them an ideal candidate for power sources in new-generation electronic devices. To boost their electrochemical performances, deriving activated carbon doped with heteroatoms such as N, O, and S are highly desirable for increasing the specific capacitance. In this regard, activated carbon (AC) self-doped with heteroatoms is directly derived from bio-waste (lima-bean shell) using different KOH activation processes. The heteroatom-enriched AC synthesized using a pretreated carbon-to-KOH ratio of 1:2 (ONS@AC-2) shows excellent surface morphology with a large surface area of 1508 m² g⁻¹. As an SC electrode material, the presence of heteroatoms (N and S) reduces the interfacial charge-transfer resistance and increases the ion-accessible surface area, which inherently provides additional pseudocapacitance. The ONS@AC-2 electrode attains a maximum specific capacitance (C_sp) of 342 F g⁻¹ at a specific current of 1 Ag⁻¹ in 1 m NaClO₄ electrolyte at the wide potential window of 1.8 V. Moreover, as symmetric SCs the ONS@AC-2 electrode delivers a maximum specific capacitance (C_sc) of 191 F g⁻¹ with a maximum specific energy of 21.48 Wh kg⁻¹ and high specific power of 14 000 W kg⁻¹ and excellent retention of its initial capacitance (98 %) even after 10000 charge/discharge cycles. In addition, a flexible supercapacitor fabricated utilizing ONS@AC-2 electrodes and a LiCl/polyvinyl alcohol (PVA)-based polymer electrolyte shows a maximum C_sc of 119 F g⁻¹ with considerable specific energy and power.     

Two-Dimensional Layered Metallic VSe2/SWCNTs/rGO Based Ternary Hybrid Materials for High Performance Energy Storage Applications

In this work, the ternary hybrid structure VSe₂/SWCNTs/rGO is reported for supercapacitor applications. The ternary composite exhibits a high specific capacitance of 450 F g⁻¹ in a symmetric cell configuration, with maximum energy density of 131.4 Wh kg⁻¹ and power density of 27.49 kW kg⁻¹. The ternary hybrid also shows a cyclic stability of 91 % after 5000 cycles. Extensive density functional theory (DFT) simulations on the structure as well as on the electronic properties of the binary hybrid structure VSe₂/SWCNTs and the ternary hybrid structure VSe₂/SWCNTs/rGO have been carried out. Due to a synergic effect, there are enhanced density of states near the Fermi level and higher quantum capacitance for the hybrid ternary structure compared to VSe₂/SWCNTs, leading to higher energy and power density for VSe₂/SWCNTs/rGO, supporting our experimental observation. Computed diffusion energy barrier of electrolyte ions (K⁺) predicts that ions move faster in the ternary structure, providing higher charge storage performance.     

Enhanced Supercapacitor Performance Using a Co3O4@Co3S4 Nanocomposite on Reduced Graphene Oxide/Ni Foam Electrodes

To avoid an enormous energy crisis in the not-too-distant future, it be emergent to establish high-performance energy storage devices such as supercapacitors. For this purpose, a three-dimensional (3D) heterostructure of Co₃O₄ and Co₃S₄ on nickel foam (NF) that is covered by reduced graphene oxide (rGO) has been prepared by following a facile multistep method. At first, rGO nanosheets are deposited on NF under mild hydrothermal conditions to increase the surface area. Subsequently, nanowalls of cobalt oxide are electro-deposited on rGO/Ni foam by applying cyclic-voltammetry (CV) under optimized conditions. Finally, for the synthesis of Co₃O₄@Co₃S₄ nanocomposite, the nanostructure of Co₃S₄ was fabricated from Co₃O₄ nanowalls on rGO/NF by following an ordinary hydrothermal process through the sulfurization for the electrochemical application. The samples are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The obtained sample delivers a high capacitance of 13.34 F cm⁻² (5651.24 F g⁻¹) at a current density of 6 mA cm⁻² compared to the Co₃O₄/rGO/NF electrode with a capacitance of 3.06 F cm⁻² (1230.77 F g⁻¹) at the same current density. The proposed electrode illustrates the superior electrochemical performance such as excellent specific energy density of 85.68 W h Kg⁻¹, specific power density of 6048.03 W kg⁻¹ and a superior cycling performance (86% after 1000 charge/discharge cycles at a scan rate of 5 mV s⁻¹). Finally, by using Co₃O₄ @Co₃S₄/rGO/NF and the activated carbon-based electrode as positive and negative electrodes, respectively, an asymmetric supercapacitor (ASC) device was assembled. The fabricated ASC provides an appropriate specific capacitance of 79.15 mF cm⁻² at the applied current density of 1 mA cm⁻², and delivered an energy density of 0.143 Wh kg⁻¹ at the power density of 5.42 W kg⁻¹.     

Strong and Robust Polyaniline‐Based Supramolecular Hydrogels for Flexible Supercapacitors

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid‐state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline–polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g^?1). The flexible solid‐state supercapacitor based on PPH provides a large capacitance (306 mF cm^?2 and 153 F g^?1) and a high energy density of 13.6 Wh kg^?1, superior to other flexible supercapacitors. The robustness of the PPH‐based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge–discharge cycles. The high activity and robustness enable the PPH‐based supercapacitor as a promising power device for flexible electronics.