Simplified fabrication of high areal capacitance all-solid-state micro-supercapacitors based on graphene and MnO2 nanosheets

A universal simplified strategy was developed to fabricate all-solid-state planar micro-supercapacitors with high areal capacitance (~355 mF/cm²), based on interdigital patterned films of 2D pseudocapacitive MnO₂ nanosheets and electrochemically exfoliated graphene.     

Paper-based all-solid-state flexible asymmetric micro-supercapacitors fabricated by a simple pencil drawing methodology

A simple and novel methodology was developed for manufacturing interdigitated asymmetric all-solid-state flexible micro-supercapacitors (MSCs) by a facile pencil drawing process followed by electrodepositing MnO₂ on one of the as-drawn graphite electrode as anode and the other as cathode.     

In Situ Growth of Hierarchical Ni-Mn-O Solid Solution on a Flexible and Porous Ni Electrode for High-Performance All-Solid-State Asymmetric Supercapacitors

To endow all-solid-state asymmetric supercapacitors with high energy density, cycling stability, and flexibility, we design a binder-free supercapacitor electrode by in situ growth of well-distributed broccoli-like Ni_0.75Mn_0.25O/C solid solution arrays on a flexible and three-dimensional Ni current collector (3D-Ni). The electrode consists of a bottom layer of compressed but still porous Ni foam with excellent flexibility and high electrical conductivity, an intermediate layer of interconnected Ni nanoparticles providing a large specific surface area for loading of active substances, and a top layer of vertically aligned mesoporous nanosheets of a Ni_0.75Mn_0.25O/C solid solution. The resultant 3D-Ni/Ni_0.75Mn_0.25O/C cathode exhibits a specific capacitance of 1657.6 mF cm⁻² at 1 mA cm⁻² and shows no degradation of the capacitance after 10 000 cycles at 3 mA cm⁻². The assembled 3D-Ni/Ni_0.75Mn_0.25O/C//activated carbon asymmetric supercapacitor has a high specific capacitance of 797.7 mF cm⁻² at 2 mA cm⁻² and an excellent cycling stability with 85.3 % of capacitance retention after 10 000 cycles at a current density of 3 mA cm⁻². The energy density and power density of the asymmetric supercapacitor are up to 6.6 mW h cm⁻³ and 40.8 mW cm⁻³, respectively, indicating a fairly promising future of the flexible 3D-Ni/Ni_0.75Mn_0.25O/C electrode for efficient energy storage applications.     

Interfacial synthesis of crystalline quasi-two-dimensional polyaniline thin films for high-performance flexible on-chip micro-supercapacitors

Quasi-two-dimensional (q2D) conducting polymer thin film synergizes the advantageous features of long-range molecular ordering and high intrinsic conductivity, which are promising for flexible thin film-based micro-supercapacitors (MSCs). Herein, we present the high-performance flexible MSCs based on highly ordered quasi-two-dimensional polyaniline (q2D-PANI) thin film using surfactant monolayer assisted interfacial synthesis (SMAIS). Owing to high electrical conductivity, rich redox chemistry, and thin-film morphology, the q2D-PANI MSCs show high volumetric specific capacitance (ca. 360 F/cm³) and energy density (17.9 mWh/cm³), which outperform the state-of-art PANI thin-film based MSCs and promise for future flexible electronics.     

Rational design of quinones for high power density biofuel cells

Enzymatic fuel cells (EFCs) are devices that can produce electrical energy by enzymatic oxidation of energy-dense fuels (such as glucose). When considering bioanode construction for EFCs, it is desirable to use a system with a low onset potential and high catalytic current density. While these two properties are typically mutually exclusive, merging these two properties will significantly enhance EFC performance. We present the rational design and preparation of an alternative naphthoquinone-based redox polymer hydrogel that is able to facilitate enzymatic glucose oxidation at low oxidation potentials while simultaneously producing high catalytic current densities. When coupled with an enzymatic biocathode, the resulting glucose/O₂ EFC possessed an open-circuit potential of 0.864 ± 0.006 V, with an associated maximum current density of 5.4 ± 0.5 mA cm^–2. Moreover, the EFC delivered its maximum power density (2.3 ± 0.2 mW cm^–2) at a high operational potential of 0.55 V.     

A high-performance asymmetric supercapacitor achieved by surface-regulated MnO2 and organic-framework–derived N-doped carbon cloth

It is possible to achieve high energy density and power density simultaneously for asymmetric supercapacitors by using pseudocapacitive materials with abundant ion intercalation/de-intercalation sites on the surface. Herein, a positive electrode based on feather-like MnO₂ anchored on the activated carbon cloth is prepared, in which oxygen-enriched MnO₂ nanorods with a radial sheet-like structure (OMO@AC) further form via electrochemical oxidation. Because of the large contact area with electrolyte and abundant oxidation functional groups on its surface, the OMO@AC displays excellent capacitance of 3,160 mF/cm² at 1 mA/cm². For the nitrogen-doped active carbon negative electrode, the capacitance is up to 1,875 mF/cm² at 4 mA/cm² due to the increase in disorder and defect on the carbon surface by N-doping. Furthermore, we verify the good electrochemical activity on the OMO@AC electrode surface by first-principles calculations and confirm the good matching degree between the positive and negative electrodes by CV testes. The aqueous oxygen-enriched MnO₂// nitrogen-doped active carbon asymmetric supercapacitor exhibits an ultrahigh energy density of 8.723 mWh/cm³ at a power density of 14.248 mW/cm³ and display excellent cycle stability maintaining 95.5% after 10,000 cycles. The facile synthesis method and excellent performance provide a feasible way for the preparation of high-performance electrode materials for energy storage devices.     

Fabrication of Vertical-Standing Co-MOF Nanoarrays with 2D Parallelogram-like Morphology for Aqueous Asymmetric Electrochemical Capacitors

Metal organic frameworks (MOFs) have been considered as one of the most promising electrode materials for electrochemical capacitors due to their large specific surface area and abundant pore structure. Herein, we report a Co-MOF electrode with a vertical-standing 2D parallelogram-like nanoarray structure on a Ni foam substrate via a one-step solvothermal method. The as-prepared Co-MOF on a Ni foam electrode delivered a high area-specific capacitance of 582.0 mC cm⁻² at a current density of 2 mA cm⁻² and a good performance rate of 350.0 mC cm⁻² at 50 mA cm⁻². Moreover, an asymmetric electrochemical capacitor (AEC) device (Co-MOF on Ni foam//AC) was assembled by using the as-prepared Co-MOF on a Ni foam as the cathode and a active carbon-coated Ni foam as the anode to achieve a maximum energy density of 0.082 mW cm⁻² at a power density of 0.8 mW cm⁻², which still maintained 0.065 mW cm⁻² at a high power density of 11.94 mW cm⁻². Meanwhile, our assembled device exhibited an excellent cycling stability with a capacitance retention of nearly 100% after 1000 cycles. Therefore, this work provides a simple method to prepare MOF-based material for the application of energy storage and conversion.     

Catechol-Coordinated Framework Film-based Micro-Supercapacitors with AC Line Filtering Performance

Coordination polymer frameworks (CPFs) have broad applications due to their excellent features, including stable structure, intrinsic porosity, and others. However, preparation of thin-film CPFs for energy storage and conversion remains a challenge because of poor compatibility between conductive substrates and CPFs and crucial conditions for thin-film preparation. In this work, a CPF film was prepared by the coordination of the anisotropic four-armed ligand and Cu^II at the liquid–liquid interface. Such film-based micro-supercapacitors (MSCs) are fabricated through high-energy scribing and electrolytes soaking. As-fabricated MSCs displayed high volumetric specific capacitance of 121.45 F cm⁻³. Besides, the volumetric energy density of MSCs reached 52.6 mWh cm⁻³, which exceeds the electrochemical performance of most reported CPF-based MSCs. Especially, the device exhibited alternating current (AC) line filtering performance (−84.2° at 120 Hz) and a short resistance capacitance (RC) constant of 0.08 ms. This work not only provides a new CPF for MSCs with AC line filtering performance but also paves the way for thin-film CPFs preparation with versatile applications.     

Enhanced Energy Density of Coaxial Fiber Asymmetric Supercapacitor Based on MoS2@Fe2O3/Carbon Nanotube Paper and Ni(OH)2@NiCo2O4/Carbon Nanotube Fiber Electrodes

Fiber supercapacitors are promising energy storage devices for potential application in wearable and miniaturized portable electronics, which currently suffer from difficulties in achieving high capacitance and energy density synchronously owing to the limited specific surface area of the electrode materials and material incompatibility between the two electrodes. Herein, a strategy is developed for the manufacture of coaxial asymmetric fiber supercapacitors by wrapping a core of PVA-KOH gel electrolyte-coated Ni(OH)₂@NiCo₂O₄/CNT fibers with MoS₂@Fe₂O₃/CNT paper. The as-prepared coaxial fiber asymmetric supercapacitors exhibit a specific capacitance of 373 mF cm⁻² (at a current density of 2 mA cm⁻²) and energy density of 0.13 mW h cm⁻² (at a power density of 3.2 mW cm⁻²), and also show good rate capability, long cycle life, and excellent flexibility. This work provides the possibility for the practical application of fiber supercapacitors in wearable and portable energy storage equipment.     

Tunning of Templated CuWO4 Nanorods Arrays Thickness to Improve Photoanode Water Splitting

The fabrication of the photoanode of the n-type CuWO₄ nanorod arrays was successfully carried out through electrochemical deposition using anodic aluminum oxide (AAO) control templates and for the first time produced distinct gaps between the nanorod arrays. The effectiveness and efficiency of the resulting deposition was shown by the performance of the photoelectrochemical (PEC) procedure with a current density of 1.02 mA cm⁻² with irradiation using standard AM 1.5G solar simulator and electron changed radiation of 0.72% with a bias potential of 0.71 V (vs. Ag/AgCl). The gap between each nanorod indicated an optimization of the electrolyte penetration on the interface, which resulted in the expansion of the current density as much as 0.5 × 10²⁴ cm⁻³ with a flat band potential of 0.14 V vs. Ag/AgCl and also a peak quantum efficiency of wavelength 410 nm. Thus, also indicating the gaps between the nanorod arrays is a promising structure to optimize the performance of the PEC water splitting procedure as a sustainable energy source.     

General Interfacial Self‐Assembly Engineering for Patterning Two‐Dimensional Polymers with Cylindrical Mesopores on Graphene

Free‐standing 2D porous nanomaterials have attracted considerable interest as ideal candidates of 2D film electrodes for planar energy storage devices. Nevertheless, the construction of well‐defined mesopore arrays parallel to the lateral surface, which facilitate fast in‐plane ionic diffusion, is a challenge. Now, a universal interface self‐assembly strategy is used for patterning 2D porous polymers, for example, polypyrrole, polyaniline, and polydopamine, with cylindrical mesopores on graphene nanosheets. The resultant 2D sandwich‐structured nanohybrids are employed as the interdigital microelectrodes for the assembly of planar micro‐supercapacitors (MSCs), which deliver outstanding volumetric capacitance of 102 F cm^?3 and energy density of 2.3 mWh cm^?3, outperforming most reported MSCs. The MSCs display remarkable flexibility and superior integration for boosting output voltage and capacitance.     

B-Co3O4/C复合纳米材料的制备及其电催化析氧性能

本文以雪莲果为碳源,采用热解法制备碳材料(C),以硝酸钴、四硼酸钠和碳材料为原料,通过热解法合成硼掺杂四氧化三钴/碳(B-Co₃O₄/C)复合纳米材料。运用XRD、FTIR、SEM、XPS等手段对其结构、形貌和组成进行表征。利用线性扫描(LSV)和Tafel曲线等电化学测试方法研究了B-Co₃O₄/C复合纳米材料的电催化析氧反应(OER)性能。结果表明,该材料具有较好的电催化OER活性。在1.0mol/L的KOH电解液和10mA·cm^-2的电流密度下,B-Co₃O₄/C复合纳米材料的过电位为293mV,Tafel斜率为45.0mV·dec^-1。在10mA·cm^-2电流密度下连续测试10h, B-Co₃O₄/C的电位变化不大,通过法拉第效率测试该催化剂的产氧效率为94%,说明硼原子的掺入改变了B-Co₃O₄...     

Vanadium-Substituted Dawson-Type Polyoxometalate–TiO2 Nanowire Composite Film as Advanced Cathode Material for Bifunctional Electrochromic Energy-Storage Devices

Polyoxometalates (POMs) demonstrate potential for application in the development of integrated smart energy devices based on bifunctional electrochromic (EC) optical modulation and electrochemical energy storage. Herein, a nanocomposite thin film composed of a vanadium-substituted Dawson-type POM, i.e., K₇[P₂W₁₇VO₆₂]·18H₂O, and TiO₂ nanowires were constructed via the combination of hydrothermal and layer-by-layer self-assembly methods. Through scanning electron microscopy and energy-dispersive spectroscopy characterisations, it was found that the TiO₂ nanowire substrate acts as a skeleton to adsorb POM nanoparticles, thereby avoiding the aggregation or stacking of POM particles. The unique three-dimensional core−shell structures of these nanocomposites with high specific surface areas increases the number of active sites during the reaction process and shortens the ion diffusion pathway, thereby improving the electrochemical activities and electrical conductivities. Compared with pure POM thin films, the composite films showed improved EC properties with a significant optical contrast (38.32% at 580 nm), a short response time (1.65 and 1.64 s for colouring and bleaching, respectively), an excellent colouration efficiency (116.5 cm² C⁻¹), and satisfactory energy-storage properties (volumetric capacitance = 297.1 F cm⁻³ at 0.2 mA cm⁻²). Finally, a solid-state electrochromic energy-storage (EES) device was fabricated using the composite film as the cathode. After charging, the constructed device was able to light up a single light-emitting diode for 20 s. These results highlight the promising features of POM-based EES devices and demonstrate their potential for use in a wide range of applications, such as smart windows, military camouflage, sensors, and intelligent systems.     

Metal Oxide Nanostructures Generated from In Situ Sacrifice of Zinc in Bimetallic Textures as Flexible Ni/Fe Fast Battery Electrodes

An “in situ sacrifice” process was devised in this work as a room‐temperature, all‐solution processed electrochemical method to synthesize nanostructured NiO_x and FeO_x directly on current collectors. After electrodepositing NiZn/FeZn bimetallic textures on a copper net, the zinc component is etched and the remnant nickel/iron are evolved into NiO_x and FeO_x by the “in situ sacrifice” activation we propose. As‐prepared electrodes exhibit high areal capacities of 0.47 mA h cm⁻² and 0.32 mA h cm⁻², respectively. By integrating NiO_x as the cathode, FeO_x as the anode, and poly(vinyl alcohol) (PVA)‐KOH gel as the separator/solid‐state electrolyte, the assembled quasi‐solid‐state flexible battery delivers a volumetric capacity of 6.91 mA h cm⁻³ at 5 mA cm⁻², along with a maximum energy density of 7.40 mWh cm⁻³ under a power density of 0.27 W cm⁻³ and a maximum tested power density of 3.13 W cm⁻³ with a 2.17 mW h cm⁻³ energy density retention. Our room‐temperature synthesis, which only consumes minute electricity, makes it a promising approach for large‐scale production. We also emphasize the in situ sacrifice zinc etching process used in this work as a general strategy for metal‐based nanostructure growth for high‐performance battery materials.     

Polyoxometalate derived p-n heterojunction for optimized reaction interface and improved HER

MoS₂ is a typical electrocatalyst for hydrogen evolution reaction (HER), but the HER activity is spoilt by intensive adsorption towards H*, which requires further improvement. For n-type MoS₂, the construction of p-n heterojunction with p-type MoO₃ can reverse this situation, because inner electronic field in p-n heterojunction can facilitate H* desorption. Based on this hypothesis, p-n heterojunction is built between MoS₂ and MoO₃ with polyoxometalate compound as precursor. The obtained MoO₃/MoS₂ exhibits excellent HER activity, which only requires 68 mV to obtain 10 mA/cm². With MoO₃/MoS₂ as cathode material and Zn slice as anode, Zn-H⁺ battery is assembled. Its open circuit voltage achieves 1.11 V with short circuit current 151.4 mA/cm². The peak power density of this Zn-H⁺ battery reaches 47.6 mW/cm². When discharge at 10 mA/cm², the specific capacity and energy density reach 728 mAh/g and 759 Wh/kg. In this process, H₂ production rate of Zn-H⁺ battery achieves 364 μmol/h with Faradic efficiency 97.8%. It realizes H₂ production and electricity generation simultaneously.     

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.     

Enhanced Metal-Support Interactions Boost the Electrocatalytic Water Splitting of Supported Ruthenium Nanoparticles on a Ni3N/NiO Heterojunction at Industrial Current Density

Developing highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure-induced-strategy to optimize the metal-support interaction (MSI) and the EWS activity of Ru-Ni₃N/NiO. Density functional theory (DFT) calculations firstly predicted that the Ni₃N/NiO-heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru-Ni₃N/NiO compared to Ru-Ni₃N and Ru-NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof-of-concept, the Ru-Ni₃N/NiO catalyst with a 2D Ni₃N/NiO-heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which exhibited excellent HER and OER activity with overpotentials of 190 mV and 385 mV at 1000 mA cm⁻², respectively. Furthermore, the Ru-Ni₃N/NiO-based EWS device can realize an industrial current density (1000 mA cm⁻²) at 1.74 V and 1.80 V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000 h (@ 500 mA cm⁻²) in alkaline pure water.     

High electro-catalytic graphite felt/MnO<Subscript>2</Subscript> composite electrodes for vanadium redox flow batteries

A mild and simple synthesis process for large-scale vanadium redox flow batteries (VRFBs) energy storage systems is desirable. A graphite felt/MnO₂ (GF-MNO) composite electrode with excellent electrocatalytic activity towards VO²⁺/VO₂⁺ redox couples in a VRFB was synthesized by a one-step hydrothermal process. The resulting GF-MNO electrodes possess improved electrochemical kinetic reversibility of the vanadium redox reactions compared to pristine GF electrodes, and the corresponding energy efficiency and discharge capacity at 150 mA cm^?2 are increased by 12.5% and 40%, respectively. The discharge capacity is maintained at 4.8 A h L^?1 at the ultrahigh current density of 250 mA cm^?2. Above all, 80% of the energy efficiency of the GFMNO composite electrodes is retained after 120 charge-discharge cycles at 150 mA cm^?2. Furthermore, these electrodes demonstrated that more evenly distributed catalytic active sites were obtained from the MnO₂ particles under acidic conditions. The proposed synthetic route is facile, and the raw materials are low cost and environmentally friendly. Therefore, these novel GFMNO electrodes hold great promise in large-scale vanadium redox flow battery energy storage systems.     

Three‐Dimensional NiMoO4 Nanosheets Supported on a Carbon Fibers@Pre‐Treated Ni Foam (CF@PNF) Substrate as Advanced Electrodes for Asymmetric Supercapacitors

Herein, we report a nanoarchitectured nickel molybdate/carbon fibers@pre‐treated Ni foam (NiMoO₄/CF@PNF) electrode for supercapacitors. The synthesis of NiMoO₄/CF@PNF mainly consists of a direct chemical vapor deposition (CVD) growth of dense carbon fibers (CFs) onto pre‐treated Ni foam (PNF) as the substrate, followed by in situ growth of NiMoO₄ nanosheets (NSs) on the CF@PNF substrate by means of a hydrothermal process. The NiMoO₄/CF@PNF electrode exhibits a high areal capacitance (5.14 F cm^?2 at 4 mA cm^?2) and excellent cycling stability (97 % capacitance retention after 2000 cycles at 10 mA cm^?2). Furthermore, we have successfully assembled NiMoO₄ NSs//activated carbon (AC) asymmetric supercapacitors, which can achieve an energy density of 45.6 Wh kg^?1 at 674 W kg^?1, and excellent stability with 93 % capacitance retention after 2000 cycles at 5 mA cm^?2. These superior properties hold great promise for energy‐storage applications.     

Blue TiO2 nanotube arrays as semimetallic materials with enhanced photoelectrochemical activity towards water splitting

In the past years there has been a great interest in self-doped TiO₂ nanotubes (blue TiO₂ nanotubes) compared to undoped ones owing to their high carrier density and conductivity. In this study, blue TiO₂ nanotubes are investigated as photoanode materials for photoelectrochemical water splitting. Blue TiO₂ nanotubes were fabricated with enhanced photoresponse behavior through electrochemical cathodic polarization on undoped and annealed TiO₂ nanotubes. The annealing temperature of undoped TiO₂ nanotubes was tuned before cathodic polarization, revealing that annealing at 500 °C improved the photoresponse of the nanotubes significantly. Further optimization of the blue TiO₂ nanotubes was achieved by adjusting the cathodic polarization parameters. Blue TiO₂ nanotubes obtained at the potential of –1.4 V (vs. SCE) with a duration of 10 min exhibited twice more photocurrent response (0.39 mA cm^-2) compared to the undoped TiO₂ nanotube arrays (0.19 mA cm^-2). Oxygen vacancies formed through the cathodic polarization decreased charge recombination and enhanced charge transfer rate; therefore, a high photoelectrochemical activity under visible light irradiation could be achieved.