Characterization and performance of hydrous manganese oxide prepared by electrochemical method and its application for supercapacitors

Hydrous manganese oxide was deposited on graphite substrates at anodic potentials of 0.5-0.95 V versus saturated calomel electrode (SCE) in 0.25 M Mn(CH₃COO)₂ solution at 25 °C. Morphology of manganese oxide prepared was examined by scanning electron microscopy (SEM). Manganese oxide deposited at various anodic potentials was evaluated by cyclic voltammetry with various potential scan rates in different electrolytes. Results indicated that the pseudocapacitive behaviors of manganese oxide were excellent both in 2 M KCl and 2 M (NH₄)₂SO₄ solutions at room temperature. Manganese oxide deposited at 0.5 V versus SCE showed better capacitive behaviors, the specific capacitances were 275 F/g in 2 M KCl solution and 310 F/g in 2 M (NH₄)₂SO₄ solution, respectively. Besides, better electrochemical reversibility could be obtained in 2 M KCl solution.     

Chemical synthesis of Co and Mn co-doped NiO nanocrystalline materials as high-performance electrode materials for potential application in supercapacitors

Co and Mn co-doped with NiO nanostructued materials, such as, Ni_0.95Co_0.01Mn_0.04O_1−δ, Ni_0.95Co_0.04Mn_0.01O_1−δ and Ni_0.95Co_0.025Mn_0.025O_1−δ were synthesized by chemical synthesis route and studied for potential application as electrode materials for supercapacitors. The phase structure of the materials was characterized by X-ray diffraction (XRD) and the crystallographic parameters were found out and reported. FTIR (Fourier Transform Infrared) spectroscopy revealed the presence of M–O bond in the compounds. The particle size of the materials was found to be in the range of 291.5–336.5 nm. The morphological phenomenon of the materials was studied by scanning electron microscopy (SEM) and the particles were found to be in spherical shape with average grain size of 14–28 nm. EDAX analysis confirmed the presence of appropriate levels of elements in the samples. The in-depth morphological characteristics were also studied by HR-TEM (High Resolution Tunneling Electron Microscopy). Cyclic voltammetry, chronopotentiometry and electrochemical impedance measurements were applied in an aqueous electrolyte (6 mol L⁻¹ KOH) to investigate the electrochemical performance of the Co and Mn co-doped NiO nanostructured electrode materials. The results indicate that the doping level of Co and Mn in NiO had a significant role in revealing the capacitive behaviors of the materials. Among the three electrode materials studied, Ni_0.95Co_0.025Mn_0.025O_1−δ electrode material shows a maximum specific capacitance of 673.33 F g⁻¹ at a current density of 0.5 A g⁻¹. The electrochemical characteristics of blank graphite sheet were studied and compared with the performance of Co/Mn co-doped NiO based electrode materials. Also, Ni_0.95Co_0.025Mn_0.025O_1−δ has resulted in a degradation level of 4.76% only after 1000 continuous cycles, which shows its excellent electrochemical performance, indicating a kind of potential candidate for supercapacitors.     

Development of Co-doped MnFe2O4 nanoparticles for electrochemical supercapacitors

Transition metal ferrites are the essential components utilized in the latest modern-day technology and these include greater elements whose oxidation states and ionic radii are important for exploring their magnetic, optical, structural, and electrochemical properties. The present investigation was targeted on the preparation, physical and electrochemical characterizations of Co-doped MnFe₂O₄ nanomaterials such as 2 wt% Co-doped MnFe₂O₄, 4 Wt.% Co-doped MnFe₂O₄, and 8 Wt.% Co-doped MnFe₂O₄. More specifically, the study will focus on the techniques which have been employed to raise the specific capacitance of the metal oxides. Electrochemical properties such as cyclic voltammetry (CV), potentiostatic and impedance were used to analyse the super capacitive performance of Co-doped MnFe₂O₄ electrodes. Based on the outcomes, it is determined that 2 wt% of Co-doped MnFe₂O₄ has higher super capacitive behaviour than different samples. Precise capacitance for this nanocomposite from GCD was determined to be 551.39 F/g at a current density of 1 mA/cm². Accordingly, Co-doped MnFe₂O₄ may be utilized as a promising electrode for energy storage applications. It could be believed that this form of composites indicates excellent capability as electrochemical supercapacitors.     

Lamellar flower inspired hierarchical alpha manganese vanadate microflowers for high-performance flexible hybrid supercapacitors

Hybrid flexible supercapacitors (HFS) offer high power density and stability making them an ideal choice for the energy storage system in wearable devices. In this work, the synthesis of lamellar flower-like alpha manganese vanadate (α-Mn₂V₂O₇) on nickel foam was proposed for efficient and highly stable HFS applications for the first time. The voltammetric characterization indicated that the capacitance contribution of α-Mn₂V₂O₇ is derived from the diffusion-controlled (battery-type, 89.93%) and capacitive controlled (10.07%) mechanisms in aqueous electrolyte (0.5 M KOH). The optimized α-Mn₂V₂O₇ electrode exhibited an impressive specific capacity of 125.6 mAhg^?1 (760.3 Fg^-1). In the HFS device configuration, the utilization of α-Mn₂V₂O₇ resulted in a remarkable specific capacitance of 35.7 F g^?1 with energy, and a power density of 28.4 Whkg^?1 and 8.5 kWkg^?1, respectively. Furthermore, the α-Mn₂V₂O₇ fabricated device is found to operate in a wide potential window exhibiting remarkable and stable electrochemical performance in the gel electrolyte even under mechanical stress conditions. Importantly, the α-Mn₂V₂O₇ HFS showed an impressive and stable performance over 5000 cycles. The superior specific capacitance performances obtained in the present study are noted to be the best results reported for vanadium-based ternary oxides so far.     

Excellent performance MWCNTs-GONRs/Ni(OH)2 electrode for outstanding supercapacitors

Due to the unconventional properties of MWCNTs-GONRs (multiwalled carbon nanotubes-graphene oxide nanoribbons), we have tried to use it as a carbon resource for supercapacitors. MWCNTs-GONRs/Ni(OH)₂ electrode was obtained by hydrothermal method. Velvet α-Ni(OH)₂ was prepared above NF (nickel-foam) loaded with MWCNTs-GONRs. This layered design can effectively promote the diffusion of ions and increase the active site for MWCNTs-GONRs/Ni(OH)₂ electrode, thus enhancing the electrochemical performance. The electrode exhibits extraordinary electrochemical performances in electrochemical testing, such as supernal specific capacitance (1713.2 F g⁻¹) and prominent working time. In addition, supercapacitors was assembled with MWCNTs-GONRs/Ni(OH)₂ and active carbon as materials. Which represents a prominent energy density (41.23 Wh kg⁻¹), high power (6.80 kW kg⁻¹) and prominent cycling stability property (95.18%, 3000 times). The electrode prepared in this work provides a clue to enlighten people for energy storage.     

MWCNTs-GONRs/Co3O4 electrode with needle-like arrays for outstanding supercapacitors

Multiwalled carbon nanotubes-graphene oxide nanoribbons (MWCNTs-GONRs) exhibit high specific surface area and good electroconductivity because of their unique three-dimensional cross-linking structure with the properties of both CNTs and GONRs. In this study, a hydrothermal method was employed to anchor MWCNTs–GONRs onto a Ni foam (NF) to obtain a precursor substrate. Subsequently, Co₃O₄ arrays were grown on the NF substrate to synthesize a MWCNTs–GONR/Co₃O₄ electrode. The electrode showed a capacitance of 846.2 F g⁻¹ at 1 A g⁻¹ and a capacitance retention of 90.1% after 3000 cycles. Furthermore, MWCNTs–GONRs/Co₃O₄ and active carbon (AC) were used as the positive and negative electrodes, respectively, to assemble a supercapacitor, which delivered a maximum energy density of 38.23 W h kg⁻¹ and a high power density of 6.80 kW kg⁻¹. In addition, the specific capacitance of the device reached a maximum of 91.5% after 9000 cycles. Thus, the MWCNTs–GONRs/Co₃O₄ electrode showed huge potential for supercapacitor applications.     

Nitrogen-enriched bituminous coal-based active carbons as materials for supercapacitors

The paper presents the results of a study on obtaining N-enriched active carbons from bituminous coal and on testing its use as an electrode material in supercapacitors. The coal was carbonised, activated with KOH and ammoxidised by a mixture of ammonia and air at the ratio 1:3 at 300 °C or 350 °C, at different stages of the production, that is, at those of precursor, carbonisate, and active carbon. The products were microporous N-enriched active carbon samples of well-developed surface area reaching from 1577 to 2510 m²/g and containing 1.0 to 8.5 wt% of nitrogen. The XPS measurements have shown that in the active carbons enriched in nitrogen at the stage of precursor and at the stage of carbonisate, the dominant nitrogen species are the N-5 groups, while in the samples ammoxidised at the last stage of the treatment the dominant nitrogen species are the surface groups of imines and/or nitriles, probably accompanied by amines and amides. The paper reports the results of a comprehensive study of the effect of the structure and chemical composition of a series of active carbon samples of different properties on their capacity performance in water solutions of H₂SO₄ or KOH, with the behaviour of positive and negative electrodes analysed separately.     

Mechanochemical preparation of polydiphenylamine and its electrochemical performance in hybrid supercapacitors

A simple mechanochemical route for the synthesis of high quality inorganic anion doped polydiphenylamines (PDPAs) is reported in this article. Elemental analysis performed for the PDPAs indicated the presence of dopant anions in the polymeric chain. PDPA prepared in the presence of 96 wt% H₂SO₄ (PDPA–H₂SO₄) was found to be better doped than the other polymeric salts. Spectroscopic profiles of the polymers showed that the PDPAs were in a doped conducting state. The X-ray diffraction (XRD) pattern of the as-prepared polymeric powders revealed the presence of more crystalline phases in PDPA–H₂SO₄. Field emission scanning electron microscopic (FESEM) images highlighted the formation of inorganic anion doped PDPA particles with different sizes (80–100 nm). Electrochemical studies performed for the polymeric particles depicted the redox behavior and good electrochemical activity of PDPA salts. Thermogravimetric analysis (TGA)/differential thermal analysis (DTA) proved that all the PDPA salts were thermally stable up to 300 °C. The electrochemical performance of PDPA–H₂SO₄ in hybrid supercapacitors was evaluated due to its superior physicochemical properties. The maximum specific capacitance of the hybrid supercapacitor constructed out of PDPA–H₂SO₄ powder was found to be 108 F g⁻¹.     

Decoration of carbon cloth by manganese oxides for flexible asymmetric supercapacitors

Here we describe the production of carbon cloth coated with MnO₂ nanosheets or MnOOH nanorods through a normal temperature reaction or a hydrothermal approach, respectively. Of note, the electrochemical performance of MnO₂-coated carbon cloth was better (429.2 F g⁻¹) than that of MnOOH-coated carbon cloth. When the MnO₂-coated carbon cloth is introduced as the positive electrode and the Fe₂O₃-coated carbon cloth as the negative electrode, a flexible asymmetric supercapacitor was obtained with an energy density of 22.8 Wh kg⁻¹ and a power density of 159.4 W kg⁻¹. Therefore, such a hierarchical MnO₂-coated carbon cloth nanocomposite is a promising high-performance electrode for flexible supercapacitors.     

Growth of yolk-shell CuCo2S4 on NiO nanosheets for high-performance flexible supercapacitors

A poor electrical conductivity and short cycle life limits the wide application of transition metal oxides in energy storage applications. In this study, yolk-shell structured CuCo₂S₄ was grown on NiO nanosheets (NiO@CuCo₂S₄) via a hydrothermal method and vulcanization, which combined the synergistic interactions between Ni, Co, and Cu. The effect of varying the amount of the vulcanizing agent (thiourea) on the electrochemical performance of NiO@CuCo₂S₄ was also investigated. Moreover, the amount of thiourea not only tuned the morphology of the composite, but significantly influenced its electrochemical performance. When the Cu²⁺: Co²⁺: thiourea molar ratio in the precursor solution was 1:2:6, the obtained NiO@CuCo₂S₄ exhibited the best electrochemical performance of the various systems examined, with a specific capacitance of 1658 F g^?1 being achieved at 1 A g^?1. Density functional theory calculations further confirmed the excellent synergistic effect between NiO and CuCo₂S₄. In addition, the asymmetric supercapacitor composed of a NiO@CuCo₂S₄ positive electrode reached an ultrahigh energy density of 73 Wh kg^?1 at a power density of 802 W kg^?1, as well as excellent cycling stability (i.e., 91% capacitance retention after 5000 cycles). These results suggest that NiO@CuCo₂S₄ is a promising candidate for use in energy storage applications.     

Control of a Hybrid Energy Storage System for a Hybrid Compensation System

The combination of two or more different energy storage technologies in a hybrid energy storage system appears to be advantageous if the combination of technologies fulfils the storage purpose better than a single storage technology. Herein, requirements regarding the performance of the storage system are determined for a hybrid compensation system for provision of system services in medium‐voltage grids. In hybrid storage systems, a common control system ensures that the present storage technologies are utilized in such a way that total storage efficiency is highest and that usability of the application is maximized. The control system of a hybrid storage system consisting of a redox flow battery and high‐speed flywheel storage is introduced and evaluated.     

NiFe2O4/SiO2 nanostructures as a potential electrode material for high rated supercapacitors

Engineered materials are crucial for the higher efficiency of supercapacitors. Current work presents roughly shaped spherical NiFe₂O₄ nanoparticles dispersed in the SiO₂ matrix NiFe₂O₄/SiO₂ as a newfangled electrode material for supercapacitors with remarkable performance. Designing the NiFe₂O₄/SiO₂ nanostructure with a sol-gel method followed by the Stober method to grow silica has instigated NiFe₂O₄/SiO₂ as dynamic material with higher electrochemical activity. Physicochemical aspects of NiFe₂O₄/SiO₂ nanostructures are evaluated using Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analysis. The electrochemical activity is evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) representing the comparable efficiency and reversibility of the electrode materials. The prepared electrode shows a capacitance of 925 F/g (154.1 mAh/g or 555 C/g) at 1 A/g, with 95.5% capacitance retention after 5000 cycles at 20 mA/cm². The improved electrochemical performance of the NiFe₂O₄/SiO₂ electrode can be subjected to prompt diffusion process provided by NiFe₂O₄/SiO₂ and enhanced redox reactions owing to the high surface area. The mentioned features decrease the total impedance of the electrodes as suggested by electrochemical impedance spectroscopy (EIS).     

Anchoring mesoporous Fe3O4 nanospheres onto N-doped carbon nanotubes toward high-performance composite electrodes for supercapacitors

Fe-based oxide electrodes for practical applications in supercapacitors (SCs) suffer from low conductivity and poor structural stability. To settle these issues, we report on the design and synthesis of Fe₃O₄/carbon nanocomposites via firmly anchoring mesoporous Fe₃O₄ nanospheres onto N-doped carbon nanotubes (N-CNTs) via C–O–Fe bonds. Mesoporous Fe₃O₄ nanospheres are featured by rich electroactive sites and short ion diffusion pathways. The N-CNTs, on the other hand, serve as the scaffolds, which not only provide conductive networks but also suppress the accumulation between mesoporous Fe₃O₄ nanospheres as well as alleviate volume changes during charge/discharge cycles. Accordingly, the constructed Fe₃O₄/N-CNTs nanocomposite electrode demonstrates improved specific capacity values of up to 314 C g⁻¹ at 1 A g⁻¹, with 92% retention of the initial capacity after 5000 cycles at 10 A g⁻¹. In addition, the assembled Fe₃O₄/N-CNTs//active carbon (AC) asymmetric supercapacitor (ASC) device possesses an energy density of 25.3 Wh kg⁻¹, suggesting that the prepared Fe₃O₄/N-CNTs nanocomposites are promising electrode materials for use in SCs.     

Synthesis of La-doped NiO nanofibers and their electrochemical properties as electrode for supercapacitors

La-doped NiO nanofibers were synthesized by the electrospinning method. The X-ray diffraction (XRD) pattern showed that La doping does not change the crystal structure up to the doping ratio of La/Ni=1.5%. Electrochemical properties of La-doped NiO nanofibers were investigated using cyclic voltammetry and galvanostatic charge/discharge. The results showed that the La doping can enhance the charge/discharge specific capacitance and electrochemical stability of the NiO nanofibers. Especially, the sample with doping ratio of La/Ni=1.5% could reach a discharge specific capacitance of 94.85 F g⁻¹ at a constant current density of 5 mA cm⁻².     

Facile synthesis of NiMn2O4 nanosheet arrays grown on nickel foam as novel electrode materials for high-performance supercapacitors

Nanostructured spinel NiMn₂O₄ arrays have been fabricated by a facile hydrothermal approach and further investigated as binder-free electrode for high-performance supercapacitors. Compared with Mn₃O₄, NiMn₂O₄ exhibited higher specific capacitances (662.5 F g⁻¹ and 370.5 F g⁻¹ in different electrolytes at the current density of 1 A g⁻¹) and excellent cycling stability (~96% capacitance retention after 1000 cycles) in a three-electrode system. Such a novel microstructure grown directly on the conductive substrate provided sufficient active sites for redox reaction resulting in their enhanced electrochemical behaviors. Their improved performances suggested that ultrathin sheet-like NiMn₂O₄ arrays on Ni foam substrate were a promising electrode material for supercapacitors.     

Oxygen vacancy-rich flower-like nickel cobalt layered double hydroxides for supercapacitors with ultrahigh capacity

One of the main difficulties for high-performance supercapacitors (SCs) is to design rational structures with excellent electrochemical properties. Herein, oxygen vacancy-rich nickel-cobalt layered double hydroxide, which has excellent supercapacitor performance, is prepared through an electrodeposition procedure and in situ oxidation process on nickel foam substrate. The conductivity and electrochemical properties are significantly improved by oxygen vacancies, which can be adjusted via hydrogen peroxide treatment. NiCo-LDH with oxygen vacancy (O_v-NiCo-LDH) attains a superior specific capacity of 1160 C g^?1 at the current density of 1 A g^?1 and shows a good capacity retention rate (61% of its original specific capacity is left at 20 A g^?1). Significantly, when the power density is 1.75 kW kg^?1, the energy density of the assembled symmetric supercapacitor (SSC) device is up to 216.19 Wh·kg^?1. This vacancy engineering strategy is helpful to the design of active materials for energy storage devices in the future.     

Hydrothermally synthesized FeCo2O4 nanostructures: Structural manipulation for high-performance all solid-state supercapacitors

The exploration of high performance supercapacitors has received emerging the worldwide research interests in satisfying the gradually increased energy consumption. In this paper, we adopt a facile hydrothermal strategy to synthesize ternary FeCo₂O₄ directly on nickel foam. A series of structure such as nanowires, nanoflake@nanowire hetero-structure and hierarchical nanospheres have been achieved via modulating the synthetic time. The morphology and structure of the as-prepared samples are characterized by using scanning electron microscopy and X-ray diffraction spectroscopy. The relationship between the detail processing parameters and electrochemical performance are also revealed by cyclic voltammetry, galvanostatic charge-discharge measurements, cycle stability tests and electrochemical impedance spectroscopy. Notably, the as-prepared nanoflake@nanowire hetero-structure exhibits a high specific capacitance of about 969 F g^?1 at 2 A g^?1 in alkaline aqueous solution and a remarkable cycling stability (91% capacity retention after 2000 cycles). The excellent supercapacitors performance of nanoflake@nanowire hetero-structure can be attributed to the high conductivity, large active area as well as robust architectures that derive from structural synergetic effects. Furthermore, a symmetric all solid-state supercapacitor has been fabricated by using nanoflake@nanowire hetero-structure as both the anode and cathode electrodes. The as-fabricated supercapacitor delivers excellent electrochemical performance. It's anticipated that FeCo₂O₄ would be a promising material for electrochemical energy storage applications.     

Fabrication and electrochemical properties of carbon nanotube array electrode for supercapacitors

The multiwalled carbon nanotube (MWNT) array was fabricated by chemical vapor deposition (CVD) in the template of porous alumina from the carbonaceous source of C₂H₂ in the presence of a catalyst of ferric metals. To utilize the external surface other than the inner surface of the carbon nanotubes, 1 mol/L sulfuric acid was applied to remove off the most part of AAO template on the carbon nanotube electrode. The electrochemical performances of the carbon nanotube array electrode were investigated by use of the cyclic voltammetry, galvanostatic charge/discharge and ac impedance methods for its application in supercapacitors. The specific capacitance of 365 F/g of the electrode was achieved with the discharge current density of 210 mA/g in the solution of 1 mol/L H₂SO₄. In addition, the carbon nanotube array electrode was found to have low equivalent series resistance (ESR) and good cycling stability.     

Solvothermal synthesis of porous MnCo2O4.5 spindle-like microstructures as high-performance electrode materials for supercapacitors

This study presents the facile preparation of novel MnCo₂O_4.5 microspindles (MSs) for the first time through a rapid solvothermal method combined with subsequent calcination of the precursor at 450 °C for 4 h in air. The MnCo₂O_4.5 MSs have an average length of 4–5 µm and diameter of 2–4 µm, respectively, achieving a specific surface area as high as 83.3 m² g⁻¹. In addition, the size and morphology of the MnCo₂O_4.5 microstructures could be easily tuned by some parameters including reaction time, volume ratio of ethanol to water, and dosage of urea. The electrochemical performance was further evaluated in three-electrode system, detailed electrochemical characterizations revealed that such MnCo₂O_4.5 MSs exhibited both high specific capacitance of 343 F g⁻¹ at a current density of 0.5 A g⁻¹ and excellent cycling performance of 81.3% capacitance retention after 5000 cycles at a current density of 4 A g⁻¹ in 2 M of KOH electrolyte, which made it a potential electrode material for an advanced supercapacitor. Furthermore, the present synthetic method is simple and can be extended to the synthesis of other electrode materials based on transition metal oxides.     

Influence of electrode preparation on the electrochemical behaviour of carbon-based supercapacitors

This work investigates the influence of electrode preparation on the electrochemical behaviour of carbon-based supercapacitors. Studies were performed using the same activated carbon and polymer polyvynilidene fluoride (PVDF) in the same proportions (10 wt.% PVDF). Only the way in which these components were mixed was modified. The procedure for mixing the activated carbon and the polymer has a significant influence on the electrochemical behaviour of the electrode used in a supercapacitor, as this determines the surface area accessible to the electrolyte. The mixing procedure can be selected in order to ensure optimum performance of the electrode. The use of N-methyl-2-pyrrolidone (NMP) in the mixing procedure, the most common method reported in the literature, blocks a significant part of the porosity of the activated carbon, causing a decrease in capacitance. The addition of the polymer using one of the other methods studied reduces the accessible surface area to a lesser extent, although the use of ball milling causes a decrease in the size of the carbon particles which, in turn, increases the electrode resistance.