Nitrogen-doped porous carbon coated on MnCo2O4 nanospheres as electrode materials for high-performance asymmetric supercapacitors

Spinel-based nanostructured materials are commonly used as promising electrode materials for supercapacitor applications. The combination of heteroatom-doped carbon material with spinel oxides substantially improves the specific capacitance and cyclic stability. In this work, dopamine-derived nitrogen-doped carbon was coated on spinel phase MnCo₂O₄ nanospheres using simple solvothermal and calcination methods. Surface morphology and the crystalline structure of the prepared MnCo₂O₄@Nitrogen-doped carbon were confirmed by FESEM and X-ray diffraction. The electrochemical performance of MnCo₂O₄@Nitrogen-doped carbon electrode material was analyzed by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy techniques. MnCo₂O₄@nitrogen-doped carbon exhibits the highest specific capacitance of 1200 F/g compared to MnCo₂O₄ spheres are 726 F/g at 1 A/g and exhibits excellent cyclic stability (capacitance retention of 87% at 7 A/g after 3000 cycles). The enhanced performance of the composite might be benefitted from the synergistic effect between nitrogen-doped carbon on porous MnCo₂O₄ spheres. Furthermore, an asymmetric supercapacitor device was fabricated by using the optimized composition of MnCo₂O₄@NC-2 as a positive electrode and nitrogen, sulfur-doped reduced graphene oxide (NS-rGO) as a negative electrode, respectively. This asymmetric supercapacitor device achieves a maximum energy density of 61.0 Wh/kg at a power density of 2889 W/kg and possesses excellent capacitance retention of 95% after 5000 cycles at 7 A/g.     

Hybrid Fibers Made of Molybdenum Disulfide,Reduced Graphene Oxide,and Multi‐Walled Carbon Nanotubes for Solid‐State,Flexible, Asymmetric Supercapacitors

One of challenges existing in fiber‐based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two‐dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS₂) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy‐related applications. Herein, by incorporating MoS₂ and reduced graphene oxide (rGO) nanosheets into a well‐aligned multi‐walled carbon nanotube (MWCNT) sheet followed by twisting, MoS₂‐rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid‐state, flexible, asymmetric supercapacitors. This fiber‐based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density.     

Hybrid Fibers Made of Molybdenum Disulfide,Reduced Graphene Oxide,and Multi‐Walled Carbon Nanotubes for Solid‐State,Flexible, Asymmetric Supercapacitors

One of challenges existing in fiber‐based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two‐dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS₂) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy‐related applications. Herein, by incorporating MoS₂ and reduced graphene oxide (rGO) nanosheets into a well‐aligned multi‐walled carbon nanotube (MWCNT) sheet followed by twisting, MoS₂‐rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid‐state, flexible, asymmetric supercapacitors. This fiber‐based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density.     

Multi-walled carbon nanotubes as electrode materials for electrochemical studies of organometallic compounds in organic solvent media

Abstract  

Films of vertically aligned multi-walled carbon nanotubes (MWCNT) were selectively synthesized on silicon dioxide substrate by catalytic chemical vapor deposition using either benzene or acetonitrile as carbon source and ferrocene (1% w/w) as catalyst. The MWCNT were extensively characterized by using scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and Raman spectroscopy. In order to examine the prospective application of the fabricated MWCNT films for the detection of electro-active compounds in organic solvent media, electrochemical studies of the oxidation of cobaltocene (CoCp₂) to cobaltocenium cation (CoCp₂⁺) (Cp = cyclopentadienyl anion) in acetonitrile were performed on these films. For this purpose, cyclic voltammetry and electrochemical impedance spectroscopy were employed. The electrochemical parameters for the CoCp₂^+/0 couple in acetonitrile were derived and compared with those obtained using a conventional glassy carbon electrode. The results demonstrate that the synthesized MWCNT films are promising electrode materials for the electrochemical detection of electro-active species in organic solvents. The MWCNT film formed upon decay of benzene has higher capacitance, less Warburg impedance, and less charge transfer resistance, and consequently it provides faster electron transfer kinetics.     

High performance pliable supercapacitor fabricated using activated carbon nanospheres intercalated into boron nitride nanoplates by pulsed laser ablation technique

Pliable supercapacitor, yielding specific capacitance (C_s) and energy density as high as 348 F g⁻¹ and 48.3 Wh Kg⁻¹ respectively was fabricated using modified activated carbon electrodes. The nanospheres of activated carbon (AC) were anchored on the nanoplates of boron nitride (BN) by employing the facile technique of pulsed laser ablation in liquid (PLAL) using 532 nm focused laser beam. Four different variants of electrode materials were synthesized by varying the weight percentage (1%, 3%, 5% and 10%) of BN in AC in the PLAL precursor solution. The morphological characteristics, the elemental composition and the structural analysis of the synthesized electrode materials were studied respectively by FESEM, XPS and XRD. The morphological studies indicated that the PLAL synthesis of the electrode materials resulted in proper intercalation of carbon nanospheres into BN nanoplates, which resulted in the observed enhanced performance of the fabricated supercapacitor. Four supercapacitors in this work were fabricated using the four variants of synthesized electrode materials in conjunction with gel polymer electrolyte (GPE). GPE are well known for their non-corrosive nature and best sealing ability to avoid any leakage that results in increasing the cycle life of the device. The performance of the fabricated supercapacitors was evaluated using cyclic voltammetry (CV), galvanostatic charge discharge (GCD) measurement and electrochemical impedance spectroscopy (EIS). The results indicate that the supercapacitor fabricated using 3% BN in AC as electrode material manifested the best specific capacitance and energy density. Also it was found that the supercapacitor maintained 85% of its initial capacitance even after 5000 charge/discharge cycles.     

Three-dimensional bundle-like multiwalled carbon nanotubes composite for supercapacitor electrode application

Bundle-type mutil-walled carbon nanotubes (MWCNTs) composite electrode is the first investigation and publication for the supercapacitor application. According to the thermogravimetric analysis results, as-synthesized BCNTs are considered as the electrode materials for supercapacitors and electrochemical double-layer capacitor in this study. The Brunauer–Emmett–Teller specific surface area of as-prepared bundled carbon nanotubes (BCNTs) is 95.29 m²/g given to a type III isotherm and H3 hysteresis loops. Slow scanning rates promote and enhance to achieve high C_b because of the superior conductivity of CNT bundles and one side close-layered Ni/Mg/Mo alloy inside the BCNT-based electrode and facile electron diffusivity between electrolyte and electrode. The specific capacitance C_s (1,560 F/g) is nearly equal to the maximum specific capacitance, which the BCNT-based composite electrode can actually be able to charge or fill in. The maximum energy density value is 195 Wh/kg with corresponding power density values of 0.21 kW/kg. Furthermore, the active 3D BCNTs material fabricated electrode enhances to contact the electrolyte directly and decreases the ion diffusion limitation. Electrochemical impedance spectroscopy spectrum summarized as the low-frequency area controls by mass transfer limitation, and the high-frequency area dominates by charge transfer of kinetic control. After 2,000 consecutive cyclic voltammetry sacnings and galvanostatic charge-discharge cycles at a current density of 1.67 A/g performs, the specific capacitance retentions of 3D BCNTs electrodes achieved 128.2 and 77.3%, respectively. Three-dimensional BCNT composite electrodes exhibit good conductivity and low charge transfer resistance, which is beneficial to fast charge transfer between the BCNTs electrode materials and electrolytes.     

Synthesis and characterization of co-precipitated nickel phosphate [Ni3(PO4)2] nanoparticles prepared at varying precursor concentrations

This work investigated the structural, morphological, elemental, optical, and electrochemical characteristics of nickel phosphate nanoparticles co-precipitated at varying molar concentrations. Structural results gave monoclinic crystalline phase with nanorod morphology. EDX plots confirmed deposition of constituent element: nickel, phosphorus and oxygen. The films exhibited good absorbance feature with optical energy band gap values ranging from 1.58 eV to 2.2 eV. Good cyclic reversibility as obtained using 0.1 M of sodium hydroxide as electrolyte. The specific capacitance values of the electrodes ranged from 624.38 F/g to 1017.2 F/g at a scan rate of 1 mV/s. The Ni₃(PO₄)₂ electrode prepared at 0.3 M recorded maximum energy and power densities of 239.49 Wh/kg and 2.52 W/kg respectively. The synthesized samples find potential application in optical and electrochemical devices.     

High-voltage aqueous symmetric electrochemical capacitor based on Ru0.7Sn0.3O2·nH2O electrodes in 1 M KOH

A mild hydrothermal process is applied to synthesize hydrous ruthenium–tin binary oxides (Ru_0.7Sn_0.3O₂·nH₂O) with good capacitive performance in alkaline system. Then, a symmetric electrochemical capacitor (EC) is fabricated based on the as-synthesized Ru_0.7Sn_0.3O₂·nH₂O material and 1 M KOH aqueous electrolyte. Electrochemical performance of the symmetric EC is investigated by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy tests. Electrochemical tests demonstrate that the symmetric EC surprisingly can operate with a high upper cell voltage limit of 1.45 V in 1 M KOH electrolyte. Maximum specific capacitance and energy density of the symmetric aqueous EC are approximately 160 F/g and 21 Wh/kg, respectively, delivered at a current density of 1.25 A/g. And the specific energy density decreases to approximately 15 Wh/kg when the specific power density increases up to approximately 1,770 W/kg. The promising specific energy and power densities are obtained simultaneously for the unwonted symmetric EC due to its larger operating potential range. Moreover, the symmetric EC exhibits electrochemical stability with 85.2% of the initial capacitance over consecutive 1,000 cycle numbers.     

The study of EDLC device fabricated from plasticized magnesium ion conducting chitosan based polymer electrolyte

Plasticized biopolymer electrolytes based on chitosan (CS) doped with magnesium acetate (Mg(CH₃COO)₂) and various amounts of glycerol have been prepared for energy storage electrochemical double-layer capacitor (EDLC) application. In this work the dielectric and electrochemical properties have been examined using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and linear sweep voltammetry (LSV). It is confirmed from the frequency changing of the impedance spectra that relatively high dielectric constant has been recorded at low frequency region. From tan δ and M″ spectra, relaxation peaks are clearly seen. It has been found that as the glycerol concentration increased, the DC conductivity increases. In the fabricated system (CS: Mg(CH₃COO)₂: glycerol.), ions are responsible for charge carrying as the ion transference number is higher than the electron transference number. The electrochemical stability of the system extends to 2.4 V as shown in the LSV. The mechanism of the charge storage has been investigated and indicated that the non-Faradaic dominates where the specific capacitance is significantly affected by scan rate. The fabricated EDLC possessed a constant value of specific capacitance (78.2 F/g), energy density (8.8 Wh/kg), and ESR (78.2 F/g). The EDLC has an tremendous cycleability as high number of Columbic efficiency has accomplished. The value of efficiency of the EDLC has been in the range of 97%–99%.     

Nanoflake-like cobalt hydroxide/ordered mesoporous carbon composite for electrochemical capacitors

Nanocomposites consisting of mesoporous carbon CMK-3 and cobalt hydroxide nanoflakes are synthesized by a chemical precipitation method. The successful growth of nanometer-sized Co(OH)₂ flakes on the surface of CMK-3 is confirmed by scanning electron microscopy. The Co(OH)₂/CMK-3 composite electrodes are investigated for its use in the electrochemical capacitors with cyclic voltammograms, chronopotentiometric measurements, and electrochemical impedance spectroscopy. Experimental studies reveal that the Co(OH)₂/CMK-3 composite electrode with the 20 wt.% CMK-3 presents excellent electrochemical performance with specific capacitance of 750 F/g (or 910 F/g after being corrected for the weight percentage of the Co(OH)₂ phase). The overall improved electrochemical behavior accounts for the unique structure design in the Co(OH)₂/CMK-3 composite in terms of porous nanostructure, large specific surface area, and good electrical conductance. The Co(OH)₂/CMK-3 composite electrode also shows better rate capability and cyclic stability, suggesting its potential applications as the electrode materials for electrochemical capacitors.     

ZIF-67 derived hollow Ni-Co-Se nano-polyhedrons for flexible hybrid supercapacitors with remarkable electrochemical performances

Nano-polyhedral NiSe₂/CoSe₂ (Ni-Co-Se) with hollow architectures are synthesized by selenizing the precursors of Ni-Co bimetallic hydroxides that are directly derived from ZIF-67. The as-fabricated Ni-Co-Se electrodes exhibit high specific capacitance of 1668 F/g at 1 A/g accompanying with outstanding rate capability (about 82.8% retention of the initial capacity at 20 A/g). The corresponding Ni-Co-Se//AC all-solid-state hybrid supercapacitors are assembled by directly using the Ni-Co-Se on carbon fabric as the positive electrode, which deliver high energy density and power density (38.5 Wh/kg at 802.1 W/kg, 32.0 Wh/kg at 8008.8 W/kg), excellent cyclic stability (82.3% retention after 5000 cycle) and robust mechanical flexibility (no obvious attenuation at bending to different angles). This work will provide a new and smart route for constructing transition metal selenides for supercapacitor devices.     

Free‐standing and Flexible MoS2/rGO Paper Electrode for Amperometric Detection of Folic Acid

The development of flexible electrodes is of considerable current interest because of the increasing demand for modern electronics, portable medical products, and compact devices. We report a new type of flexible electrochemical sensor fabricated by integrating graphene and MoS₂ nanosheets. A highly flexible and free‐standing conductive MoS₂ nanosheets/reduced graphene oxide (MoS₂/rGO) paper was prepared by a two‐step process: vacuum filtration and chemical reduction treatment. The MoS₂/graphene oxide (MoS₂/GO) paper obtained by a simple filtration method was transformed into MoS₂/rGO paper after a chemical reduction process. The obtained MoS₂/rGO paper was characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy. The electrochemical behavior of folic acid (FA) on MoS₂/rGO paper electrode was investigated by cyclic voltammetry and amperometry. Electrochemical experiments indicated that flexible MoS₂/rGO composite paper electrode exhibited excellent electrocatalytic activity toward the FA, which can be attributed to excellent electrical conductivity and high specific surface area of the MoS₂/rGO paper. The resulting biosensor showed highly sensitive amperometric response to FA with a wide linear range.     

Electrophoretically deposited L-cysteine functionalized MoS2@MWCNT nanocomposite platform: a smart approach toward highly sensitive and label-free detection of gentamicin

The exploitation of antibiotics has caused many side effects on the agriculture, environment, and human health. The existing methods have numerous shortcomings in determining gentamicin (GEN), a broad-spectrum antibiotic that causes nephrotoxicity and ototoxicity when found in excess. Here, an immunosensing platform to detect GEN using multiwalled carbon nanotubes (MWCNTs) and molybdenum disulfide (MoS₂) nanocomposite, deposited electrophoretically on indium tin oxide (ITO) glass has been developed. A novel 2-D graphene analog MoS₂@ MWCNTs nanocomposite was made via a facile and low-cost hydrothermal technique using l-cysteine to achieve remarkable electrochemical properties. Subsequently, a highly sensitive electrochemical immunosensor was fabricated by assembling monoclonal antibodies against gentamicin (anti-GEN) on a MoS₂@MWCNTs modified ITO electrode. The hetero-nanostructure formed on the immunosensor surface appeared relatively good conductor for accelerating the electron transfer. GEN was determined on anti-GEN modified electrodes by utilizing the differential pulse voltammetry technique by measuring the difference in current owing to the transfer of electrons directly between the redox species and immunoelectrodes. Under optimal experimental conditions, the fabricated immunosensor had a wide linear detection range of 1 × 10^?6–40 μg/mL, a high sensitivity of 13.55 μA (log μg/mL)^?1 and a low limit of detection and limit of quantification of 0.039 μg/mL and 0.130 μg/mL, respectively. The developed immunosensor also exhibits high reproducibility, repeatability, and good selectivity against various interferences. This electrochemical immunosensor having MoS₂ modified MWCNTs displays the excellent potential for the point-of-care device for GEN testing.     

One-step synthesis of biomass derived O,N-codoped hierarchical porous carbon with high surface area for supercapacitors

We report a convenient method to synthesize O, N-codoped hierarchical porous carbon by one-step carbonization of the mixture of KHCO₃, urea and alginic acid. Benefiting from KHCO₃ and urea synergistic effect, the obtained O, N-codoped hierarchical porous carbon (NPC-700) material has a well-developed interconnected porous framework with ultrahigh specific surface area (2846 m²/g) and massive heteroatoms functional groups. Consequence, such porous carbon displays high specific capacitance (324 F/g at 1 A/g), excellent rate performance (212 F/g at 30 A/g) and good electrochemical stabilization in 6 mol/L KOH solution. More importantly, the assembled NPC-700//NPC-700 symmetrical supercapacitor can achieve a high energy density of 18.8 Wh/kg and good electrochemical stabilization in 1 mol/L Na₂SO₄ solution. This process opens up a new way to design heteroatoms-doped hierarchical porous carbon derived from biomass materials for supercapacitors.     

Preparation of 3D MnO2/Polyaniline/Graphene Hybrid Material via Interfacial Polymerization as High‐Performance Supercapacitor Electrode

MnO₂/polyaniline/graphene composite as a supercapacitor electrode material was synthesized through an interfacial polymerization approach in the interface of oil/water phase. The as‐synthesized MPG is characterized by infrared spectroscopy, XRD, XPS, SEM and TEM, and its electrochemical performance is measured by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The 3D nanostructure of MPG and loose nanorod structure of polyaniline (PANI) coated with round MnO₂ pellets could be clearly observed. The maximum energy density of MPG is 45.4 Wh/kg (at a power density of 67.8 kW/kg) and the highest power density is 229.2 kW/kg (at an energy density of 25.7 Wh/kg). The capacitance retentions after 500 cycles at the scan rate of 5 mV/s for MGP composite and PANI/graphene are 70.4% and 59.1%, respectively, and the capacitance values after 500 cycles are 158.4 F/g and 114.8 F/g, respectively. The improved performance of MPG is due to the 3D nanostructure, loose nanorod structure of PANI and stable support of graphene, which prevent the mechanical deformation effectively during the fast charge/discharge process and facilitate the diffusion of the electrolyte ions into the inner region of active materials. The composite material is very promising for the next generation of high‐performance supercapacitors electrode.     

Understanding the oxygen-containing functional groups on multiwall carbon nanotubes toward supercapacitors

Typical functionalization treatment by strong acid is used to introduce functional groups into/onto the multiwall carbon nanotubes (MWCNTs), to enhance the desired redox activity for electrochemical applications. The influence of various functional groups on the redox of MWCNT has been studied in recent years. Different functional groups on MWCNT can be removed selectively using different thermal annealing temperatures. By this method, it is recognized that carboxyl, anhydride, and phenol groups play essential roles in the redox reaction. A designed carboxyl/anhydride-rich defective MWCNT is fabricated with a superior specific areal capacitance of 34.55 mF/cm². These results provide more information for the study of the MWCNTs' electrochemical applications toward supercapacitors and batteries.     

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.     

Vertical crosslinking MoS2/three-dimensional graphene composite towards high performance supercapacitor

The vertical crosslinking MoS₂/three-dimensional graphene composite has been prepared by hydrothermal method, which delivered a superior and stable electrochemical capacitive performance.     

Controlled synthesis of MnSn(OH)6/graphene nanocomposites and their electrochemical properties as capacitive materials

We report the synthesis of novel MnSn(OH)₆/graphene nanocomposites produced by a co-precipitation method and their potential application for electrochemical energy storage. The hydroxide decorated graphene nanocomposites display better performance over pure MnSn(OH)₆ nanoparticles because the graphene sheets act as conductive bridges improving the ionic and electronic transport. The crystallinity of MnSn(OH)₆ nanoparticles deposited on the surface of graphene sheets also impacts the capacitive properties as electrodes. The maximum capacitance of 31.2 F/g (59.4 F/g based on the mass of MnSn(OH)₆ nanoparticles) was achieved for the sample with a low degree of crystallinity. No significant degradation of capacitance occurred after 500 cycles at a current density of 1.5 A/g in 1 M Na₂SO₄ aqueous solution, indicating an excellent electrochemical stability. The results serve as an example demonstrating the potential of integrating highly conductive graphene networks into binary metal hydroxide in improving the performance of active electrode materials for electrochemical energy storage applications.     

Porous carbon globules with moss-like surfaces from semi-biomass interpenetrating polymer network for efficient charge storage

The bio-nanotechnological fabrication of high-surface-area carbons has attracted widespread interest in supercapacitor applications by using readily-available natural products as raw materials or bio-templates, and is expected to refine on pore accessibility for compact energy storage. Here, a renovated design strategy of semi-biomass interpenetrating polymer network (IPN) derived carbon is demonstrated through physically knitting the biomacromolecule (sodium alginate, SA) polymeric chains into the highly crosslinked resorcinol-formaldehyde (RF) network and subsequent thermochemical conversion. Molecule-level interlacing forces in such IPN efficiently relieve the RF skeleton shrinkage when producing carbon, while the other SA network addresses the macrophase separation issue to sacrifice as an in-knitted porogen and a morphology-directing agent. As a result, porous carbon globules are equipped with moss-like surfaces and interconnected pore architecture for high accessible electrode surface (1013 m²/g), and efficient electrochemical responses are reached with the specific capacitance of 312 F/g at 1 A/g. Taking the advantage of 9 mol/kg NaClO₄ complex-solvent electrolyte, the voltage window is extended to 2.4 V, endowing the two-electrode device with the high energy delivery of 32.3 Wh/kg at 240 W/kg.