Electrochemical capacitance of nickel oxide nanotubes synthesized in anodic aluminum oxide templates

Nickel oxide (NiO) nanotubes for supercapacitors were synthesized by chemically depositing nickel hydroxide in anodic aluminum oxide templates and thermally annealing at 360 °C. The synthesized nanotubes have been characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The capacitive behavior of the NiO nanotubes was investigated by cyclic voltammetry, galvanostatic charge–discharge experiment, and electrochemical impedance spectroscopy in 6 M KOH. The electrochemical data demonstrate that the NiO nanotubes display good capacitive behavior with a specific capacitance of 266 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent specific capacitance retention of ca. 93% after 1,000 continuous charge–discharge cycles, indicating that the NiO nanotubes can become promising electroactive materials for supercapacitor.     

Glycine-assisted hydrothermal synthesis of nanostructured Co x Ni1−x –Al layered triple hydroxides as electrode materials for high-performance supercapacitors

Nanostructured Co _x Ni_1−x –Al layered triple hydroxides (Co _x Ni_1−x –Al LTHs) have been successfully synthesized by a facile hydrothermal method using glycine as chelating agent. The samples were characterized by X-ray diffraction, thermogravimetry, Fourier transform infrared spectroscopy and scanning electron microscopy. The morphologies of Co _x Ni_1−x –Al LTHs varied with the Co content and its effect on the electrochemical behavior was studied by cyclic voltammetry and galvanostatic charge–discharge techniques. Electrochemical data demonstrated that the Co _x Ni_1−x –Al LTHs with Co/Ni molar ratio of 3:2 owned the best performance and delivered a maximum specific capacitance of 1,375 F g⁻¹ at a current density of 0.5 A g⁻¹ and a good high-rate capability. The capacitance retained 93.3% of the initial value after 1,000 continuous charge–discharge cycles at a current density of 2 A g⁻¹.     

Structural and electrochemical behavior of Mn–V oxide synthesized by a novel precipitation method

Manganese–vanadium oxide had been synthesized by a novel simple precipitation technique. Scanning electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis/differential scanning calorimetry, and X-ray photoelectron spectroscopy were used to characterize Mn–V binary oxide and δ-MnO₂. Electrochemical capacitive behavior of the synthesized Mn–V binary oxide and δ-MnO₂ was investigated by cyclic voltammetry, galvanostic charge–discharge curve, and electrochemical impedance spectroscope methods. The results showed that, by introducing V into δ-MnO₂, the specific surface area of the mixed oxide increased due to a formation of small grain size. The specific capacitance increased from 166 F g⁻¹ estimated for MnO₂ to 251 F g⁻¹ for Mn–V binary oxide, and the applied potential window extended to −0.2–1.0 V (vs. saturated calomel electrode). Through analysis, it is suggested that the capacitance performance of Mn–V binary oxide materials may be improved by changing the following three factors: (1) small grain and particle size and large activity surface area, (2) appropriate amount of lattice water, and (3) chemical state on the surface of MnO₂ material.     

Synthesis and supercapacitance of flower-like Co(OH)<Subscript>2</Subscript> hierarchical superstructures self-assembled by mesoporous nanobelts

A facile hydrothermal strategy was first proposed to synthesize flower-like Co(OH)₂ hierarchical microspheres. Further physical characterizations revealed that the flower-like Co(OH)₂ microspherical superstructures were self-assembled by one-dimension nanobelts with rich mesopores. Electrochemical performance of the flower-like Co(OH)₂ hierarchical superstructures were investigated by cyclic voltammgoram, galvanostatic charge–discharge and electrochemical impedance spectroscopy in 3 M KOH aqueous electrolyte. Electrochemical data indicated that the flower-like Co(OH)₂ superstructures delivered a specific capacitance of 434 F g⁻¹ at 10 mA cm⁻² (about 1.33 A g⁻¹), and even kept it as high as 365 F g⁻¹ at about 5.33 A g⁻¹. Furthermore, the SC degradation of about 8% after 1,500 continuous charge–discharge cycles at 5.33 A g⁻¹ demonstrates their good electrochemical stability at large current densities.     

RuO2/Co3O4 thin films prepared by spray pyrolysis technique for supercapacitors

RuO₂/Co₃O₄ thin films with different RuO₂ content were successfully prepared on fluorine-doped tin oxide coated glass plate substrates by spray pyrolysis method, and their capacitive behavior was investigated. Electrochemical property was performed by cyclic voltammetry, constant current charge/discharge, and electrochemical impedance spectra. The capacitive performance of RuO₂/Co₃O₄ thin films with different RuO₂ content corresponded to a contribution from a main pseudocapacitance and an additional electric double-layer capacitance. The specific capacitance of pure Co₃O₄, 15.5%, 35.6%, and 62.3% RuO₂ composites at the current density of 0.2 A g⁻¹ were 394 ± 8, 453 ± 9, 520 ± 10, and 690 ± 14 F g⁻¹, respectively; 62.3% RuO₂ composite presented the highest specific capacitance value at various current densities, whereas 35.6% RuO₂ composite exhibited not only the largest specific capacitance contribution from RuO₂ (C _sp ^RuO2) at the current density of 0.5, 1.0, 1.5, and 2.0 A g⁻¹ but also the highest specific capacitance retention ratio (46.3 ± 2.8%) at the current density ranging from 0.2 to 2.0 A g⁻¹. Electrochemical impedance spectra showed that the contact resistance dropped gradually with the decrease of RuO₂ content, and the charge-transfer resistance (R _ct) increased gradually with the decrease of RuO₂ content.     

Immobilization of flavine adenine dinucleotide onto nickel oxide nanostructures modified glassy carbon electrode: fabrication of highly sensitive persulfate sensor

A simple method was used to fabricate flavin adenine dinucleotide (FAD)/NiOx nanocomposite on the surface of glassy carbon (GC) electrode. Cyclic voltammetry technique was applied for deposition nickel oxide nanostructures onto GC surface. Owing to its high biocompatibility and large surface area of nickel oxide nanomaterials with immersing the GC/NiOx-modified electrode into FAD solution for a short period of time, 10–140 s, a stable thin layer of the FAD molecules immobilized onto electrode surface. The FAD/NiOx films exhibited a pair of well-defined, stable, and nearly reversible CV peaks at wide pH range (2–10). The formal potential of adsorbed FAD onto nickel oxide nanoparticles film, E ^o′ vs. Ag/AgCl reference electrode is −0.44 V in pH 7 buffer solutions was similar to dissolved FAD and changed linearly with a slope of 58.6 mV/pH in the pH range 2–10. The surface coverage and heterogeneous electron transfer rate constant (k _s ) of FAD immobilized on NiOx film glassy carbon electrode are 4.66 × 10⁻¹¹ mol cm⁻² and 63 ± 0.1 s⁻¹, indicating the high loading ability of the nickel oxide nanoparticles and great facilitation of the electron transfer between FAD and nickel oxide nanoparticles. FAD/NiOx nanocomposite-modified GC electrode shows excellent electrocatalytic activity toward S₂O₈²⁻ reduction at reduced overpotential. Furthermore, rotated modified electrode illustrates good analytical performance for amperometric detection of S₂O₈²⁻. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 3 μM–1.5 mM, 0.38 μM and 16.6 nA/μM, respectively.     

Sulfide-enhanced electrochemical capacitance of cobalt hydroxide on nanofibered parent substrate

Two approaches—substrate nanostructuring and incorporation of sulfide—were studied with the aim to increase electrochemical capacitance of cobalt (hydro)oxide. A fiber structure of cobalt was deposited electrochemically with the fibers in the order of tens of nanometers in thickness and hundreds of nanometers in length. Cobalt hydroxide film was formed on the nanostructured substrate by anodic polarization in an alkaline solution. The hydroxide formation and its electrochemical capacitance have been studied by cyclic voltammetry in conjunction with the electrochemical quartz crystal microbalance (EQCM). An irreversible behavior was typical of the first anodic polarization cycle; it turned gradually to a reversible one during subsequent cycling. EQCM measurements indicated exponential electrode mass growth during the first cycle, with subsequent transition to a quasipassive state. The redox transitions Co(II) → Co(III) → Co(IV), which determine pseudocapacitance, did not cause remarkable electrode mass change. The electrochemical capacitance of the nanofiber sample was found up to five times higher when compared to that formed on conventional cobalt (abraded surface). Specifics of “per 1 g” evaluation of capacitance performance is discussed. Measurements showed that about 10% of the entire hydroxide structure took part in the capacitive process. The capacitance value determined per 1 g of active Co(OH)₂ was in agreement with the limiting value predicted by the Faraday’s law (2,421 F g⁻¹) sulfide-enhanced system with 18% CoS exhibited up to three times higher capacitance when compared to that of the sulfide-free counterpart. The system shows promise for practical applications due to its low cost and technical simplicity.     

Preparation and characterization of Ca1 − x Ce x MnO3 perovskite electrodes

The electrochemical properties of Ca_1 − x Ce _x MnO₃ perovskite-type oxide electrode have been investigated by cyclic voltammetry in Na₂SO₄ aqueous solutions with pH 14. The structural and morphological characterizations have also been investigated and the information used to interpret the electrochemical behavior. An estimation of the electrode’s capacitance and roughness factor has been obtained by means of cyclic voltammetry. The specific capacitance and consequently the roughness factor values are affected by the presence of Ce ions in the oxide. These findings are in agreement with the increase of the oxide-specific surface area by the introduction of Ce ion. The open-circuit potential and the voltammetric patterns are dependent on the presence of Ce ion in the electrodes and support that the surface electrochemistry of the perovskite oxide electrodes is governed by the Mn⁴⁺–Mn³⁺ redox couple.     

Synthesis and electrochemical capacitive behaviors of Co3O4 nanostructures from a novel biotemplating technique

A novel approach is developed to synthesize Co₃O₄ nanoparticles utilizing sawdust as a bio-template. Sawdust was first infiltrated with cobalt dichloride aqueous solution, and then, in situ precipitation reaction took place when different precipitators (NaOH or H₂C₂O₄) were added. Finally, the precursors, Co(OH)₂ and CoC₂O₄, were calcined to produce the final Co₃O₄ nanoparticles and the template was removed simultaneously. The structure and morphology of the obtained products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. The observations revealed the formation of cubic phase Co₃O₄ with the average diameter of about 40 and 60 nm, respectively. Their electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge–discharge tests. The highest specific capacitance of 289.7 F g⁻¹ for the obtained Co₃O₄ electrode was obtained even at a discharge current of 20 mA after the 100th cycle and it increased by about 4% after the 1,000th cycle, demonstrating good electrochemical stability of such electrode materials.     

Electrochemical deposition of silicate–cetyltrimethylammonium bromide nanocomposite film on glassy carbon electrode for sensing of methyl parathion

A novel electrochemical sensor for methyl parathion based on silicate– cetyltrimethylammonium bromide nanocomposite film has been fabricated by electro-assisted deposition onto glassy carbon electrode in one-step via an electrochemical modulation of pH at the electrode/solution interface to promote controlled gelification of tetraethylorthosilicate sol, and was characterized with scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The electrochemical sensing of methyl parathion on the film-modified electrode was investigated applying cyclic voltammetry and square wave voltammetry. Compared to the unmodified electrode, the shapes of the redox peaks were improved and the peak currents significantly increased. Experimental parameters such as deposition time, pH value, and accumulation conditions have been optimized. A linear relationship between the peak current and methyl parathion concentration was obtained in the range from 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.04 × 10 ⁻⁸ mol L⁻¹ (S/N = 3) after accumulation at 0 V for 120 s. The film electrode shows great promise for determination of methyl parathion in real samples.      

Preparation and electrochemical performance of activated carbon thin films with polyethylene oxide-salt addition for electrochemical capacitor applications

The effect of polymer–salt addition in the activated carbon electrode for electric double-layer capacitor (EDLC) has been investigated. A series of composite thin film electrode consisting of activated carbon, carbon black, polytetrafluoroethylene and polymer–salt complex (polyethyleneoxide–LiClO₄) with an appropriate weight ratio were prepared and examined their performance for EDLCs using 1 mol L⁻¹ LiClO₄ in ethylene carbonate:diethylcarbonate electrolyte solution. The electrochemical capacitance performances of these electrodes with different compositions were characterized by cyclic voltammetry, galvanostatic charge–discharge cycling, and AC impedance measurements. By comparison, the best results were obtained with a composite electrode rich in polymer–salt additive (132 F g⁻¹ at 100 mA g⁻¹ of galvanostatic experiment). In general, the polymer–salt-containing electrode had shown improved performance over activated carbon electrodes without polymer–salt at high current density.     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn~(4+)掺杂的Co_3O_4复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn~(4+)掺杂,Co_3O_4复合纳米纤维的电化学性能得到明显改善。当nCo∶nMn=20∶2时,相应的复合纤维具有较大比表面积68 m2·g-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g-1的电流密度下,放电比电容量为585 F·g-1,这比纯Co_3O_4纳米纤维的416 F·g-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co_3O_4纳米纤维则是76.4%。     

Nanocrystalline nickel cobalt hydroxides/ultrastable Y zeolite composite for electrochemical capacitors

A novel nanocomposite of Co(OH)₂−Ni(OH)₂ and ultrastable Y molecular sieves was synthesized by an improved chemical precipitation method for electrochemical capacitors. The Co(OH)₂−Ni(OH)₂/ultrastable Y zeolite (USY) composite and its microstructure were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Electrochemical characterization was performed by cyclic voltammetry and galvanostatic charge–discharge measurements. The results show that Co(OH)₂−Ni(OH)₂/USY microstructure applied for the electrochemical energy storage has displayed superior capacitive performance. The effect of heat treatment conditions on specific capacitance properties was also systemically explored. Upon annealing at 250 °C, the maximum specific capacitance was up to 479 F/g (or 1,710 F/g after correcting for the weight percent of Co(OH)₂−Ni(OH)₂ phase). Annealing temperatures higher than 250 °C may cause the hydroxide to form oxide phase and decrease the surface activity of the oxide, thereby leading to a decline of the specific capacitance.     

Electrochemical performance of Co–Al layered double hydroxide nanosheets mixed with multiwall carbon nanotubes

Regular hexagonal Co–Al layered double hydroxides (Co–Al LDH) were synthesized by urea-induced homogeneous precipitation. This material proved to be nanosheets by scanning electron microscopy and X-ray diffraction measurements. The electrochemical capacitive behavior of the nanosheets in 1 M KOH solution were evaluated by constant current charge/discharge and cyclic voltammetric measurements, showing a large specific capacitance of 192 F·g⁻¹ even at the high current density of 2 A·g⁻¹. When multiwall carbon nanotubes (MWNTs) were mixed with the Co–Al LDH, it was found that the specific capacitance and long-life performance of all composite electrodes at high current density are superior to pure LDH electrode. When the added MWNTs content is 10 wt%, the specific capacitance increases to 342.4 F·g⁻¹ and remains at a value of 304 F·g⁻¹ until the 400th cycle at 2 A·g⁻¹, showing that this is a promising electrode material for supercapacitors working at heavy load. According to the electrochemical impedance spectra, MWNTs greatly increase the electronic conductivity between MWNTs and the surface of Co–Al LDH, which consequently facilitates the access of ions in the electrolyte and electrons to the electrode/electrolyte interface.     

Microwave-assisted synthesis of organic–inorganic poly(3,4-ethylenedioxythiophene)/RuO2·xH2O nanocomposite for supercapacitor

An organic–inorganic poly(3,4-ethylenedioxythiophene) (PEDOT)/RuO₂·xH₂O nanocomposite (approximately 1 wt.% RuO₂) has been successfully prepared for the first time under microwave irradiation within 5 min with power 900 W via in situ chemical polymerization. The morphology and structure of the resultant material is characterized by transmission electron microscope and Fourier transform infrared. Moreover, the electrochemical properties of the synthesized nanocomposite can be controlled by adjusting the annealing temperature, which is definitely illustrated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectra. Electrochemical data have shown that the PEDOT/RuO₂·xH₂O nanocomposite annealed at 150 °C possesses the most favorable charge/discharge ability with a specific capacitance of 153.3 F g⁻¹ at a current density of 150 mA g⁻¹ and the high efficient utilization of PEDOT at various current densities. Furthermore, such composite has a less capacitance degradation of 23.8% after 1,000 continuous cycles. The improved electrochemical performance are mainly attributed to the large electroactive surface of nanocomposite and the existence of amorphous RuO₂·xH₂O particles as well as a synergistic effect of the polymer PEDOT and annealed RuO₂·xH₂O. Thus, the PEDOT/RuO₂·xH₂O nanocomposite annealed at 150 °C can act as a promising electroactive material for supercapacitor application.     

Speciation analysis of chromium in natural water samples by electrothermal atomic absorbance spectrometry after separation/preconcentration with nanometer-sized zirconium oxide immobilized on silica gel

Silica gel was prepared by the sol–gel method, modified with nanometer-sized zirconium oxide, and this material was characterized by X-ray diffraction. A micro-column packed with silica gel modified with nanometer zirconium oxide as sorbent has been developed for the quantitative separation and preconcentration of trace amounts of chromium(III) prior to their determination by electrothermal atomic absorption spectrometry. Total chromium was determined after the reduction of chromium(VI) to chromium(III) by 10% (m/v) of aqueous ascorbic acid as reducing reagent. The adsorption capacity for chromium(III) was found to be 2.36 mg g⁻¹. The detection limit for chromium(III) was 15 ng L⁻¹ with an enrichment factor of 100. The relative standard deviation was 3.2% (n = 7, c = 2.0 ng mL⁻¹).     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn⁴⁺掺杂的Co₃O₄复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn⁴⁺掺杂,Co₃O₄复合纳米纤维的电化学性能得到明显改善。当n_Co∶n_Mn=20∶2时,相应的复合纤维具有较大比表面积68 m²·g^-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g^-1的电流密度下,放电比电容量为585 F·g^-1,这比纯Co₃O₄纳米纤维的416 F·g^-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co₃O₄纳米纤维则是76.4%。     

A solid-contact Pb2+-selective polymeric membrane electrode with Nafion-doped poly(pyrrole) as ion-to-electron transducer

Conducting polymer poly(pyrrole) (PPy) doped with Nafion was successfully used as ion-to-electron transducer in the construction of a solid-contact Pb²⁺-selective polymeric membrane electrode. The Nafion dopant can effectively increase the capacitance of the conducting polymer and improve the mechanical robustness of the coating. The transducer layer, PPy-Nafion, characterized by cyclic voltammetry and electrochemical impedance spectroscopy, exhibits a sufficiently high bulk (redox) capacitance and fast ion and electron transport process. The new Pb²⁺-selective polymeric membrane electrode, based on PPy-Nafion film as solid contact, shows stable Nernstian characteristics in Pb(NO₃)₂ solution within the concentration range of 1.0 × 10⁻⁷–1.0 × 10⁻³ M, and the detection limit is 4.3 × 10⁻⁸ M. The potential stability of the electrode and the influence of the interfacial water layer were also evaluated by chronopotentiometry and potentiometric water layer test, respectively. The results show that the solid-contact Pb²⁺-selective electrode, based on PPy-Nafion film as ion-to-electron transducer, can effectively overcome the potential drift and reduce the water layer between the PPy-Nafion transducer layer and the ion-selective membrane.     

Tunable activity in electrochemical reduction of oxygen by gold–polyaniline porous nanocomposites

Oxygen electrochemical reduction on gold–polyaniline (Au–PANI) porous nanocomposite-modified glassy carbon electrode in basic media was described. The as-prepared Au–PANI porous nanocomposite showed superior tunable activity for electrochemical reduction of oxygen. The specific surface area of Au–PANI porous nanocomposites was evaluated to be about 11.3 m² g⁻¹ through a convenient voltammetric approach. Rotating ring-disk electrode experiments further demonstrated the number of electrons exchanged in oxygen reduction increased from 2e to 4e with increasing the trigger potential from 300, to 500, 700 mV. The tunable activity in electrochemical reduction of oxygen was achieved as a result of positive potential-induced formation and reduction of Au surface oxide. However, the tunable oxygen reduction reaction is fit for applying potential in a linear positive-going potential sweep. Irreversible ORR tunability was found after a more active surface formed at 700 mV. To optimize the applied potential window on these Au-based porous materials has potential applications such as in electrochemical sensing, fuel cells, or getting rid of the interference from the coexisted substances.     

Electrochemical study of spinel oxide systems with nominal compositions Ni1− x Cu x Co2O4 and NiCo2− y Cu y O4

Studies on the electrochemical behaviour of Ni_{1− x} Cu _x Co₂O₄ (x ≤ 0.75) and NiCo_{2− y} Cu _y O₄ (y ≤ 0.30) electrodes in 5 mol dm⁻³ KOH aqueous solutions are presented. The oxide layers have been prepared by thermal decomposition of aqueous nitrate solutions on nickel supports at 623 K. Powder samples were also prepared by thermal decomposition under the same conditions. The powder samples and the oxide layers were characterised by X-ray powder diffraction. The influence of the copper content on the voltammetric response of the electrodes and activity towards oxygen evolution reaction is analysed and correlated with the surface composition of the electrodes by means of X-ray photoelectron spectroscopy data. The analysis of the results reveals that the presence of Cu affects the electrode behaviour and its influence depends on which cation has been replaced. Received: 22 February 1999 / Accepted: 26 October 1999