Preparation and properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods as supercapacitor material

Co₃O₄ nanorods have been successfully synthesized by thermal decomposition of the precursor prepared via a facile and efficient microwave-assisted hydrothermal method, using cetyltrimethylammonium bromide (CTAB) with ordered chain structures as soft template for the first time. The obtained Co₃O₄ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements. The results demonstrate that the as-synthesized nanorods are single crystalline with an average diameter of about 20 to 50 nm and length up to several micrometers. Preliminary electrochemical studies, including cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) measurements, are carried out in 6 M KOH electrolyte. Specific capacitance of 456 F g⁻¹ for a single electrode could be achieved even after 500 cycles, suggesting its potential application in electrochemical capacitors. This promising method could provide a universal green chemistry approach to synthesize other low-cost and environmentally friendly transition metal hydroxide or oxide.     

Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Improved performances of mechanical-activated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/MWNTs cathode for aqueous rechargeable lithium batteries

LiMn₂O₄/multi-walled carbon nanotubes (MWNTs) composite was synthesized by mechanical activation reaction followed by a heat-treatment (500 °C). The LiMn₂O₄ and LiMn₂O₄/MWNTs as cathodes were investigated in 1 M Li₂SO₄ by cyclic voltammetry (CV), galvanostatic charge/discharge (GC), and electrochemical impedance spectroscopy (EIS). The LiMn₂O₄/MWNTs cathode delivered higher discharge capacity (117 mAh g⁻¹) than LiMn₂O₄ (84.6 mAh g⁻¹). Furthermore, the results from EIS showed that LiMn₂O₄/MWNTs had a faster kinetic process for lithium ion intercalation/de-intercalation than LiMn₂O₄. Besides, LiMn₂O₄/MWNTs had better cycling stability and rate capability than LiMn₂O₄, which was confirmed by GC testing. SEM images showed that a three-dimensional network structure was formed during the mechanical activation, giving a decrease of particle size.     

Facile Solvothermal Synthesis Ni(OH)<Subscript>2</Subscript> Nanostructure for Electrochemical Capacitors

Nickel hydroxide nanosheets were successfully synthesized by facile solvothermal method without any template. The structure and morphology of the as-prepared sample were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. The observations revealed the formation of hexagonal phase β-Ni(OH)₂ nanosheets with an average diameter of about 100–120 nm. Electrochemical studies were carried out using cyclic voltammetry and galvanostatic charge–discharge tests, respectively. A maximum specific capacitance of 2,342 F g⁻¹, which is the highest reported for a β-Ni(OH)₂ electrode, could be achieved in 6 mol L⁻¹ KOH electrolyte within the potential range of 0–0.50 V (vs. SCE) for the obtained β-Ni(OH)₂ electrode at 0.4 A g⁻¹, suggesting its potential application in the electrode material for electrochemical capacitors.     

Electrochemical Properties of a 4.7 V-Class LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> Positive Electrode Material for High Power Li-Ion Battery

The LiNi_0.5Mn_1.5O₄ cathode material for high power lithium-ion battery is successfully synthesized by sol–gel method. The structure, the morphology and the electrochemical characteristics of the compound are studied by X-ray diffraction (XRD), a field emission scanning electron microscope (FE-SEM), cyclic voltammogram (CV) and charge–discharge techniques, respectively. The results indicate that LiNi_0.5Mn_1.5O₄ sample has cubic spinel structure and its particles crystallized well with submicro size. There are a higher voltage plateau around 4.7 V and a lower voltage plateau above 4 V at 3.3–5.0 V in the charge–discharge curves of LiNi_0.5Mn_1.5O₄, corresponding to two redox peaks of Ni²⁺/Ni⁴⁺ and Mn³⁺/Mn⁴⁺ of its CV respectively. The LiNi_0.5Mn_1.5O₄ with ordered Fd3m space group has 150.57 mAh g⁻¹ initial charge capacity and 139.57 mAh g⁻¹ initial discharge capacity, showing excellent electrochemical performance. A short arc at more high frequency zone from 4.4 V potential emerges in electrochemical impedance spectroscopy (EIS), attributing to oxidative decomposition of the electrolyte at high voltage. The equivalent circuit selected could fit the EIS experiment data very well.     

The enhancement effect of phosphomolybdic acid (H<Subscript>3</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>) on Pd/C catalyst for the electroreduction of hydrogen peroxide

A Pd/C electrode modified by H₃PMo₁₂O₄₀ was prepared and its catalytic performance for H₂O₂ electroreduction in acidic medium was investigated by cyclic voltammograms. Pd nanoparticles supported on Vulcan XC-72 carbon were prepared by chemical reduction of PdCl₂ in aqueous solution using NaBH₄ as the reducing agent. X-ray diffraction analysis indicated that the particle size of Pd is around 9.7 nm. The modified electrode was prepared by cyclic voltammograms in H₂SO₄ solution containing H₃PMo₁₂O₄₀. The results showed that H₃PMo₁₂O₄₀ can efficiently enhance the electrocatalytic activity for H₂O₂ electroreduction on Pd/C. The effect of H₃PMo₁₂O₄₀ content on the electrocatalytic activity of the catalyst was also investigated by CV. The best results appeared at the concentration of H₃PMo₁₂O₄₀ = 0.5 mmol L⁻¹.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Cathodic behaviour of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel electrodes in alkaline medium

Spinel type CoFe₂O₄ thin films have been prepared, on stainless steel supports, by thermal decomposition of aqueous solutions of mixed cobalt and iron nitrates in 1:2 molar ratio at 400 °C. The electrochemical behaviour of the CoFe₂O₄/1 M KOH interface was investigated by cyclic voltammetry, chronoamperometry and impedance techniques. The studies allowed finding out the redox reactions occurring at the oxide surface. The results were compared with colloidal electrodes prepared by alkaline precipitation of Fe(II) or Fe(III) hydrous oxi-hydroxides on platinum electrodes. In addition, it has been concluded that the processes are diffusion-controlled and the diffusion of the hydroxide ion, through the oxide, acts as the rate-determining step. The diffusion coefficient of OH⁻ through the oxide film was determined using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques.     

Improvement in dielectric and mechanical performance of CaCu<Subscript>3.1</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12.1</Subscript> by addition of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The properties of CaCu_3.1Ti₄O_12.1 [CC3.1TO] ceramics with the addition of Al₂O₃ nanoparticles, prepared via a solid-state reaction technique, were investigated. The nanoparticle additive was found to inhibit grain growth with the average grain size decreasing from approximately 7.5 μm for CC3.1TO to approximately 2.0 μm for the unmodified samples, while the Knoop hardness value was found to improve with a maximum value of 9.8 GPa for the 1 vol.% Al₂O₃ sample. A very high dielectric constant > 60,000 with a low loss tangent (approximately 0.09) was observed for the 0.5 vol.% Al₂O₃ sample at 1 kHz and at room temperature. These data suggest that nanocomposites have a great potential for dielectric applications.     

Influence of Cobalt Doping on the Physical Properties of Zn<Subscript>0.9</Subscript>Cd<Subscript>0.1</Subscript>S Nanoparticles

Zn_0.9Cd_0.1S nanoparticles doped with 0.005–0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn_0.9Cd_0.1S sphalerite phase. For low cobalt concentration (≤0.05 M) particle size, d _XRD is ~3.5 nm, while for high cobalt concentration (>0.05 M) particle size decreases abruptly (~2 nm) as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm) irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie–Weiss temperature of −75 K with antiferromagnetic coupling was obtained for the high cobalt concentration.     

Hexavalent chromium synthesized polyaniline nanostructures: Magnetoresistance and electrochemical energy storage behaviors

In this work, the oxidant Cr(VI) dose was observed to have influenced the polyaniline (PANI) nanostructures as well as the crystallization structure. The temperature dependent resistivity study revealed a quasi 3-dimensional variable range hopping (VRH) electrical conduction mechanism. The permittivity was found to be affected by the PANI nanostructures. The observed positive MR at room temperature in the synthesized PANI samples was analyzed by the wave-function shrinkage model. The electrochemical energy storage was investigated using the cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. The highest gravimetric capacitance of 298.5 F g⁻¹ was obtained in the prepared PANI sample using 3 mmol K₂Cr₂O₇ derived from the CV at a scan rate of 5 mV s⁻¹ and the maximum value of gravimetric capacitance of 330.2 F g⁻¹ was achieved in the galvanostatic charge–discharge measurements at a current density of 0.5 A g⁻¹. After applying an external magnetic field, the capacitance decreased due to the observed positive magnetoresistance phenomenon. The cyclic stability studies revealed that the synthesized PANI samples exhibited good durability and retained around 80% of the capacitance even after 1000 charge–discharge galvanostatic cycles.     

Voltammetric behavior and the determination of quercetin at a flowerlike Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles modified glassy carbon electrode

Flowerlike Co₃O₄ nanoparticles were used as a modifier on the glassy carbon electrode to fabricate a quercetin (Qu) sensor. The morphology and crystallinity of the prepared Co₃O₄ material were investigated by scanning electron microscopy and X-ray diffraction. Electrochemical behavior of Qu at the sensor was studied by cyclic voltammetry and semi-derivative voltammetry. Results suggested that the modified electrode exhibited a strong electrocatalytic activity toward the redox of Qu. The electron transfer coefficient (α), the number of electron transfer (n), and the diffusion coefficient (D) of Qu at the sensor were calculated. Under the optimum conditions, the catalytic peak currents of Qu were linearly dependent on the concentrations of Qu in the range from 5.0 × 10⁻⁷ to 3.3 × 10⁻⁴ M, with a detection limit of 1.0 × 10⁻⁷ M. This proposed method was successfully applied to determine the quercetin concentration in Ginkgo leaf tablet and human urine samples.     

Enhanced electrochemical performance of FeS<Subscript>2</Subscript> synthesized by hydrothermal method for lithium ion batteries

Iron disulfide (FeS₂) powders were successfully synthesized by hydrothermal method. Cetyltrimethylammonium bromide (CTAB) had a great influence on the morphology, particle size, and electrochemical performance of the FeS₂ powders. The as-synthesized FeS₂ particles with CTAB had diameters of 2–4 μm and showed a sphere-like structure with sawtooth, while the counterpart prepared without CTAB exhibited irregular morphology with diameters in the range of 0.1–0.4 μm. As anode materials for Li-ion batteries, their electrochemical performances were investigated by galvanostatic charge–discharge test and electrochemical impedance spectrum. The FeS₂ powder synthesized with CTAB can sustain 459 and 413 mAh g⁻¹ at 89 and 445 mA g⁻¹ after 35 cycles, respectively, much higher than those prepared without CTAB (411 and 316 mAh g⁻¹). The enhanced rate capability and cycling stability were attributed to the less-hindered surface layer and better electrical contact from the sawtooth-like surface and micro-sized sphere morphology, which led to enhanced process kinetics.     

NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Nanoparticles Stabilized by Porous Silica Shells

Abstract  

NiFe₂O₄ nanoparticles stabilized by porous silica shells (NiFe₂O₄@SiO₂) were prepared using a one-pot synthesis and characterized for their physical and chemical stability in severe environments, representative of those encountered in industrial catalytic reactors. The SiO₂ shell is porous, allowing transport of gases to and from the metal core. The shell also stabilizes NiFe₂O₄ at the nanoparticle surface: NiFe₂O₄@SiO₂ annealed at temperatures through 973 K displays evidence of surface Ni, as verified by H₂ TPD analyses. At 1,173 K, hematite forms at the surface of the metallic cores of the NiFe₂O₄@SiO₂ nanoparticles and surface Ni is no longer observed. Without the silica shell, however, even mild reduction (at 773 K) can draw Fe to the surface and eliminate surface Ni sites.     

Photoelectrochemical characterization of the synthetic crednerite CuMnO<Subscript>2</Subscript>

High quality crednerite CuMnO₂ was prepared by solid state reaction at 950 °C under argon flow. The oxide crystallizes in a monoclinically distorted delafossite structure associated to the static Jahn–Teller (J–T) effect of Mn³⁺ ion. Thermal analysis showed that it converts reversibly to spinel Cu _x Mn_3−x O₄ at ~420 °C in air and further heating reform the crednerite above 940 °C. CuMnO₂ is p-type, narrow semiconductor band gap with a direct optical gap of 1.31 eV. It exhibits a long-term chemical stability in basic medium (KOH 0.5 M), the semi logarithmic plot gave an exchange current density of 0.2 μA cm⁻² and a corrosion potential of ~−0.1 V_SCE. The electrochemical oxygen insertion/desinsertion is evidenced from the intensity–potential characteristics. The flat band potential (V _fb = −0.26 V_SCE) and the holes density (N _A  = 5.12 × 10¹⁸ cm⁻³) were determined, respectively, by extrapolating the curve C ⁻² versus the potential to the intersection with C ⁻²  = 0 and from the slope of the Mott–Schottky plot. From photoelectrochemical measurements, the valence band formed from Cu-3d wave function is positioned at 5.24 ± 0.02 eV below vacuum. The Nyquist representation shows straight line in the high frequency range with an angle of 65° ascribed to Warburg impedance originating from oxygen intercalation and compatible with a system under mass transfer control. The electrochemical junction is modeled by an equivalent electrical circuit thanks to the Randles model.     

A study of the lithium intercalation into nanoparticles of LiCoO<Subscript>2</Subscript> from an aqueous solution

Nanoparticles of lithium cobalt oxide (LiCoO₂) were synthesized by means of a citrate sol–gel combustion route. The particles were characterized by scanning and transmission electron microscopies (SEM and TEM), energy-dispersive X-ray spectroscopy, and X-ray diffraction (XRD) measurements. Near spherical nanoparticles of around 100 nm were observed in SEM and TEM micrographs. XRD data indicated that the as-prepared nanoparticles presented pure phase of LiCoO₂ with R-3m symmetry. The kinetics of electrochemical intercalation of lithium into the nanoparticles were investigated by means of cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS) with special emphasis on the application potential as cathode material for aqueous rechargeable lithium batteries. CV studies of the nanoparticles at slow scan rate of 0.1 mV s⁻¹ between 600 and 820 mV versus Ag/AgCl, demonstrated that the nanoparticles represented well-defined reversible peaks. The non-linear chemical diffusion of lithium into the nanoparticles was explored by EIS. In this regards, the results were discussed based on an equivalent circuit, distinguishing the kinetic properties of lithium intercalation. The kinetic parameters of lithium intercalation were obtained using the equivalent circuit, which were in good agreement with the experimental results. The changes of kinetic parameters of lithium intercalation with potential were also discussed in detail.     

Determination of hydrogenation ability and exchange current of H<Subscript>2</Subscript>O/H<Subscript>2</Subscript> system on hydrogen-absorbing metal alloys

A detailed analysis of potential versus time measurements at galvanostatic charge/discharge conditions (external current change from −1 to +1 mA cm⁻²) for two La–Ni alloys in Ar-saturated 0.1 M KOH solution is presented. It is shown that passivation of the electrodes does not affect the potential jump as a result of current switching over. The value of potential jump allows to calculate the exchange current density for H₂O/H₂ system on the tested material. Anodic potential of the hydrogenated electrode (at i _a = const) linearly increases with logarithm of time which allows to evaluate precisely time necessary for oxidation of hydrogen absorbed during cathodic charging. The method described enables to determine effectiveness of hydrogen absorption by materials applied for negative electrodes of NiMH batteries.     

Effect of HCl Concentration on the Dispersity of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles

In this paper, monodisperse 6 nm-sized Fe₃O₄ nanoparticles with spinel crystalline structure were synthesized via a co-precipitation method. The effect of HCl concentrations on Fe₃O₄ samples was investigated by TEM, VSM and UV–vis. HCl-modified Fe₃O₄ nanoparticles solution was a stable, clear, transparent cationic colloid. The results showed that HCl had a great influence on the dispersity of Fe₃O₄ nanoparticles and almost no influence on the materials magnetism.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Comparative study of the preparation and electrochemical performance of LiNi<Subscript>1</Subscript><Subscript>/2</Subscript>Mn<Subscript>1/2</Subscript>O<Subscript>2</Subscript> electrode material for rechargeable lithium batteries

Positive electrode material LiNi_1/2Mn_1/2O₂ was synthesized via the carbonate co-precipitation method and the hydroxide precipitation route to study the effects of the precursor on its structural and electrochemical properties. The results of X-ray diffraction and Rietveld refinement show that the carbonate precursor of Ni²⁺ and Mn²⁺ exhibits one phase at a pH of 8.5, while the hydroxide deposit separates into Ni(OH)₂ and Mn(OH)₂ phases under the same experimental conditions. LiNi_1/2Mn_1/2O₂ material prepared from the hydroxide precursor shows 8.9% Li/Ni exchange and a large capacity loss of 11.3% in the first 10 cycles. By contrast, more uniform distribution of transition metal ions and stable Mn²⁺ in the carbonate precursor contribute to only 7.8% Li/Ni disorder in the obtained LiNi_1/2Mn_1/2O₂, which delivers a reversible capacity of about 182 mAh g⁻¹ at a current rate of 14 mA g⁻¹ between 2.5 and 4.8 V.