Electrochemical dissolution of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> in acidic solutions

The cyclic voltammetry method was used to study the regularities of the electrochemical behavior of cobalt cobaltite in an acidic medium. It is shown that cathodic reduction of Co₃O₄ in the studied range of potentials of +1.0 to −0.8 V is a multistage process occurring according to the scheme:      

2-pyrrolidone - capped Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocrystals

Water-soluble Mn₃O₄ nanocrystals have been prepared through thermal decomposition in a high temperature boiling solvent, 2-pyrrolidone. The final product was characterized with XRD, SEM, TEM, FTIR and Zeta Potential measurements. Average crystallite size was calculated as ∼15 nm using XRD peak broadening. TEM analysis revealed spherical nanoparticles with an average diameter of 14±0.4 nm. FTIR analysis indicated that 2-pyrrolidone coordinates with the Mn₃O₄ nanocrystals only via O from the carbonyl group, thus confining their growth and protecting their surfaces from interaction with neighboring particles.      

Electrochemical properties of nano-crystalline LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> synthesized by polymer-pyrolysis method

LiNi_0.5Mn_1.5O₄ powders were prepared through polymer-pyrolysis method. XRD and TEM analysis indicated that the pure spinel structure was formed at around 450 °C due to the very homogeneous intermixing of cations at the atomic scale in the starting precursor in this method, while the well-defined octahedral crystals appeared at a relatively high calcination temperature of 900 °C with a uniform particle size of about 100 nm. When cycled between 3.5 and 4.9 V at a current density of 50 mA/g, the as prepared LiNi_0.5Mn_1.5O₄ delivered an initial discharge capacity of 112.9 mAh/g and demonstrated an excellent cyclability with 97.3% capacity retentive after 50 cycles.     

Electrochemical synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles in alkaline aqueous solutions containing complexing agents

Ultrafine magnetite particles are prepared through an electrochemical process, at room temperature, from an iron-based electrode immersed in an alkaline aqueous medium containing complexing compounds. XRD and chemical analysis indicate that the product is pure magnetite, Fe₃O₄. The size and morphology of the particles are studied by SEM. The magnetite nanoparticles present a magnetoresistance of almost 3%, at 300 K, under a magnetic field of 1 T. A reactive mechanism for the electrochemical process is proposed.     

Rational design of double-confined Mn<Subscript>2</Subscript>O<Subscript>3</Subscript>/S@Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocube cathodes for lithium-sulfur batteries

Due to the high specific capacities and environmental benignity, lithium-sulfur (Li-S) batteries have shown fascinating potential to replace the currently dominant Li-ion batteries to power portable electronics and electric vehicles. However, the shuttling effect caused by the dissolution of polysulfides seriously degrades their electrochemical performance. In this paper, Mn₂O₃ microcubes are fabricated to serve as the sulfur host, on top of which Al₂O₃ layers of 2 nm in thickness are deposited via atomic layer deposition (ALD) to form Mn₂O₃/S (MOS) @Al₂O₃ composite electrodes. The MOS@Al₂O₃ electrode delivers an excellent initial capacity of 1012.1 mAh g^?1 and a capacity retention of 78.6% after 200 cycles at 0.5 C, and its coulombic efficiency reaches nearly 99%, giving rise to much better performance than the neat MOS electrode. These findings demonstrate the double confinement effect of the composite electrode in that both the porous Mn₂O₃ structure and the atomic Al₂O₃ layer serve as the spacious host and the protection layer of sulfur active materials, respectively, for significantly improved electrochemical performance of the Li-S battery.     

Solid solutions in the MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Coexisting solid solutions with spinel and corundum structure were synthesized at 1773 K and two pressures, 1 bar and 25 kbar. Samples were analyzed by electron microprobe analysis and X-ray powder diffraction. Pressure and temperature were shown to affect the properties of the solid solutions in different ways. Pressure governs the composition of the defect spinel Mg_1−xAl₂O₄, and temperature changes the cation distribution between coexisting phases. This allows one to separate the effects of cation exchange and magnetic contribution to the heat capacity in thermodynamic modeling. The defect spinel itself can form only because γ-Al₂O₃ exists, polymorph with spinel structure.     

Electrochemical dissolution of magnetite in acid solutions

The present paper deals with the electrochemical behavior of magnetite microcrystals in an acid medium. A voltammetric method employing a carbon-paste electroactive electrode (CPEE) with an organic binder was used. It was found that the cathodic voltammograms, which were recorded at different scan rates, formed a set bounded in the space of i–E parameters by a generalizing voltammetric curve corresponding to the effective potential scan rate _eff. In other words, all curves are situated under one enveloping curve, just as the smaller dolls sit in the largest doll of a Russian doll. Reverse currents (a cathodic current in the anodic direction of the potential scan) were observed on the cyclic voltammogram. Forward and reverse currents obey the same laws and have one and the same generalizing curve, which could be taken as the magnetite characteristic.     

Thermodynamic,thermogravimetric and permittivity studies of hausmannite (Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>) in air

Some manganese oxides are considered hyperactive under microwave irradiation because of their extremely high heating rates in air. In order to further understand this hyperactivity, thermodynamic calculations, thermogravimetric analysis and both real and imaginary permittivity determinations were performed for hausmannite (Mn₃O₄) as a function of temperature in an air atmosphere. The thermodynamic results demonstrated reasonable agreement with the thermogravimetric analysis data. A comparison of the derivative thermogravimetric analysis data with the derivative of both the real and the imaginary permittivities confirmed that the extremely high values of the permittivities were due to the conversion of the hausmannite to bixbyite (Mn₂O₃). The microwave hyperactivity of the manganese oxides in air is explained in terms of the high permittivities of bixbyite.     

Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>/carbon nanotubes nanocomposites as improved anode materials for lithium-ion batteries

Mn₃O₄ and Mn₃O₄ (140)/CNTs have been investigated as high-capacity anode materials for lithium-ion batteries (LIBs) applications. Nanoparticle Mn₃O₄ samples were synthesized by hydrothermal method using Mn(Ac)₂ and NH₃·H₂O as the raw materials and characterized by XRD, TG, EA, TEM, and SEM. Its electrochemical performances, as anode materials, were evaluated by galvanostatic discharge-charge tests. The Mn₃O₄ (140)/CNTs displays outstanding electrochemical performances, such as high initial capacity (1942 mAh g^?1), stable cycling performance (1088 mAh g^?1 and coulombic efficiency remain at 97% after 60 cycles) and great rate performance (recover 823 mAh g^?1 when return to initial current density after 44 cycles). Compared to pure Mn₃O₄ (140), the improving electrochemical performances can be attributed to the existence of very conductive CNTs. The Mn₃O₄ (140)/CNTs with excellent electrochemical properties might find applications as highly effective materials in electromagnetism, catalysis, microelectronic devices, etc. The process should also offer an effective and facile method to fabricate many other nanosized metallic oxide/CNTs nanocomposites for low-cost, high-capacity, and environmentally benign materials for LIBs.     

Preparation and characterization of high specific surface area Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> from electrolytic manganese residue

Mn₃O₄ powders have been produced from Electrolytic Manganese Residue (EMR). After leaching of EMR in sulfuric acid, MnSO₄ solution containing various ions was obtained. Purifying the solution obtained and then adding aqueous alkali to the purified MnSO₄ solution, Mn(OH)₂ was prepared. Two methods were employed to produce Mn₃O₄. One way was oxidation of Mn(OH)₂ in aqueous phase under atmosphere pressure to obtain Mn₃O₄. The other way was roasting Mn(OH)₂ precursors in the range of 500°C to 700°C. The prepared samples were investigated by using several techniques including X-ray powder diffraction (XRD), Fourier Transformation Infra-Red (FTIR) spectra, and Brunauer-Emmett-Teller (BET) specific surface area instrument. Particle distribution and magnetic measurements were carried out on laser particle size analyzer, vibrating sample magnetometer (VSM). Through XRD, FTIR and determination of total Mn content (TMC), the products prepared were confirmed to be a single phase Mn₃O₄. BET specific surface areas can reach to 32 m² g⁻¹. The results indicated that products synthesized by aqueous solution oxidation method had higher specific surface areas and smaller particle size than those prepared by means of roasting. However the products prepared using the above two methods showed no obvious differences in magnetic property.      

Electrochemical oxidation and reduction of La<Subscript>4</Subscript>Ni<Subscript>3</Subscript>O<Subscript>10</Subscript> in alkaline media

In this work we used electrochemical polarization for oxidizing and reducing, in a controlled way, the Ruddlesden-Popper phase La₄Ni₃O₁₀. With a careful choice of electrochemical parameters, we were able to obtain samples of La₄Ni₃O_10± never obtained before. The oxygen stoichiometry can range between 9.78 (=–0.22) and 10.12 (=0.12). The oxidized phase, La₄Ni₃O_10.12, was obtained using a galvanostatic mode (I=20 A) and the reduced phase, La₄Ni₃O_9.78, using potentiostatic conditions (E=0.46 V). The evolution of the electrical conductivity has been studied as a function of .     

Comparison of the Solubility of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> in High Temperature Water

As the solubility is a direct measure of stability, this study compares the solubilities of ZnFe₂O₄, Fe₃O₄ and Fe₂O₃ in high temperature water. Through literature analysis and formula derivation, it is shown that it is reasonable to assume ZnFe₂O₄ and Fe(OH)₃ coexist when ZnFe₂O₄ is dissolved in water. Results indicated that the solubility of ZnFe₂O₄ is much lower than that of Fe₂O₃ or Fe₃O₄. The low solubility of ZnFe₂O₄ indicates that it is more protectively stable as an anticorrosion phase. Moreover, the gap between the solubility of ZnFe₂O₄ and that of Fe₃O₄ or Fe₂O₃ was enlarged with an increase of temperature. This means that ZnFe₂O₄ is more protective at higher temperatures. Further analysis indicated that with the increase of temperature, the solubility of ZnFe₂O₄ changed little while those of Fe₂O₃ or Fe₃O₄ changed a lot. Little change of the solubility of ZnFe₂O₄ with increase of temperature showed that ZnFe₂O₄ is stable. The very low and constant solubility of ZnFe₂O₄ suggests that it is more protective than Fe₂O₃ and Fe₃O₄, especially in water at higher temperature.     

Preparation and electrochemical performance of nano-structured Li<Subscript>2</Subscript>Mn<Subscript>4</Subscript>O<Subscript>9</Subscript> for supercapacitor

Nano-structured spinel Li₂Mn₄O₉ powder was prepared via a combustion method with hydrated lithium acetate (LiAc·2H₂O), manganese acetate (MnAc₂·4H₂O), and oxalic acid (C₂H₂O₄·2H₂O) as raw materials, followed by calcination of the precursor at 300 °C. The sample was characterized by X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopy techniques. Electrochemical performance of the nano-Li₂Mn₄O₉ material was studied using cyclic voltammetry, ac impedance, and galvanostatic charge/discharge methods in 2 mol L⁻¹ LiNO₃ aqueous electrolyte. The results indicated that the nano-Li₂Mn₄O₉ material exhibited excellent electrochemical performance in terms of specific capacity, cycle life, and charge/discharge stability, as evidenced by the charge/discharge results. For example, specific capacitance of the single Li₂Mn₄O₉ electrode reached 407 F g⁻¹ at the scan rates of 5 mV s⁻¹. The capacitor, which is composed of activated carbon negative electrode and Li₂Mn₄O₉ positive electrode, also exhibits an excellent cycling performance in potential range of 0–1.6 V and keeps over 98% of the maximum capacitance even after 4,000 cycles.     

Glass formation in the CaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> and SrO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> systems

A physicochemical study of glasses based on the MO-Bi₂O₃-B₂O₃ and SrO-Bi₂O₃-B₂O₃ systems was performed. Glass formation regions were found. The structural and optical properties, as well as the thermal behavior of the glasses, were studied.     

Mechanism of the Enhanced Electrochemical Properties of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> Cathode Materials by a Pre-Sintering Process

α-NaFeO₂ layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials were synthesized by mechanical milling accompanied by the solid phase sintering. The sample exhibited a good crystallinity and layered structure while sintered at 900°C, which can be further improved by adding a pre-sintering process at 500°C before high temperature sintering. The sample with a pre-sintering process presents an average particle size about 0.6 μm, and a hexagonal crystalline structure. The optimally fabricated sample showed a first charge capacity of 210.2 mA h/g, discharge capacity of 171.2 mA h/g with a current rate of 0.2 C within the voltage range of 2.7~4.5 V. With increasing the current rate to 1 C, the charge–discharge capacity faded quickly during the cycling process, which can be partially recovered while operated at a low current rate. However, the capacity fading at a current rate of 2 C was largely irreversible. The evolution of the surface chemical states was evaluated using X-ray photoelectron spectroscopy on the charged and discharged samples to understand the high rate capacity fading.     

Changes in the heat capacity of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> solid solutions near the point of antiferromagnetic phase transition in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>

Al₂O₃-Cr₂O₃ solid solutions with 0, 4, 7, 10 and 20 mol% of corundum were synthesized using a high-pressure/high-temperature apparatus and characterized by X-ray powder diffraction. Calorimetric measurements were carried out using DSC-111 (Setaram). Heat capacity was measured by the enthalpy method in a temperature range of 260–340 K, near magnetic phase transition in pure Cr₂O₃ (305 K). Magnetic contribution into the heat capacity was derived and found to change irregularly with the composition.     

Promoted porous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for ammonia decomposition

Transition metal catalysts have been considerably used for NH₃ decomposition because of the potential application in CO_x-free H₂ generation for fuel cells. However, most transition metal catalysts prepared via traditional synthetic approaches performed the inferior stability due to the agglomeration of active components. Here, we adopted an efficient method, aerosol-assisted self-assembly approach (AASA), to prepare the optimized cobalt-alumina (Co₃O₄-Al₂O₃) catalysts. The Co₃O₄-Al₂O₃ catalysts exhibited excellent catalytic performance in the NH3 decomposition reaction, which can reach 100% conversion at 600 °C and maintain stable for 72 h at a gaseous hourly space velocity (GHSV) of 18000 cm³ g_cat^?1 h^?1. The catalysts were characterized by various techniques including transmission electron microscope (TEM), scanning electron microscope (SEM), nitrogen sorption, temperature-programmed reduction by hydrogen (H₂-TPR), ex-situ/in-situ Raman and ex-situ/in-situ X-ray diffraction (XRD) to obtain the information about the structure and property of the catalysts. H₂-TPR and in-situ XRD results show that there is strong interaction between the cobalt and alumina species, which influences the redox properties of the catalysts. It is found that even a low content of alumina (10 at%) is able to stabilize the catalysts due to the adequate dispersion and rational interaction between different components, which ensures the high activity and superior stability of the cobalt-alumina catalysts.     

Co-precipitation spray-drying synthesis and electrochemical performance of stabilized LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode materials

In this paper, the LiNi_0.5Mn_1.5O₄ cathode materials of lithium-ion batteries are synthesized by a co-precipitation spray-drying and calcining process. The use of a spray-drying process to form particles, followed by a calcination treatment at the optimized temperature of 750 °C to produce spherical LiNi_0.5Mn_1.5O₄ particles with a cubic crystal structure, a specific surface area of 60.1 m² g^?1, a tap density of 1.15 g mL^?1, and a specific capacity of 132.9 mAh g^?1 at 0.1 C. The carbon nanofragment (CNF) additives, introduced into the spheres during the co-precipitation spray-drying period, greatly enhance the rate performance and cycling stability of LiNi_0.5Mn_1.5O₄. The sample with 1.0 wt.% CNF calcined at 750 °C exhibits a maximum capacity of 131.7 mAh g^?1 at 0.5 C and a capacity retention of 98.9% after 100 cycles. In addition, compared to the LiNi_0.5Mn_1.5O₄ material without CNF, the LiNi_0.5Mn_1.5O₄ with CNF demonstrates a high-rate capacity retention that increases from 69.1% to 95.2% after 100 cycles at 10 C, indicating an excellent rate capability. The usage of CNF and the synthetic method provide a promising choice for the synthesis of a stabilized LiNi_0.5Mn_1.5O₄ cathode material.

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Graphical Abstract Micro/nanostructured LiNi_0.5Mn_0.5O₄ cathode materials with enhanced electrochemical performances for high voltage lithium-ion batteries are synthesized by a co-precipitation spray-drying and calcining routine and using carbon nanofragments (CNFs) as additive.

     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

High-Temperature X-Ray Diffraction Investigation of the Decomposition Process in Manganese-Gallium Spinel Mn<Subscript>1.5</Subscript>Ga<Subscript>1.5</Subscript>O<Subscript>4</Subscript>

The stability of spinel-type mixed Mn_1.5Ga_1.5O₄ oxide prepared in an inert medium (1000 °C, Ar) is studied by thermogravimetry and high-temperature X-ray diffraction in air in a wide temperature range 30–1000 °C. On heating, reversible decomposition processes of initial spinel are observed. From 30 °C to 600 °C oxygen atoms attach to the surface layer of initial Mn_1.5Ga_1.5O₄ spinel to form a new phase distinct from parent oxide by the oxygen stoichiometry (cation vacancies are formed). The product of decomposition is two oxides: Mn_1.5Ga_1.5O₄ and Mn_1.5–xGa_1.5–x[·]_xO₄. On the contrary, above 600 °C a loss of oxygen occurs, the concentration of cation vacancies decreases in Mn_1.5–xGa_1.5–x[·]_xO₄, and the reverse process of single phase oxide crystallization takes place. At 1000 °C the spinel phase forms again whose composition is similar to that of the initial parent phase Mn_1.5Ga_1.5O₄. On cooling the decomposition of this phase is again observed due to oxygen attachment.