Electrode reactions of manganese oxides for secondary lithium batteries

Nanorods of MnO₂, Mn₃O₄, Mn₂O₃ and MnO are synthesized by hydrothermal reactions and subsequent annealing. It is shown that though different oxides experience distinct phase transition processes in the initial discharge, metallic Mn and Li₂O are the end products of discharge, while MnO is the end product of recharge for all these oxides between 0.0 and 3.0 V vs. Li⁺/Li. Of these 4 manganese oxides, MnO is believed the most promising anode material for lithium ion batteries while MnO₂ is the most promising cathode material for secondary lithium batteries.     

Identification of oxidation states of metal oxides by MALDI-TOF MS

For the detection of inorganic species, we have developed chemical reaction laser desorption ionization mass spectrometry, and applied it to the analysis of metal oxides in different oxidation states. Metal oxide species insoluble in common organic solvents were finely grounded in a mortar and suspended in a solvent. The turbid suspension was placed on a sample holder on which a suitable chelating reagent had been previously spotted in a similar manner for sample preparation employed in the matrix-assisted laser desorption mass spectrometry (MALDI-MS). By using this method, the mass spectra of manganese (II and IV) oxides (MnO and MnO₂), cobalt (II and III) oxides (CoO and Co₂O₃), and chromium (III and VI) oxides (Cr₂O₃ and CrO₃) were successfully obtained. By adjusting the experimental conditions, such as ionization modes and chelating reagents, the non-identical mass spectra were obtained for the elements in the different oxidation state. Thus, the oxidation states could be identified clearly.     

Activity—composition relations of solid solutions and stabilities of manganese and nickel titanates at 1250°C as derived from equilibria in the systems MnOCoOTiO2 and MnONiOTiO2

Equilibria between a metal phase (either cobalt or nickel), a gas phase of known oxygen pressures, and pairs of solid-solution phases in the systems MnOCoOTiO₂ and MnONiO₂ are used to calculate activity—composition relations in the solid-solution series Mn₂TiO₄Co₂TiO₄, MnTiO₃CoTiO₃, MnTi₂O₅CoTi₂O₅, Mn₂TiO₄Ni₂TiO₄ and MnTiO₃NiTiO₃, and free energies of formation of the manganese titanates Mn₂TiO₄, MnTiO₃ and MnTi₂O₅ and of nickel orthotitanate, Ni₂TiO₄.     

Simple baths for the deposition of nickel oxides

In the present investigation new baths have been adopted for the anodic deposition of different nickel oxides. The deposition of the different oxides was carried out from their metal salt solutions in the presence of a complexing agent. The following oxides were obtained: NiO₂ from nickel chloride in the presence of ammonium chloride and sodium fluoride; Ni₂O₃ from nickel sulphate in the presence of ammonium chloride and citric acid; Ni₃O₄ from nickel chloride in the presence of sodium hydroxide, formaldehyde and potassium chloride, and finally NiO from nickel chloride in the presence of sodium carbonate, sodium chloride and ethanol.     

Thermal behaviour of cobalt oxides doped with ZrO2 and ThO2 and the possible cubic phase stabilization of zirconia

The effects of doping cobalt oxides with different amounts of ZrO₂ and ThO₂ (1.5–9 mol%) on the thermal stability of Co₃O₄ and the re-oxidation of CoO by O₂ to Co₃O₄ were investigated. The techniques employed were DTA, with a controlled rate of heating and cooling, X-ray diffraction, and IR spectrometry.The results obtained by DTA revealed that the addition of both Th⁴⁺ and Zr⁴⁺ (up to 6 mol%) exerted no appreciable effect on the thermal stability of Co₃O₄. Increasing the amount of the dopant ions to 9% resulted in no further change in the thermal stability of Co₃O₄ in the case of Th⁴⁺, and an increase of 16% in case of Zr⁴⁺-doping. However, ThO₂-doping of cobalt oxide was accompanied by an enhancement in the reactivity of CoO towards re-oxidation by O₂ to Co₃O₄ to an extent proportional to the amount of dopant oxide.The X-ray investigation of ZrO₂-doped cobalt oxides calcined in air at 1000°C revealed the presence of highly crystalline and stable zirconia in the cubic form. Such a stable phase could not be obtained at temperatures below 2370°C in the absence of stabilizing agents.X-ray and IR investigations of different solids showed the presence of free thoria and zirconia together with new thorium—cobalt and zirconium—cobalt compounds. However, the slow cooling of Zr-treated cobalt oxides from 1000°C to room temperature led to the decomposition of the newly formed compound. The d-spacings and absorption bands of the newly formed compounds were determined.     

Effect of the oxidation state of manganese in the manganese oxides used in the synthesis of Mn-substituted cordierite on the properties of the product

Catalysts based on Mn-substituted cordierite 2MnO · 2Al₂O₃ · 5SiO₂ have been synthesized using different manganese oxides (MnO, Mn₂O₃, and MnO₂) at a calcination temperature of 1100°C. The catalysts differ in their physicochemical properties, namely, phase composition (cordierite content and crystallinity), manganese oxide distribution and dispersion, texture, and activity in high-temperature ammonia oxidation. The synthesis involving MnO yields Mn-substituted cordierite with a defective structure, because greater part of the manganese cations is not incorporated in this structure and is encapsulated and the surface contains a small amount of manganese oxides. This catalyst shows the lowest ammonia oxidation activity. The catalysts prepared using Mn₂O₃ or MnO₂ are well-crystallized Mn-substituted cordierite whose surface contains different amounts of manganese oxides differing in their particle size. They ensure a high nitrogen oxides yield in a wide temperature range. The product yield increases with an increasing surface concentration of Mn³⁺ cations. The highest NO_x yield (about 76% at 800–850°C) is observed for the MnO₂-based catalyst, whose surface contains the largest amount of manganese oxides.     

Correlation between structure and catalytic activity of manganese oxides in liquid-phase oxidation of 1-octene

We have studied the correlation between the crystal structure and the catalytic activity of manganese oxides MnO, MnO₂, Mn₃O₄, and Mn₂O₃ in liquid-phase oxidation of 1-octene by molecular oxygen. The catalytic activity decreases in the series of oxides with octahedral coordination environment for the manganese atoms MnO−Mn₂O₃−MnO₂. The oxide Mn₃O₄ (with mixed tetrahedral and octahedral environment for the Mn atoms) catalyzes the process according to a different mechanism. L'vov Polytechnic State University, 12 S. Bandery ul., L'vov-13 290646, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 5, pp. 324–327, September–October, 1998.     

Application of Differential Scanning Calorimetry to the Reduction of Several Manganese Oxides

The aim of this work was to study the thermal transitions of several manganese oxides (MnO, MnOOH, Mn₂O₃, Mn₃O₄ and MnO₂) under reducing conditions. Differential scanning calorimetry (DSC) was used to analyse the transitions of some oxides into others. A comparison of the behavior of the synthetic samples with that of a natural manganese dioxide demonstrated that DSC is a quick tool for the distinction of natural manganese dioxide from synthetic γ-MnO₂ from other manganese oxides. This revised version was published online in July 2006 with corrections to the Cover Date.     

Transformations of manganese oxides under different thermal conditions

Thermal decomposition of various synthetic manganese oxides (MnO, Mn₃O₄, Mn₂O₃, MnOOH) and a natural manganese dioxide (MnO₂) from Gabon was studied with the help of termogravimetry in inert, oxidizing and reducing atmospheres. The compounds were characterized by XRD and electrochemical activity was tested by cyclic voltammetry using a carbon paste electrode. The natural manganese dioxide showed the best oxidizing and reducing capacity, confirmed by the lower temperatures of the transitions, the extent of the reactions and electrochemical performance in cyclic voltammograms.     

Sur la thermogravimétrie des précipités analytiques: Dosage du manganèse

The pyrolysis curves given by the precipitates used in the determination of manganese have been studied. The peroxide MnO₂, rnanganous acid H₂MnO₃ and manganic oxide Mn₂O₃, have not been considered. Manganous oxide, MnO, is stable at relatively high temperatures. For the automatie determination, only the steps shown at low temperatures by the sulphate, the oxalate, tlio oxinate and the anthranilate are reeommended. According to the determination in question, the basic salt begins to form at various temperatures between 456° and 1000°.     

Studies on the formation of manganese molybdate

The reaction of MoO₃ with various oxides of manganese (MnO, Mn₂O₃, Mn₃O₄ and MnO₂) and with MnCO₃ has been studied in air and nitrogen atmospheres employing DTA, TG and X-ray diffraction methods, with a view to elucidating the conditions for the formation of MnMoO₄. Thermal decomposition of MnCO₃ has also been studied in air and nitrogen atmospheres to help understand the mechanism of the reaction between MnCO₃ and MoO₃. The studies reveal that, whereas MnO, Mn₂O₃ and MnO₂ react smoothly with MoO₃ to form MnMoO₄, Mn₃O₄ does not react with MoO₃ in the temperature range investigated (48O–6OO°C). An equimolar mixture of MnCO₃ and MoO₃ reacts in air to yield MnMoO₄, while only a mixture of Mn₃O₄ and MoO₃ remains as final product when the same reaction is carried out in nitrogen. Marker studies reveal that manganese ions are the main diffusing species in the reaction between MoO₃ and manganese oxides that result in MnMoO₄.     

Synthesis of cobalt-containing nanoparticles by cobalt formate thermolysis in hydrocarbon oil without stabilizing ligands

A simple and available method is proposed for the synthesis of cobalt-containing nanoparticles. This method comprises cobalt formate thermolysis in hydrocarbon oil without extra stabilizing ligands. The size, composition, and structure of the nanoparticles are determined by transmission electron microscopy, X-ray powder diffraction, and electron diffraction. The average particle size is 10–14 nm. The major components are cobalt oxides CoO and Co₃O₄. Apart from these oxides, the particles contain minor metallic cobalt.     

CoN1O2 Single-Atom Catalyst for Efficient Peroxymonosulfate Activation and Selective Cobalt(IV)=O Generation

High-valent metal-oxo (HVMO) species are powerful non-radical reactive species that enhance advanced oxidation processes (AOPs) due to their long half-lives and high selectivity towards recalcitrant water pollutants with electron-donating groups. However, high-valent cobalt-oxo (Co^IV=O) generation is challenging in peroxymonosulfate (PMS)-based AOPs because the high 3d-orbital occupancy of cobalt would disfavor its binding with a terminal oxygen ligand. Herein, we propose a strategy to construct isolated Co sites with unique N₁O₂ coordination on the Mn₃O₄ surface. The asymmetric N₁O₂ configuration is able to accept electrons from the Co 3d-orbital, resulting in significant electronic delocalization at Co sites for promoted PMS adsorption, dissociation and subsequent generation of Co^IV=O species. CoN₁O₂/Mn₃O₄ exhibits high intrinsic activity in PMS activation and sulfamethoxazole (SMX) degradation, highly outperforming its counterpart with a CoO₃ configuration, carbon-based single-atom catalysts with CoN₄ configuration, and commercial cobalt oxides. Co^IV=O species effectively oxidize the target contaminants via oxygen atom transfer to produce low-toxicity intermediates. These findings could advance the mechanistic understanding of PMS activation at the molecular level and guide the rational design of efficient environmental catalysts.     

Partially substituted lithium manganese oxides as 3 V cathode materials for secondary lithium batteries

Low temperature synthesis and electrochemical properties of partially substituted lithium manganese oxides are reported. We demonstrate various metallic cations (Cu²⁺, Ni²⁺, Fe³⁺, Co³⁺) can be incorporated in the 3 V layered cathodic material Li_0.45MnO_2.1. New compounds Li_0.45Mn_0.88Fe_0.12O_2.1, Li_0.45Mn_0.84Ni_0.16O_2.05, Li_0.45Mn_0.79Cu_0.21O_2.3, Li_0.45Mn_0.85Co_0.15O_2.3 are prepared. These 3 V cathode materials are characterized by the same shape of discharge-charge profiles but different values of the specific capacity, between 90 mAh g⁻¹ and 180 mAh g⁻¹. The best results in terms of capacity and cycle life are obtained with the selected content of 0.15 Co per mole of oxide, as the optimum composition. The high kinetics of Li⁺ transport in Li_0.45Mn_0.85Co_0.15O_2.3 compared to that in the Co-free material is consistent with a substitution of Mn(III) by Co(III) in MnO₂ sheets.     

Nanostructured cobalt oxide-based composites for rechargeable Li-ion batteries

Cobalt oxide-based nanocomposites are prepared using Co₃O₄, various metals (Al, Mg), carbon powders, and a simple high-energy mechanical milling technique. X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy show that the cobalt oxide-based composites are mainly composed of nanostructured CoO/Al₂O₃, CoO/MgO, and Co₃O₄/C composites, respectively. Based on concepts related to the enhanced electrical conductivity of the Co₃O₄/C nanocomposite using conducting carbon matrix and to the resistance of inactive ceramic matrices (Al₂O₃, MgO) against active CoO particle growth during cycling, various nanostructured cobalt oxide-based composites are tested for use as anode materials. Among the composites, the Co₃O₄/C nanocomposite anode exhibits good electrochemical characteristics, such as high-capacity, good initial Coulombic efficiency, and long cycle behavior for Li-ion batteries.     

Metal-Organic Gel-Derived Co/CoO/Co3O4 Composite for the Electrochemical Detection of Diethylstilbestrol

A novel three-phase composite of Co/CoO/Co₃O₄ is synthesized through straightforward calcination treatment towards cobalt-based metal-organic gel (Co MOG) precursor, which is constructed with the metal source of cobalt chloride and organic ligand of 4, 4', 4”-((1, 3, 5-triazine-2, 4, 6-triyl) tris (azanediyl)) tribenzoic acid at room temperature. The morphology, structure and composition of the derived Co/CoO/Co₃O₄ is confirmed through scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectrums (XPS). Furthermore, the composite of Co/CoO/Co₃O₄ is employed as electrode modified material with the excellent electrochemical performances of accelerating the electron transfer and boosting the electrode interface reaction. As a proof of concept, the electrochemical redox behaviors of diethylstilbestrol (DES) have been systemically investigated at the modified electrode interface and the established analytical approach for DES with the broad linear range and satisfied recovery. This work not only provided a facile approach to obtain electrode material with excellent electrochemical performance but also enriched the application of MOG materials in the electrochemical field.     

Thermische Analyse eines chloridhaltigen basischen Cobaltcarbonates

The thermal decomposition of a chloride and water-containing basic cobalt carbonate was studied. As a first step, crystal water is lost without change of structure. The following decomposition steps overlap and proceed in different ways, depending on the atmosphere over the sample: under nitrogen, chloride volatilizes as HCl and CoCl₂; in air, oxidation occurs. CoO and Co₃O₄, respectively, are the final solid products at 700–800°.     

The thermodynamic method for selecting oxygen carriers used for chemical looping air separation

Chemical looping air separation (CLAS) has been suggested as a new and energy saving method for producing oxygen from air. The selection of suitable oxygen carriers is the key issue for CLAS system. This paper shows a comprehensive thermodynamic method for selecting oxygen carriers used for CLAS through studying the properties of 34 different oxygen releasing reactions referring to 18 elements at different temperatures. The research mainly includes analysis of oxygen releasing capacity by calculating the Gibbs free energy change (ΔG) and the equilibrium partial pressure of oxygen of the reduction or oxidation reaction at different temperatures. Oxygen content and transport capacity were calculated. The spontaneous reaction temperatures for oxygen releasing reactions were presented to determine the operating temperatures. Also, the minimum demand of the steam for the reduction reaction was discussed. On the basis of the comprehensive thermodynamic study, the oxide systems of CrO₂/Cr₂O₃, PbO₂/Pb₃O₄, PbO₂/PbO, Pb₃O₄/PbO, MnO₂/Mn₂O₃, and Ag₂O/Ag have been found suitable for the CLAS process in low temperatures (500–800 K). The systems of PdO₂/PdO, PdO₂/Pd, PdO/Pd, MnO₂/MnO, and MnO₂/Mn₃O₄ were suitable for medium temperatures (800–1100 K) CLAS process. And Co₃O₄/CoO, CuO/Cu₂O, Mn₂O₃/Mn₃O₄, and OsO₂/Os systems only worked successfully in high temperatures (1100–1400 K). In addition, the CaO₂/CaO system was not suitable for CLAS because of the reaction with steam. The various binders such as SiO₂, TiO₂, Al₂O₃, Y₂O₃, ZrO₂, and YSZ which have been used for CLC could also be the supports for CLAS oxygen carriers.     

硫中毒对Co3O4/CeO2复合氧化物上炭黑催化燃烧的影响

采用共沉淀法制备了CeO₂,Co₃O₄和一系列Co₃O₄/CeO₂复合氧化物催化剂,在400 ℃下含SO₂的氧化气氛中对催化剂进行了硫中毒处理,通过原位红外光谱、X射线衍射、程序升温脱附和X射线光电子能谱对新鲜和硫中毒的样品进行了表征. 结果表明,所有测试的硫中毒样品上均形成了硫酸盐,CeO₂上累积的硫酸盐明显比Co₃O₄上的多,Co₃O₄/CeO₂复合氧化物在硫中毒过程中形成了硫酸钴和硫酸铈. 对新鲜和硫化样品在NO/O₂气氛下进行了催化炭黑燃烧实验,发现Co₃O₄/CeO₂复合氧化物的活性和抗硫性能优于CeO₂,但抗硫性能低于Co₃O₄.     

Phase equilibrium in the system Ln-Mn-O VI: Ln=Ho and Tb at 1100°C

Phase equilibria were established in Ho-Mn-O and Tb-Mn-O systems at 1100°C by varying the oxygen partial pressure from −log(P_O2/atm)=0-13.00, and phase diagrams for the corresponding Ln₂O₃-MnO-MnO₂ systems at 1100°C were presented. Stable Ln₂O₃, MnO, Mn₃O₄, LnMnO₃, and LnMn₂O₅ phases were found at 1100°C, whereas Ln₂Mn₂O₇, Ln₂MnO₄, Mn₂O₃, and MnO₂ were not found to be stable. Small nonstoichiometric ranges were found in the LnMnO₃ phase, with the composition of LnMnO₃ represented as functions of log(P_O2/atm), and . Activities of the components in the solid solution were calculated from these equations. The composition of LnMnO₃ may range from Ln₂O₃ rich to Ln₂O₃ poor, while MnO is slightly nonstoichiometric, being oxygen rich and LnMn₂O₅ seems to be nonstoichiometric. Lattice constants of LnMnO₃ quenched at different oxygen partial pressures and of LnMn₂O₅ quenched in air were determined. The standard Gibbs energy changes of the reactions appearing in the phase diagrams were also calculated. The relationship between the tolerance factor of LnMnO₃ and ΔG⁰of reaction, (1/2)Ln₂O₃+MnO+(1/4)O₂=LnMnO₃, is shown graphically.