Chemical and structural transformations in manganese aluminum spinel of the composition Mn1.5Al1.5O4 during heating and cooling in air

Single phase cubic spinel of the composition Mn_1.5Al_1.5O₄ is synthesized. Its crystal structure refinement shows that 0.4Mn+0.6Al are in the octahedral sites and 0.7Mn+0.3Al are in the tetrahedral sites. High temperature X-ray diffraction is used to analyze Mn_1.5Al_1.5O₄ behavior during heating and cooling in air. In a temperature range of 600°C to 700°C, initial spinel splits into layers, and the sample represents a twophase system: cubic spinel Mn_0.4Al_2.4O₄ and a phase based on β-Mn₃O₄. Above 900°C the sample again turns into single phase cubic spinel. The role of oxidizing processes in the decomposition of Mn_1.5Al_1.5O₄ caused by oxygenation and partial oxidation of Mn²⁺ to Mn³⁺ is shown. A scheme of structural transformations of manganese aluminum spinel during heating from room temperature and cooling from 950°C is proposed.     

Thermal activation effect on catalytic systems MnO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for deep oxidation of hydrocarbons

The effect of thermal activation, sharp increase in the catalytic activity of the system MnO _x -Al₂O₃ in reactions of deep oxidation of CO and hydrocarbons after calcination of the catalyst at 900–1000°C was discovered and investigated. With the use of X-ray phase analysis, X-ray electron spectroscopy, EXAFS, IR spectroscopy, electronic spectroscopy of diffuse reflections, electron microscopy etc. it was established that the effect of thermal activation is related to reversible phase transitions in the system at heating and cooling. On cooling from 1100°C to 650°C disperse particles of cubic spinel of composition Mn_{2.1 ? x} · Al_{0.9 + x} O₄ are conserved on the corundum surface. On further cooling the spinel decomposes and finally the nanocristalline species of β-Mn₃O*₄ containing up to 15 at% of Al³⁺ form and govern the activity.The thermal activation effect was implemented in an industrial catalyst IK-12-40. Joint Stocks Co “KATALIZATOR” produced and supplied to customers hundreds of tons of this catalyst. The catalyst was awarded with a silver medal of the International exhibition EUREKA in Brussels (1995).     

Thermal decomposition of managanese oxyhydroxide

Temperature-programmed thermal decomposition of γ- and α-manganese oxyhydroxide has been studied between 20 and 670°C under vacuum and under a low pressure (10 Torr) of oxygen. Solid products at various temperatures have been analyzed by X-ray diffractometry. Under vacuum γ-MnOOH decomposed below 400°C to a mixture of Mn₅O₈, α-Mn₃O₄, and water according to the reaction scheme: 8MnOOH → Mn₅O₈ + Mn₃O₄ + 4H₂O. Above this temperature Mn₅O₈ was converted to α-Mn₃O₄ as a result of oxygen removal. The vacuum dehydration at 250°C of oxyhydroxide rich in α-MnOOH led to the formation of a new modification of Mn₂O₃ isostructural with corundum (α-Al₂O₃). In oxygen both oxyhydroxides decomposed to β-MnO₂. γ-MnOOH transformed directly to β-MnO₂ while α-MnOOH appeared to transform via corundum-phase Mn₂O₃ as an intermediate.     

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.     

Hydride lithiation of spinels LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Undoped lithiation of stoichiometric spinel using lithium hydride LiH up to the composition Li_2.25Mn₂O₄ was performed. A homogeneous material with a given Li: Mn ratio was obtained by mechanochemical activation with sequential annealing of a LiMn₂O₄–LiH mixture in a high-purity argon atmosphere and then in air or oxygen at 373–553 K.     

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.     

Phase Transformations in the Mn–Ga–O System Depending on the Preparation Conditions

Manganese-gallium samples with cation ratios Mn:Ga = 1:2, 1.5:1.5, and 2:1 are synthesized by coprecipitation with subsequent annealing in air in a temperature range 600–1200 °C. Powder XRD, TEM, and BET methods are used to study the physicochemical characteristics of the samples. It is found that in the air at the annealing temperature of 600 °C finely dispersed low-temperature Mn_3–xGa_xO₄ spinels primarily form in all series, but in the whole temperature range (600–1200 °C) the system is multiphase. Annealing at 800–1200 °C leads to an increase in the concentration of simple oxides (β-Mn₃O₄ and β-Ga₂O₃). Only simple α-Mn₂O₃ and β-Ga₂O₃ oxides exist in a Mn:Ga = 2:1 series at 800 °C. In the sample with a cation ratio Mn:Ga = 1.5:1.5 annealed in air at 1000 °C, the formation of a superstructure based on the spinel structure is found.     

BiFeO<Subscript>3</Subscript>-coated spinel LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> with improved electrochemical performance as cathode materials for lithium-ion batteries

Spinel LiNi_0.5Mn_1.5O₄ cathode material is a promising candidate for next-generation rechargeable lithium-ion batteries. In this work, BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials were prepared via a wet chemical method and the structure, morphology, and electrochemical performance of the materials were studied. The coating of BiFeO₃ has no significant impact on the crystal structure of LiNi_0.5Mn_1.5O₄. All BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials exhibit cubic spinel structure with space group of Fd3m. Thin BiFeO₃ layers were successfully coated on the surface of LiNi_0.5Mn_1.5O₄ particles. The coating of 1.0 wt% BiFeO₃ on the surface of LiNi_0.5Mn_1.5O₄ exhibits a considerable enhancement in specific capacity, cyclic stability, and rate performance. The initial discharge capacity of 118.5 mAh g^?1 is obtained for 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ with very high capacity retention of 89.11% at 0.1 C after 100 cycles. Meanwhile, 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ electrode shows excellent rate performance with discharge capacities of 117.5, 110.2, 85.8, and 74.8 mAh g^?1 at 1, 2, 5, and 10 C, respectively, which is higher than that of LiNi_0.5Mn_1.5O₄ (97.3, 90, 77.5, and 60.9 mAh g^?1, respectively). The surface coating of BiFeO₃ effectively decreases charge transfer resistance and inhibits side reactions between active materials and electrolyte and thus induces the improved electrochemical performance of LiNi_0.5Mn_1.5O₄ materials.     

The influence of Li sources on physical and electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode materials for lithium-ion batteries

LiNi_0.5Mn_1.5O₄ cathode materials were successfully prepared by sol–gel method with two different Li sources. The effect of both lithium acetate and lithium hydroxide on physical and electrochemical performances of LiNi_0.5Mn_1.5O₄ was investigated by scanning electron microscopy, Fourier transform infrared, X-ray diffraction, and electrochemical method. The structure of both samples is confirmed as typical cubic spinel with Fd3m space group, whichever lithium salt is adopted. The grain size of LiNi_0.5Mn_1.5O₄ powder and its electrochemical behaviors are strongly affected by Li sources. For the samples prepared with lithium acetate, more spinel nucleation should form during the precalcination process, which was stimulated by the heat released from the combustion of extra organic acetate group. Therefore, the particle size of the obtained powder presents smaller average and wider distribution, which facilitates the initial discharge capacity and deteriorates the cycling performance. More seriously, there exists cation replacement of Li sites by transition metal elements, which causes channel block for Li ion transference and deteriorates the rate capability. The compound obtained with lithium hydroxide exhibits better electrochemical responses in terms of both cycling and rate properties due to higher crystallinity, moderate particle size, narrow size distribution and lower transition cation substitute content.     

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.     

Thermal stability of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) of an α-Bi₂O₃ sample revealed staged phase transitions in the range 720–800°C (at 720, 780, and 800°C) and the elimination of oxygen to the composition Bi₂O_2.967 during heating to 895°C in air at 16 K/min. In dynamic vacuum (p = 1.33 Pa) at 780–800°C, Bi₂O₃ consecutively transforms to a phase with the cubic γ-Bi₂O₃ structure and tetragonal Bi₂O_2.3?2.4. In the latter, electron diffraction in a transmission electron microscope (ED/TEM) shows a superstructure with the superstructure vector q ₁₁₀ ≈ 1/9, which indicates an ordered arrangement of oxygen vacancies.     

The Microstructure of Cobalt Silica Gel Catalyst in the Presence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Additive

The physico-chemical characteristics and microstructure of cobalt silica gel catalysts with an Al₂O₃ additive (up to 10%) for the synthesis of hydrocarbons by the Fischer–Tropsch method are studied using a set of methods including X-ray diffraction, BET, IR spectroscopy, and temperature-programmed reduction of H₂, as well as scanning and transmission electron microscopy. Phases with a spinel structure, Со₃О₄, CoAl₂O₄, and solid solutions on their basis are identified in the samples. The addition of Al₂O₃ changes the degree of heterogeneity and the orientation of the cobalt crystallites in the oxide and reduced forms of the catalysts. Addition of 1% Al₂O₃ stabilizes Со₃О₄ in the spinel form with a structure close to the normal one and promotes the formation of cobalt with a unimodal distribution of particles with an average size of 8 nm. The catalyst is characterized by maximum activity and selectivity with respect to C⁵⁺ carbons.     

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.

     

Glass formation in the Al(IO<Subscript>3</Subscript>)<Subscript>3</Subscript>-Al<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript>-HIO<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system

On the basis of experimental data obtained in the study of glass-formation boundaries in the Al₂(SO₄)₃-HIO₃-H₂O, Al(IO₃)₃-Al₂(SO₄)₃-H₂O, and Al(IO₃)₃-HIO₃-H₂O systems and using geometrical analysis, we predict the positions of glass-formation boundaries in the Al(IO₃)₃-Al₂(SO₄)₃-HIO₃-H₂O four-component system along 60, 40, and 25 wt % H₂O sections.     

Al-doped La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> as oxide anode for solid oxide fuel cells using dry C<Subscript>3</Subscript>H<Subscript>8</Subscript> fuel

Direct hydrocarbon type solid oxide fuel cells are attractive from simple gas feed process and also high energy conversion efficiency. In this study, La_0.5Sr_0.5MnO₃ (LSM55) perovskite oxide was studied as oxide anode for direct hydrocarbon type solid oxide fuel cell (SOFC). Although reasonable power density like 1 W/cm² and open circuit voltage (OCV) (1.1 V) at 1273 K was exhibited when H₂ was used as fuel, the power density as well as OCV of the cell using LSM55 for anode was significantly decreased when dry C₃H₈ was used for fuel. After power generation measurement, LSM55 phase was decomposed to MnO and La₂MnO₄. Effects of various dopants to Mn site in LSM55 were studied and it was found that partial substitution of Mn in LSM55 with other cation, especially transition metal, is effective for increasing maximum power density. In particular, reasonable high power density can be achieved on the cell using Ni-doped LSM55 for anode. On the other hand, Al substitution is effective for increasing stability against reduction and so, dopant effects of Al were studied in more details for dry C₃H₈ fuel. The power density as well as OCV increased with increasing Al content and the highest power density was achieved at x = 0.4 in La_0.5Sr_0.5Mn_1 ? x Al _x O₃. Among the examined composition, it was found that the cell using La_0.5Sr_0.5Mn_0.6Al_0.4O₃ anode shows the largest power density (0.2 W/cm²) at 1173 K and high OCV (1.01 V) against dry C₃H₈ fuel.     

Physicochemical study of composite gel in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> system

We show a feasibility of preparing a highly homogeneous composite gel (CG) based on hydrolysis products of Al₂O₃-ZrO₂ salts. The phase composition of a sample calcined at 1250°C for 2 h is as follows: α-Al₂O₃, t-ZrO₂, and m-ZrO₂ where the t-ZrO₂/m-ZrO₂ phase ratio ranges from 2.8 to 3.8 depending on gel preparation conditions. The investigative tools used are powder X-ray diffraction, differential thermal analysis (atmosphere: Ar), and IR spectroscopy.     

Phase formation in the Ag<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-MgMoO<Subscript>4</Subscript>-Al<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> system

The subsolidus region of the Ag₂MoO₄-MgMoO₄-Al₂(MoO₄)₃ ternary salt system has been studied by X-ray phase analysis. The formation of new compounds Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ (0 ≤ x ≤ 0.4) and AgMg₃Al(MoO₄)₅ has been determined. The Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ variable-composition phase is related to the NASICON type structure (space group R \(\bar 3\) c). AgMg₃Al(MoO₄)₅ is isostructural to sodium magnesium indium molybdate of the same formula unit and crystallizes in triclinic system (space group P \(\bar 1\), Z = 2) with the following unit cell parameters: a = 9.295(7) Å, b = 17.619(2) Å, c = 6.8570(7) Å, α = 87.420(9)°, β = 101.109(9)°, γ = 91.847(9)°. The compounds Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ and AgMg₃Al(MoO₄)₅ are thermally stable up to 790 and 820°C, respectively.     

The effect of spinel type support FeAlO<Subscript>3</Subscript>, ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, CrAl<Subscript>3</Subscript>O<Subscript>6</Subscript> on physicochemical properties of Cu,Ag, Au,Ru supported catalysts for methanol synthesis

The comparative study of the role of binary oxide support on catalyst physico-chemical properties and performance in methanol synthesis were undertaken and the spinel like type structures (ZnAl₂O₄, FeAlO₃, CrAl₃O₆) were prepared and used as the supports for 5% metal (Cu, Ag, Au, Ru) dispersed catalysts. The monometallic 5% Cu/support and bimetallic 1% Au (or 1% Ru)-5% Cu/support (Al₂O₃, ZnAl₂O₄, FeAlO₃, CrAl₃O₆) catalysts were investigated by BET, XRD and TPR methods. Activity tests in methanol synthesis of CO and CO₂ mixture hydrogenation were carried out. The order of Cu/support catalysts activity in methanol synthesis: CrAl₃O{ia6} > FeAlO₃ > ZnAl₂O₄ is conditioned by their reducibility in hydrogen at low temperature. Gold appeared more efficient than ruthenium in promotion of Cu/support catalysts. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 2, pp. 242–248. The article is published in the original.     

Electrochemical dissolution of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> in acid solutions

The present study deals with the electrochemical reductive dissolution of Mn₃O₄, which was added to carbon-paste electroactive electrodes (CPEEs) in acid solutions. It was found that in the experimental conditions the thermodynamically stable form of manganese was . Kinetic features of the electrochemical reductive dissolution of Mn₃O₄, which was realized under potential cycling conditions (+1.0 V→−0.7 V→+1.0 V), were determined by the electrode polarization direction. It was shown that the cathodic reduction of Mn₃O₄ was accomplished in three stages. Manganese was dissolved in the supporting solution only at the third stage. The first two stages involved solid-phase reactions. The anodic cycling stage included an active dissolution of Mn₃O₄ and the lower manganese oxide (MnO) accumulated on the electrode surface during the cathodic reduction.     

Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.