Synthesis and microstructure of (LaSr)MnO3 and (LaSr)FeO3 ceramics by a reaction-sintering process

(La_xSr_1−x)MnO₃ (LSMO) and (La_xSr_1−x)FeO₃ (LSFO) (x = 0.2–0.4) ceramics prepared by a simple and effective reaction-sintering process were investigated. Without any calcination involved, La₂O₃ and SrCO₃ were mixed with MnO₂ (LSMO) or Fe₂O₃ (LSFO) then pressed and sintered directly. LSMO and LSFO ceramics were obtained after 2 and 4 h sintering at 1350–1400 and 1200–1280 °C, respectively. Grain size decreased as La content increased in LSMO and LSFO ceramics.     

Preparation and characterization of nano-particle LiFePO4 and LiFePO4/C by spray-drying and post-annealing method

Pure, nano-sized LiFePO₄ and LiFePO₄/C cathode materials are synthesized by spray-drying and post-annealing method. The influence of the sintering temperature and carbon coating on the structure, particle size, morphology and electrochemical performance of LiFePO₄ cathode material is investigated. The optimum processing conditions are found to be thermal treatment for 10 h at 600 °C. Compared with LiFePO₄, LiFePO₄/C particles are smaller in size due to the inhibition of crystal growth to a great extent by the presence of carbon in the reaction mixture. And that the LiFePO₄/C composite coated with 3.81 wt.% carbon exhibits the best electrode properties with discharge capacities of 139.4, 137.2, 133.5 and 127.3 mAh g⁻¹ at C/5, 1C, 5C and 10C rates, respectively. In addition, it shows excellent cycle stability at different current densities. Even after 50 cycles at the high current density of 10C, a discharge capacity of 117.7 mAh g⁻¹ is obtained (92.4% of its initial value) with only a low capacity fading of 0.15% per cycle.     

An optimized Ni doped LiFePO4/C nanocomposite with excellent rate performance

Both Ni doping and carbon coating are adopted to synthesize a nano-sized LiFePO₄ cathode material through a simple solid-state reaction. It is found that the Ni²⁺ has been successfully doped into LiFePO₄ without affecting the phospho-olivine structure from the XRD result. The images of SEM and TEM show that the size of particles is distributed in the range of 20-60 nm, and all the particles are coated with carbon completely. The results of XPS show the valence state of Fe and Ni in the LiFePO₄. The electronic conductivity of the material is as high as 2.1 × 10⁻¹ S cm⁻¹, which should be ascribed to the coefficient of the conductive carbon network and Ni doping. As a cathode material for lithium-ion batteries, the Ni doped LiFePO₄/C nanocomposite delivers a discharge capacity of 170 mAh g⁻¹ at 0.2 C, approaching the theoretical value. Moreover, the material shows excellent high-rate charge and discharge capability and long-term cyclability. At the high rates of 10 and 15 C, this material exhibits high capacities of 150 and 130 mAh g⁻¹, retaining 95% after 5500 cycles and 93% after 7200 cycles, respectively. Therefore, the as-prepared material is capable of such large-scale applications as electric vehicles and plug-in hybrid electric vehicles.     

Large increase of Curie temperature in (110)-oriented La0.7Sr0.3MnO3 films

From the perspectives of scientific researches and practical applications, it is desirable to explore high operating temperature ferromagnetic films. The effect of biaxial strain on magnetic properties of (110)-oriented La_0.7Sr_0.3MnO₃ films was studied. High quality La_0.7Sr_0.3MnO₃ films were grown on (110)-oriented perovskite single crystal substrates using pulsed laser deposition, varying substrate-induced misfit strains from ??2.27–0.75%. A remarkable enhancement of Curie temperature has been achieved for (110)-oriented La_0.7Sr_0.3MnO₃ films clamped with small misfit strains (i.e., grown on LAST (110)). The enhanced Curie temperature of (110)-oriented La_0.7Sr_0.3MnO₃ films could be attributed to the misfit strain between the films and the underlying substrates and may have technological implication for applications at high temperature environments.     

Study on impedance spectra of La0.7Sr0.3MnO3 and Sm0.2Ce0.8O1.9-impregnated La0.7Sr0.3MnO3 cathode in single chamber fuel cell condition

Impedance spectroscopy was used to study the electrochemical performance of pure and ion-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathodes on YSZ (Y₂O₃-stabilized ZrO₂) electrolytes in single chamber fuel cell conditions, i.e. a mixture gas with oxygen as oxidant, methane as fuel and nitrogen as dilute gas. Measurements were taken at the furnace temperature range of 550-750 °C and the CH₄/O₂ ratios from 1 to 2. Polarization resistances (R_p) for pure and impregnated LSM cathodes increased obviously as the CH₄/O₂ ratio increased at 650-750 °C. Polarization resistances of Sm_0.2Ce_0.8O_1.9 (SDC) impregnated LSM cathode were much smaller than the ones of pure LSM cathode under the same conditions. Overtemperatures were occurred at both cathodes due to the partial oxidation of methane.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.     

Hydrothermal synthesis and magnetocaloric effect of La0.7Ca0.2Sr0.1MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.7Ca_0.2Sr_0.1MnO₃ have been studied. The La_0.7Ca_0.2Sr_0.1MnO₃ can be produced as phase-pure, crystalline powder in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 240 °C in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped or rod-shaped particles with typical dimension of 4.0 μm. Heat treatment is necessary to improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change (∣ΔS_M∣) for the sample annealed at 1200 °C for 6 h is 2.85 J kg^− 1 K^− 1 at the magnetic field change of 2.0 T and 2.23 J kg^− 1 K^− 1 at the magnetic field change of 1.5 T at 315 K. The hydrothermal synthesis method is a feasible route to prepare high quality perovskite material for magnetic refrigeration application.     

Enhanced electrochemical performance of carbon nanospheres-LiFePO4 composite by PEG based sol-gel synthesis

The carbon nanospheres-LiFePO₄ (CNSs-LiFePO₄) composite has been synthesized by PEG (polyethylene glycol, mean molecular weight of 30,000) based sol-gel route. Highly conductive CNSs (30-40 nm) were adopted to improve the electronic conductivity of LiFePO₄. PEG was used to promote the dispersion of CNSs with the surface functionalization of CNSs, which could facilitate the coating of CNSs on the surface of the LiFePO₄ particles. The sample was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Raman scattering. Electrochemical performance of the CNSs-LiFePO₄ composite was characterized by the charge-discharge test and electrochemical impedance spectra measurement. The results indicated that LiFePO₄ particles were well coated with the conductive CNSs to overcome the intrinsic low electronic conductivity problem of LiFePO₄. The CNSs-LiFePO₄ composite delivered an enhanced rate capability (146, 128 and 113 mAh g⁻¹ at 0.1 C, 1 C and 5 C rate). The PEG based sol-gel route enables LiFePO₄ networked with CNSs, which offered a higher electrochemical performance.     

Synthesis,characterization and electrochemical performances of MoO2 and carbon co-coated LiFePO4 cathode materials

The MoO₂ and carbon co-coated LiFePO₄ cathode materials were synthesized by a combined technique of solid state synthesis and the sol–gel method. Phase compositions and microstructures of the products were characterized by X-ray powder diffraction (XRD), Raman, SEM and TEM. Results indicate that MoO₂ can sufficiently coat on the LiFePO₄ surface and does not alter LiFePO₄ crystal structure, and the existence of MoO₂ increases the graphitization degree of carbon. SEM and TEM images reveal that MoO₂ presence has little impact on LiFePO₄ particle size. The electrochemical behavior of cathode materials was analyzed using galvanostatic measurement and cyclic voltammetry (CV). The results show that the existence of MoO₂ improves electrochemical performance of LiFePO₄ cathode material in specific capability and low-temperature behavior. The apparent lithium ion diffusion coefficient increases with MoO₂ content and maximizes around the MoO₂ content of x=5 wt%. It has been had further proved that the higher electronic conductivity of MoO₂ and carbon enhances the lithium ion transport to improve the electrochemical performance of LiFePO₄ cathode materials.     

Influence of carbon sources on LiFePO4/C composites synthesized by the high-temperature high-energy ball milling method

Carbon-coated LiFePO₄ composites were synthesized by a new method of high-temperature high-energy ball milling (HTHEBM). Fe₂O₃ and LiH₂PO₄ were used as raw materials. Glucose, sucrose, citric acid and active carbon were used as reducing agents and carbon sources, respectively. In this method, high-energy ball milling and carbon coating worked together and, therefore, fine and homogeneous LiFePO₄/C particles with excellent properties were obtained in a relatively short synthesis time of 9 h. Moreover, the synthesis process could be completely finished at a relatively lower temperature of 600 °C for high-energy ball milling transforming mechanical energy into thermal energy. The results of X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical performance tests indicated that carbon source had an important influence on the properties of LiFePO₄/C composites synthesized by the HTHEBM method. It was proved that the LiFePO₄ composites coated with glucose had the best properties with 1 μm geometric mean diameter and 150.3 mA h g⁻¹ initial discharge capacity at a current rate of 0.1 C. After the 20th cycle test, the reversible capacity was 148 mA h g⁻¹ at 0.1 C, showing a retention ratio to the initial capacity of 98.5%.     

Polypyrrole and La1−xSrxMnO3 (0≤ x ≤0.4) composite electrodes for electroreduction of oxygen in alkaline medium

Composite G/PPy/PPy(La_1−xSr_xMnO₃)/PPy electrodes made of the perovskite La_1−xSr_xMnO₃ embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La_1−xSr_xMnO₃) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm⁻³ pyrrole (Py) plus 0.05 mol dm⁻³ K₂SO₄ with and without containing a suspension of 8.33 g L⁻¹ oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm⁻³ K₂SO₄ plus 5 mmol dm⁻³ KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.     

La1−xSrxFeO3−δ perovskites as redox materials for application in a membrane reactor for simultaneous production of pure hydrogen and synthesis gas

This work reports on the preparation and characterization of perovskitic materials with the general formula La_1−xSr_xFeO₃ (x = 0, 0.3, 0.7, 1) for application in a dense mixed conducting membrane reactor process for simultaneous production of synthesis gas and pure hydrogen. Thermogravimetric experiments indicated that the materials are able to loose and uptake reversibly oxygen from their lattice up to 0.2 oxygen atoms per “mole” for SrFeO₃ with x = 1 at 1000 °C. The capability of the prepared powders to convert CH₄ during the reduction step, in order to produce synthesis gas, as well as their capability to dissociate water during the oxidation step, in order to produce hydrogen were evaluated by pulse reaction experiments in a fixed bed pulse reactor. The high sintering temperatures (1100-1300 °C) required for the densification of the membrane materials result in decreased methane conversion and H₂ yields during the reduction step compared to the corresponding values obtained with the perovskite powders calcined at 1000 °C. Addition of small quantities of NiO, by simple mechanical mixing, to the perovskites after their sintering at high temperatures, increases substantially both their methane decomposition reactivity, their selectivity towards CO and H₂ and their water splitting activity. Maximum H₂ yield during the reduction step is achieved with the La_0.7Sr_0.3FeO₃ sample mixed with 5% NiO and is 80% of the theoretically expected H₂, based on complete methane decomposition. In the oxidation - water splitting step, 912 μmol H₂ per gr solid are produced with the La_0.3Sr_0.7FeO₃ sample mixed with 5% NiO. The experimental results of this work can be equally well applied for the “chemical-looping reforming” process since they concern using the lattice oxygen of the perovskite oxides for methane partial oxidation to syngas, in the absence of molecular oxygen, and subsequent oxidation of the solid.     

Carbon coated Li3V2(PO4)3 cathode material prepared by a PVA assisted sol-gel method

Carbon coated Li₃V₂(PO₄)₃ cathode material was prepared by a poly(vinyl alcohol) (PVA) assisted sol-gel method. PVA was used both as the gelating agent and the carbon source. XRD analysis showed that the material was well crystallized. The particle size of the material was ranged between 200 and 500 nm. HRTEM revealed that the material was covered by a uniform surface carbon layer with a thickness of 80 Å. The existence of surface carbon layer was further confirmed by Raman scattering. The electrochemical properties of the material were investigated by charge-discharge cycling, CV and EIS techniques. The material showed good cycling performance, which had a reversible discharge capacity of 100 mAh g⁻¹ when cycled at 1 C rate. The apparent Li⁺ diffusion coefficients of the material ranged between 9.5 × 10⁻¹⁰ and 0.9 × 10⁻¹⁰ cm² s⁻¹, which were larger than those of olivine LiFePO₄. The large lithium diffusion coefficient of Li₃V₂(PO₄)₃ has been attributed to its special NASICON-type structure.     

Optimization of electrochemical properties of LiFePO4/C prepared by an aqueous solution method using sucrose

LiFePO₄ can be used as a positive electrode material for lithium-ion batteries by making composite with electrical conductive carbonaceous materials. In this study, LiFePO₄/C (carbon) composite was prepared by a soft chemistry route, in which sucrose was used as a carbon source of a low price. We tried to optimize a Li/(LiFePO₄/C) cell performance through changing synthetic conditions and discussed the factors affecting the electrochemical performances of the cell, such as the amount of the carbon source, synthetic temperature, gas flow rate of pyrolysis and the formation of secondary phases. It was found that the connection of the residual carbon and Fe₂P to LiFePO₄ particles and the amount of these two phases were important factors. In our experimental conditions, LiFePO₄/C including 9.72 wt.% of residual carbon, prepared at 800 °C for 12 h showed the highest reversible capacity and the best C rate performance among the synthesized materials; 130 mAh g⁻¹ at 10C rate and 50 °C.     

Electrochemical properties of the single crystal La0.7Pb0.3MnO3 electrode

Electrochemical properties of the single crystal La_0.7Pb_0.3MnO₃ were studied. This oxide is stable only at the anodic potential region in alkaline solution. It was found that the catalytic activities for the oxygen reduction and evolution reactions are relatively high due to the effect of the B site Mn cation on the oxide surface. However, the mechanisms of the oxygen reduction and evolution reactions are different from the case of La_1-xSr_xMnO₃ electrodes and it was presumed that these differences are assigned to the influence of the A site Pb cation in La_0.7Pb_0.3MnO₃ and that of the (100) crystal plane.     

One-step microwave synthesis and characterization of carbon-modified nanocrystalline LiFePO4

The precursors of LiFePO₄ were prepared by a sol-gel method using lithium acetate dihydrate, ferrous sulfate, phosphoric acid, citric acid and polyethylene glycol as raw materials, and then the carbon-modified nanocrystalline LiFePO₄ (LiFePO₄/C) cathode material was synthesized by a one-step microwave method with the domestic microwave oven. The effect of microwave time and carbon content on the performance of the resulting LiFePO₄/C material was investigated. Structural characterization by X-ray diffraction and scanning electron microscopy proved that the olivine phase LiFePO₄ was synthesized and the grain size of the samples was several hundred nanometers. Under the optimal conditions of microwave time and carbon content, the charge-discharge performance indicated that the nanosized LiFePO₄/C had a high electrochemical capacity at 0.2 C (152 mAh g⁻¹) and improved capacity retention; the exchange current density was 1.6977 mA cm⁻². Furthermore, the rate capability was improved effectively after LiFePO₄ was modified with carbon, with 59 mAh g⁻¹ being obtained at 20 C.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.     

Effect of propellant on the combustion synthesized Sr-doped LaMnO3 powders

Lanthanum strontium manganite (LSM) powders of composition La_0.7Sr_0.3MnO₃ are good candidates for cathode application in solid oxide fuel cells. This paper reports the synthesis of LSM powders from nitrate precursors by the combustion method, using two different propellants (urea and glycine) and varying the propellant/nitrate ratio. Thermogravimetric analysis (TGA) revealed two or three decomposition stages of the as-synthesized samples, with complete burn out of organics at about 850–900 °C. X-ray diffraction (XRD) patterns showed formation of only LSM phase for the sample synthesized with excess of urea, whereas SrCO₃ and MnCO₃ phases were also found for the samples prepared from glycine. The powder is better crystallized when a homogeneous gel is formed before burning. The crystallite size calculated using the Scherrer equation is in the range of 15–20 nm. Scanning electron microscopy (SEM) revealed the presence of agglomerates, formed by fine particles of different shapes.     

Synthesis and characterization of LiFePO4/(Ag + C) composite cathodes with nano-carbon webs

LiFePO₄/(Ag + C) composite cathodes with a new type of nano-sized carbon webs were synthesized by two methods of an aqueous co-precipitation and a sol-gel process, respectively. Simultaneous thermogravimetric-differential thermal analysis indicates that the crystallization temperature of LiFePO₄ is about 455-466 °C, which is close to the pyrolysis temperature of polypropylene, 460 °C. The silver and carbon co-modifying does not affect the olivine structure of LiFePO₄ but improves its kinetics in terms of discharge capacity and rate capability. Discharge capacities were improved from 153.4 mA h g^− 1 of LiFePO₄/C to 160.5 mA h g^− 1and 162.1 mA h g^− 1 for LiFePO₄/(Ag + C) cathodes synthesized by the co-precipitation and sol-gel methods, respectively. The possible reasons for the small difference in discharge capacity of two LiFePO₄/(Ag + C) cathodes were discussed. AC impedance measurements show that the Ag + C co-modification decreases the charge transfer resistance of LiFePO₄/(Ag + C) cathodes.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.