Synthesis and characterization of nanostructured Li2MnO3 from nanostructured MnOOH precursors

Li₂MnO₃ with different nanostructures was synthesized through a solid-state reaction. MnOOH nanorods and nanowires prepared via the hydrothermal method were used as precursors, respectively, to react with Li(OH)·H₂O to prepare nanostructured Li₂MnO₃ in the temperature range from 500 to 800 °C. The samples were characterized by XRD, TEM, ESR and FTIR results. Based on the experimental results, the dehydration-oxidation-combination (DOC) formation mechanism of Li₂MnO₃ was proposed.     

Reentrant spin glass behavior in antiferromagnetic single crystalline Ba6Mn24O48 nanoribbons

Single crystalline Ba₆Mn₂₄O₄₈ nanoribbons with diameters ranging from one hundred nanometers to a few hundred nanometers and length up to tens of microns are synthesized via a facile molten salt method. These nanoribbons are characterized by a range of methods including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). The magnetic properties of Ba₆Mn₂₄O₄₈ nanoribbons are investigated by the zero-field-cooled (ZFC), field-cooled (FC) magnetization, and ac susceptibility. Upon cooling, we find the reentrant spin glass (RSG) behavior in these nanoribbons, i.e., paramagnetic (PM), antiferromagnetic (AFM), and spin glass (SG). The RSG behavior might be due to the surface spin disorder, geometrical frustration and Mn³⁺/Mn⁴⁺ mixture in Ba₆Mn₂₄O₄₈ nanoribbons.     

Synthesis and characterization of lithium manganese oxides with core-shell Li4Mn5O12@Li2MnO3 structure as lithium battery electrode materials

By a facile LiNO₃ flux method, lithium manganese oxide composites (xLi₄Mn₅O₁₂? yLi₂MnO₃) were synthesized using a hierarchical organization precursor of manganese dioxide. Li₄Mn₅O₁₂ and Li₂MnO₃ have spinel and rocksalt structures, respectively. The lithiation and structural transformation from the precursor to the composites occurred topotactically from exterior toward interior in the precursor particle with the increase of reaction time, and the composites had core-shell spinel@rocksalt structures in addition to the original hierarchical core-shell organization. The electrochemical measurements at 50 °C after 50 cycles confirmed that a typical spinel@rocksalt cathode had higher capacity retention (87.1%) than that with the composition close to the stoichiometric spinel (64.6%), indicating the Li₂MnO₃ shell can improve cycling stability for the composite electrode at elevated temperature.     

Synthesis and characterization of ZrO2/MnO2/carbon clusters nanocomposite materials

Nano-sized ZrO₂/MnO₂/carbon clusters composite materials has been successfully obtained by the calcination of a Zr(acac)₄/Mn(acac)₃/epoxy resin complex under an oxygen atmosphere. The compositions of the resulting composite materials were determined using inductively coupled plasma (ICP) spectroscopy, elemental analysis and surface characterization by X-ray diffraction (XRD), scanning electron microscopy and transmission electron microscopy (TEM). The ultraviolet–visible (UV–VIS), X-ray photoelectron spectra (XPS) and electron spin resonance (ESR) spectra of the composites were also measured. ESR spectral examinations suggest the possibility of an electron transfer in the process of MnO₂ → carbon clusters → ZrO₂. The visible light-responsive oxidation–reduction ability of the calcined material was also investigated.     

One-step synthesis and electrochemical behavior of LiMnO2 and its composite from MnO2 in the presence of glucose

LiMnO₂ and 0.23Li₂MnO₃·0.77LiMnO₂ were prepared by a convenient one-step solid-state reaction from MnO₂ using glucose as organic carbon resource. The crystal structure and morphology of the as-prepared materials was examined by X-ray powder diffraction and field emission scanning electron microscopy, respectively. The ration of Li to Mn was determined by means of atomic absorption spectrometry and the Li/Mn molar ratio in the products was 1.23. The electrochemical properties were investigated by charge-discharge test and electrochemical impedance measurements. The prepared composite material presented an initial discharge capacity of 45 mAh g^-1 and a good cycling performance with reversible capacity of 218 mAh g^-1 after 30 cycles. On the basis of the experimental results, the discharge efficiency of this composite material more than 100% was also discussed.     

Large-scale synthesis of Ga2O3 nanoribbons by a two-step gas flow control

β-Ga₂O₃ nanoribbons have been prepared by a two-step gas flow control, involving adjusting the pressure inside the tube before and after the formation of the nanoribbons. In different temperature areas, separated nanoribbons and nanowires were obtained, which grew via solid–liquid–vapor–solid (SLVS) and vapor–liquid–solid (VLS) mechanisms, respectively. The samples obtained were characterized by means of scanning electron microscopy, transmission electron microscopy, micro-Raman scattering, and photoluminescence. It was found that Ga₂O₃ nanoribbons had a perfect monoclinic single-crystal structure with a [002] growth direction. The Ga₂O₃ nanoribbons give ultraviolet, cyan and green light emission at room temperature under excitation at 254 and 325 nm.     

结合会聚束电子衍射和高分辨电子显微术来测定十四铌酸锂的结构

我们在一台有0.4nm点分辨率的分析透射电子显微镜上,结合会聚束电子衍射(CBED)和高分辨电子显微术(HREM)研究了十四铌酸锂的结构。CBED结果证明十四铌酸锂的空间群是C2/m,HREM结构象表明十四铌酸锂是由4×4氧八面体方块组成,方块中3×3通道及八面体中心的金属原子可以清楚地看到,其距离是0.38nm。结合CBED和HREM来做结构分析是发展电子晶体学的重要的一步。 关键词：     

Charge ordering modulations in Bi0.4Ca0.6MnO3 film with a thickness of 110 nm

Low temperature sample stage in transmission electron microscope is used to investigate the charge ordering behaviours in Bi_0.4Ca_0.6MnO₃ film with a thickness of 110 nm at 103 K. Six different types of superlattice structures are observed using selected-area electron diffraction (SAED) technique, while three of them match well with the modulation stripes in high-resolution transmission electron microscopy (HRTEM) images. It is found that the modulation periodicity and direction are completely different in the region close to the Bi_0.4Ca_0.6MnO₃/SrTiO₃ interface from those in the region a little far from the Bi_0.4Ca_0.6MnO₃/SrTiO₃ interface, and the possible reasons are discussed. Based on the experimental results, structural models are proposed for these localized modulated structures.     

Structure of Li2MnO3 with different degrees of defects

The synthesis and structural properties of the layered oxide Li₂MnO₃ have been studied in details. It represents a key for a better understanding of the complex structural evolutions pointed out in the materials like Li(Li,Ni,Mn,Co)O₂ when they are used as positive electrode materials in lithium-ion batteries. Li₂MnO₃ samples were prepared either via coprecipitation or via a two step solid state reaction followed by different annealing treatments. Using X-ray and electron diffraction in combination with diffraction data simulations, we show that in function of the synthesis conditions, Li₂MnO₃ is obtained with various degrees of disorder, along the c monoclinic direction, in the stacking of the ordered Li_1/3Mn_2/3 sheets within the cfc oxygen packing. We show that this disorder decreases when the synthesis temperature increases but the synthesis of a material free of stacking faults is not possible with these synthesis routes. Finally, the similarities between the evolutions pointed out in Li₂MnO₃ due to the synthesis conditions and those previously observed in the materials like Li(Li,Ni,Mn,Co)O₂ related to the evolution of the cations distribution in the slabs are underlined.     

Electrical and magnetic behavior of La0.7Ca0.3MnO3/La0.7Sr0.2Ca0.1MnO3 composites

The electrical transport properties and the magnetoresistance of La_0.7Ca_0.3MnO₃/La_0.7Sr_0.2Ca_0.1MnO₃ composites are investigated as a function of sintering temperature. On the basis of an analysis by X-ray powder diffraction and scanning electron microscopy we suggest that raising the sintering temperature enhanced the interfacial reaction and creates interfacial phases at the boundaries of the La_0.7Ca_0.3MnO₃ and La_0.7Sr_0.2Ca_0.1MnO₃. Results also show that in 3 kOe, and at the Curie temperature, the magnetoresistance value of 14% was observed for the composite sintered at 1300 °C. Based on the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the experimental resistivity—temperature data from 50-300 K and find that the activation barrier decreases as temperature is increased.     

Preparation and electrochemistry of one-dimensional nanostructured MnO2/PPy composite for electrochemical capacitor

One-dimensional nanostructured manganese dioxide/polypyrrole (MnO₂/PPy) composite was prepared by in situ chemical oxidation polymerization of pyrrole in the host of inorganic matrix of MnO₂, using complex of methyl orange (MO)/FeCl₃ as a reactive self-degraded soft-template. The morphology and structure of the composite were characterized by infrared spectroscopy (IR) X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the MnO₂/PPy composite consists of α-MnO₂ and PPy with nanotube-like structure. Electrochemical properties of the composite demonstrated the material showed good electrochemical reversibility after 500 charge-discharge cycles in the potential range of −0.4 to 0.6 V, the tube-like nanocomposite has the potential application in electrochemical capacitor.     

Influence of Gd-doping in La0.7Ca0.3MnO3 on its structural and magneto-electrical properties

Bulk samples of gadolinium doped manganites with compositional formula La_0.7−xGd_xCa_0.3MnO₃ (x=0.0 and 0.1) were prepared by conventional solid state reaction method. After characterizing the samples by X-ray diffraction, scanning electron microscope and energy dispersive X-ray spectrometer, a systematic investigation of electrical and magneto-transport properties has been investigated. The replacement of La ion by Gd results in a decrease of the metal-insulator transition temperature T_MI and the magnetoresistance as well as the resistivity are found to increase. The electrical resistivity in the entire temperature range fit well with the phenomenological percolation model, which is based upon an approach that the system consists of the phase separated ferromagnetic metallic and paramagnetic insulating regions.     

Electrical transport behavior of La0.67Ca0.33MnO3/Fe3O4 composites

The influence of Fe₃O₄ contents on the electrical transport properties (resistivity and ac susceptibility) of a series of composite samples of La_0.67Ca_0.33MnO₃/Fe₃O₄ is studied. Results show that the Fe₃O₄ phase not only shifts the intrinsic insulator-metal (I-M) transition temperature T_P1 to a lower temperature, but also causes a new I-M transition at a lower temperature T_P2 (T_P2<T_P1). On the basis of an analysis by scanning electron microscopy and X-ray diffraction, we suggest that the decrease of the I-M transition temperature and the formation of the new I-M transition are caused by the segregation of a new phases related to the Fe₃O₄ at grain boundaries or surfaces of the La_0.67Ca_0.33MnO₃ grains.     

Effect of post heat treatment on microstructure and photocatalytic activities of TiO2 nanoribbons

Low-dimensional TiO₂ nanoribbons were synthesized by a simple one-step hydrothermal method. The TiO₂ nanoribbons were calcined over the temperature range 200-800 °C in order to enhance their photocatalytic properties by altering their crystal phase and increasing crystallization. Effects of hydrothermal temperature, calcinated temperature and calcination time on the formation of nanostructures have been observed and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The (BET) specific surface area of the samples which with different post treatments were determined by N₂ absorption-desorption experiment. In addition, photocatalytic activities of the nanoribbons were evaluated by photodegradation of organic dyes methyl orange under the radiation of UV light. The results reveal that the post-treatments have great effects on the microstructures and the photocatalytic activities of TiO₂ nanoribbons.     

Synthesis and structural characterization of perovskite 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 nanotubes

We report the synthesis and structural characterization of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (PMN-PT) nanotubes prepared by a novel sol-gel template method. X-ray diffraction (XRD) and selected-area electron diffraction (SAED) investigations demonstrated that the postannealed (650 °C for 1 h) PMN-PT nanotubes were polycrystalline with perovskite crystal structure. The field emission scanning electron microscope (FE-SEM) shows that as prepared PMN-PT nanotubes were hollow with diameter to be about 200 nm. High resolution transmission electron microscope (HRTEM) analysis confirmed that the obtained PMN-PT nanotubes made up of nanoparticles (10-20 nm) which were randomly aligned in the nanotubes. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the stoichiometric 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃. The possible formation mechanism of PMN-PT nanotubes was proposed at the end.     

Features of the local structural disorder in Li2O-CaF2-P2O5 glass-ceramics with Cr2O3 as nucleating agent

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of Cr₂O₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy (EDS), differential thermal analysis and conventional spectroscopic techniques. The X-ray diffraction and scanning electron microscopic studies reveal the presence of lithium phosphate, calcium phosphate and chromium phosphate (complexes of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions) crystal phases. The study on DTA suggests that the crystallization is predominantly due to the surface crystallization when the concentration of nucleating agent Cr₂O₃ is around 0.8 mol%. The IR and Raman spectral studies of these samples indicate that the sample crystallized with 0.8 mol% Cr₂O₃ is more compact and possesses high rigidity due to the presence of chromium ions largely in tetrahedral positions.     

Magnetocaloric effect in (La0.47Gd0.2)Sr0.33MnO3 polycrystalline nanoparticles

In this paper, nanosized particles of (La_0.47Gd_0.2)Sr_0.33MnO₃ perovskite-type oxides were successfully synthesized at a relatively low calcinated temperature at 800 °C for 10 h using amorphous molecular alloy as precursor. X-ray diffraction (XRD) and electron diffraction (ED) revealed that the resulting product is of pure single-phase rhombohedral structure. The Curie temperature T_C and magnetic entropy change (MCE) in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline nanoparticles are determined and compared to those of similar systems prepared by the conventional solid-state reaction method. The Curie temperature T_C is shifted to 298 k, and a relatively large MCE with a broad peak around Curie temperature is observed in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline particles. These results suggested that this material is a suitable candidate as working substance in magnetic refrigeration near room temperature.     

非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3-0.1V2O5的电学性质和电子自旋共振研究

对两种非晶态B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15),用差热分析、电导率测量、X射线衍射和电子自旋共振进行研究,发现:1)V₂O₅不仅作非晶网络形成剂,而且改变了晶化过程;2)对B₂O₃-Li_{2关键词：}     

Synthesis and characterization of oxide cathode materials of the system (1-x-y)LiNiO<Subscript>2</Subscript>·xLi<Subscript>2</Subscript>MnO<Subscript>3</Subscript>·yLiCoO<Subscript>2</Subscript>

Composite cathode materials produced by integrating isostructural (2D-layered) compounds LiNiO₂, LiCoO₂, and Li₂MnO₃ (Li(Li_1/3Mn_2/3)O₂) have been investigated utilizing a compositional phase diagram. The samples were characterized by multiple techniques to establish structure–property relationships. Specifically, for structural characterization, powder X-ray diffraction, scanning electron microscopy, thermo-gravimetric analysis, and X-ray photoelectron spectroscopy were carried out. For properties, electrochemical characterization was carried out. The best composition showed a discharge capacity of 244 mAh/g (C/15 rate) in the testing range of 4.6–2 V, with good coulombic efficiency and cyclability.     

Preparation and characterization of rod-shaped MnO2 crystal

Rod-shaped MnO₂ crystal was synthesized by a new route, the sample was a multicrystal with the mixture of α- and γ-MnO₂. From TEM results, it could be seen that the sample has a length of 250-350 nm and a diameter of 15-25 nm. The ratio of length to the diameter could reach more than 15:1. In the preparation process, the KMnO₄ was used as oxidant and MnCl₂ was the manganese source. The polyethylene glycol (PG) was added as the dispersant and the high molecular weight polyacrylamide (PAM) was introduced at the same time. When the reaction finished, the product was treated with steam for 3 h and then the rod-shaped MnO₂ crystal was obtained. The crystal was characterized by X-ray diffraction (XRD), electron diffraction (ED), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM).