A Facile Route for Synthesis of LiFePO4/C Cathode Material with Nano-sized Primary Particles

A facile and practical route was introduced to prepare LiFePO4/C cathode material with nano-sized primary particles and excellent electrochemical performance. LiH2PO4 was synthesized by using H3PO4 and LiOH as raw materials. Then, as-prepared LiH2PO4, reduced iron powder andα-D-glucose were ball-milled, dried and sin-tered to prepare LiFePO4/C. X-ray diffractometry was used to characterize LiH2PO4, ball-milled product and LiFePO4/C. Differential scanning calorimeter-thermo gravimetric analysis was applied to investigate possible reac-tions in sintering and find suitable temperature for LiFePO4 formation. Scanning electron microscopy was em-ployed for the morphology of LiFePO4/C. As-prepared LiH2PO4 is characterized to be in P21cn（33） space group, which reacts with reduced iron powder to form Li3PO4, Fe3（PO4）2 and H2 in ball-milling and sintering. The appro-priate temperature for LiFePO4/C synthesis is 541.3-976.7 ℃. LiFePO4/C prepared at 700 ℃ presents nano-sized primary particles forming aggregates. Charge-discharge examination indicates that as-prepared LiFePO4/C displays appreciable discharge capacities of 145 and 131 mA·h·g^-1 at 0.1 and 1 C respectively and excellent discharge ca-pacity retention.     

High-rate properties of LiFePO4/carbon composites as cathode materials for lithium-ion batteries

Electrochemical properties of LiFePO₄/carbon composites were investigated to achieve a high-rate lithium electrode performance. LiFePO₄/carbon composites were synthesized by a hydrothermal reaction of a solution of FeSO₄·7H₂O, H₃PO₄, and LiOH·H₂O mixed with carbon powders under nitrogen atmosphere followed by annealing under 1% H₂–99% Ar atmosphere. Particle size of the obtained LiFePO₄/carbon composites observed by scanning electron microscopy was less than 100 nm. At a high current density of 1000 mA g⁻¹, the LiFePO₄/carbon composites showed a high discharge capacity of 113 mA h g⁻¹, and a flat discharge potential plateau was observed around 3.4 V. The discharge capacity at the high current density, 85% of that at a low current density of 30 mA g⁻¹, is a quite high value for LiFePO₄ cathodes. Homogeneous microstructure consisting of small particles contributed to the high-rate properties of the LiFePO₄/carbon composites.     

Influence of synthesis parameters on the properties of LiFePO4/C cathode material☆

The influence of sintering temperature,carbon content and dispersive agent in ball-milling was investigated on the properties of Li Fe PO_4/C prepared using Fe_2O_3,NH_4H_2PO_4,Li_2CO_3 and glucose via solid state reaction.X-ray powder diffraction,scanning electron microscopy and charge–discharge test were applied to the characterization of the Li Fe PO_4/C samples synthesized under different conditions.Sintering temperature affects the crystallite/particle size and degree of crystallinity of LiF eP O_4,formation of Fe_2 P and maintenance of carbon in LiF e PO_4/C.Carbon maintenance is favored by low sintering temperature,and 700 °C is optimum for synthesis of LiF eP O_4/C with superior electrochemical performance.A higher carbon content in the range of 4.48%–11.03% results in a better rate capability for Li Fe PO_4/C.The dispersive agent used in ball-milling impacts the existent state of carbon in the final product which subsequently determines its charge–discharge behavior.The sample prepared at700 °C by using acetone as the dispersive agent in ball-milling exhibits an excellent rate capability and capacity retention without any fade at 0.1C,1C and 2C,with corresponding average discharge capacities of 153.8,128.3and 121.0 m A·h·g~(-1),respectively,in the first 50 cycles.     

Synthesis of sub-micrometer lithium iron phosphate particles for lithium ion battery by using supercritical hydrothermal method简

A supercritical hydrothermal method was employed to prepare sub-micrometer LiFePO4 particles with high purity and crystallinity. The structure and morphology of LiFePO4 particles were characterized by X-ray diffraction and scanning electron microscope. The electrochemical tests were carried out to determine the reversible capacity, rate and cycling performance of the LiFePO4 particles as cathode material for lithium ion battery. Experimental results show that solvent and calcining time have significant effects on purity, size and morphology of LiFePO4 particles. Mixed solvent contained deionized water and ethanol is conducive to synthesize smaller and more uniform particles. The size of LiFePO4 particles as-prepared is about 100-300 nm. The specific discharge capacities of the LiFePO4 particles are 151.3 and 128.0 mA. h. g-1 after first cycle at the rates of 0.1 and 1.0 C, respectively. It retains 95.0% of the initial capacity after 100 cycles at 1.0 C.     

片状LiFePO4/C正极材料制备及其电化学性能研究

在温和的反应条件下，使用十二烷基苯磺酸钠(SDBS)成功合成了片状二水磷酸铁，并将其与氢氧化锂、柠檬酸球磨混合，采用碳热还原法制备了具有纳米厚度的片状LiFePO₄/C电极材料。研究了SDBS对磷酸铁形貌以及LiFePO₄/C电极材料电化学性能的影响。利用X-射线衍射、扫描电子显微镜和充放电测试等技术手段，对合成样品的物相、形貌和电化学性能进行了分析测试。电化学测试表明，在25℃，2.0～4.2 V电压范围条件下，使用片状二水磷酸铁为前驱体制备的LiFePO₄/C样品，在0.1 C下放电比容量高达166.4 mA·h·g^-1，且首次库仑效率达到99.6%，在1 C下循环500次容量保持率为99%，表现出了优异的电化学性能。     

Investigation of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ based cathode SOFC: II. The effect of CO2 on the chemical stability

The effect of carbon dioxide on the chemical stability of a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ cathode in the real reaction environment at 450 °C was investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), temperature programmed desorption (TPD), X-ray diffraction (XRD) and electrochemical impedance spectra (EIS) techniques. It was found that the presence even of very small quantities of CO₂ seriously deteriorates the fuel cell performance at 450 °C. XPS, TPD and XRD results strongly evidenced the formation of carbonates involving strontium and possibly barium after the BSCF cathode was operated in 1% CO₂/O₂ gas mixture at 450 °C for 24 h. SEM-EDX analysis of the BSCF cathode surface, after treatment in CO₂/O₂ environment at 450 °C, showed small particles on the surface probably associated with a carbonate phase and a segregated phase of the perovskite. The corresponding EDX spectra confirmed the presence of a carbonate layer and also revealed the surface enrichment of strontium and barium elements. EIS results indicated that both ohmic and polarization resistances increased gradually with the introduction of carbon dioxide in the oxidant stream, which could be interpreted by the decreased oxygen reduction kinetics and the formation of carbonate insulating layer.     

LiFePO/C cathode materials synthesized by co-precipitation and microwave heating

LiFePO₄/C cathode materials were synthesized by a combination of co-precipitation and microwave heating using polyethylene glycol (PEG) as a carbon resource and the influence of microwave heating time on the structure and electrochemical performance of the materials was also discussed. The samples were characterized by X-ray diffraction (XRD), TEM, particle-size analysis and constant current charge-discharge experiment. The results show that the LiFePO₄/C heated for 9 min has a pure olive-type phase and excellent electrochemical performance. The initial discharge capacities of this sample are 154.3, 139.7, 123.9 mAh/g at the rates 0.1C, 0.2C, 1C at room temperature, respectively, and after 20 cycles remain 152.3, 134.3, 118.5 mAh/g, respectively.     

Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

Long-term cyclability of nanostructured LiFePO4

Amorphous LiFePO₄ was obtained by lithiation of FePO₄ synthesized by spontaneous precipitation from equimolar aqueous solutions of Fe(NH₄)₂(SO₄)₂·6H₂O and NH₄H₂PO₄, using hydrogen peroxide as oxidizing agent. Nano-crystalline LiFePO₄ was obtained by heating amorphous nano-sized LiFePO₄ for different periods of time. The materials were characterized by TG, DTA, X-ray powder diffraction, scanning electron microscopy (SEM) and BET. All materials showed very good electrochemical performance in terms of energy and power density. Upon cycling, a capacity fading affected the materials, thus reducing the electrochemical performance. Nevertheless, the fading decreased upon cycling and after the 200th cycle the cell was able to cycle for more than 500 cycles without further fading.     

镁离子掺杂磷酸铁锂的制备及其电化学性能

通过简单水热反应制备磷酸铁锂前驱体,并结合后期热处理过程制备了镁离子掺杂碳包覆的磷酸铁锂正极材料。利用X射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）等表征了镁离子掺杂磷酸铁锂的成分、形貌和结构。元素分布结果证明镁离子均匀掺杂在磷酸铁锂材料中。通过恒流充放电和循环伏安、交流阻抗等方法对材料的电化学性能进行测试。结果表明,镁离子掺杂后的磷酸铁锂材料具有较高的放电比容量（0.1C放电比容量为 160.1 mA·h/g）和优越的倍率性能（20C放电比容量为77.2 mA·h/g）,同时减小了极化和电荷迁移电阻。这条合成路线是提高水热法制备磷酸铁锂正极材料电化学性能的有效方法。     

前驱体二水磷酸铁对磷酸铁锂电化学性能的影响

以钛白生产副产物七水硫酸亚铁为铁源,工业磷酸二氢铵为磷源,双氧水为氧化剂,采用共沉淀法合成了不同粒径和形貌的二水磷酸铁,并以此为前驱体,通过碳热还原法制备了粒径不同的LiFePO₄/C正极材料。经过对样品进行X射线衍射（XRD）、扫描电镜（SEM）以及恒电流充放电测试,研究了二水磷酸铁及LiFePO₄/C的结构、形貌以及电化学性能。结果表明,以较细的二水磷酸铁为铁源,制备得到的LiFePO₄/C颗粒较细,且具有更优异的电化学性能。0.1、0.5、1、2、5、10 C放电比容量分别为154、148、144、140、130、120 mA·h/g。     

Effect of Al addition on the synthesis of Ti3SiC2 bulk material by pulse discharge sintering process

Ti₃SiC₂ bulk materials were synthesized from the starting powders of 1Ti/1Si/2TiC–xAl and 3Ti/1SiC/1C–xAl (molar ratios, x ranges from 0.05 to 0.15) at temperatures between 1100 and 1400 °C for 15 min by pulse discharge sintering technique. X-ray diffraction and scanning electron microscopy were used to characterize the synthesized materials. It was found that the addition of Al decreases the content of TiC in the sintered samples and expands the optimal temperature range for the synthesis of Ti₃SiC₂ bulk materials. By addition of Al, Ti₃SiC₂ bulk materials of high phase-purity have been synthesized at 1100 and 1200 °C from 1Ti/1Si/2TiC and 3Ti/1SiC/1C starting powders, respectively.     

The improvement in oxidation resistance of carbon by a graded SiC/SiO2 coating

A dense functionally gradient SiC/SiO₂ coating has been developed to improve the oxidation resistance of carbon at elevated temperatures. SiC was coated on the surface of a graphite substrate by a reaction between thermally evaporated silicon and carbon at 1400 °C. The SiO₂ layer was deposited by exposing the SiC coated specimens next to a bed of Si powder in a flowing H₂–H₂O gas (P_H2O=2.6×10⁻² atm) at 1400 °C. The formed SiC/SiO₂ layers were dense and had gradient compositions with good adhesion to the carbon substrate. However, as the coating thickness increased, the coating layer became cracked and delaminated from the substrate due to thermal stress. The specimens with the continuous SiC/SiO₂ layer showed a remarkably improved oxidation resistance up to 1200 °C.     

水热法一步合成磷酸铁锂及其性能研究

为优化液相法一步制备磷酸铁锂（LiFePO₄）技术,以七水合硫酸亚铁、磷酸二氢铵、一水合氢氧化锂为原料,通过添加十二烷基苯磺酸钠（SDBS）作为表面活性剂,采用液相水热法合成技术,一步合成了LiFePO₄正极材料。研究了水热法一步合成技术对LiFePO₄材料的组成、结构、形貌、粒度等的影响,通过电感耦合等离子体发射光谱仪（ICP-OES）、X射线衍射仪（XRD）、扫描电镜（SEM）、粒度分析仪等对材料进行了表征分析,并测试了材料的电化学性能。研究结果表明,合成得到的LiFePO₄材料为微米级球形颗粒形貌的正交晶系非化学计量比的Li_1.02Fe_0.994PO₄材料。电化学性能测试结果表明,在0.1C倍率下首次充、放电比容量分别为162.0、159.9 mA·h/g,库伦效率达到98.7%、倍率性能（以1C/0.1C保持率计）为92.3%,0.1C倍率循环100次容量保持率为96.4%,展现出良好的电化学性能。     

Preparation, structural and optical characterization of BaWO4 and PbWO4 thin films prepared by a chemical route

Polycrystalline BaWO₄ and PbWO₄ thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO₄ and PbWO₄ phase crystallize at 500 °C from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 °C and the appearance of two sharp and intense bands between 1000 and 600 cm⁻¹ assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO₄ and PbWO₄ thin films have Eg=5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO₄ and PbWO₄ thin films.     

响应面法优化碳热还原合成LiFePO4/C的工艺参数（英文）

A statistically based optimization strategy is used to optimize the carbothermal reduction technology for the synthesis of LiFePO4/C using LiOH,FePO4 and sucrose as raw materials.The experimental data for fitting the response are collected by the central composite rotatable design(CCD).A second order model for the discharge ca-pacity of LiFePO4/C is expressed as a function of sintering temperature,sintering time and carbon content.The ef-fects of individual variables and their interactions are studied by a statistical analysis(ANOVA).The results show that the linear effects and the quadratic effects of sintering temperature,carbon content and the interactions among these variables are statistically significant,while those effects of sintering time are insignificant.Response surface plots for spatial representation of the model illustrate that the discharge capacity depends on sintering temperature and carbon content more than sintering time.The model obtained gives the optimized reaction parameters of sinter-ing temperature at 652.0 ℃,carbon content of 34.33 g?mol-1 and 8.48 h sintering time,corresponding to a dis-charge capacity of 150.8 mA·h·g-1.The confirmatory test with these optimum parameters gives the discharge ca-pacity of 147.2 and 105.1 mA·h·g-1 at 0.5 and 5 C,respectively.     

Ordering and quality factor in 0.95BaZn1/3Ta2/3O3–0.05SrGa1/2Ta1/2O3 production resonators

Ordering of the B-site cations in UMTS (universal mobile telecommunications systems) standard resonator pucks composed of perovskite structured, 0.95BaZn_1/3Ta_2/3O₃–0.05SrGa_1/2Ta_1/2O₃ (BZT–SGT) has been investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and powder neutron diffraction (PND). XRD patterns from samples sintered at 1550 °C/2 h but annealed and quenched at 50 °C intervals between 1400 and 1600 °C revealed that the order–disorder phase transition was at 1500 °C. In addition, a peak at 29.5° 2θ attributed to a Ba₈ZnTa₆O₂₄ phase was present due to ZnO loss. Electron diffraction patterns revealed that samples heat treated 1500 °C (including as sintered samples, 1525 °C/2h,) exhibited short-range 1:2 ordering along all <111> directions giving rise to an average short-range face centred cubic structure. Samples annealed and quenched from below 1500 °C showed 1:2 order. To avoid excessive ZnO loss, an annealing temperature was chosen at 1275 °C (for 24 and 168 h). Neutron diffraction data were best refined using two ordered BZT phases with slightly different lattice parameters. TEM revealed a microstructure in each case consisting of 1:2 small ordered domains in the centre of all grains but with every second grain exhibiting a concentric shell composed of an ordered single domain, containing elongated translational (APBs) but not orientational domains. The formation of the concentric ordered shell was attributed to grain boundary migration during grain growth. As-sintered samples gave unloaded quality factors (Q)=54,000 at 2 GHz which rose to 78,000 at 2 GHz after annealing for 24 h. No further improvement in Q was observed for longer annealing times.     

球形LiMnPO4/C正极材料的喷雾干燥法制备及性能研究

以氢氧化锂、乙酸锰、磷酸二氢铵和聚乙二醇为原料,采用一次喷雾干燥法制备了球形LiMnPO₄/C正极材料,并研究了煅烧温度对球形LiMnPO₄/C样品形貌、结构和电化学性能的影响。通过X射线衍射（XRD）和场发射扫描电镜（SEM）对其进行了结构和形貌的表征。结果表明,经700 ℃焙烧的LiMnPO₄/C为橄榄石型结构,在SEM下呈规则的球形,由粒径约为50 nm的一维纳米颗粒堆积而成。该样品在室温0.1C倍率下首次放电比容量可达148 mA·h/g,循环80圈后的放电比容量依然在140 mA·h/g左右,容量保持率为94.6%。     

Synthesis and characterization of Li ion conducting La2/3−xLi3xTiO3 by a polymerizable complex method

Ultrafine lithium ion conducting La_2/3−xLi_3xTiO₃ (x = 0.11, LLT) powder was synthesized by a simple polymerizable complex method based on the Pechini-type process. The formation mechanism, homogeneity and microstructure of the samples were investigated by thermal analysis (TG/DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD analysis indicated the formation of pure perovskite-type phase. The powder synthesized at a temperature as low as 900 °C in a much shorter time than solid-state reaction method was well crystallized. The lithium ion conductivity of the LLT ceramics sintered at 1200 °C was found to be 9 × 10⁻⁴ S/cm at room temperature.     

Thermal conductivity of AlN ceramics sintered with CaF2 and YF3

Dense AlN ceramics with a thermal conductivity of 180W/m·K were obtained at the sintering temperature of 1750 °C using CaF₂ and YF₃ as additives. At temperatures below 1650 °C, the shrinkage of AlN ceramics is promoted by liquid (Ca,Y)F₂ and Ca₁₂Al₁₄O₃₂F₂. Liquid CaYAlO₄ mainly improves the densification of the sample when the sintering temperature increases to 1750 °C. The formation of liquid (Ca,Y)F₂ at a relatively low temperature results in homogeneous YF₃ distribution around the AlN particles, which benefits the removal of oxygen impurity in the AlN lattice, and thus a higher thermal conductivity.