Electrochemical performance of LiFePO4 cathode material for Li-ion battery

In the search for improved materials for rechargeable lithium batteries, LiFePO4 offers interesting possibilities because of its low raw materials cost, environmental friendliness and safety. The main drawback with using the material is its poor electronic conductivity and this limitation has to be overcome. Here Al-doped LiFePO4/C composite cathode materials were prepared by a polymer-network synthesis technique. Testing of X-ray diffraction, charge-discharge, and cyclic voltammetry were carried out for its performance. Results show that Al-doped LiFePO4/C composite cathode materials have a high initial capacity, good cycle stability and excellent low temperature performance. The electrical conductivity of LiFePO4 material can be obviously improved by doping Al. The better electrochemical performances of Al-doped LiFePO4/C composite cathode materials have a connection with its conductivity.     

硫酸体系有色金属电沉积用3D-Pb阳极的制备与性能（英文）

研究Pb²⁺浓度、电流密度、沉积时间和温度对沉积Pb结构的影响。在低Pb²⁺浓度条件下(～0.15 mol/L),Pb沉积物呈杨桃状,而在高Pb²⁺浓度条件下(≥0.30 mol/L),Pb沉积物呈立锥状。进一步对比研究杨桃状Pb阳极(Cara-Pb)、立锥状Pb阳极(Pyra-Pb)和Pb阳极的氧化膜层和阳极电位。在160 g/L H₂SO₄溶液中恒流极化(50 mA/cm²)72 h后,Pyra-Pb阳极氧化膜层厚度大于Cara-Pb和Pb阳极,进而显著减缓金属基底的晶界腐蚀。此外,Pyra-Pb阳极氧化膜层具有更大表面积和更高Pb O₂含量,因此,极化72 h后Pyra-Pb阳极电位较Cara-Pb和Pb阳极的低40mV。综上,在Pb阳极表面构建立锥状3D-Pb结构具有降低电沉积能耗、延长阳极寿命的潜力。     

Cu-14Al-X合金在5.0%H2SO4溶液中的腐蚀行为

通过静态浸泡腐蚀实验、电化学实验、X射线衍射分析、扫描电镜、电子探针、光电子能谱等方法研究高铝青铜合金Cu-14Al-X在5.0%H2SO4溶液中的耐蚀性能及腐蚀行为。结果表明：在H2SO4溶液中,Cu-14Al-X合金有良好的耐蚀性能,合金中的（α＋γ2）共析体与β′相、α相和κ相相比,具有优先腐蚀倾向,合金主要发生脱铝腐蚀。腐蚀钝化膜的形成及热处理后合金各相成分趋于一致,均使合金耐腐蚀性能得到改善。     

Kinetics of leaching lithium from α-spodumene in enhanced acid treatment using HF/H2SO4 as medium

An enhanced leaching of Li from α-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid (HF/H₂SO₄) as the medium. Based on the optimized leaching conditions, the leaching kinetics of Li was investigated in an ore/HF/H₂SO₄ ratio of 1:3:2 g:mL:mL with leaching temperature ranging from 50 to 100 °C. The results indicate that the leaching kinetics of Li fitted well with a model based on the shrinking core model. In addition, the leaching rate of Li was controlled by chemical reactions and diffusion through the product layers. The apparent activation energy E_a was calculated to be 32.68 kJ/mol. Solid films were formed because of the generation of insoluble products such as cryolithionite (Na₃Li₂Al₂F₁₂), cryolite (Na₃AlF₆), calcium fluoride (CaF₂), potassium cryolite (K₂AlF₅), aluminum fluoride (AlF₃), and fluorosilicates (Na₂SiF₆ or KNaSiF₆). Furthermore, the effects of the ore/HF ratio and leaching temperature on the leaching behavior of Li, Al and Si were investigated. The results indicate that the ore/HF ratio and leaching temperature could clearly affect the distribution of HF molecules on the leaching of Li, Al and Si, which are important for the selective leaching of Li over Al and Si with this fluorine-based chemical method.     

在H2SO4-HCl-H2O复合体系中氧化浸出镍钼矿冶炼烟尘中的硒

对在H2SO4-HCl-H2O复合体系中氧化浸出镍钼矿冶炼烟尘中的硒进行热力学分析,确定从镍钼矿冶炼烟尘中浸出硒的新工艺及其最优技术参数.采用XRD对镍钼矿冶炼烟尘及其浸出渣进行表征.结果表明:在最佳技术条件下,硒浸出率达到98%,浸出渣含硒0.16%(质量分数);冶炼烟尘中硒以单质形式存在,未见硒及其化合物出现,表明烟尘中的硒浸出较完全;浸出渣主要由SiO2、CaSO4、A12SiO5、As2O3和KAlSi3O8组成.     

Complexation extraction of scheelite and transformation behaviour of tungsten-containing phase using H2SO4 solution with H2C2O4 as complexing agent

The extraction of tungsten from scheelite was carried out using a sulfuric acid solution with oxalic acid as the chelating agent. Tungsten was obtained in the form of highly soluble hydrogen aqua oxalato tungstate (H₂[WO₃(C₂O₄)·H₂O]) during the leaching process, while calcium remained in the residue as calcium sulfate dihydrate (CaSO₄·2H₂O). About 99.2% of the tungsten was leached at 70 °C, 1.5 mol/L sulfuric acid, 1 mol/L oxalic acid, a liquid/solid ratio of 25:1 (mL/g), an oxalic acid to sulfuric acid molar ratio of 1:1, a stirring speed of 300 r/min and a leaching time of 2 h. H₂[WO₃(C₂O₄)·H₂O] was thermally decomposed into tungstic acid (H₂WO₄), and tungsten trioxide (WO₃) was directly produced by calcining H₂WO₄ at 700 °C for 2 h. The surface chemical reaction was determined to be the controlling step during tungsten leaching, and the apparent activation energy was calculated to be 51.43 kJ/mol.     

氟碳铈矿盐酸浸出过程的动力学

考察盐酸浓度、浸出温度、液固比和矿物粒度对浸出速度的影响.结果表明:在盐酸浓度6 mol/L、浸出温度90C、液固比15:1、矿物粒度25 μm的条件下浸出90 min后,氟碳铈矿中稀土碳酸盐的浸出率达到89.6％,而稀土氟化物的浸出率仪为1.5％.氟碳铈矿浸出过程符合产物层扩散模型,稀土碳酸盐和氟化物浸出过程的表观活...     

Leaching of cuprite through NH4OH in basic systems

Cuprite is a difficult oxide to leach under acidic conditions (for the maximum extraction of 50%). In this research, the feasibility of leaching cuprite in an ammoniacal medium was studied. The working conditions addressed here were the liquid/solid ratio (120:1–400:1 mL/g), stirring speed (0–950 r/min), temperature (10–45 °C) and NH₄OH concentration (0.05–0.15 mol/L). In addition, different ammoniacal reagents (NH₄F and (NH₄)₂SO₄) were analyzed. The experiments were performed in a 2 L reactor with a heating mantle and a condenser. The most important results were that the maximum leaching rate was obtained at pH 10.5, 0.10 mol/L NH₄OH, 45 °C, 4 h, 850 r/min and a liquid/solid ratio of 400:1, reaching a copper extraction rate of 82%. This result was related to the non-precipitation of copper in solution by the formation of copper tetra-amine. The liquid/solid ratio and stirring speed were essential for increasing the cuprite leaching. The maximum leaching rate was achieved at higher temperatures; however, significant copper leaching rate occurred at temperatures near the freezing point of water (17.9% over 4 h). Increasing NH₄OH concentration and decreasing particle size increased the cuprite leaching rate. The two ammoniacal reagents (NH₄F and (NH₄)₂SO₄) had low extraction rate of copper compared with NH₄OH. The kinetic model representing cuprite leaching was a chemical reaction on the surface. The order of the reaction with respect to the NH₄OH concentration was 1.8, and it was inversely proportional to the radius of the ore particles. The calculated activation energy was 44.36 kJ/mol in the temperature range of 10–45 °C.     

球形磷酸铁锂正极材料制备中试研究

用湿法球磨-喷雾干燥法制备LiFe0.98Mg0.02PO4/C复合正极材料;用激光粒度分析仪、X射线衍射仪、扫描电镜和恒流充放电等对前驱体和磷酸铁锂样品进行表征;考察不同球磨工艺对磷酸铁锂颗粒形貌、粒度分布、振实密度和电化学性能的影响。结果表明:用湿法球磨-喷雾干燥法可以制得球形颗粒、高振实密度且电化学性能优良的磷酸铁锂正极材料,原料经粗磨后再超细球磨制得的材料性能更佳,振实密度达1.67 g/cm3,在0.1 C、0.5 C和1.0 C倍率下的首次放电比容量分别为151、143和132 mA·h/g。     

Behavior of S2O32- And SO32- In sulfur-bearing aqueous solution system for gold leaching

The concentrations of S₂O₃^2? and SO₃^2? were measured in gold leaching systems, including thiosulfate system, polysulfide system and the modified lime sulfur synthetic solution (ML) system in the process of chemical reaction. The interactions among S₂O₃^2?, SO₃^2? and S^2? were discussed. The behavior mechanism of sulfur-bearing reagents was proposed to describe the process reactions and their Gibbs free energy. The proper quantity oxygen and SO₃^2? reduce decomposition of S₂O₃^2? and react with sulfur derived from the decomposition of S_X^2?. So, SO₃^2? ions have action to stabilize sulfur-bearing system and are favorable to leach gold.     

Controlling limiting length of tunnels on Al foil electroetched in HCl-H2SO4 solution

The limiting length of tunnels, llim, of Al foil electro-etched in HCl-H2SO4 solution and the corresponding anodic polarization curves in the same solution were measured. It is found that there is a dependence of llim on the potential difference, △φ, between the pitting potential, φpit, and the corrosion potential, φcorr, of Al foil, when the temperature and H2SO4 concentration of HCl-H2SO4 electrolyte are changed. The dynamic equation on the tunnel growing and the linear equation between llim and △φ were deduced by analyzing the relationship among the over-potential on Al foil surface, the transport over-potential in tunnel solution and the over-potential at tunnel tip during the electro-etching. The results show that the growing velocity of tunnels decreases with their extending in length and the changing trend of llim can be judged by measuring △φ, which supplies a convenient access to explore new kinds of etchants.     

含锗真空炉渣在HCl-CaCl2-H2O体系中浸出锗的动力学研究

为提高真空炉渣中锗的浸出率提供理论依据,对含锗真空炉渣在HCl-CaCl2-H2O体系中锗的浸出动力学进行了研究。结果表明,浸出过程属于生成固体产物层的"未反应核收缩模型",其宏观动力学方程为:1–2/3x–(1–x)2/3=4.66×10-3CHCl1.027CCaCl21.046d-0.862exp(–21068/RT)t,表观活化能为21.068kJ/mol,浸出过程受灰分层扩散控制;提高盐酸的浓度、氯化钙浓度、浸出温度、液固比及减小矿物粒度均可加快锗的浸出速度,提高锗的浸出率。     

Corrosion and wear behaviors of Al-bronzes in 5.0% H2SO4 solution

Steady-state corrosion and wear behaviors of two Al-bronzes, Cu-14Al-X and QAl9-4, in 5.0% H2SO4 solution were investigated. It is found that wear loss of bronzes in 5.0% H2SO4 solution is lower than that in water or in air, namely, it exhibits negative synergy between corrosion and wear. Further analysis shows that corrosive solution plays an important role in cooling of specimen during the sliding wear to prevent the reduction of the surface hardness of specimen, induced by frictional heat. On the other hand, the bronzes suffer a de-alloying corrosion, and a noble copper subsurface and patina form on the specimen surface in corrosive solution, which has a passive function for further corrosion. The noble copper subsurface experiences strain hardening during the corrosion and wear, resulting in the increase of the surface hardness thus the increase in wear resistance.     

Kinetics of SiO2 leaching from Al2O3 extracted slag of fly ash with sodium hydroxide solution

Kinetics of SiO₂ leaching from Al₂O₃ extracted slag of fly ash with sodium hydroxide solution was studied. The effect of leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed on SiO₂ leaching rate was investigated. The results show that increasing leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed increases SiO₂ leaching rate. The SiO₂ leaching rate is 95.66% under the optimized conditions. There are two stages for the SiO₂ leaching process, and the leaching reaction is very rapid in the first stage but quite slow in the second stage. The whole leaching process follows the shrinking core model, and the outer diffusion of no product layer is the rate-controlling step. The activation energies of the first and second stages are calculated to be 8.492 kJ/mol and 8.668 kJ/mol, respectively. The kinetic equations of the first and the second stages were obtained, respectively.     

固相法合成原位碳包覆LiFePO4复合正极材料及其性能

以LiH2PO4和FeC2O4.2H2O为原料,聚乙烯醇为碳源,通过机械化学活化辅助固相法合成原位碳包覆的LiFePO4材料;考察合成温度对LiFePO4/C材料晶体结构、物理和电化学性能的影响。结果表明:700℃下处理的产物结晶良好、分布均匀、颗粒细小;在最佳的热处理条件下,热解碳在LiFePO4颗粒表面形成了良好的纳米导电层,LiFePO4/C材料在0.1C、0.5C、1C和2C倍率下放电比容量分别为155.7、150.1、140.1和130 mA.h/g,且材料在0.1～2C范围内充放电都有很平稳的平台,极化小,并具有较高的高倍率(2C)放电比容量和较好的循环性能。     

Pt和PtBi在H2SO4-CH3OH中的氧还原性能

采用氩弧熔炼后热处理方法制备了PtBi金属间化合物材料.采用循环伏安和旋转圆盘电极手段进行电化学性能测试.通过在0.5 mol/L H2SO4 0.25 mol/L CH3OH溶液中对氧还原的起始电位和电流密度大小比较发现,与光滑铂电极相比,PtBi金属间化合物具有良好的氧还原催化性能和抗甲醇中毒性能.从结构方面分析了PtBi具有抗甲醇中毒性能的原因,认为是PtBi中大的Pt-Pt间距不利于甲醇的吸附解离.X射线光电子能谱(XPS)结果表明,PtBi材料中Pt的d电子空穴增加,可能是导致PtBi电极表面氧还原电流增大的原因.     

Na_2SO_3从硒碲富集物中浸出硒动力学(英文)

研究用Na2SO3溶液从硒碲富集物中浸出硒的动力学。该硒碲富集物的微观形貌主要为球状体和柱状体,其粒径范围为17.77～56.58μm,且其主要成分为41.73%Se和40.96%Te。研究Na2SO3浓度(126～315 g/L)、搅拌速度(100～400 r/min)、反应温度(23～95°C)、液固比(7:1～14:1)及硒碲富集物平均粒径(17.77～56.58μm)对Se浸出率的影响。结果表明:增加Na2SO3浓度、提高搅拌速度、升高反应温度和增加液固比均可以提高Se浸出率,而增大硒碲富集物的粒径会导致Se的浸出率降低;反应温度对Se浸出率影响较大,当反应温度从23°C升高至95°C时,Se浸出率从21%增至67%;该浸出过程符合Avrami模型,其模型特征参数和表观活化能分别为0.235和20.847kJ/mol。     

硫酸钠溶液中2024—T3铝合金孔蚀过程的电化学噪声特征

高强度航空铝合金结构材料2024-T3在3.0%（质量分数（Na2SO4溶液中发生局部腐蚀的过程中,电位噪声的谱功率密度（SPD）曲线都具有相同的特征,即在极低频下为白噪声,随着频率的升高逐渐转化为1/f^α噪声,相应于一个噪声信号波,有一个腐蚀孔出现,在孔蚀诱导期,白噪声水平升高,截止频率增大,SPD曲线的倾斜段直线斜率小于-20dBv/decade,且趋于增大,孔蚀发生后,上述3个参量则各自朝着上述方向的塑方向变化,孔蚀时的Hurst指数（H）小于非孔蚀期的Hurst指数,而孔蚀时的系统分维（D）则大于非孔蚀期的系统分维。     

氨-硫酸铵体系过硫酸盐氧化含钙镁碳酸盐低品位铜矿的浸出动力学(英文)

研究在氨?硫酸铵体系中用过硫酸盐氧化低品位铜矿浸出动力学,确定搅拌速度、浸出温度、矿物粒度及氨、硫酸铵和过硫酸钠的浓度对浸出的影响。结果表明,搅拌速度在300r/min以上时对浸出速度无影响,浸出速度随反应温度及氨、硫酸铵和过硫酸钠浓度的增大而增加。对浸出渣的EDS和物相定量分析表明斑铜矿被过硫酸盐氧化而溶解于氨?硫酸铵溶液。用产物层的界面传质和扩散控制的收缩核模型分析铜矿的溶解动力学,其表观活化能为22.91kJ/mol,同时获得了描述浸出过程的半经验动力学方程,其对氨、硫酸铵和过硫酸钠的浓度的表观反应级数分别为0.5、1.2和0.5。