机械活化氧化法制备锰酸锂及其性能研究

以高纯金属锰粉和碳酸锂为原料,通过机械活化氧化法合成了尖晶石LiMn2O4材料。采用X射线衍射(XRD)和扫描电镜(SEM)对LiMn2O4样品结构及形貌进行表征,用充放电测试和交流阻抗技术对LiMn2O4样品进行电化学性能研究。结果表明,所制备的LiMn2O4具有完整的尖晶石型结构,且颗粒形貌规整,颗粒大小均匀。所制备的LiMn2O4材料室温(25℃)在3.0~4.3V电压范围,在0.1C倍率下首次放电比容量为125.8mAh/g;2C首次放电容量为120.1mAh/g,300次循环后放电容量保持103.9mAh/g,容量保持率为86.51%。且样品具有较好的高温性能和较小的阻抗。     

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。     

以Mn3O4为前驱体的LiMn2O4及其电化学性能

对传统的固相反应进行了改进,以控制结晶法合成出来的Mn3O4为前驱体,和LiOH混合煅烧,制备出锂离子电池正极活性材料尖晶石LiMn2O4。对由此方法得到的尖晶石LiMn2O4的结构和电化学性能进行了研究。通过X线光衍射和扫描电镜分析表明,该材料为纯相尖晶石LiMn2O4,不含其它杂质相,而且晶粒大小比较均匀;通过电化学性能测试表明,该尖晶石LiMn2O4具有良好的电化学性能：其首次放电比容量为128mAh/g,经过10次充放电循环后,其放电比容量仍有124mAh/g。     

锌掺杂正极材料尖晶石LiMn_2O_4的制备及电化学性能

为改善锂离子电池正极材料LiMn2O4的电化学循环性能,以乙酸锂、乙酸锰和乙酸锌为原料,采用固相法制备了LiMn2-xZnxO4(x=0.02、0.04、0.06),并与未掺杂的LiMn2O4进行性能比较。X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明所制备的LiMn2-xZnxO4具有与LiMn2O4同样的尖晶石结构,锌的掺入细化了尖晶石颗粒,增强了Li+在固相中的扩散能力。电化学测试结果显示锌掺杂能抑制LiMn2O4的电化学容量衰减现象,使其循环性能得到显著提高。其中LiMn1.96Zn0.04O4表现出最佳的循环性能,循环20次后放电容量可保持在106.6mAh/g。     

LiFePO4/C制备工艺的优化及其性能

用共沉淀法制备了球形NH4FePO4·H2O前驱体,再与Li2CO3和葡萄糖混合用固相焙烧法制备了LiFePO4/C正极材料.利用正交实验考察了焙烧温度、焙烧时间、球磨时间、x(Li):x(Fe)和葡萄糖用量等对材料首次放电比容量的影响,得到了最佳工艺条件.通过XRD、SEM、FTIR和恒流充放电测试仪等测试了材料的结构和电化学性能.所得材料在室温下电流密度为0.1、0.5和1C时首次放电比容量分别为147.6、136.7和122.3mAh/g,循环50次后容量分别为142.8、127.3和106.7mAh/g;在60℃下电流密度为0.5C时,其首次放电比容量为163.8mAh/g,循环性能良好.     

锂离子电池正极材料锰酸锂的优化合成

运用动态多重扫描速率法，根据四条不同升温速率下的DSC曲线，计算出在空气气氛下动态合成LiMn2O4过程中的动力学参数，据此提出一个优化的LiMn2O4固相合成工艺，采用固相分段焙烧法制备LiMn2O4正极材料，第一段和第二段的温度分别设在600和830℃。用XRD对合成的粉体材料进行了相结构分析；用恒电流充放电仪对LiMn2O4的电化学性能进行测试，结果表明，合成样品具有良好的尖晶石相结构，在充放电循环时初始放电容量达122mAh／g，同时具备良好的容量保持能力。     

焙烧温度对醋酸盐体系液相燃烧合成尖晶石型LiMn2O4的影响

以醋酸锂、醋酸锰为原料，尿素为燃料，用液相燃烧合成方法制备尖晶石型LiMn2O4物质，考察了焙烧温度（300-800℃焙烧5h）对产物的组成结构、晶粒大小及电化学性能的影响。实验结果表明，未焙烧产物中主晶相为LiMn2O4及少量Mn2O3，但在300-800℃焙烧5h后都可得到单相的LiMn2O4粉体材料，焙烧温度为900℃时，LiMn2O4部分分解为Mn3O4；产物颗粒随焙烧温度升高而长大，≤600℃时，产物颗粒〈100nm，≥700℃时产物颗粒〉100nm，可观察到LiMn2O4的特征八面体结构；在焙烧温度800℃以下，产物的电化学性能随焙烧温度的升高而增加。当电流密度为C/3时，焙烧温度为800℃的首次放电容量为105mAh／g，但循环性能较差，30次循环后仅剩83％。     

尖晶石型Li1-xMgxMn2O4正极材料的制备和性质

采用高温固相分段反应法制备了尖晶石LiMn2O4和Mg2 掺杂的Li1-xMgxMn2O4(x=0.05、0.1)材料,对材料进行了XRD结构分析和电化学性能等测试,结果表明:Mg2 掺杂样品Li1-xMgxMn2O4(x=0.05、0.1)仍保持尖晶石相Fd3m结构;循环性能明显改善,室温条件下50次循环后,样品Li0.9Mg0.1Mn2O4的放电容量为100mAh/g,容量保持率为9.9%,而LiMn204容量衰减率仅为18.1%.     

Bi3+掺杂尖晶石型LiMn2O4的合成及性能研究

采用固相反应的方法,以Li2CO3、MnO2、Bi(NO3)3·5H2O和柠檬酸为原料,合成了具有尖晶石结构的锂离子电池正极材料LiMn2-xBixO4(x=0、0.03、0.06).对材料进行了X射线衍射、扫描电镜、红外光谱、充放电等测试.实验结果表明,所合成的LiMn1.97Bi0.03O4材料具有标准的尖晶石结构,较平滑的表面外观,较高的比容量及优异的循环性能.在0.2C放电速率下,首次放电容量为117.8 mAh/g,循环30次后,容量保持率接近100%.     

石墨烯包覆掺杂Al~(3+)的LiMn_2O_4正极材料的研究

采用石墨烯包覆掺杂Al 3+的LiMn2O4正极材料,用XRD、SEM分析其晶体结构及微观形貌,EIS、CV及充放电测试分析其电化学特性。实验结果表明,掺杂Al 3+的LiMn2O4为尖晶石结构,表面微观形貌接近菱形,包覆石墨烯后正极材料的阻抗值减少,可逆容量增加,电池大电流充放电性能增强。电池充放电测试数据表明:石墨烯的包覆提高了电池的充放电性能和循环特性,包覆材料在0.5C首次放电容量为116mAh/g;在0.5C倍率充放电50次循环后,其比容量为106mAh/g,容量保持率为92.17%。     

Estimation of Parameters of Universal Distribution of Moments of Failure of Products

A method is proposed for estimating the parameters of a mixture of exponential and Weibull distributions for which the accuracy of preliminary estimates obtained by graphical analysis is refined in accordance with the criterion of maximum likelihood. The efficiency of the proposed method is supported by the results of statistical modeling.     

Assessment of intakes of mixtures of radionuclides

Australia has several uranium mines and a large number of mineral sand mines, with associated processing facilities. Exposures resulting from these mining and processing operations usually involve intakes of mixtures of radionuclides. This work describes the development of a suite of first order, linear compartment models, based on the ICRP Publication 66 respiratory tract model, and an analytical solution to the decay equations, for assessing the consequences of such intakes. The computer programs based on these models directly compute excretion, organ retention and organ and whole-body doses for intakes of either single radionuclides or any mixture of radionuclides belonging to the same radioactive decay chain. The intake can be via inhalation, ingestion or injection, and can be acute, chronic or of limited duration. The starting concentration and degree of secular (dis)equilibrium can be specified for each radionuclide. No assumptions need to be made about the relative magnitudes of the radioactive half-lives of the different nuclides.     

Analysis of the rate of propagation of the wave of change of boiling modes

An approximate analytical expression is derived for the velocity of the front of the wave of change of boiling modes on a rod and on a plate. The impact of the Thomson effect and of the heater orientation in the gravity field is included. Adequate agreement is demonstrated between the derived relations and experimental data.     

Evaluation of optical properties of highly scattering media by moments of distributions of times of flight of photons

A novel method for the determination of the optical properties of tissue from time-domain measurements is presented. The data analysis is based on the evaluation of the first moment and the second centralized moment, i.e., the mean time of flight and the variance of the measured distribution of times of flight (DTOF) of photons injected by short (picosecond) laser pulses. Analytical expressions are derived for calculation of absorption and of reduced scattering coefficients from these moments by application of diffusion theory for infinite and semi-infinite homogeneous media. The proposed method was tested on experimental data obtained with phantoms, and results for absorption and reduced scattering coefficients obtained by the proposed method are compared with those obtained by fitting of the same data with analytical solutions of the diffusion equation. Furthermore, the accuracy of the moment analysis was investigated for a range of integration limits of the DTOF. The moment analysis may serve as a comparatively fast method for evaluating optical properties with sufficient accuracy and can be used, e.g., for on-line monitoring of optical properties of biological tissue.     

Analysis of anisotropy of properties on the basis of studies of texture of coarse-grained ingots of thermoelectric materials

An analysis of anisotropy of the properties of a Bi₂Se_0.3Te_2.7 solid solution was carried out using construction of demonstrative surfaces for thermoelectric effectiveness and thermal expansion coefficients. It is shown that the texture is an important factor forming anisotropy of properties and technological fitness of ingots for manufacturing modules. Anisotropy of properties based on the studies of the ingot textures obtained using the float-zone method and Bridgman method (growing thermoelectric plates in a flat cavity) was studied.     

Numerical study of methods of linearization of the output characteristics of radio-frequency sensors of the level of dielectric media

Different constructions of the sensing elements of radio-frequency level sensors based on sections of long lines are numerically investigated by means of the Matlab program for the purpose of minimizing the measurement error caused by the nonlinearity of the output characteristic. It is shown that the nonlinearity is lowest for U-shaped designs. The nonlinearity factor KN may be regulated by varying the capacitance of a correcting capacitor connected to the input of the sensing element and (or) the length of one of the sections of the long line. In selecting an optimal capacitance of the correcting capacitor KN ≤ 0.15% for control media with dielectric permittivity in the range 2.2–30.     

Possibilities of Decreasing the Errors of Determination of the Height of the Pole of a Sessile Drop of Melt

We analyze the possibilities of decreasing the errors of measuring the height of the pole of a sessile drop of melt above its equator by determining the position of the equator according to the midpoints of vertical chords of the image of the drop. The optimal distance between these chords and the edge of the image of the drop is chosen within 10–20% of the radius of the equator. The proposed method guarantees the same level of errors of evaluation of the height of the pole and the radius of the equator, which enables one to substantially increase the accuracy of evaluation of the capillary constant and the surface energy of the melt according to the geometric parameters of the sessile drop.     

Estimation of potentialities of methods of summation of direct measurement errors

Conventional methods for summation of direct measurement errors are considered. Conditions under which these methods provide consistent results are stated. It is proposed to utilize for characteristic of the total error, its interval estimator or the half-sum of the value obtained by adding up its arithmetic and geometric random errors.Translated from Izmeritel'naya Tekhnika, No. 4, pp. 10–12, April, 1995.