ZnFe2O4的固相法和水热法制备及其电化学性能研究

本文用固相反应法和水热法制备了ZnFe₂O₄材料,X射线衍射(X-ray diffraction, XRD)表明制备出来的ZnFe₂O₄为尖晶石结构,表面形貌测试 (scanning electron microscopy, SEM) 显示两种方法制备的材料的平均粒径分别为500 nm和200 nm.比表面积测试结果表明,两种方法制备的样品的比表面积分别为136.7 m² g^{-1关键词： 2O₄')" href="#">ZnFe₂O₄ 尖晶石结构 电化学性能 锂离子电池}     

NiFe2O4纳米线阵列的制备与磁性

在氧化铝模板的纳米孔洞中, 用电化学的方法沉积铁镍合金纳米线，经过550℃30h氧化处理 , 成功制备出 NiFe2O4纳米线阵列. 分别用扫描电子显微镜 (SEM) 、透射电 子显微镜 (TEM) 、x射线衍射仪 (XRD) 和振动样品磁场计 (VSM) 对样品的形貌、晶体结构 和磁学性质进行了表征测试. SEM和TEM观察结果显示氧化铝模板的孔洞分布均匀，孔心距约 为110nm; 纳米线的直径约为70nm. XRD显示纳米线阵列的物相结构为NiFe2O4; VSM测试结果表明，NiFe2O4纳米线阵列膜的易磁化方向垂直于膜面. 当垂直 磁化时磁滞回线的矩形比约为05，矫顽力为41×103A/m，比氧化处理前的铁镍合金 纳米线阵列都有显著提高. 关键词： 纳米线 Ni Fe2O4 矫顽力     

Al掺杂的尖晶石型LiMn2O4的结构和电子性质

采用基于密度泛函理论的第一性原理方法, 在广义梯度近似(GGA)和GGA+U方法下对尖晶石型LiMn₂O₄及其Al掺杂 的尖晶石型LiAl_0.125Mn_1.875O₄晶体的结构和电子性质进行了计算. 结果表明: 采用GGA方法得到尖晶石型LiMn₂O₄是立方晶系结构, 其中的Mn离子为+3.5价, 无法解释它的Jahn-Teller 畸变. 给出的LiMn₂O₄能带结构特征也与实验结果不符. 而采用GGA+U方法得到在低温下的LiMn₂O₄和其掺杂 体系LiAl_0.125Mn_1.875O₄的晶体都是正交结构, 与实验一致. 也能明确地确定Mn的两种价态Mn³⁺/Mn⁴⁺的分布并且能够说明Mn³⁺O₆的z方向有明显的Jahn-Teller 畸变, 而Mn⁴⁺O₆则没有畸变. LiMn₂O₄的能带结构与实验比较也能够符合. 采用GGA+U方法对Al掺杂体系的LiAl_0.125Mn_1.875O₄的研究表明, 用Al替换一个Mn不会明显地改变晶体的电子性质, 但可以有效地消除Al³⁺O₆ 八面体的Jahn-Teller畸变, 从而改善正极材料LiMn₂O₄的性能, 这与电化学实验的观察结果相一致.     

溶剂热制备锂电池负极材料CNT-ZnFe2O4及其电化学性能

为了改善锂离子电池负极材料ZnFe₂O₄导电性差和循环寿命低的缺点,利用溶剂热反应方法制备了ZnFe₂O₄,并通过复合碳纳米管对ZnFe₂O₄进行改性。充放电测试结果表明：经过50次充放电后,碳纳米管复合改性后的ZnFe₂O₄容量保持在860 mA·h·g^-1,具有较好的循环稳定性。碳纳米管具有良好的导电性与导热性,改善了ZnFe₂O₄导电性差的缺点。     

插层化合物LiV2O4的制备与实验研究

用化学方法从层状化合物LiVO₂中引出0.5个Li后得到Li_0.5VO₂,再经过低温真空热处理制备出尖晶石结构化合物LiV₂O₄,类似地处理Li_0.465VO₂,得到缺Li的Li_0.93V₂O₄,LiV₂O₄和Li_0.93V 关键词：     

ZnAl2O4：Tb3+荧光粉的合成、结构及其光学性能研究

通过溶胶-凝胶法制备出不同Tb³⁺掺杂浓度和不同二次煅烧温度下的ZnAl₂O₄:Tb³⁺荧光粉, 并利用X射线衍射(XRD)和荧光光谱等对样品进行了表征。由XRD结果可知,当Tb³⁺掺杂的摩尔分数不大于9%,二次煅烧温度在600℃以上时,所得粉体为结晶性良好的尖晶石相。在紫外光激发下,ZnAl₂O₄:Tb³⁺荧光粉的发射光谱由位于488 nm(⁵D₄→⁷F₆)、542 nm(⁵D₄→⁷F₅)、587 nm(⁵D₄→⁷F₄ )和621.5 nm(⁵D₄→⁷F₃)的4个发射峰组成。研究发现,Tb³⁺的掺杂浓度和二次煅烧温度对样品发光强度有着重要影响,当Tb³⁺的摩尔分数为5%,二次煅烧温度为900℃时,ZnAl₂O₄:Tb³⁺荧光粉的发光最强,继续增加Tb³⁺掺杂浓度或提高煅烧温度,分别会出现浓度猝灭和温度猝灭现象。     

NiFe2O4外延薄膜的制备及后退火效应研究

本文利用脉冲激光沉积方法制备了NiFe2O4磁性绝缘薄膜.X-射线衍射线性扫描测量表明,在MgO(110)单晶衬底上可以生长出高质量的NiFe2O4外延薄膜,原子力显微镜显示其具有平整的表面形貌.我们还研究了后退火处理对样品结构、表面形貌和磁性的影响.结果表明,后退火后薄膜的结构和表面形貌都发生了明显的改变,样品的磁性得到增强.这些效应可归结为在氧气氛下退火处理导致的氧含量的变化以及退火过程中阳离子分布和价态发生改变.     

尖晶石结构自旋有序CaTi2O4单晶生长和磁化率特性研究

通过助溶剂熔融法并在氩气气氛炉中成功生长出高质量大尺寸的CaTi₂O₄的单晶.X射线衍射实验及能量损失谱EDS证实,制备的CaTi₂O₄单晶晶胞参数a=9.781?,b=9.966?,c=3.148?,所有样品均为单相,且符合化学计量比,样品高纯.通过直流磁化率的测量,首次给出了晶体的Van-Vleck顺磁因子为6.85×10^-5cm³/mol,Cure-Weiss温度为-0.44 K,呈弱反铁磁性.同时,通过单晶各向磁化率的测量,进一步确认了CaTi₂O₄晶体中一维有序Ti-Ti反铁磁dimer链的形成,并明确了其方向. 关键词： 2O₄')" href="#">CaTi₂O₄ 磁化率 各向异性 反铁磁二聚化     

NiFe2O4纳米固体的穆斯堡尔谱研究

利用反滴共沉淀法制备了ＮｉＦｅ₂O₄纳米粒子，并在高压下（４.５ＧＰａ）压制成块状纳米固体材料．Ｘ射线衍射显示，ＮｉＦｅ₂O₄纳米固体的晶体结构和平均晶粒尺寸在高压下均没有发生变化．但其室温和低温穆斯堡尔谱结果表明，高压对纳米固体内部的磁相互作用和界面原子状态有很大的影响．在高压下，纳米固体内部的颗粒间磁偶极相互作用和界面离子间的超交换相互作用显著增强．从而明显抑制了ＮｉＦｅ₂O_{4关键词：}     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合铁电薄膜. 研究了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi₄Ti< 关键词： 2Ta₂O₉')" href="#">SrBi₂Ta₂O₉ 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 复合铁电薄膜 溶胶凝胶工艺     

Configurational entropy-induced phase transition in spinel LiMn2O4

The spinel-type LiMn$_{2}$O$_{4}$ is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety. Experimentally, it is observed that in this compound there occur the structural phase transitions from cubic ($Fd\bar{3}m)$ to tetragonal ($I4_{1}/{amd}$) phase at slightly below room temperature. To understand the phase transition mechanism, we compare the Gibbs free energy between cubic phase and tetragonal phase by including the configurational entropy. Our results show that the configurational entropy contributes substantially to the stability of the cubic phase at room temperature due to the disordered Mn$^{3+}$/Mn$^{4+}$ distribution as well as the orientation of the Jahn-Teller elongation of the Mn$^{3+}$O$_{6}$ octahedron in the the spinel phase. Meanwhile, the phase transition temperature is predicted to be 267.8 K, which is comparable to the experimentally observed temperature. These results serve as a good complement to the experimental study, and are beneficial to the improving of the electrochemical performance of LiMn$_{2}$O$_{4}$ cathode.     

微波-模板法合成锂离子电池正极材料LiMn2O4机理的光谱学研究

采用微波-PAM模板法合成了具有尖晶石结构的锰酸锂材料,利用动态红外光谱（FTIR）对该方法的反应机理进行了研究。在前驱体的制备和在LiMn2O4晶核形成过程中,由于聚丙烯酰胺与反应母体之间的弱键合作用,使其在晶粒生长过程中对LiMn2O4的团聚规律与缺陷结构起到重要调控作用。     

Pressure dependence of the thermal stability in LiMn2O4

Structural stability in terms of the decomposition temperature in LiMn₂O₄ was systematically investigated by a series of high-temperature and high-pressure experiments.LiMn₂O₄ was found to have structural stability up to 5 GPa at room temperature.Under ambient pressure,the compound decomposed at 1300℃.The decomposition temperature decreased with increasing pressure,yielding more complex decomposed products.Below the decomposition temperature,the crystal structure of LiMn₂O₄ varied with pressure.The presented results in this study offer new insights into the thermal and pressure stability of LiMn₂O₄ materials as a cathode for lithium-ion batteries that can operate under extreme conditions.Therefore,these findings may serve as a useful guide for future work for improving lithium-ion batteries.     

Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries

To improve the cycle performance of spinel LiMn₂O₄ as the cathode of 4-V-class lithium secondary batteries, spinel phases LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) were successfully prepared using the sol–gel method. The spinel materials were characterized by powder X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Electrochemical studies were carried out using the Li|LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) cells. These cathodes were more tolerant to repeated lithium extraction and insertion than a standard LiMn₂O₄ spinel electrode in spite of a small reduction in the initial capacity. The improvement in cycling performance is attributed to the stabilization in the spinel structure by the doped metal cations.     

Formation mechanism of Ge nanocrystals embedded in SiO2 studied by fluorescence x-ray absorption fine structure

This paper reports that the Ge nanocrystals embedded in SiO2 matrix are grown on Si（100） and quartz-glass substrates, and the formation mechanism is systematically studied by using fluorescence x-ray absorption fine structure （XAFS）. It is found that the formation of Ge nanocrystals strongly depends on the properties of substrate materials. In the as-prepared samples with Ge molar content of 60%, Ge atoms exist in amorphous Ge （about 36%） and GeO2 （about 24%） phases. At the annealing temperature of 1073 K, on the quartz-glass substrate Ge nanocrystals are generated from crystallization of amorphous Ge, rather than from the direct decomposition of GeO2 in the as-deposited sample. However, on the Si（100） substrate, the Ge nanocrystals are generated partly from crystallization of amorphous Ge, and partly from GeO2 phases through the permutation reaction with Si substrate. Quantitative analysis reveals that about 10% of GeO2 in the as-prepared sample are permuted with Si wafer to form Ge nanocrystals.     

Titanium local structure in tektite probed by X‐ray absorption fine structure spectroscopy

The local structure of titanium in tektites from six strewn fields was studied by Ti K‐edge X‐ray absorption near edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti—O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high‐temperature TiO₂–SiO₂ glass and TiO₂ anatase. All samples showed that the valence of Ti is 4+. Based on the Ti—O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four‐coordinated tetrahedral site with Ti—O distances of 1.84–1.79 Å; type II, Ti occupies a five‐coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti—O distances of 1.92–1.89 Å; type III, Ti occupies a six‐coordinated octahedral site with Ti—O distances of 2.00–1.96 Å. Although Ti occupies the TiO₆ octahedral site in most titanium minerals under ambient conditions, some tektites have four‐ and five‐coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages.     

Si/Gen/Si(001)异质结薄膜的掠入射荧光X射线吸收精细结构研究

利用掠入射荧光X射线吸收精细结构(XAFS)方法研究了在400℃的温度下分子束外延生长的Si/Gen/Si(001)异质结薄膜(n=1,2,4和8个原子层)中Ge原子的局域环境结构.结果表明,在1至2个Ge原子层(ML)生长厚度的异质结薄膜中,Ge原子的第一近邻配位主要是Si原子.随着Ge原子层厚度增加到4 ML,Ge原子的最近邻配位壳层中的Ge-Ge配位的平均配位数增加到1.3.当Ge原子层厚度增加到8 ML时,第一配位壳层中的Ge-Ge配位占的比例只有55%.这表明在400℃的生长条件下,Ge原子有很强的迁移到Si覆盖层的能力.随着Ge层厚度从1增加到2,4和8 ML,Ge原子迁移到Si覆盖层的量由0.5 ML分别增加到1.5,2.0和3.0 ML.认为在覆盖Si过程中Ge原子的迁移主要是通过产生Ge原子表面偏析来降低表面能和Ge层的应变能.     

Electrochemical activities of yttrium doped spinel LiMn2O4

It was found for the first time that the catalysis of yttrium doping of spinel LiMn₂O₄ can enhance the electrochemical activities of manganese, leading to both improvement of electrochemical capacity and reactivity with the electrolyte of manganese. A proper amount of doping was 0.5%, and such yttrium-doped sample, Li(Y_0.005Mn_0.995)₂O₄, had an initial capacity of 130 mAh g⁻¹ over that of the undoped one with the capacity retention to reach 92.3% exceeding that of the undoped one at 100th cycle.     

Lithium extraction/insertion from LiMn2O4 — effect of crystallinity

Effect of host crystallinity on lithium extraction/insertion of LiMn₂O₄ was studied. LiMn₂O₄ powders with different crystallinity were prepared via lithium-manganese-tartrates by heat treatment at various temperatures above 300 °C. First charge-discharge capacity around 4 V depended on lattice parameter a₀ and lattice strain . On the other hand, the first discharge capacity around 3 V was found to be independent of these parameters.     

Electron density distribution of LiMn_2O_4 cathode investigated by synchrotron powder x-ray diffraction

Electron density plays an important role in determining the properties of functional materials. Revealing the electron density distribution experimentally in real space can help to tune the properties of materials. Spinel Li Mn2 O4 is one of the most promising cathode candidates because of its high voltage, low cost, and non-toxicity, but suffers severe capacity fading during electrochemical cycling due to the Mn dissolution. Real-space measurement of electron distribution of Li Mn2 O4 experimentally can provide direct evaluation on the strength of Mn–O bond and give an explanation of the structure stability.Here, through high energy synchrotron powder x-ray diffraction(SPXRD), accurate electron density distribution in spinel Li Mn2 O4 has been investigated based on the multipole model. The electron accumulation between Mn and O atoms in deformation density map indicates the shared interaction of Mn–O bond. The quantitative topological analysis at bond critical points shows that the Mn–O bond is relatively weak covalent interaction due to the oxygen loss. These findings suggest that oxygen stoichiometry is the key factor for preventing the Mn dissolution and capacity fading.