球形纳米晶LiFePO4和Li4Ti5O12的制备及电池研究

分别通过"控制结晶"和"外凝胶"工艺合成了球形纳米晶LiFePO4/C和Li4Ti5O12/C材料.通过XRD、SEM、比表面及电化学性能测试等分析手段表明,合成的LiFePO4/C和Li4Ti5O12/C材料均为纳米一次粒子(晶粒)组成的球形二次粒子(颗粒),具有较大的比表面积,振实密度分别达到1.25和1.71g/cm3;1C倍率下的首次放电比容量分别达到144.0和144.2mAh/g,并表现出优良的循环性能.以LiFePO4/C和Li4Ti5O12/C为正负极材料组成的1.8V锂离子电池具有平稳的充放电电压平台和优异的循环性能.     

Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model

Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO(4) and FePO(4). As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a 'domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities.     

Li4Ti5O12合成及电化学性质研究

报道一种合成Li4Ti5O12的新颖方法。XRD结果表明该方法合成的Li4Ti5O12化合物为尖晶石结构。用扫描透射显微镜对该化合物的粒径和形貌进行了分析．并对Li4Ti5O12的电化学性能进行测试。结果表明，通过该法合成的尖晶石材料在3．2-0．8V电压范围，采用一定电流密度下进行充放电，具有较高的放电容量（235mAh／g）和较好的循环性能。该法合成的具有良好电化学性能的Li4Ti5O12,使得其成为很有潜力的锂离子电池负极材料。     

Atomic and electronic structures of Li4Ti5O12/Li7Ti5O12 (001) interfaces by first-principles calculations

We have performed density-functional theory calculations for Li₄Ti₅O₁₂/Li₇Ti₅O₁₂ (LTO/Li-LTO) interfaces and made a detailed analysis of the local atomic and electronic structures. In the bulk regions of the supercell, the atomic and electronic structures are well reproduced to be similar to those of the LTO and Li-LTO bulk crystals. The present (001) interface models show abrupt structural changes between the cubic spinel-based LTO and ordered rock-salt Li-LTO phases, while there occur no substantial strains around the interface due to the little volume change or lattice mismatch. Thus, the calculated interfacial energy is very small. The calculated O–K electron energy-loss near-edge structure/X-ray adsorption near-edge structure (ELNES/XANES) spectra in the bulk regions are similar to those of the bulk crystals, while the O–K edge spectra at the two kinds of interfaces have specific shapes, differently from the simple superposition of the bulk spectra. The preferential occurrence of the (001) interface can be understood from the preferential Li diffusion along the [110] direction in LTO and the small interfacial energy.     

锂离子筛前驱体Li4Mn5O12的制备及性能研究

吸附法是目前从低锂浓度的盐湖卤水中提取锂的最有前途的方法。采用EDTA-柠檬酸络合法制备了Li₄Mn₅O₁₂前驱体, 经酸浸脱锂后得到对Li⁺具有特殊选择性的锰氧化物锂离子筛。通过热重、XRD、SEM、FT-IR、化学组成、吸附动力学及共存金属离子的分配系数等手段对样品的晶相结构和Li⁺选择性吸附性能进行了研究。结果表明: 煅烧时间对Li₄Mn₅O₁₂前驱体生成有较大影响, 由400℃煅烧24 h所得的前驱体几乎为纯相的Li₄Mn₅O₁₂化合物, 经酸浸脱锂后的离子筛仍保持着与前驱体相同的尖晶石结构; 前驱体Li₄Mn₅O₁₂和离子筛MnO₂均为 200 nm左右的球状颗粒; 离子筛的最大吸附容量为43.1 mg/g, 并具有较好的Li⁺选择性。     

Li4Ti5O12-聚苯胺复合材料的制备与电化学性能

以醋酸锂和钛酸四丁酯为原料，以乙醇为溶剂，采用溶胶．凝胶法制备Li4Ti5O12；以苯胺、过硫酸铵为原料，以盐酸为溶剂，采用原位聚合法合成Li4Ti5O12-聚苯胺复合材料。采用x射线衍射、红外光谱和电化学测试等对复合材料进行了表征。结果表明，聚苯胺的加入明显提高了Li4Ti5O12的电子导电性能，Li4rri5O12-PAn复合材料具有比Li4Ti5O12更好的高倍率性能和循环稳定性。0.1C和2.0C放电时Li4Ti5O12-PAn的放电容量达到了191．3和148．9mAh．g^-1，经80次循环后二者平均每次循环容量衰减率分别为0．13％和0．61％。     

非对称电化学电容器用新型Li4Ti5O12的制备与研究

采用新的溶胶凝胶工艺,即在溶胶中加入活性炭与柠檬酸、聚乙烯醇和聚乙二醇等添加剂,制得具有尖晶石结构的新型准纳米晶Li4Ti5O12.测试表明,加入活性炭和聚乙二醇制备出的材料性能最优异,首次嵌脱锂效率可达99.2%,20mA/g电流条件下的可逆嵌锂容量为122.1mAh/g,嵌脱锂平台非常稳定.将其制成嵌锂电极后与活性炭电极构成新型的Li4Ti5O12/AC非对称电化学电容器.电化学测试表明,在20mA/g电流条件下,其Li4Ti5O12电极比电容量为103.5mAh/g,充放电效率达96%,充放电曲线的对称性、线性保持较好,电容器内阻小,大电流充放电性能突出.     

液相法制备锂离子电池用钛酸锂负极材料的研究进展

钛酸锂(Li4Ti5O12)材料具有嵌锂过程中其晶型结构不发生改变的“零应变”特性,符合下一代锂离子电池循环寿命更长、充电过程更快、安全性更高的要求.详细综述了溶胶-凝胶法、水热合成法、直接熔盐法、原位水解法、溶液沉积法和共沉淀法等液相法制备Li4Ti5O12负极材料的研究现状,比较了各种方法的优缺点,结合笔者的研究探讨了Li4Ti5O12的发展方向.     

锂离子电池负极材料Li4Ti5O12的结构和性能

合成了锂离子电池负极材料钛酸锂(Li4TisO12),并将结构单一、组成较纯的钛酸锂负极材料组装成电池,研究了合成温度对钛酸锂结构及物种的影响.结果表明,合成温度低于650℃时生成两种结构的TiO2,严重影响了钛酸锂的结构,合成温度高于650℃时TiO2逐渐消失,在800℃保温24 h之后得到单相Li4Ti5O12,电化学性能良好.     

水热法制备花状纳米片簇Li4Ti5O12及其储锂性能

以氢氧化锂和钛酸四丁酯为原料,采用水热法制备出花状纳米片簇Li4Ti5O12粉体,研究了不同原料配比对产物晶体结构的影响。采用XRD、SEM对Li4Ti5O12的晶体结构和形貌进行了分析,结果表明所得产物是由Li4Ti5O12纳米片层组成的花状微球,所得晶体为尖晶石型结构。恒电流充放电实验表明,Li4Ti5O12在充放电倍率为0.1、1和2C下首次放电比容量分别为160、141和128mAh/g。     

Electrochemically active flame-made nanosized spinels: LiMn2O4, Li4Ti5O12 and LiFe5O8

Electrochemically active LiMn₂O₄, Li₄Ti₅O₁₂, and LiFe₅O₈ particles with spinel structure (normal, mixed and mixed inverse) were made at production rates of 10–20 g h⁻¹ by flame spray pyrolysis (FSP), a scalable, one-step, dry process. These materials were characterized by X-ray diffraction and nitrogen adsorption, and had a primary crystallite size in the range of 8–30 nm and exhibited high temperature stability. Electrochemical properties, as measured by slow cyclic voltammetry, are reported for LiMn₂O₄ and Li₄Ti₅O₁₂ as potential cathode and anode materials, respectively, in secondary lithium-ion batteries. LiFe₅O₈ nanoparticles were made also by FSP containing the electrochemically active β-phase as shown by the corresponding cyclic voltammogram and specific charge–discharge spectra.     

Optimized Li4Ti5O12 nanoparticles by solvothermal route for Li-ion batteries

Li4Ti5O12 (LTO) nanoparticles were successfully synthesized by solvothermal technique using cost-effective precursors in polyol medium and post-annealed at temperatures of 400, 500, and 600 degrees C. The XRD patterns of the samples were clearly indexed to the spinel shaped Li4Ti5O12 (space group, Fd-3 m). The particle size and morphology of samples were identified using field-emission SEM. The electrochemical performance of solvothermal samples revealed fairly high initial discharge/charge specific capacities in the range 230-235 and 170-190 mAh/g, at 1 C-rate, while that registered for the solid-state sample has been 160 and 150 mAh/g, respectively. Furthermore, among these samples, LTO annealed at 500 degrees C exhibited highly improved rate performances at C-rates as high as 30 and 60 C. This was attributed to the achievement of small particle sizes with high crystallinity in nano-scale dimensions and hence shorter diffusion paths combined with larger contact area at the electrode/electrolyte interface.     

Li4Ti5O12负极材料的制备及其电化学性能研究

采用二步固相烧结法制备了Li4TiO12负极材料,优化了制备工艺条件.利用X射线衍射分析(XRD)、扫描电镜(SEM)等表征了材料的形貌和结构,并用充放电测试仪、循环伏安(CV)和交流阻抗(EIS)研究了材料的电化学性能.结果表明,合成的Li4Ti5O12具有单一的尖晶石结构和良好的电化学性能,0.1C首次放电比容量为158.9 mAh/g,循环20次后容量保持率为97.6％,1C倍率首次放电比容量为108.9mAh/g,循环20次后容量下降了3.05％.     

Li4Ti5O12/Li3SbO4/C composite anode for high rate lithium-ion batteries

Nanocrystalline Li₄Ti₅O₁₂/Li₃SbO₄/C composite-prepared by mechanical ball-milling of Li₄Ti₅O₁₂ (synthesized by aqueous combustion), Li₃SbO₄ (synthesized by solid state method) and activated carbon, has been investigated as anode in lithium-ion coin cells and compared to pristine Li₄Ti₅O₁₂. Galvanostatic charge–discharge measurements in the potential window of 0.05–2.0 V show three plateau regions corresponding to Li insertion/extraction in the composite: a large flat plateau at ~ 1.52/1.59 V, followed by a second plateau at ~ 0.75/1.1 V and a sloppy tail at ~ 0.4/0.6 V. While the plateaus at ~ 0.4/0.6 V and ~ 1.52/1.59 V correspond to Li₄Ti₅O₁₂, the other one at ~ 0.75/1.1 V corresponds to Li₃SbO₄. At a high rate of ~ 15 C, the capacity for Li₄Ti₅O₁₂/Li₃SbO₄/C composite is found to be 105 mAhg^?1 retaining ~ 78% of its initial capacity compared to only 58 mAhg^?1 (~ 27% of the initial capacity) at 14 C for pristine Li₄Ti₅O₁₂ up to 100 cycles. Thus, such composite material might find application in lithium-ion batteries requiring high rate of charge and discharge.     

复合熔盐法合成Li4Ti5O12及其电化学性能研究

采用LiOH-LiNO3复合熔盐合成锂离子电池负极材料尖晶石结构Li4Ti5O12,应用XRD、SEM、CV以及恒流充放电测试等手段对所合成材料进行了结构表征和性能测试.结果表明,当反应物中n(Li):n(Ti)=4时合成的样品为纯的尖晶石相Li4Ti5O12,合成所需时间短、熔盐比例低.以电流密度15mA/g进行恒流充放电测试,其首次放电比容量为164.4mAh/g,电压平台宽,平台电压为1.55V.循环15周后放电比容量为156.7mAh/g,容量保持率为95.3%,循环性能优良.     

尖晶石Li4Ti5O12-xFx的制备与电化学计量性能研究

为了改善尖晶石型Li4Ti5O12材料的电子电导率和离子导电性,许多研究者认为阳离子掺杂改性是较有效的途径之一。主要通过金属阳离子V5+,Mn4+,Fe3+,Al3+,Ga3+Co3+,Cr3+,Ni2+,Mg2+等取代锂位或者钛位来提高导电性,改善电化学特性。本文主要是通过高温固相法合成F-掺杂的尖晶石化合物Li4Ti5O12-xFx及对其电化学性能的影响。