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。     

磷酸铁前驱体纳米孔洞结构对磷酸铁锂电性能的影响

利用液相结晶法制备出球状且表面具有纳米孔洞结构的磷酸铁前驱体,并通过高温固相法进一步制备成磷酸铁锂,通过XRD、SEM、FT-IR和电化学测试等手段对样品进行表征。结果表明,有纳米孔洞结构的磷酸铁前驱体制备的磷酸铁锂比无纳米孔洞结构的磷酸铁前驱体制备的磷酸铁锂在0.1 C倍率性能下的首次充放电容量提升了17%,达到149.38 m Ah/g,电极电荷转移电阻降低了约88%,仅为54.91Ω。     

共沉淀法合成磷酸铁锂掺碳复合正极材料

采用共沉淀法合成了纯相橄榄石型磷酸铁锂(LiFePO4)和磷酸铁锂掺碳(LiFePO4/C)复合正极材料.利用X射线衍射(XRD)、原子吸收(AAS)、扫描电镜(SEM)、红外吸收(FT-IR)、振实密度测定等方法对其进行表征,并组装成电池研究其电化学性能.结果表明:HFePO4和LiFePO4/C具有单一的橄榄石型晶体结构,前者的振实密度可达1.58 g/cm2,LiFePO4/C振实密度有所降低,但充放电平台非常平稳.与纯相LiFePO4相比,LiFePO4/C具有更高的放电比容量和循环性能,室温下以0.05 C和0.1 C倍率电流充放电,首次放电比容量达到158.1,150.0 mA·k/g.充放电循环20次后放电比容量仍保持在154.2,137.2 mA·h/g.     

铜掺杂碳包覆磷酸铁锂的微波合成及性能研究

研究了铜掺杂碳包覆磷酸铁锂（LiFePO₄）的微波合成。通过X射线衍射（XRD）表征了样品的化学组成和晶体结构,通过扫描电镜（SEM）考察了样品的微观形貌。分别用铜掺杂磷酸铁锂、碳包覆磷酸铁锂、铜掺杂碳包覆磷酸铁锂作为锂离子电池正极材料,进行了电化学性能测试比较。充放电测试表明,微波合成的铜掺杂碳包覆磷酸铁锂具有良好的充放电性能和循环寿命,首次放电比容量达到145 mA•h/g,循环30次后比容量仍然有143.5 mA•h/g,为初始容量的98.96%,容量几乎无衰减。     

硝酸铁和磷酸共沉淀法制备电池级磷酸铁工艺研究

以硝酸铁和磷酸为原料，利用共沉淀法制备了电池级磷酸铁，研究了反应温度、反应物浓度、投料比和反应时间对磷酸铁产率和粒径的影响，并通过正交优化得到了最佳的工艺条件：硝酸铁浓度为1.1 mol/L、投料比(磷酸与硝酸铁物质的量比)为1.1、反应温度为90℃、反应时间为8 h。采用扫描电镜(SEM)、激光粒度仪、X射线衍射仪(XRD)、热重-差式扫描量热仪(TG-DTA)等对制备的磷酸铁进行表征分析。分析结果表明：在优化条件下得到的二水磷酸铁为单斜晶，纯度高，二次粒径D₅₀为2.41μm，均符合电池级磷酸铁的要求。以磷酸铁为前驱体制备的LiFePO₄/C性能良好，将其作为正极材料组成的电池在0.05C、0.1C、1C倍率下首次放电比容量分别为143.9、136.8、131.4 mA·h/g。     

球形磷酸铁锂材料的制备及其18650电池的测试

采用高能球磨和喷雾干燥法制备了球形磷酸铁锂材料LFP-1,并制作18650实装电池,测试电极片的压实密度,同时选择一种商业化磷酸铁锂材料LFP-2作为对比。测试结果显示,2种LFP材料均由平均粒径为300~500 nm的一次颗粒组成,比表面积为13~15 m²/g,碳质量分数为1.5%左右。通过CR2032纽扣型电池充放电测试表明,在0.2C时,LFP-1的比放电容量约为165 mA·h/g,与商业化磷酸铁锂材料LFP-2相近。制备18650电池的结果表明,商业化磷酸铁锂LFP-2材料制备的电极片的最高压实密度可以达到2.52 g/cm³,显著高于实验室制得的磷酸铁锂材料LFP-1的最高压实密度2.25 g/cm³,这可能与材料的颗粒粒度分布不同有关。     

三聚磷酸铁的制备及其防锈和电化学性能初探

通过高温缩合反应合成了三聚磷酸铁(Fe H₂P₃O₁₀·2H₂O),采用扫描电镜(SEM)和X射线衍射(XRD)进行了表征,初步研究了其防锈性能,以及作为前驱体所合成的三聚磷酸铁锂正极材料的比容量和库伦效率。结果表明,所合成的三聚磷酸铁颗粒为类球形,粒径约0.5～1μm,防锈性能略优于三聚磷酸铝。三聚磷酸铁锂的比容量为210m Ah·g^-1,明显高于磷酸铁锂的理论比容量(170m Ah·g^-1),库伦效率接近100%,充放电可逆性好。该材料具有优良的防锈性能和电化学性能,具有很好的潜在应用前景。     

球磨对磷酸铁锂正极材料性能的影响

采用高温固相合成法制备锂离子正极材料磷酸铁锂,在合成过程中分别采用湿法球磨和干法球磨,讨论了球磨时间对合成磷酸铁锂电化学性能的影响。用扫描电镜对合成材料进行表征,并对磷酸铁锂正极材料进行电化学性能测试。结果表明,相对于干法球磨,湿法球磨制备的磷酸铁锂样品具有更好的电化学性能。湿法球磨10 h所得的材料电化学性能最好,0.1 C下首次放电比容量为114 mA·h/g。     

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。     

石墨烯包覆磷酸铁锂正极材料的合成及性能研究

通过溶胶凝胶法合成了石墨烯包覆的橄榄石型LiFePO4/石墨烯正极复合材料.实验采用在磷酸铁锂前驱体制备过程中加入石墨烯,经高温煅烧后实现了石墨烯与磷酸铁锂的均匀包覆.研究了石墨烯对正极材料的结构和电化学性能的影响.研究结果表明,LiFePO4/石墨烯复合材料的颗粒尺寸比纯LiFePO4明显减小,石墨烯包覆后的LiFePO4材料的电荷转移电阻显著降低,在0.1C电流密度下的首次充放电比容量达到143.6 mAh/g,循环性能也得到较大提高.     

The comparison of mechanical behavior of MgO-MgAl2O4 with MgO-ZrO2 and MgO-MgAl2O4-ZrSiO4 composite refractories

Mechanical properties of different compositions obtained from the additions of 5, 10, 20 and 30 wt.% zircon (ZrSiO₄) into the MgO-spinel composite refractories and ZrO₂ into MgO have been examined, the variations that occurred have been determined, and the parameters affecting those factors have been investigated with the reasons. The density, strength, Young's modulus, fracture toughness, fracture surface energy and work of fracture were measured and evaluated. Microstructural variations and fracture surfaces have been examined and the formation of new phases has been identified depending on the additive type and quantity. The relationships between mechanical properties and structural variations for different compositions have been examined. In MgO-spinel materials, strength, Young's modulus and fracture toughness values decrease up to 20% spinel addition and stay almost constant for further loads. ZrO₂ addition displays same trend but not as effective as spinel. Besides, since ZrO₂ is stable in cubic form, it does not show any toughening mechanism. Forsterite formation is the most important factor for 2-fold improvement in the mechanical properties of MgO-spinel-zircon refractories. The more the zircon addition, the more the mechanical properties improve. The generation of natural bonding between matrix particles with forsterite formation, on the other hand, causes the fracture path to turn to transgranular fracture with an increase in fracture surface energy and a decrease in work of fracture, among which the latter is considered as an indicator of thermal shock resistance of the materials being high.     

Rate of the MnO−4/MnO2−4 and MnO2−4/MnO3−4 electrode reactions in alkaline solutions at solid electrodes

The influence of the ionic strength, pH, nature of the background electrolyte and its concentration as well as the influence of the electrode material (Pt, glassy carbon, carbon paste) on the electrode kinetics of the MnO^?₄/MnO^?2₄ and MnO^2?₄/MnO^3?₄ systems has been investigated by means of cyclic voltammetry and the rotating disc electrode method. Rate constants determined with the use of the carbon paste electrode agreed well with those which were in some instances available in the literature. At the Pt. electrodes the rate could be only estimated.The rate constants obtained for both electrode reactions were considered in terms of the Marcus theory. Also the charge of rate constants and formal potentials with studied parameters was discussed.     

Laser surface nanostructuring for reliable Si3N4/Si3N4 and Si3N4/Invar joined components

IR pulsed laser radiation in air was applied to Si₃N₄ and Invar to obtain reliable Si₃N₄/Si₃N₄ and Si₃N₄/Invar adhesive bonded components. The laser pre-treatment produced a homogeneous nanostructured oxide layer on the surfaces, which effectively increased the adhesion at the adhesive/adherends interface and led to cohesive failure in the joining material. The mechanical strength of Si₃N₄/ Si₃N₄ and Si₃N₄/Invar joined components was measured, with and without laser nanostructuring, before and after thermal cycling from room temperature to 50?K, and it resulted that the exposure to extremely low temperatures did not affect the mechanical integrity of the joints. It was also demonstrated that this laser pre-treatment did not alter the mechanical properties of the ceramic substrate.     

Cycling-induced stress in lithium ion negative electrodes: LiAl/LiFePO4 and Li4Ti5O12/LiFePO4 cells

In this work, we examined the electrochemical behaviour of lithium ion batteries containing lithium iron phosphate as the positive electrode and systems based on Li-Al or Li-Ti-O as the negative electrode. These two systems differ in their potential versus the redox couple Li⁺/Li and in their morphological changes upon lithium insertion/deinsertion. Under relatively slow charge/discharge regimes, the lithium-aluminium alloys were found to deliver energies as high as 438 Wh kg⁻¹ but could withstand only a few cycles before crumbling, which precludes their use as negative electrodes. Negative electrodes consisting solely of aluminium performed even worse. However, an electrode made from a material with zero-strain associated to lithium introduction/removal such as a lithium titanate spinel exhibited good performance that was slightly dependent on the current rate used. The Li₄Ti₅O₁₂/LiFePO₄ cell provided capacities as high as 150 mAh g⁻¹ under C-rate in the 100th cycle.     

稀土固体超强酸SO2-4/TiO2/La3+催化合成醋酸丁酯

研究了以固体超强酸SO24-/TiO2/La3+催化剂,醋酸和正丁醇为原料合成醋酸丁酯,并考察了影响反应的因素.结果表明醇酸物质的摩尔比为1.61、催化剂用量0.6 g、带水剂甲苯7 mL、反应时间2.5 h是最适宜的反应条件,其酯化率可达96.2%.     

Studies of Silica-Structure Phases: I, GaPO4, GaAsO4, and GaSbO4

In the course of work on all compositions which would probably yield silica-structure phases, a detailed study was made of the A³⁺B⁵⁺O₄-type compounds with gallium as the trivalent element. Two forms of GaPO₄ exist corresponding to quartz and cristobalite; the quartz form has a thermal expansion of the low-quartz type and no stable α-β transition is found in this phase. It inverts stably to the cristobalite form at 933°± 4°C. The cristobalite form melts at 1670°C. and the liquid cannot be made to form a glass. The cristobalite form also has a metastable displacive transition at 616°± 2°C. GaAsO₄ exists only in a form corresponding to the lowquartz structure. It disproportionates into Ga₂O₃ and As₂O₅ at about 1000°C. GaSbO₄ could only be prepared in one form corresponding to the rutile structure. The influence of such phases on SiO₂ was determined by studying a few mixtures in the system SiO₂-GaPO₄. The SiO₂ end member appears to admit about 25% GaPO₄ into solid solution in the cristobalite phase at the highest temperature. Even under hydrothennal conditions, however, equilibrium cannot be easily attained at the lower temperatures in a few hundred hours. The results are presented in a not-impossible diagram for the system GaPO₄-SiO₂.     

Synthesis of Al4SiC4

The conditions necessary for synthesizing Al₄SiC₄ from mixtures of aluminum, silicon, and carbon and kaolin, aluminum, and carbon, as starting materials, were examined in the present study. The standard Gibbs energy of formation for the thermodynamic reaction SiC( s ) + Al₄C₃( s ) = Al₄SiC₄( s ) changed from positive to negative at 1106°C. SiC and Al₄C₃ formed as intermediate products when the mixture of aluminum, silicon, and carbon was heated in argon gas, and Al₄SiC₄ then formed by reaction of the SiC and Al₄C₃ at >1200°C. Al₄C₃, SiO₂, Al₂O₃, SiC, and Al₄O₄C formed as intermediate products when the mixture of kaolin, aluminum, and carbon was heated under vacuum, and Al₄SiC₄ formed from a reaction of those intermediate products at >1600°C.     

Equilibria of SiF4 with SiO2, Be2SiO4, and BeO in Molten Li2BeF4

Equilibrium partial pressures of SiF₄ were measured for the reactions 2SiO₂( c )+2BeF₂( d )⇋SiF₄( g )+Be₂SiO₄( c ) (log P _siF4(mm) = [8.790 - 7620/ T ] ±0.06(500°–640°C)) and Be₂SiO₄( c ) +2BeF₂( d )⇋SiF₄( g ) +4BeO( c )(log P _siF4(mm) = [9.530–9400/T] ±0.04 (700°–780°C)), wherein BeF₂ was present in solution with LiF as molten Li₂BeF₄. The solubility of SiF₄ was low (∼0.04 mol kg^-1 atm^-1) in the melt. The results for the first equilibrium were combined with available thermochemical data to calculate improved Δ H_f and Δ G_f values for phenacite (–497.57 ±2.2 and –470.22±2.2 kcal, respectively, at 298°K). The few measurements above 700°C for the second equilibrium are consistent with the temperature of the subsolidus decomposition of phenacite to BeO and SiO₂ and with the heat of this decomposition as determined by Holm and Kleppa. Below 700°C, the pressures of SiF₄ generated showed an increasing positive deviation from the expression given for the equilibrium involving Be₂SiO₄ and BeO. This deviation might have been caused by the formation of an unidentified phase below 700°C which replaced the BeO; it more likely resulted from a metastable equilibrium involving BeO and SiO₂.