煅烧温度对锂电池正极材料LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2的结构和电学性能影响

采用氢氧化物共沉淀法合成前驱体Ni_(0.5)Co_(0.2)Mn_(0.3)O_2,进一步用高温固相法与锂源共混煅烧得到LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2。通过TGA、XRD、SEM、电化学测试等初步探讨了前驱体与锂源在高温煅烧过程中的反应机理及不同煅烧温度对材料结构和性能的影响。结果表明:前驱体与锂源的融合反应发生在750℃之前,继续升高温度是晶体的不断完善过程,材料质量几乎没有变化;对750~900℃煅烧的材料进行结构分析表明,所有材料均具有良好的α-NaFeO_2层状结构和较小的阳离子混排度,850℃煅烧的材料晶体生长和表面结构最完美,其在0.2 C,2.5~4.6 V的充放电测试条件下,具有最高的首次放电容量193.7mAh/g,循环30次后的容量保持率为94.2%,并且具有最好的倍率性能。     

Cr3+掺杂LiNi0.5Mn1.5O4材料的制备及性能研究

采用高温固相法合成了Cr₃₊掺杂的LiNi_0.5Mn_1.5O₄正极材料,研究了掺杂量对材料物理性能和电化学性能的影响。利用XRD、SEM对材料的结构和形貌进行了表征,结果显示样品具有棱边清晰的尖晶石形貌。讨论了不同Cr₃₊掺杂量对LiCr_xNi_0.5-0.5xMn_1.5-0.5xO₄(x=0,0.05,0.1,0.15,0.2)正极材料性能的影响。充放电测试、循环伏安和交流阻抗测试结果表明：当Cr₃₊的掺杂量为x=0.1时(LiCr_0.1Ni_0.45Mn_1.45O₄)正极材料的性能最好,0.1C、0.5C、1C、2C及5C的首次放电比容量依次为131.54mAh g_-1、126.84mAh g_-1、121.28mAh g_-1、116.49mAh g_-1和96.82mAh g_-1,1C倍率下循环50次,容量保持率仍为96.5%。     

定-转子反应器制备LiFe1-xMxPO4 (M= Mn, Ni)粉体及其性能研究

采用具有高效传质和微观混合性能的定-转子反应器制备了LiFe_1-xMn_xPO₄ (x=0.0, 0.1, 0.2, 0.3)和LiFe_1-xNi_xPO₄ (x=0.00, 0.03, 0.05, 0.07)粉体,分别用作正极材料制成电池后,采用电池测试系统测定了电池的电化学性能随温度的变化规律。结果表明,粉体颗粒呈类球形,尺寸分布均匀,粒径范围为5~10 μm,Mn和Ni的掺杂没有改变粉体的晶体结构。以LiFe_0.8Mn_0.2PO₄和LiFe_0.95Ni_0.05PO₄两种组成的粉体性能最好,在倍率0.1 C下,所得电池的首次充放电比容量在室温和50 _oC时,分别为153.2和155.7 mAh/g,及156.4和160.4 mAh/g;100次充放电循环后电池的容量保持率分别为95.4和96.5%,及93.8和95.0%。借助具有过程强化作用的定-转子反应器制备的Mn和Ni掺杂LiFePO₄正极材料的电性能得到显著提高。原因是定-转子反应器一方面可以制备颗粒尺寸均匀的粉体,另一方面又可使掺杂的Mn和Ni在粉体颗粒中均匀分布,两者同时提高了电池中Li₊的扩散速率,进而提高了锂离子电池的电化学性能和高温电性能。     

锂离子电池正极材料LiNi0.8Co0.15Al0.05O2的制备及电化学性能

首先以AlO2-为铝源,采用三元共沉淀法制备前驱体Ni_(0.8)Co_(0.15)Al_(0.05)(OH)_2。对前驱体进行500℃高温处理,随后与过量的锂盐混合均匀,在氧气气氛下700℃煅烧12 h制得LiNi_(0.8)Co_(0.15)Al_(0.05)O_2(NCA)材料。采用X射线衍射仪(XRD)测试可知,所得的NCA材料呈典型的α-NaFeO_2层状结构,属于R-3m空间群。扫描电子显微镜(SEM)测试显示,NCA为粒径5～6μm的球状颗粒。材料在电流倍率为0.1C下首次放电容量为167.1mAh/g,循环200次以后容量保持率为96.2%。倍率测试表明,0.1、10 C下NCA的容量分别为184.0、112.7 mAh/g,到恢复到0.1 C时,容量仍可达179.7mAh/g,具有比较好的倍率性能。     

丝网印刷氧化石墨烯对锂离子电池LiNi1/3Co1/3Mn1/3O2 三元正极的改性及性能影响

通过丝网印刷方法,在由LiNi_1/3Co_1/3Mn_1/3O₂、导电添加剂和聚偏氟乙烯制成的电极表面涂覆了一层薄薄的氧化石墨烯。在充电截止电压为4.3 V的条件下进行了循环性能和倍率性能测试。结果表明：未改性电极在恒电流充放电测试中容量下降且极化增加,而包覆改性后电极的容量衰减程度和极化增加速度降低。这是由于氧化石墨烯涂层抑制了LiNi_1/3Co_1/3Mn_1/3O₂电极和电解质之间的部分副反应,使得改性电极的循环稳定性和倍率性能显著提高,为提升LiNi_1/3Co_1/3Mn_1/3O₂电极性能提供了一种环境友好且非常有效的方法。     

Ba(Mg1/3Ta2/3)O3热障涂层的制备及抗热震性能研究

本文以BaCO₃、MgO、Ta₂O₅为原料,采用固相反应法合成了Ba(Mg_1/3Ta_2/3)O₃(简称BMT)陶瓷粉末,利用大气等离子喷涂技术制备了BMT/YSZ双层陶瓷涂层。利用XRD、SEM和金相显微镜检测了BMT粉体及涂层的物相组成和显微结构。采用水淬法考核了涂层的抗热震性能。结果表明：1450℃下煅烧4h可合成出具有复合钙钛矿结构的BMT粉末,粉末具有良好的高温相结构稳定性。等离子喷涂制备的BMT/YSZ涂层组织致密,涂层系统中各界面结合紧密。涂层在室温至1150℃间热震9次后发生片状剥落,剥落位置位于BMT层间,BMT材料低的断裂韧性和第二相Ba₃Ta₅O₁₅的存在是导致涂层失效的主要原因。     

钙钛矿型La1-xSrxCoO3-δ粉体的制备及其在银基电接触材料中的应用

采用溶胶-凝胶法和粉末冶金工艺分别制备了颗粒状和网孔状La_0.5Sr_0.5CoO_3-δ(LSCO)粉体及其Ag-LSCO电接触复合材料。优化了溶液pH,溶胶预处理温度等工艺对LSCO粉体微结构的影响,并考察成型压力,烧结温度等对Ag-LSCO材料电学、力学性能的影响研究。采用扫描电镜、X-射线衍射仪、D60K数字金属电导率测量仪和HVS-1000型数显显微硬度计等对LSCO粉体及Ag-LSCO电接触材料进行了微观形貌、物相结构、电导率与硬度等性能表征。结果表明：以柠檬酸为单一胶凝剂,当pH为9.5,在700℃烧结8h可获得颗粒状LSCO_p粉体;而以柠檬酸和EDTA为复合胶凝剂时,于前驱体溶液pH=9.5,溶胶预处理温度200℃,烧结温度700℃,8h条件下合成网孔块体结构的LSCO_w粉体。经成型压力及烧结制度的优化结果可知,成型压力(1100MPa)、烧结温度900℃,6h 为制备Ag/LSCO_w电接触材料的最佳工艺参数。相比于Ag-LSCO_p电接触复合材料,Ag-LSCO_w表现出更低的电阻率(2.5μΩcm)。     

三元共晶成分Al2O3/YAG/ZrO2粉体及陶瓷的制备与组织性能研究

本文采用醇水共沉淀法制备了三元共晶成分Al₂O₃/YAG/ZrO₂粉体,在600-1350_oC温度范围煅烧后研究其物相转变过程。经1300_oC煅烧后Al₂O₃/YAG/ZrO₂共晶成分粉体的物相由α-Al₂O₃、c-ZrO₂和YAG构成,且具有α-Al₂O₃相包裹c-ZrO₂相的特殊结构。将煅烧粉体在1550_oC下热压烧结,制备具有内晶型结构的共晶成分Al₂O₃/YAG/ZrO₂复相陶瓷,其致密度、室温抗弯强度、断裂韧性和高温(1000_oC)抗弯强度分别为98.8%、420 MPa、3.69 MPa.m_1/2和464 MPa,并对复相陶瓷组织结构的形成机理进行了探讨。     

高阻尼高强度铸态SiCp/Mg94Zn5Y1 复合材料的综合性能

采用铸造方法制备具有不同SiC_p含量（0.5%~2.0%,质量分数,下同）的SiC_p/Mg₉₄Zn₅Y₁复合材料,并研究了复合材料的力学性能和阻尼性能。通过扫描电子显微镜和X射线衍射仪测试复合材料的微观组织结构和物相组成。在基体中加入SiC_p之后,SiC_p均匀分布在基体中,增强体细化了复合材料的微观组织结构。SiC_p/Mg₉₄Zn₅Y₁复合材料包括α-Mg、I相（准晶相）和SiC_p相。分别使用动态热机械分析仪和AG-X试验机测试了SiC_p/Mg₉₄Zn₅Y₁复合材料的阻尼性能和力学性能。复合材料的力学性能优于Mg₉₄Zn₅Y₁合金,1.0%SiC_p/Mg₉₄Zn₅Y₁复合材料的抗压缩强度高达350 MPa;所有复合材料的阻尼性能都远高于基体合金的阻尼性能,其中0.5%SiC_p/Mg₉₄Zn₅Y₁复合材料具有最佳的阻尼性能。此外,根据功效系数法,SiC_p含量为1.0%的SiC_p/Mg₉₄Zn₅Y₁复合材料具有良好的综合性能。     

水热法制备C3N4/CuGaO2 复合物及其气敏性能

采用简单水热法合成了一系列C₃N₄/CuGaO₂复合材料。采用XRD、SEM、TEM和XPS对制备的样品进行了表征。研究了一系列C₃N₄/CuGaO₂复合材料的气敏性能。结果表明,基于C₃N₄/CuGaO₂-0.3复合材料（C₃N₄与CuGaO₂的摩尔比为0.3:1）的气体传感器对甲苯的传感性能优于CuGaO₂传感器。相比较于CuGaO₂传感器的工作温度（140 ℃）,C₃N₄/CuGaO₂-0.3复合材料传感器的最佳工作温度仅为25 ℃,对100 μL/L甲苯气体的响应达到28,检出限低至0.01 μL/L。对100 μL/L甲苯气体的响应时间和恢复时间分别为114.2和27.4 s。此外,用于检测甲苯的C₃N₄/CuGaO₂-0.3复合材料传感器还具有优异的长期稳定性、良好的重复性和优异的抗湿性能。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

Sol-gel synthesis of Bi3.25La0.75Ti3O12 nanotubes

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) nanotubes were synthesized by sol-gel technique using nanochannel porous anodic aluminum oxide (AAO) templates, and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). BLT nanotubes with diameter of around 240 nm and the wall thickness of about 25 nm exhibited a single orthorhombic perovskite structure and highly preferential crystal growth along the [1 1 7] orientation, which have smooth wall morphologies and well-defined diameters corresponding to the diameter of the applied template. The formation mechanism of BLT nanotubes was discussed.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

FRICTION WELDING OF Zr55Al10Ni5Cu30 BULK METALLIC GLASS

采用摩擦焊对Zr₅₅Al₁₀Ni₅Cu₃₀块体金属玻璃进行了焊接, 当焊机主轴转速为4.0×10³---5.0×10³ r/min, 摩擦压力为80---100 MPa, 摩擦时间为0.2---0.4 s, 顶锻压力和保压时间分别为200 MPa和2 s时, 能够成功实施Zr₅₅Al₁₀Ni₅Cu₃₀金属玻璃的焊接. 用SEM, XRD和TEM观察分析未检测到晶化相, 焊缝处金属仍保持非晶状态. 金属玻璃的塑性在玻璃转变点T_g附近随温度变化很大, 在T_g以上具有良好的塑性变形能力, 这是实施摩擦焊焊接的重要基础.     

固相-水热法制备LiFePO4-Li3V2（PO4）3复合材料及其电化学性能（英文）

分别采用固相-水热法和球磨法制备磷酸亚铁锂-磷酸钒锂复合正极材料(LiFePO4-Li3V2(PO4)3)。电化学性能测试表明,LiFePO4-Li3V2(PO4)3复合正极材料的电化学性能远远高于 LiFePO4和 Li3V2(PO4)3单独作为正极材料的性能,并且以固相-水热法制备的复合材料性能优于以球磨法制得的复合材料。研究发现 LiFePO4-Li3V2(PO4)3复合材料有 4 个氧化还原峰,相当于 LiFePO4 和 Li3V2(PO4)3 氧化还原峰的叠加。采用固相-水热法制备的LiFePO4-Li3V2(PO4)3 复合材料形貌较为规则,且有新相物质产生,这是导致其电化学性能较好的原因。     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。     

二维ZnO/ Bi3.9Zn0.4V1.7O10.5纳米异质结构的制备及其可见光催化活性

表面建造是提高半导体光催化活性的一种有效方法。本文利用Zn5(CO3)2(OH)6纳米片为基底沉积了BiVO4再通过煅烧成功制备了二维ZnO/Bi3.9Zn0.4V1.7O10.5复合纳米片。通过X射线衍射,透射电镜和元素映像技术表征了所制样品。结果显示随着锌与铋的原子比的上升,ZnO多孔片状的表面逐渐变成Bi3.9Zn0.4V1.7O10.5物质。但其比例高于1:0.02时,在片状Bi3.9Zn0.4V1.7O10.5的区域表面又生长出BiVO4纳米颗粒。漫反射光谱测试显示出ZnO/Bi3.9Zn0.4V1.7O10.5复合物随着锌与铋的原子比的上升其在400~600 nm可见光区的吸收逐渐增强。所制样品在可见光（波长大于420 nm）进行了光催化降解罗丹明B的测试,结果表明在所制样品中,锌与铋的原子比为1:0.0133的ZnO/Bi3.9Zn0.4V1.7O10.5纳米片虽然其可见光的吸收并没有明显增强但却表现出最佳的光催化活性。荧光与电化学测试得出了低含量BZVO的ZnO纳米片可见光催化活性的提高主要是因为表面ZnO/Bi3.9Zn0.4V1.7O10.5异质结构提高了光生载流子的分离与传送。这种二维材料的表面建造有利于光催化的进行。因此,此法可应用于其它二维纳米材料的建造以提高光催化活性。     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.