工艺参数对微区沉淀法制备纳米MgAl2O4粉体的影响

采用高分子网络微区沉淀法制备纳米镁铝尖晶石（MgAl2O4）粉体，并采用TGA／DTA、XRD和TEM等分析测试技术对前驱体的热分解和所制得粉体的物相组成、形貌及颗粒尺寸进行表征，结果表明所制得的MgAl2O4粉体颗粒粒径小，结晶良好，成分单一且粒径大小均匀。而实验过程中工艺参数的改变会对生成粉体的粒径和形貌产生一定的影响，进而即研究了各种工艺参数的改变对该方法制备纳米MgAl2O4粉体的影响。     

尖晶石纳米催化剂应用于烯丙醇多相氧化制烯丙醛或烯丙酮

使用共沉淀法通过Ru对MeFe2O4的同晶取供制备了纳米级MnFe1.95Ru0.05O4催化剂。在通过过渡金属进一步改性该催化剂的过程中，发现MnFe1.95Ru0.05O4的催化剂性能优异于文献报道的其他多相醇氧化催化剂，XRD测试表明该催化剂仍保持尖晶石结构。该纳米催化剂能有效地将不同烯丙醇类氧化成烯丙醛类或烯丙酮类，与文献报道的其他多相氧化催化体系相比，该催化剂具有更高的活性转换数。借助于EXAFS等表征结果和1－辛醇与4－辛醇的竞争反应，判断出单核的Ru类反应的活性中心，EXAFS的表征同时表明由于Cu的添加而产生的Ru=0能加快反应速率。作者在此基础上提出反应机理，认为Ru在反应过程中形成醇化物，再经过β消除反应生成相应的醛或酮。     

抗水合氧化铝载体研究进展

氧化铝系载体用于含水或有水生成的催化过程时，均会发生再水合现象，从而造成催化剂强度的下降，并导致其比表面积大幅下降，使催化剂不可逆失活。镁铝尖晶石的抗水合性远高于氧化铝系载体，是一种很好的催化剂载体。综述了氧化铝系载体的再水合现象、改进载体抗水合性能的方法以及镁铝尖晶石粉体和载体的制备方法及改进措施。     

In situ synchrotron X-ray studies on copper-nickel 5 V Mn oxide spinel cathodes for Li-ion batteries

Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the cycle life characteristics of the cathode. Substitution with either metal or a combination of both metals in the spinel lattice structure reduces the 3.9-4.2 V potential plateaus associated with the conversion of Mn³⁺ to Mn⁴⁺. Higher potential plateau associated with oxidation of the substituted transition elements is also observed. These substituents also significantly alter the onset of Jahn-Teller distortions in the 3 V potential plateau. Synchrotron based in situ X-ray absorption (XAS) was used to determine the exact nature of the oxidation state changes in order to explain the overall observed capacities at different potential plateaus. The studies on LiCu_0.5Mn_1.5O₄ show single phase behavior in the 4-5 V potential region with a good cycle life. Lower cycle life characteristic observed in cycling LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ versus Li metal are ascribed to coexistence of several phases in this potential region. However, LiCu_0.5Mn_1.5O₄ shows onset of Jahn-Teller distortions in the 3 V potential plateau, in contrast to LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ cathode materials.     

掺杂型尖晶石Li_(1.05)Mg_xMn_(2-x)O_4的合成及性能研究

采用高温固相法制备了尖晶石正极材料L iMxMn2-xO4(X=0.04,0.06,0.08,0.10),并用XRD、SEM、ICP-AES、充放电测试等手段研究了其组成、结构、表观形貌和电化学性能。结果表明:该法制备的尖晶石正极材料L iMxMn2-xO4为单一尖晶石结构,粒径分布均匀,其比容量和循环性能较未掺杂尖晶石L iMn2O4有显著的提高。     

Synthesis and electrochemical characterization of a new Se-doped spinel material for lithium secondary batteries

A new Se-doped spinel material, LiAl_0.18Se_0.02Mn_1.8O₄ powder with a phase-pure polycrystalline was synthesized by a sol–gel method. The material in the 3 V region (2.4 3.5 V) and both the 3 and 4 V region (2.4 4.4 V) initially deliver a discharge capacity of 81 and 178 mA h g^–1 which increase with cycling to reach 110 and 204 after 50 cycles, respectively. The material shows excellent cycleability in the 4 V region (3.0 4.4 V) with almost no capacity loss. The structural integrity of the Se-doped spinel was characterized by charge–discharge cycling tests and X-;ray diffraction.     

TiO2加入量对富铝尖晶石烧结性能的影响

以α-Al2O3、分析纯的MgO及分析纯的TiO2为原料,研究了在1400℃、1500℃、1600℃保温3 h下,TiO2加入量(分别为0、1%、2%、4%)对Al2O3与MgO物质的量比为21的富铝尖晶石烧结性能的影响,并利用XRD进行物相组成分析,利用SEM和EDAX进行显微结构分析.结果表明由于TiO2与MgAl2O4的固溶作用,加入TiO2可显著改善富铝尖晶石的烧结性能;随着TiO2加入量的增加,试样的体积密度增加,显气孔率降低,特别是在1600℃烧结后的试样尤为显著.     

NiFe2O4及添加TiO2的尖晶石的烧结过程

以NiO和Fe2O3为主要原料,通过添加少量TiO2粉末来改善NiFe2O4试样的烧结性能。研究了NiFe2O4和TiO2-NiFe2O4 2种样品反应烧结过程中的热力学及动力学条件,同时利用球模型推导的扩散机制的烧结方程测算出2种材料的烧结活化能。结果表明：NiO和Fe2O3固相烧结过程是固相反应和致密化过程同时进行的。添加质量分数为1％TiO2粉末,当合成温度为1250℃时,TiO2-NiFe2O4样品就已达到致密,其烧结活化能由NiFe2O4样品时的245.36kJ/mol降低为142.71kJ/mol。     

Synthesis and electrochemical performance of LiNi0.5Mn1.5O4 spinel compound

Spinel compound LiNi_0.5Mn_1.5O₄ was synthesized by a chemical wet method. Mn(NO₃)₂, Ni(NO₃)₂·6H₂O, NH₄HCO₃ and LiOH·H₂O were used as the starting materials. At first, Mn(NO₃)₂ and Ni(NO₃)₂·6H₂O reacted with NH₄HCO₃ to produce a precursor, then the precursor reacted with LiOH·H₂O to synthesize product LiNi_0.5Mn_1.5O₄. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi_0.5Mn_1.5O₄ had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm². After 50 cycles, the total discharge capacity was above 118 mAh/g.     

水热法制备纳米尖晶石型NiFe_2O_4及表征

分别采用水热法、共沉淀法合成了纳米尖晶石型铁氧体—NiFe2O4晶体,对两种方法所合成的样品进行了比较,分析了不同合成方法的优缺点,确定水热法为比较适宜的合成该类复合氧化物的方法,该法合成的NiFe2O4晶体的平均粒径仅为15.9nm,且粒度分布十分均匀。此外,通过对实验结果的测定与分析探讨了影响水热制备的几种可能的因素,确定了水热合成的适宜的沉淀剂为NaOH溶液,水热合成适宜的温度为200℃。