全钒液流电池用碳毡电极的改性研究

分别采用普鲁士蓝(Prussianblue,PB)和草酸对聚丙稀腈基(PAN)碳毡进行修饰处理,通过循环伏安法研究了修饰后材料在钒溶液中的电化学性能。结果表明PB修饰碳毡电极对V(Ⅳ)/V(Ⅴ)电对具有良好的电催化性能,V(Ⅱ)/V(Ⅲ)电对在草酸修饰碳毡电极上的活性相比处理前也有较大改善。分别以这两种修饰电极为正负极组装全钒氧化还原液流电池(VRB),通过电池性能测试获得了最适宜的修饰条件。使用修饰电极的静态钒电池在电流密度为35mA·cm-2时电压效率可达83.28%。     

碳热还原法合成正极材料Li3V2(PO4)3及其性能

采用碳热还原(CTR)法以LiOH.H2O、V2O5和NH4H2PO4为原料合成了具有NASCION结构的锂离子蓄电池正极材料磷酸钒锂Li3V2(PO4)3。系统地研究了合成温度、反应时间和原料配比等因素对样品性能的影响。结果表明以n(Li)∶n(V)∶n(P)=3.05∶2.00∶3.00投入原料在800℃下煅烧24h合成的正极材料在0.1C充、放电制度下,首次充电比容量达到137mAh/g,首次放电比容量137mAh/g,充、放电效率达100%,经过20次循环后,放电容量仍然保留110mAh/g,为初始放电容量的84%。对样品进行了X射线衍射(XRD)分析,结果表明合成的样品Li3V2(PO4)3具有单斜晶体结构。     

四价钒离子VO2+在几种阳离子交换膜中的自扩散行为

研究了VO2 在3种阳离子交换膜PE01,NF120以及Nafion1135中的自扩散行为,采用UV-3802可见-紫外分光光度仪测定VO2 浓度,建立浓度与时间的关系,用Ct=Ct∞(1-exp(-αt))经验方程拟合实验数据,得到VO2 在3种膜PE01,NF120以及Nafion1135中的自扩散方程.结合Fick扩散理论,推导出了VO2 在膜中的扩散系数D与方程中经验常数α的关系,计算出了VO2 在3种阳离子交换器Nafion1135,PE01以及NF120中的扩散系数分别为2.66×10-13,2.09×10-13和3.26×10-13m2/s.在所研究的阳离子交换膜中,PE01膜对VO2 具有最好的阻隔作用.     

耒阳高岭土制备刮刀级造纸涂料

以耒阳高岭土为原料，采用除杂漂白加工方法制取刮刀级造纸涂料，试验结果表明，将高梯度磁选和络合还原漂白相结合可有效地除去高岭土中的铁钛杂质，所制产品白度超过８５％，各项性能指标均达到刮刀级涂料的标准。     

Cu掺杂对贮氢合金MI（NiCoMnAICu）5．0电化学性能的影响

采用真空感应熔炼方法，制备了一系列Cu掺杂的MI（NiCoMnAtCu）5.0即AB5.0型贮氢合金。通过电化学及X射线衍射等手段，系统地研究和分析了Cu掺杂对AB5.0型贮氢合金的电化学性能（最大放电比容量、高倍率性能和循环稳定性能）及其微结构和动力学特征的影响。     

Syntheses and applications of Eu（Ⅲ） complexes of 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline as light conversion agents

A series of europium(Ⅲ) complexes of 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized. The new complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 were characterized by elemental analysis, IR spectrum, scanning electron microscope and thermal stability analysis. The results show that the thermal stability of the Eu( Ⅲ ) complexes increases in the following order: the mononuclear complex Eu(TTA)3Phen, the binuclear complex Eu2(TPA)(TTA)4Phen2, the chain polynuclear complex Eu(TPA)(TTA)Phen. And the formation of the binuclear/polynuclear structure of the new complexes appears to be responsible for the enhancement of their thermal and optical stability. In addition, The fluorescence excitation spectra of these new complexes show more broad excitation bands than that of the complex Eu(TTA)3Phen corresponding to their formation. The enhancement of Eu3 fluorescence in the new complexes can be observed by the addition of Gd3 . The bright red luminescent plastics can be obtained when the complex EuGd(TPA)(TTA)4Phen2 is added above 0.5% (mass fraction).     

Synthesis, oxygenation and catalytic performance of manganese complex with p-aminomethyl benzoic acid Schiffbase

The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.     

掺杂锂镍钴锰氧材料的合成及电化学性能

采用改进的共沉淀法合成掺杂Al、Mg的LiNi1/3Co1/3Mn1/3O2系列材料,通过X射线衍射光谱法(XRD)、扫描电子显微镜法(SEM)、伏安法(CV)、充放电测试、交流阻抗等技术对材料进行了表征,比较了掺杂元素(Al、Mg)对电化学性能的影响.在2.8～4.3 V,0.1 C倍率下未掺杂材料的首次放电比容量达171.1 mAh/g,循环10次后为152.2 mAh/g,掺杂Al、Mg后容量有所下降,但循环性能得到改善,前10次容量衰减分别为2.5%、3.3%.采用Voigt模型对交流阻抗谱进行拟合,比较了电解液阻抗、交换膜阻抗和法拉第阻抗的变化,发现10次循环后电荷传递阻抗明显增大.     

磁场对聚苯胺结构、掺杂行为及热稳定性的影响

在恒定磁场(0.8T) 和无磁场环境下,采用化学氧化聚合法合成了分别用磺基水杨酸(SSA)、对甲基苯磺酸(TSA)以及用十二烷基苯磺钠/盐酸(SDBS HCl)掺杂的聚苯胺盐,并采用X射线光电子能谱(XPS)、傅立叶红外光谱(FT-IR)、X粉末衍射(XRD),热重分析(TGA)等手段研究了磁场对聚苯胺结构、掺杂行为及热稳定性的影响.结果表明在合成聚苯胺的过程中,作为表面活性剂的十二烷基苯磺酸钠在无机酸存在条件下转变成十二烷基苯磺酸并与无机酸共同掺杂进入聚苯胺链;磁场环境下合成的聚苯胺盐比无磁场下合成的聚苯胺盐的链更加规整,热稳定性更好,掺杂程度以及结晶性能也有所提高;从红外光谱分析中可知,磁场取向作用使分子链更加伸展,分子链离域程度更大,但磁场没有明显地改变聚苯胺的基本单元结构.     

First-principle investigation on stability of Co-doped spinel λ-Mn4-xCoxO8

The mechanism of stability of Co-doped spinel λ-MnO2 that is referred to as spinel LixMn2O4 （x=0） was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decreased remarkably due to the Co substation, resulting in a more stable structure ofλ-MnxCr2-xO4. The bond order and DOS analysis were given in detail to explain the nature of stability improvement. The calculated results show that as the content of Co dopant increases, the bond order of Mn-O becomes larger and the peak of density of states around Fermi level shifts toward lower energy. The charge density distribution illustrates that the Mn-O bonding is ionic and partially covalent, and the covalent Mn-O bonding becomes stronger with the increase of Co dopant content. The results confirm that the Co-doping will enhance the stability of λ-MnO2 and hence improve the electrochemistry performance of LixMn2O4.