ZrOCl2掺杂的磷硅酸盐凝胶的机械化学合成

纯磷硅酸盐干凝胶在潮湿环境下存放会使磷酸从中析出,导致其质子电导率显著下降。为此,人们通常采用化学改性处理的方式以解决其化学耐久性差的问题。利用ZrOCl2.8H2O通过溶胶凝胶法对磷硅酸盐进行掺杂,我们发现掺杂量为0.97%时,所得凝胶的质子电导率最高。基于此,本文利用高能球磨技术研究了磷硅酸盐凝胶的ZrOCl2掺杂。研究结果表明:机械研磨能够提高原料混合物的质子电导率,当研磨时间为10 h时,所得材料的质子电导率最大,σ130=2.4 S·m-1。这一数值与利用溶胶-凝胶法制备的同样化学成分的样品相同。但前者的质子传导激活能高于后者,造成这一差别的主要原因是两者内部的组织结构存在一定差别。31P NMR(Nuclear Magnetic Resonance核磁共振)谱测试结果表明:机械研磨处理的样品(尤其MM10 h)化学耐久性较好。     

Ce1-xGdxO2-x/2的溶胶-凝胶法合成及其性质

利用溶胶-凝胶法合成了Ce₁-xGdxO_2-x/2(x=0.1～0.6)系列固体电解质,系统地研究了其结构、热膨胀系数和导电性.XRD结果表明,160℃即完全形成立方萤石结构.由于溶胶-凝胶法合成的物质粒度均匀,颗粒小,故在较低温度(1300℃)时即可形成高致密样品,此温度明显低于传统的高温固相法烧结温度(1600～1650℃).高温X射线衍射测得Ce_0.8Gd_0.2O_1.9的热膨胀系数为8.125×10^-6K₁.阻抗谱表明,溶胶-凝胶法合成可减少或消除固体电解质的晶界电阻,600℃时Ce_0.8Gd_0.2O_1.9的电导率为5.26×10^-3S/cm,活化能E_a=0.82eV.     

BaCe0.9Nd0.1O3-δ柠檬酸盐法合成、表征及其在中温区的电导率

A precursor of BaCe_0.9Nd_0.1O_3-δ solid electrolyte was synthesized by the sol-gel method and sintered at 1400℃.The obtained gels and powder were characterized by differential and ther mogravimetric thermal analysis(TG-DTA),X-ray diffraction(XRD), transmissi on electron microscopy(TEM).Using the sintered samples as solid electrolyte and silver-palladium alloy as electrodes,electrical conductivities under different gas ambiences at intermediate temperature (400～600℃) were measured. In moist hydrogen atmosphere, the conduction is a little higher than that of dry hydrogen atmosphere. In hydrogen atmosphere, proton conduction may predominate, leading to an increase in conductivity and a decrease in activation energy.     

Ca、Ce双掺杂烧绿石型复合氧化物的合成及离子导电性能研究

Pyrochlore-type rare earth complex oxides of La_2-αCa_αZr_2-βCe_βO_7-δ were synthesized by the sol-gel method. The structure of the samples was characterized by X-ray diffraction (XRD). The ionic conduction in solid electrolyte of the sintered samples was examined using electrochemical methods at 400～800 ℃. The result indicated that the samples were pyrochlore-type structure, conductivities of the Ca and Ce doped samples were largely increased. Ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid state proton conducting cell reactor. The ammonia evolution rate of doped samples is larger than that of the undoped ones, which indicates that the samples are proton conductor and the ability of protonic conductivity is mainly decided by hole concentration.     

Al掺杂对尖晶石型LiMn2O4结构及循环性能的影响

用柠檬酸作为螯和物的载体,采用溶胶-凝胶法合成了A l3 掺杂的锂离子电池正极材料L iA lxMn2-xO4。XRD,SEM研究表明,于800℃煅烧可获得单一尖晶石结构的物相;随着A l3 掺入量的增加,L iA lxMn2-xO4的晶格常数变小,晶格更趋于完整,有利于抑制因锂的反复脱嵌而造成的结构破坏。x=0.05时,首次放电容量为103.8 mAh.g-1,25次循环后放电容量还有100.6 mAh.g-1,容量衰减仅为3.08%。     

锶掺杂对La_(1-x)Sr_xNbO_(4-σ)质子导体性能的影响

利用高温固相反应法制备了Sr掺杂LaNbO4质子导体La1-xSrxNbO4-σ(0≤x≤0.02),并且对其性能进行了表征。XRD分析表明,所有的样品具有单斜结构,晶胞体积随Sr掺杂量的增加而增大;La1-xSrxNbO4-σ样品在沸水中和二氧化碳气氛中具有很好的化学稳定性。SEM分析表明,La1-x Srx NbO4-σ粉体经1 500℃烧结8 h后均得到致密的、晶粒均匀的样品;Sr的掺杂抑制了陶瓷体裂缝的产生和晶粒的过度增长;随Sr的掺杂量增加,晶粒变小。交流阻抗谱分析表明,Sr掺杂改变了LaNbO4的电导率,其中样品La0.995Sr0.005NbO4-σ具有最高的电导率;样品在25℃水汽饱和的5%H2-Ar气氛下的电导率明显高于干燥空气气氛,在800℃时,La0.995Sr0.005NbO4-σ电导率达到0.003 S·cm-1,电导活化能为0.44 eV。     

掺杂质子酸的类型对聚苯胺结构和电导率的影响

采用化学氧化聚合法以苯胺为单体，过硫酸铵为氧化剂，在不同质子酸的水溶液中合成聚苯胺，考察质子酸对聚苯胺电性能影响，并通过傅立叶红外吸收光谱（FTIR）和紫外可见光吸收光谱（UV－vis)研究聚苯胺掺杂前后结构的变化。结果表明，龙质子酸掺杂后聚 胺具有导电性是因为其分子链上电荷离城形成了共轭结构，具有不同质子酸中生成的聚苯胺氧化程度不同；分子链共轭程度与掺杂酸对阴离子大小有关，掺杂质子酸对阴离子越大，聚苯胺分子链共轭程度越大，电导率也就越高。     

制备条件对Bi3+掺杂纳米TiO2光催化性能的影响

以钛酸四丁酯为原料,采用溶胶-凝胶法制备了掺杂铋的TiO2纳米微粒,通过正交实验法研究了溶剂乙醇量,加水量,铋掺杂百分比,抑制剂乙酸和pH调节剂浓硝酸用量等因素对光催化剂性能的影响,催化剂活性用光催化降解偶氮胭脂红溶液的降解率表示,确定了各因素的最佳水平,即浓硝酸0.2mL,铋掺杂量0.5%,水7.2mL,无水乙醇60...     

La0.8Sr0.2Ga0.8Mg0.2O3－α陶瓷的质子导电性能研究

采用溶胶-凝胶法合成了La_0.8Sr_0.2Ga_0.8Mg_0.2O_3－a陶瓷样品, 用XRD, DSC-TGA, SEM, 交流阻抗谱, 气体浓差电池及气体电化学透过等方法对样品的结构和性质进行了表征和测试. 首次对该样品的质子导电性能进行了研究. 该陶瓷样品具有良好的微观结构, 相对密度达95.1%; 氢浓差电池电动势的实测值与理论值吻合, 离子迁移数为1; 在干燥的氧气气氛中是一个纯的氧离子导体; 氢的电化学透过速率的实测值与理论值吻合, 证明该样品在氢气气氛中几乎是一个纯的质子导体, 质子电导率在1000 ℃时高达0.14 S•cm^－1.     

Ce1-xCaxO2-x的溶胶-凝胶法的合成及其性质

固体电解质;氧离子导体;Ce1-xCaxO2-x的溶胶-凝胶法的合成及其性质     

Preparation of Ce(SO4)2-doped Phosphosilicate Gels by Mechanical Milling

Ce(SO4)2-doped phosphosilicate gel was prepared by mechanical milling.Complex impedance analysis proved that the 15 h-ball-milled sample showed a maximum conductivity of 2.97 S/m at 130 ℃,which is abou...     

质子导体(Ce0.8La0.2)1－xCaxO2－δ 在合成氨中的应用

利用溶胶-凝胶法合成了萤石型稀土复合氧化物(Ce_0.8La_0.2)_1－xCa_xO_2－δ, 利用XRD、TEM和SEM对样品进行表征. 电化学方法研究表明, 合成样品在400～800 ℃温度范围内具有质子导电特性. 将(Ce_0.8La_0.2)_1－xCa_xO>_2－δ高温烧结体用于固态质子传导电池, 在常压下以氮气和氢气为原料合成氨气, 并确定了合成氨的适宜条件. 650 ℃时Ce_0.8La_0.2O_2－δ和(Ce_0.8La_0.2)_0.975Ca_0.025O_2－δ对应的氨产率分别达7.2×10^－9和7.5×10^－9 mol•s^－9•cm^－9.     

Synthesis and characterization of BaGa2O4 and Ba3Co2O6(CO3)0.6 compounds in the search of alternative materials for Proton Ceramic Fuel Cell (PCFC)

BaGa₂O₄ and Ba₃Co₂O₆(CO₃)_0.6 compounds were studied as electrolyte and cathode materials for Proton Ceramic Fuel Cells (PCFC), respectively. Not only BaGa₂O₄ rapidly reacts with atmospheric H₂O and CO₂ and leads to a progressive material decomposition, but it does not present real hydration properties in normal conditions of pressure. On the other hand, the basic cobalt oxocarbonate Ba₃Co₂O₆(CO₃)_0.6 exhibits an interesting tendency for weight uptake and formation of hydrogencarbonate groups in moist heating/cooling conditions. This material was therefore considered for complementary studies in order to confirm its potential use as mixed proton-electron conductor, taking into account the ordered intergrowth of carbonates and face sharing Co-octahedra columns forming a pseudo-one-dimensional structure. Some preliminary results concerning electrochemical properties of the barium cobalt oxocarbonate as a PCFC cathode are also described and show at the moment modest performance, possibly related to a hydrated/carbonated surface layer contribution and/or the lack of electron percolation within the electrode layer.     

Effect of CuO Doping on the Electrical Behavior of ZrO2

Electrical conductivity has been measured at different temperatures for ZrO2 doped with various molar ratios of CuO. The conductivity increases due to migration of vacancies, created by doping. The conductivity was found to increase with increase in temperature till 220℃ and thereafter decrease due to collapse of the fluorite framework. A second rise in conductivity around 500 ℃ was observed due to phase transition of ZrO2. X-ray powder diffraction, DTA and IR studies were carried out for confirming doping effect and phase transition in ZrO2.     

氯离子对介孔氧化铝质子导电性的影响

掺杂氯盐使介孔氧化铝导电率提高近一个数量级,将掺杂的介孔氧化铝浸渍在水中24h后的导电率仍为纯介孔氧化铝的3～6倍。红外光谱结果显示,氯掺杂改变了表面酸碱活性中心,导致质子更易在介孔氧化铝中发生迁移,从而提高导电性。     

Proton Conductivity Improvement Effect of Cellulose on SPEEKK Based PEM

The proton exchange membranes(PEMs) were prepared through the solution mixing method of sulfonated poly(etlier ether ketone ketoneXsPEEKK) and cellulose. Cellulose was dissolved by 1-ally 1-3-methylimidazolium chioride(AMIMC1) and then mixed with sPEEKK solution. sPEEKK/cellulose(SC) composite membranes were prepared by solution casting. The membranes have high flexibility and transparency, which meant the compounding in molecular level. Meanwhile, the composite membranes showed excellent mechanical properties and high proton conductivity. The mechanical property reached 29 MPa, and the proton conductivity was as high as 0.32 S/cm. Thus, as a kind of biomaterials, cellulose could be ail excellent reinforcing material for poly(aryl ether ketone)(PAEK) based PEMs.     

二次掺杂对聚苯胺导电复合物性能的影响

研究了聚苯胺与（苯乙烯－丁二烯）三嵌段共聚物或氯碘化聚乙烯复合物在间甲酚二次掺杂前后电导率的变化（提高２个数量级），根据二次掺杂使聚苯胺复合物增强永久形变和断面形貌脆断一次掺杂使卷曲的聚苯胺链展开并通过这间的弱相互作用而自行组成导电能通路，复合物二次掺杂前后的抗张强度和伸长率变化不大，说明其主链间的弱相互作用对应力无贡献，此外，还研究了二次掺杂对复合物在中性和酸必南中电致变色活性的影响。     

氧化铟掺杂对ZnFe2O4半导体气敏性能的影响

用化学共沉淀法在ＺｎＦｅ２Ｏ４中掺入Ｉｎ２Ｏ３．Ｘ射线衍射分析证实，Ｉｎ２Ｏ３与ＺｎＦｅ２Ｏ３之间没有新相生成，晶格常数有微小变化．掺入Ｉｎ２Ｏ３降低了ＺｎＦｅ２Ｏ４的电导，改变了该系列材料的导电机制，提高了材料对乙醇的敏感性和选择性，而且缩短了材料的响应时间