IONIC CONDUCTIVITIES OF SEGMENTED POLYETHER POLYURETHANEUREA COMPLEXES WITH LiClO4

Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10~(-4) S·cm~(-1) at 353K and～1.0×10~(-5)S·cm~(-1) at 306K were achieved. The ionic conductivity data were analyzed using the VTF (Vogel-Tamman-Fulcher) equation and WLF (Williams-Landel-Ferry) type equation. Values have been estimated for the "apparent" activation energies of ion transport from VTF equation and they lie in the range 2.70—5.53 kJ·mol~(-1).     

Energies,structures, and electronic properties of molecules in solution with the C-PCM solvation model

The conductor-like solvation model, as developed in the framework of the polarizable continuum model (PCM), has been reformulated and newly implemented in order to compute energies, geometric structures, harmonic frequencies, and electronic properties in solution for any chemical system that can be studied in vacuo. Particular attention is devoted to large systems requiring suitable iterative algorithms to compute the solvation charges: the fast multipole method (FMM) has been extensively used to ensure a linear scaling of the computational times with the size of the solute. A number of test applications are presented to evaluate the performances of the method.     

On a Stochastic Theory of Ion Transfer at Intermediate Damping

The stochastic method, which was formulated earlier by Gurevich and Kharkats on the basis of a classic solution of the Fokker-Planck equation in a phase space of coordinates and momenta, is developed to extend it to the case of intermediate damping. In contradistinction to the Gurevich-Kharkats model, the new theory is based on the Fokker-Planck equation in the energy-action coordinates. Analytical expressions for the exchange current and conductance are derived. The expressions are valid in a broad damping regime. As compared with the Gurevich-Kharkats model, the expression for the exchange current contains an additional factor, which depends on the energy losses sustained by the ion upon its collision with the cage of a crystal lattice. An explanation for the isotope effect in the high-temperature protonic conductors is suggested. It is demonstrated that the friction coefficient for these solid electrolytes may correspond to the underdamped-to-intermediate-damping regime. This fact makes it possible to put forth an explanation for the existing contradictions between their properties and simple hopping models, which ignore the interaction of ions with the crystal lattice.     

钠快离子导体Na1+xZr2-yTiySixP3-xO12系统的研究(Ⅱ)

本文介绍钠快离子导体Na_(1+x)Zr(3-y)Ti_y Si_xP_(3-x)O_(12)系统中x=2.0,y=0—2.0的一系列合成物的合成条件、相变关系及其两个单纯相—311相(相当于起始组成为Na_(3.0)Zr_(1.0)Ti_(1.0)Si_(2.0)P_(1.0)O_(12.0)和302相(相当于起始组成为Na_(3.0)Ti_(2.0)Si_(2.0)P_(1.0)O_(12.0)的电导率和激活能。 室温时,311相和302相的电导率分别为0.78×10~(-4)(Ω·cm)~(-1)和0.30×10~(-4)(Ω·cm)~(-1)。623K时,311相和302相的电导率则是0.49×10~(-1)(Ω·cm)~(-1)和0.44×10~(-4)(Ω·cm)~(-1)。在473K—623K温区里,311相和302相的电导激活能各为43.01kJ/mole和46.26kJ/mole。     

ICP-AES法测定高温质子导体中的五种元素

研究用ICP-AES法测定高温质子导体中的钡、铈、锶、钇和镱，选定了适宜的溶解方法及分析条件，在溶解酸中加入盐酸羟胺，获得了较为满意的分析结果，相对标准差小于10%。     

Effects of firing schedule on solubility limits and transport properties of ZrO2-TiO2-Y2O3 fluorites

The low Y/high Zr edge of the cubic defect fluorite solid solution in the system ZrO₂-TiO₂-Y₂O₃ in air is reassessed, as it is these compositions which have been suggested to offer the highest levels of mixed conductivity. Vegard's law is obeyed for values of x which lie within the cubic defect fluorite phase in Zr_1−x−yY_yTi_xO_2−δ for values of y=0.2 and 0.25. Measured lattice parameters show good agreement with those calculated from the Kim relation. Deviation from Vegard's law places the limit of the solid solution at x=0.18 and 0.20 for values of y=0.2 and 0.25, respectively, at 1500 °C. Discrepancies in current literature data can be shown to be due to differences in firing schedule such as slight temperature fluctuations and/or different cooling rates. A high level of care of sintering temperature and cooling profile is essential to form the most promising single-phase materials which contain maximum Ti-contents with low Y-contents. Contraction of the phase limit as a result of poor synthesis control leads to erroneously high values of bulk ionic conductivity while values of electronic conductivity are shown to be less affected.     

部花菁染料的多重电荷转移复合物的研究

自1977年夏在纽约科学院一次会议上Heeger，MacdiarAnd和百）l；英树报告了（CH）。可掺杂到金属态［1］以来，已有许多学者对共轭聚合物的化学掺杂及导电性进行了广泛地研究，用能带模型说明掺杂提高电导的原因．从能带模型可预见只有能隙小，带宽大的共轭聚合物才有可能具有较高的导电性．因为能隙小时离子化电位小，电子亲合力大，易于掺杂．带宽大则掺杂后电子易于迁移问，而与多烯具有相同。电子数的部花育染料的七。x比多烯向更长波长方向位移．例如十六碳八烯的A。。x为410O人而具有同样。电子数的部花育染料BTER的人m。x则为51…     

等离子体引发聚合制备共聚醚及其锂盐配合物的离子电导性

为改善梳形聚醚-聚甲基丙烯酸甲氧基多缩乙二醇酯[P(CH_1=C(CH_3)CO(OCH_2CH_2)_nOCH_3),n=8,22,分子量分别为400,1000,简称PMEO_8,PMEO2_(22)的力学性能,作者曾用等离子体引发聚合代替自由基引发聚合制备了PMEO_8,PMEO_(22)及其与丙烯酰胺(AM),甲基丙烯酰胺(MA)的共聚物,取得了较满意的结果。为系统地研究     

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.     

La0.9Sr0.1Al0.9Mg0.1O3-δ-Ca3(PO4)2-K3PO4复合电解质的合成及在常压天然气合成氨中的应用

La_0.9Sr_0.1Al_0.9Mg_0.1O_0.9(LSAM) was synthesized by the sol-gel method, an oxide-salt composite electrolyte LSAM-Ca₃(PO₄)₂-K₃PO₄ was prepared by mixing the LSAM and phosphates. The mixture was ground and sintered at 1 400 ℃. Using the LSAM electrolyte and its oxide-salt composite as solid electrolytes and silver-palladium alloy as electrodes, electrical conductivity was measured at different conditions. Ammonia was synthesized from wet natural gas and nitrogen at atmospheric pressure in the solid state proton conducting cell reactor and the optimal conditions for ammonia production were determined. The oxide-salt composite exhibited much higher ionic conductivity and ammonia production rate than that of the LSAM electrolyte at 400～800 ℃, the rate of evolution of ammonia was up to 5.30 × 10^-9 mol·cm^-2·s^-1.