Y1-xCaxF3-x-YOF混合相固体电解质的阻抗谱研究

用频率响应分析仪阻抗谱方法研究了Y1-xCacF3-x(X=0.05,0.23,0.25,0.27和0.29)-YOF混合相固体电解质的电导率.频率范畴10-2Hz～1MHz,温度范围为400～750℃.实验得到电导率为10-5～10-2S·cm-1.根据等效电路研究了CaF2掺杂对电导率的影响,利用Arrhenius公式算得了该固体电解质的电导激活能并分析了材料的电导激活能与掺杂成分的关系.     

表面活性剂胶束化物理化学性质研究

通过电导法考查温度和盐浓度对十二烷基硫酸钠(SDS)临界胶束浓度(CMC)的影响,研究表面活性剂形成胶束过程的物理化学性质。根据拟相分离模型求得胶束化热力学函数,并讨论体系电导活化能随温度和SDS浓度变化关系。结果表明:SDS的CMC随温度升高而增加,随氯化钠浓度增大而减小。在热力学上SDS在水溶液中形成胶束是一个自发、放热、熵增的过程;在动力学上,SDS溶液电导率与温度关系符合Arrhenius公式,通过电导活化能信息可揭示离子型表面活性剂形成胶束的机理特征。     

Arrhenius活化能理论的修正

针对Arrhenius活化能理论的不足,修正了这个理论,建立了一个修正的Arrhenius方程,它能适用于更宽的温度范围。     

PAN/PMMA凝胶聚合物电解质膜导电动力学分析

采用静电纺丝法制备PAN/PMMA(聚丙烯腈/聚甲基丙烯酸甲酯)凝胶聚合物电解质膜,用交流阻抗法测试其在不同温度下的电导率,研究温度对凝胶聚合物电解质膜离子传输性能的影响规律;并与溶液浇铸法制得的平滑膜进行对比,分析两种不同形式凝胶聚合物电解质膜的导电动力学规律,探索其导电机理与微观形貌的关系.结果发现,两种薄膜的导电机理符合Arrhenius公式,其中纺丝薄膜的离子导电活化能较低.     

交换La^3＋对NaX型分子筛Na^＋电导的影响

用X-射线衍射、原子吸收、差热热重、化学分析等方法测定了交换La3 离子NaX型分子筛的物相及组成。用交流阻抗谱仪测量了其离子电导。由电导率随温度的变化得到NaX的Na 电导表观活化能为38．8kJ／mol，适度交换La3 ，NaLaX的Na 电导表观活化能降低至27．9kJ/mol。讨论了交换La3 对分子筛中Na 迁移扩散的影响。     

离子液体[Cnpy][NTf2] (n=2, 4, 5)的动力粘度和电导率

在298.15-338.15 K和283.15-338.15 K温度范围内,分别测量了N-烷基吡啶双三氟甲磺酸亚胺(烷基链分别为:乙基、丁基、戊基)三种疏水型离子液体的动力粘度和电导率.利用Arrhenius 方程和Fulcher 方程将测量的动力粘度和电导率对温度拟合,得到了动力粘度和电导率随温度变化方程式.从电导率和密度计算出了上述三种离子液体在283.15-338.15 K温度范围内的摩尔电导率.应用Walden 规则,描述了动力粘度与摩尔电导率之间的关系.     

氟代硼酸锂玻璃的分子动力学模拟

用分子动力学模拟方法,计算了氟代硼酸锂玻璃的电导率.研究的温度范围高于和近于玻璃转变温度,共模拟了七个体系,研究的成分大致覆盖了能形成玻璃的区域.所得极限电导率、活化能以及电导率随温度的变化与实验数据符合得相当好.以往的研究认为快离子传导的典型特征是仅有一种离子发生迁移,我们的模拟表明氟离子对电导也有较大贡献.用活化能数据可顺利解释这个三元系各体系的电导率相对高低问题.     

凝胶型聚合物电解质的电导率与温度的关系

凝胶型聚合物电解质的电导率与温度的关系孙晓光，林云青，齐力，景遐斌，王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词凝胶电解质，离子电导率，活化能无定形聚合物电解质电导与温度的依赖关系一般可用Ｖｏｇｅｌ－Ｔａｍｍａｎ－Ｆｕｌｃｈｅｒｃ（Ｖ...     

两种疏水型膦类离子液体的密度、动力粘度及电导率（英文）

通过传统的方法,制备了两种对水和空气稳定的四烷基膦类离子液体。离子液体是:己基三丁基膦四氟化硼和己基三丁基膦双三氟甲基磺酸亚胺。在T=283.15-353.15 K温度范围内,测定了两个离子液体的密度、动力粘度及电导率。讨论了温度、阴离子结构对离子液体的性质的影响。结合文献报道的其它离子液体,讨论了该类离子液体性质随阳离子结构的变化规律,并与咪唑类离子液体的性质进行了比较。通过经验方程,利用密度数据计算了两个离子液体的重要热力学性质参数,例如:分子体积、标准摩尔熵及晶格能等。并将估算性质与传统的咪唑、吡啶类离子液体进行了对比。通过密度和电导率确定了离子液体的摩尔电导率。讨论了Vogel-Fulcher-Tamman(VFT)方程和Arrhenius方程对于粘度和电导率拟合的可行性,并估算了电导活化能及流动活化能。通过Walden规则,描述了密度、粘度及电导率之间的联系。有关研究对新型离子液体的合成及其工业化的应用具有十分重要意义。     

交换有La^3＋离子的NaA型分子筛的交流电导研究

本文用X—光射线衍射、原子吸收光谱及热重等方法测定了交换有La~(3+)离子的NaA分子筛LaNaA的组成,用交流阻抗谱测定了其离子电导,由电导率随温度的变化,得到了NaA和LaNaA的电导表观活化能分别为54.9KJ/mol和37.6KJ/mol。讨论了交换有La~(3+)离子后对分子筛骨架结构中Na~+离子分布、落位以及扩散迁移的影响。     

1-丁腈-3-甲基咪唑双三氟甲基磺酸亚胺的性质

制备了功能化离子液体1-丁腈-3-甲基咪唑双三氟甲基磺酸亚胺。在T为283.15-353.15 K温度范围内,测定了该功能化离子液体的密度、动力粘度、电导率及折光率。讨论了亚甲基的增减对该类功能化离子液体的密度、动力粘度、电导率及折光率等性质的影响,并与传统咪唑类、吡啶类离子液体物理化学性质的变化趋势进行了对比。通过经验方程计算了该功能化离子液体的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数。讨论了Vogel-Fulcher-Tamman (VFT)方程和Arrhenius方程的适用性,得出VFT方程适用于该功能化离子液体,而Arrhenius方程并不适用。有关研究对新型离子液体的合成及其工业化的应用具有十分重要的意义。     

Synergy of Single‐ion Conductive and Thermo‐responsive Copolymer Hydrogels Achieving Anti‐Arrhenius Ionic Conductivity

Artificial intelligence sensations have aroused scientific interest from electronic conductors to bio‐inspired ionic conductors. The conductivity of electrons decreases with increasing temperature, while the ionic conductivity agrees with an Arrhenius equation or a modified Vogel–Tammann–Fulcher (VTF) equation. Herein, thermo‐responsive poly(N‐isopropyl amide) (PNIPAm) and single‐ion‐conducting poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic lithium salt) (PAMPSLi) were copolymerized via a facile radical polymerization to demonstrate a very intriguing anti‐Arrhenius ionic conductivity behaviour during thermally induced volume‐phase transition. These smart hydrogels presented very promising scaffolds for architecting flexible, wearable or advanced functional ionic devices.     

以脲和硫氰酸铵为主体的固体电解质的研究

制得以脲和硫氰酸铵为主体的固体电解质,其室温电导率可达到４．３５×１０－２Ｓ·ｃｍ－１,比以脲和硫脲为主体固体电解质的电导率６．８４×１０－３Ｓ·ｃｍ－１提高了一个数量级。实验发现,影响电导率的因素主要有组成、温度和高分子。ＤＴＡ表明该电解质为非晶态固熔体,其导电性质既不服从Ａｒｈｅｎｉｕｓ方程,又不服从ＶＴＦ方程     

Physical–chemical properties of nickel analogs ionic liquid based on choline chloride

In this paper, a homogeneous, green analogs ionic liquid containing choline chloride and nickel chloride hexahydrate is formed. The structure of the analogs ionic liquid is preliminary investigated by Fourier transform infrared spectroscopy. It is shown that the nickel chloride hexahydrate bond via hydrogen bonds with choline chloride and urea. The physico-chemical properties of the analogs ionic liquid such as viscosity, conductivity, density, and thermal stability are measured as a function of temperature and composition. The thermal expansion coefficients (r), the molar Gibbs energy of activation (ΔG*) for viscous flow, the molar enthalpy of activation (ΔH*), and the molar entropy of activation (ΔS*) for viscous flow have been calculated. A straight-line equation is used to fit the density data while the Arrhenius equation is used to fit both viscosity and conductivity. Thermal stability of analogs ionic liquid was carried out from room temperature to 973.15 K. It indicates that analogs ionic liquid is stable from room temperature to 488.2 K.     

Polymer electrolytes based on acrylonitrile-butadiene-styrene copolymer

One of the approaches to improving the ionic conductivity and the mechanical strength of a solid polymer electrolyte is to use polymers in modified forms, such as polymer blends, copolymers and cross-linked polymers. In this study, a new polymer electrolyte based on the acrylonitrile-butadiene-styrene (ABS) copolymer has been prepared. The ionic conductivity, electrochemical stability and interfacial characteristics of the polymer electrolyte in contact with a lithium electrode have been investigated. The temperature dependence of the conductivity below 20 °C can be described by the Arrhenius equation, and above 20 °C by the VTF equation. Lithium passivation appeared to have taken place in the system. The conductivity and electrochemical characteristics of the system are somewhat similar to those of PAN-based polymer electrolytes. Received: 9 December 1998 / Accepted: 9 March 1999     

Influence of plasticizer type on the properties of polymer electrolytes based on chitosan

Polymer electrolytes were obtained by the casting technique from a solution containing chitosan, hydrochloric acid, and plasticizer such as glycerol, ethylene glycol, and sorbitol. The transparent membranes with good ionic conductivity properties were characterized by impedance and UV-vis spectroscopies, thermal analysis (DSC), and X-ray diffraction. The best ionic conductivity values of 9.5 x 10(-4) S cm(-1) at room temperature and 2.5 x 10(-3) S cm(-1) at 80 degrees C were obtained for the sample containing 59 wt% of glycerol and an equimolar amount of HCl with respect to NH2 groups in chitosan. The temperature dependence of the ionic conductivity exhibits an Arrhenius behavior with activation energy of 16.6 kJ mol(-1). The thermal analysis indicates that both glass transition temperature (-87 degrees C) and crystallinity are low for this electrolyte. The samples with 13 wt% of LiCF3SO3 showed that the ionic conductivity values of 2.2 x 10(-5) S cm(-1) at room temperature and 4 x 10(-4) S cm(-1) at 80 degrees C are predominantly amorphous and showed a low glass transition temperature of about -73 degrees C.     

物相稳定的V6O13+y

我们成功地合成了物相稳定的非化学计量的V_6O_(13)(V_6O_(13+y),y<0.2),并用X射线粉末衍射法进行了鉴定。在287-428K之间用复数阻抗技术对其进行了研究,由阻抗分析和模拟计算得出了物相稳定的V_6O_(13+y)在不同温度下的离子电导率,依赖于温度的离子电导率行为服从一个有恒定活化能E_(?)的Arrhenus型方程,由线性最小二乘拟合得出的离子迁移活化能为27.8kJ·mol~(-1)。还测定了物相稳定的V_6O_(13+y)的电子电导率,其数值在室温下高达10~(-2)S·cm~(-1)数量级。这些实验结果表明,对于室温非水二次锂电池来说,物相稳定的V_6O_(13+y)是一种有前途和实用价值的阴极材料。     

The origin of the conductivity maximum in molten salts. I. Bismuth chloride

A new theory is presented to explain the conductivity maxima of molten salts (versus temperature and pressure). In the new theory, conductivity is due to ions hopping from counterion to counterion, and its temperature dependence can be explained with an ordinary Arrhenius equation in which the frequency prefactor A (for hopping opportunities) and activation energy E(a) (for hopping) are density dependent. The conductivity maximum is due to competing effects: as density decreases, the frequency of opportunities for hopping increases, but the probability that an opportunity is successfully hopped decreases due to rising E(a) caused by the increased hopping distance. The theory is successfully applied to molten bismuth (III) chloride, and supported by density-functional based molecular dynamics simulations which not only reproduce the conductivity maximum, but disprove the long-standing conjecture that this liquid features an equilibrium between BiCl(3) molecules, and BiCl(2)(+) and BiCl(4)(-) ions that shifts to the left with increasing temperature.