Highly Conductive Anion‐Exchange Membranes from Microporous Tröger's Base Polymers

The development of polymeric anion‐exchange membranes (AEMs) combining high ion conductivity and long‐term stability is a major challenge for materials chemistry. AEMs with regularly distributed fixed cationic groups, based on the formation of microporous polymers containing the V‐shape rigid Tröger's base units, are reported for the first time. Despite their simple preparation, which involves only two synthetic steps using commercially available precursors, the polymers provide AEMs with exceptional hydroxide conductivity at relatively low ion‐exchange capacity, as well as a high swelling resistance and chemical stability. An unprecedented hydroxide conductivity of 164.4 mS cm^?1 is obtained at a relatively a low ion‐exchange capacity of 0.82 mmol g^?1 under optimal operating conditions. The exceptional anion conductivity appears related to the intrinsic microporosity of the charged polymer matrix, which facilitates rapid anion transport.     

一类侧链型磺化聚芳醚砜质子交换膜的合成及表征

以4,4'-二氟二苯砜和N-溴代丁二酰亚胺为起始原料,经两步有机反应设计并合成了一种新型活性二氟砜单体:3,3'-双(苯氧基苯基)-4,4'-二氟二苯砜,并由该单体与4,4'-二氟二苯砜、4,4'-二羟基二苯甲酮经亲核缩聚合成了侧链型聚芳醚砜聚合物(PAES-xx).通过较温和的后磺化反应,制得了一系列磺化聚芳醚砜质子交换膜(SPAES-xx).对所制侧链型聚芳醚砜质子交换膜的结构和性能分别进行了表征分析.结果表明,该类质子交换膜具有适中的吸水率和较好的尺寸稳定性,80℃时最高质子传导率达0.16 S/cm.此外,该类质子交换膜还具有良好的热稳定性和机械性能,起始分解温度约为250℃;膜的拉伸强度为29.5~42.0MPa,拉伸模量为0.62~1.23 GPa,断裂伸长率在9.0%~31.9%.磺化膜优良的综合性能主要归因于侧链磺化结构的引入和相分离结构的形成.     

酯交换反应对PBT/PC/Al_2O_3复合材料导热性能的影响

以聚对苯二甲酸丁二醇酯(PBT)与双酚A型聚碳酸酯(PC)为基体、氧化铝(Al2O3)作为导热填料,通过熔融共混法制备了PBT/PC/Al_2O_3导热复合材料,采用亚磷酸三苯酯(TPPi)作为酯交换反应抑制剂调节材料中树脂基体的相态结构,并通过红外光谱分析(FTIR)、激光导热仪、扫描电子显微镜(SEM)、示差扫描量热仪(DSC)及力学性能测试仪等对材料中的酯交换反应、导热性能、相态结构、结晶参数及力学性能进行了表征.实验结果表明,TPPi的加入可有效抑制体系中酯交换反应的发生,使PBT/PC共混物的相态结构改变,进而对填料的分布状态产生影响.当PBT/PC配比为1/1时,向其中加入1 wt%的TPPi可使体系的相态结构趋向于形成双连续相态结构,并有效提升材料的导热系数;在该体系中加入60 wt%的Al_2O_3后,材料的导热系数达到0.89 W/(m·K),相对于未加入TPPi的相同体系提升了13%.     

Superior Electrical Conductivity in Hydrogenated Layered Ternary Chalcogenide Nanosheets for Flexible All‐Solid‐State Supercapacitors

As the properties of ultrathin two‐dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next‐generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu₂WS₄ can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room‐temperature electrical conductivity of hydrogenated‐Cu₂WS₄ nanosheet film was almost 10¹⁰ times higher than that of pristine bulk sample with a value of about 2.9×10⁴ S m^?1, which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated‐Cu₂WS₄ is robust and can be retained under high‐temperature treatment. The fabricated all‐solid‐state flexible supercapacitor based on the hydrogenated‐Cu₂WS₄ nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm^?3 at a current density of 0.31 A cm^?3. This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes.     

Superionic Conduction in Co‐Vacant P2‐NaxCoO2 Created by Hydrogen Reductive Elimination

The layered P2‐Na_xMO₂ (M: transition metal) system has been widely recognized as electronic or mixed conductor. Here, we demonstrate that Co vacancies in P2‐Na_xCoO₂ created by hydrogen reductive elimination lead to an ionic conductivity of 0.045 S cm^?1 at 25 °C. Using in situ synchrotron X‐ray powder diffraction and Raman spectroscopy, the composition of the superionic conduction phase is evaluated to be Na_0.61(H₃O)_0.18Co_0.93O₂. Electromotive force measurements as well as molecular dynamics simulations indicate that the ion conducting species is proton rather than hydroxide ion. The fact that the Co‐stoichiometric compound Na_x(H₃O)_yCoO₂ does not exhibit any significant ionic conductivity proves that Co vacancies are essential for the occurrence of superionic conductivity.     

用热线法测定气体热导率的仪器改进

实验用室内温度作为测量室外壁温度t2,经过经验系数修正得到数据来测定空气的热导率误差比较大,现采用在测量室管壁上加装一个温度传感器,以数显温度作为实验中t2的方法来计算气体的热导率。两种方法加以比对,探究相同环境下的两者误差,最后提出实验改进方案。     

Insight into lattice thermal impedance via equilibrium molecular dynamics: case study on Al

Using results of equilibrium molecular dynamics simulation in conjunction with the Green–Kubo formalism, we present a general treatment of thermal impedance of a crystal lattice with a monatomic unit cell. The treatment is based on an analytical expression for the heat current autocorrelation function which reveals, in a monatomic lattice, an energy gap between the origin of the phonon states and the beginning of the energy spectrum of the so-called acoustic short-range phonon modes. Although, we consider here the f.c.c. Al model as a case example, the analytical expression is shown to be consistent for different models of elemental f.c.c. crystals over a wide temperature range. Furthermore, we predict a frequency ‘window’ where the thermal waves can be generated in a monatomic lattice by an external periodic temperature perturbation.     

基于Al_2O_3封装薄膜的OLED水汽透过率测试方法及系统研究

水汽透过率(WVTR)是衡量有机电致发光器件(OLED)封装薄膜性能的重要参数之一。本文研究了基于钙电学法的WVTR测试方法,设计并研制了可满足OLED水汽透过率测试精度和功能要求的测试系统,测试精度达1×10-6g·m-2·d-1,量程为10 g·m-2·d-1,可同时完成20个样品的快速、精确测量。利用本系统对采用原子层沉积技术制备的不同厚度Al2O3封装薄膜的WVTR进行了测试研究,结果表明,Al2O3薄膜具有良好的水汽阻挡性能。     

In vivo electrical impedance measurements during and after electroporation of rat liver

Electroporation is used for in vivo gene therapy, drug therapy and minimally invasive tissue ablation. Applying electrical pulses across cells can have a variety of outcomes; from no effect to reversible electroporation to irreversible electroporation. Recently, it has been proposed that measuring the passive electrical properties of electroporated tissues could provide real time feedback on the outcome of the treatment. Here we describe the results from the impedance characterization (single dispersion Cole model) for up to 30 min of the electroporation process in in vivo rat livers (n=8). The electroporation sequence consisted of 8 pulses of 100 micros with a period of 100 ms. Half of the animals were subjected to field magnitudes considered to have reversible effects (R group, E=450 V/cm) whereas for the other half irreversible field amplitudes were applied (I group, E=1500 V/cm). As expected, there was an immediate increase of conductivity (R group Deltasigma/sigma(t=0)=9+/-3%; I group Deltasigma/sigma(t=0)=43+/-1%). However, the overall long term pattern of change in conductivity after electroporation is complex and different between reversible and irreversible groups. This suggests the superposition of different phenomena which together affect the electrical properties.