液体介质等离子体电弧法制备纳米炭材料研究进展

以碳纳米管、碳洋葱、石墨烯为代表的碳纳米材料在能源、环境等领域表现出了优异的潜在应用价值,本文基于近年来国内外研究者利用液体等离子体法制备碳纳米材料的研究工作,对比了液氮,去离子水,盐溶液及有机溶剂作为不同放电介质的优缺点,并对其相关的反应机理进行了分析与讨论,指出了液体等离子体放电制备纳米炭材料这一领域的研究进展,对于深刻认识液体等离子体放电的概念与原理、完善实验与理论研究方法、拓展应用范围和尽早实现工业应用提出了建议与展望.     

聚合物纳米复合电解质(PEO)8-ZnO-LiClO4微结构及电导率研究

以聚氧化乙烯(PEO)为基质,成功制备出纳米ZnO掺杂的(PEO)₈-ZnO-LiClO₄离子导电聚合物电解质,并利用多种实验技术,包括扫描电子显微镜、X射线衍射(XRD)、傅里叶变换红外光谱和正电子湮没寿命谱(PALS),系统地研究了纳米ZnO与基质间相互作用及其对聚合物链段运动、纳米尺度自由体积、离子输运和复合电解质电导率的影响.实验结果发现,纳米ZnO的掺杂使聚合物电解质的离子电导率得到了大幅度提高,当ZnO与PEO质量比为6%时达到最大,(PEO)₈-ZnO-LiClO₄的电导率为1.82×10^-4 S ·cm^-1,比(PEO)₈-LiClO₄的电导率(6.58×10^-5 S ·cm^-1)提高了大约一个数量级.XRD结果显示,纳米ZnO的加入降低了PEO的结晶性,增加了锂离子传输的非晶相,从而提高了电导率.离散PALS测量结果表明,随着纳米ZnO的加入,复合电解质的自由体积、浓度和相对自由体积分数f_r均增加.连续PALS分析揭示了自由体积的分布由一个峰劈裂成两个峰,表明纳米ZnO的掺杂对聚合物的微结构有很大影响.基于实验测量的f_r和离子电导率,研究了离子导电机理.研究发现, f_r与电导率之间存在一个直接关系,即f_r越大,越有利于锂离子的传输,导致电导率越大.这个结果支持聚合物电解质导电的自由体积理论. 关键词： 正电子湮没寿命谱 聚合物纳米复合电解质 离子电导率 自由体积     

Investigation of the free volume and ionic conducting mechanism of poly（ethylene oxide）-LiClO_4 polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite（OREC） content and temperature in a range from 160 K to 300 K.According to the variation of ortho-positronium（o-Ps） lifetime with temperature,the glassy transition temperature is determined.The continuous maximum entropy lifetime（MELT） analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution.The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher（VTF） and Williams-Landel-Ferry（WLF） equations,implying a free-volume transport mechanism.A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation.It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte,which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.     

Investigation of the free volume and ionic conducting mechanism of poly（ethylene oxide）-LiClO₄ polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite(OREC) content and temperature in a range from 160 K to 300 K.According to the variation of ortho-positronium(o-Ps) lifetime with temperature,the glassy transition temperature is determined.The continuous maximum entropy lifetime(MELT) analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution.The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher(VTF) and Williams-Landel-Ferry(WLF) equations,implying a free-volume transport mechanism.A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation.It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte,which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.     

压强和温度对聚苯乙烯自由体积的影响

在30～130℃温度范围内测量了聚苯乙烯(PS)样品中的正电子素湮没寿命,据此计算了样品中自由体积的大小和自由体积分数,发现在不同的温度范围,它们随温度变化的斜率不同,由此确定了PS的玻璃化转变温度为80℃.同时,还研究了不同压强对PS的自由体积的大小、浓度及分布的影响.实验结果发现,压强从6MPa增大到20MPa时自由体积分布变窄.同时,当压强超过100MPa,o-Ps寿命分布由单峰变成双峰.这说明高的外力场作用下,样品中分子链构型发生变化,导致分子链堆积密度增加及局部有序区域的形成.