梳形联吡啶共聚醚的离子电导和电致变色特性

合成了兼具离子电导性和电致变色性能的聚合物固体电解质(PVSEO_(21))。以其为基材的固态ECD具有双面显示功能,驱动电压>1.5V,着色和消色响应时间0.6和1.1秒(+2.0～—2.0V),开路记忆半衰期约5小时,着色后的最大吸收波长549nm,能可逆地显示蓝紫色和淡黄色。     

IONIC CONDUCTIVITY IN THE COMPLEXES OF COMB-SHAPED POLYETHER WITH LITHIUM AROMATIC SULFONATE

Complexes of comb-shaped polyether and lithium aromatic sulfonates bearing different negative charge number were prepared by in situ thermal polymerization. Their conductivity depends deeply on salt content, ambient temperature and negative charge number of the added salts. Results show that anions can be partly immobilized by increasing their negative charges at lower temperature. Against discharge time the short circuit current of the battery (Li/complex film/Li_x V_3O_8) is stabilized by increasing the anionic charge number of the complex.     

梳型聚醚-聚磺酸锂共混物的锂离子导电性

本工作合成了聚甲基丙烯酸齐聚氧化乙烯酯和聚甲基丙烯酸己磺酸锂两系列聚合物,研究共聚物结构对共混物的相容性和锂离子导电性的影响.结果表明,共混物的相容性是决定离子电导率的主要因素;共混物内锂离子传导发生在非晶区,聚合物的链段运动是离子传导的主要推动力.     

聚合物固体电解质中的离子状态与导电机理的研究

制备得到了一种新颖的聚氨酯和丙烯酸酯复合梳形交联聚合物 (Combcross linkedpolymer) ,并以此聚合物为基体加入不同含量的高氯酸锂盐制得一系列聚合物固体电解质 ,其室温电导率可以达到 3 4× 10 - 5S·cm- 1 .通过Raman、DSC、SEM及电性能等研究了电解质中的盐浓度与离子存在状态及离子电导率之间的关系 .结果显示随着盐浓度的增加 ,聚合物固体电解质中离子对的比例和电导率都迅速增加 ,说明离子对 (由多个醚氧原子、阴离子和阳离子组成 )对体系导电起着积极的作用 .     

低聚醚磺酸锂／梳形聚醚复合物的单离子导电性

低聚醚磺酸锂／梳形聚醚复合物的单离子导电性郑云贵，万国祥（中国科学院成都有机化学研究所成都６１００４１）关键词低聚醚磺酸锂，单离子导体，阳离子迁移数聚合物阳离子导体一般采用单体盐与能促进离子迁移的单体通过共聚或将其均聚物共混的方式制备’‘－‘’．由于...     

梳型聚醚-聚磺酸锂共混物的锂离子导电性

 本工作合成了聚甲基丙烯酸齐聚氧化乙烯酯和聚甲基丙烯酸己磺酸锂两系列聚合物,研究共聚物结构对共混物的相容性和锂离子导电性的影响.结果表明,共混物的相容性是决定离子电导率的主要因素;共混物内锂离子传导发生在非晶区,聚合物的链段运动是离子传导的主要推动力.     

LITHIUM ION CONDUCTING POLYMER ELECTROLYTES BASED ON ALTERNATING MALEIC ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE CHAINS

A comb polymer with oligo-oxyethylene side chains of the type -(CH_2CH_2O)_(12)CH_3was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethyleneglycol) methyl ether. The polymer can dissolve LiClO_4 salt to form homogeneous amor-phous polymer electrolyte. The ac ion conduction was measured using the complex impedancemethod, and conductivities were investigated as functions of temperatures and salt con-centration. The complexes were first found to have two classes of glass transition whichincrease with increasing salt content. The optimum conductivity attained at 25℃ is inthe order of 5.50×10~(-6)Scm~(-1). IR spectroscopy was used to study the cation-polymerinteraction.     

梳形聚醚全固态聚合物电解质的电导率研究

应用阳离子开环聚合反应合成含二缩三乙二醇单甲醚侧链的梳形聚醚POE,并与高氯酸锂复配制成聚合物电解质.交流阻抗测试表明,当POE电解质内的氧锂比(O/L i)为20时,其电导率最高,室温下为10-4.43S/cm,80℃时则达到10-3.44S/cm.用DSC和XPS分别表征了链段运动能力和锂盐在POE中的溶解状态对电导率的影响.     

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).     

IONIC CONDUCTIVITY OF EPOXY NETWORK/POLYETHYLENE GLYCOL- LITHIUM PERCHLORATE COMPLEX IPN SYSTEM

In an attempt to prepare a polymeric solid electrolyte with both high ionic conductivity at ambient temperature and adequate mechanical strength, an ionic conducting IPN composed of bisphenol A epoxy resin/polyethylene glycol containing LiClO_4 was synthesized. The dependence of conductivity was investigated as a function of salt content, composition and temperature. It has been revealed that a maximum of conductivity appeared when EO/Li=25, where EO denotes the—(CH_2CH_2O)-unit in polyethylene glycol, and that the temperature dependence of conductivity followed VTF equation, suggesting that the motion of ionic carriers resulted from the segmental motion of the polymer. When glycerol epoxy resin was used instead of bisphenol A epoxy, the ambient temperature (25℃) conductivity could somewhat further be raised up to 3×10~(-5) S/cm.     

IONIC CONDUCTIVITY OF METHYLSILOXANE TERMINATED POLYETHYLENE OXIDE WITH LITHIUM PERCHLORATE NETWORK FILMS

Complex films of crosslinked poly(methylsiloxane-co-ethylene oxide) and lithium perchlorate were prepared. These solid state polymeric electrolytes show a markedly higher ionic conductivity, and excellent flexibility. The ionic conductivity of the network films closed to 10~(-5) Scm~(-1) at room temperature. The effects of Li~+ content, species and contents of crosslinking agents, molecular weight of poly(ethylene oxide) and temperature on the ionic conductivity of the network films were also investigated.     

锂离子电池凝胶聚合物电解质研究进展

使用聚合物电解质可以避免传统液态锂离子电池的漏液问题,提高电池的安全性能和能量密度,并可实现电池的薄型化、轻便化和形状可变等优点.目前,聚合物电解质的研究集中在凝胶型的复合和多孔聚合物电解质两大类.本文对各类凝胶聚合物电解质的特点、功能及研究情况逐一进行了介绍,对凝胶聚合物电解质的发展趋势进行了展望.     

聚丁二酸丁二酯与高氯酸锂络合物的结构与离子导电性

本文从丁二酸二甲酯和丁二醇合成了聚丁二酸丁二酯,并以高氯酸锂为掺杂剂制备了固体电解质。FT-IR、NMR、XPS测试发现酯基上的氧原子参与络合。WAXD、DSC等测试分析结果表明:络合物和聚酯的晶体相同;LiClO_4主要溶解在无定形区;盐的溶解降低聚酯的熔点、结晶度和结晶速度,而提高玻璃化温度;在低盐浓度区络合物熔点与盐浓度关系符合Flory-Huggins理论。络合物的电导率随盐浓度变化出现极大值,在低盐浓度区电导率与浓度的对数成线性关系。电解质的导电行为不能简单地为Arrhenius和WLF方程所解释。从扩散角度推导了导电方程,并描述了离子导电过程。     

高分子固体电解质LiNO_3-LiOOCCH_3/聚丙烯酸锂的合成与性能研究

以丙烯酸和氢氧化锂为原料用反相乳液聚合法合成聚丙烯酸锂 (PAALi) ,将其熔于低共熔盐 (一定比例的LiNO3 LiOOCCH3混合物 )中得到新型高分子固体电解质 (SPE) ,用XRD、IR、DTA、TG DTG等技术进行了表征 ,讨论了影响合成PAALi工艺及新型固体电解质电阻率的主要因素 ,在LiNO3 LiOOCCH3摩尔比为 1∶1时 ,将其按质量百分比 80∶2 0与聚丙烯酸锂混合均匀并熔融 ,得到的电解质其室温离子电导率可达 2× 10 - 5S·cm- 1 ,大量低共熔盐的加入可明显提高SPE的离子导电率 .XRD、DTA及TG DTG结果表明低共熔盐与聚丙烯酸锂形成了新的配合物     

三元共聚物P(EO-PO-AGE)-LiCLO_4络合物的离子电导

本文合成了聚(环氧乙烷-环氧丙烷-烯丙基缩水甘油醚,三元共聚物,P(EO-PO-AGE)。扭辨分析、DSC、X-射线衍射结果表明,三元共聚物的玻璃化转变温度较低(T_g=-74℃),无定形结构含量～98％,并确定了与LiClO_4组成为Li/O(mole)=0.25的结晶络合物存在。络合物电导行为的研究发现,络合物电导与盐浓度有关,在Li/O(mole)=0.05时具有较大值,室温下电导可达5×10~-5)scm~(-1)。     

STUDY ON THE PREPARATION AND PERFORMANCES OF P(VAc-MMA) POLYMER ELECTROLYTES FOR LITHIUM ION BATTERY

A random copolymer P(VAc-MMA)was synthesized via seeded emulsion copolymerization with vinyl acetate (VAc)and methyl methacrylate(MMA)as monomers,and the polymer electrolytes comprising blend of corresponding copolymer P(VAc-MMA)as a host polymer and LiClO_4 as a dopant were prepared by solution casting technique. Performances of the synthesized copolymer and prepared polymer membrane and electrolyte were studied by FTIR,XRD, TG,DSC,mechanical testing and AC impedance.According to the study of FTIR and D...     

钐与磷酸二甲酯配合物的合成和结构

合成了钐与磷酸二甲酯的配合物,该配合物的组成为Sm〔(CH_3O)_2PO_2〕_3,测定了该配合物的红外和拉曼光谱。x射线单晶衍射法测定配合物的晶体属单斜晶系,P2_(1/c)空间群,α=10.434(4)A,b=16.541(3)A,c=10.804(4)A,β=111.75(3)°,V=1731.7(9)A~3,Z=4。钐与6个氧原子配位,每2个相邻的钐原子通过双“O—P—O”桥相连接,形成奇特的“双桥24元环”的环套环网状结构。钐氧配位多面体为稍微扭曲的正八面体。     

低压离子色谱法测定CeO2产品中微量氟的研究

采用氟碳铈矿为原料冶炼成的稀土氧化物产品中 ,氟含量的测定在检验稀土产品纯度中起着重要的作用。目前此类产品中氟含量的测定主要有二甲酚橙 锆退色法和氟试剂法[1 ] 。而采用低压离子色谱法分析稀土氧化物产品中氟含量还未见报道[2 ,3] 。本文研究用低压离子色谱 (ＬＰＩＣ)法测定稀土ＣｅＯ2 中氟含量。试验证明 ,样品预处理时 ,在ＨＣｌＯ4介质中加入ＡｇＣｌＯ4以消除阴离子干扰 ,并用水蒸气将氟蒸馏出 ,以ＫＯＨ溶液吸收。选择 1 .2ｍｍｏｌ/ＬＮａ2 ＣＯ3作淋洗液 ,ＬＰＩＣ测氟。与氟试剂法 (ＧＢ)作比较分析 ,两种方法测定结果一…     

NMR STUDY OF EXCHANGE KINETICS OF THE LITHIUM ION WITH CRYPTAND C222 IN BINARY ACETONITRILE-NITROMETHANE MIXTURES

Abstract

The exchange kinetics of the lithium ion with cryptand C222 were studied in acetonitrile-nitromethane mixtures by lithium-7 NMR line-shape analysis. In all solvent mixtures used, and over the entire temperature range studied, the chemical exchange of the Li⁺ ion between the solvated and complexed sites was found to occur via a bimolecular mechanism. The activation parameters E_a, δH?, δS? and δG? for the exchange have been determined. The free energy barrier for the exchange process appears to be nearly independent of the binary mixture composition. The results confirm the preferential solvation of the lithium ion with acetonitrile in the binary mixed solvent systems used.     

高聚物固体电解质聚氧化乙烯－溴化铜复阻抗谱及介电常数的静水压效应

采用分子量５００万的聚氧化乙烯和无水溴化铜，通过混溶蒸发法制备成高聚物固体电解质Ｐ（ＥＯ）ｎ－ＣｕＢｒ２薄膜，并在０．１～３００ＭＰａ范围不同的流体静水压下详细测量其复平面阻抗谱，分别得到在不同压力下离子电导率和介电常数与测量频率的关系．进一步解谱准确地求出Ｐ（ＥＯ）ｎ－ＣｕＢｒ２（ｎ＝１２、１６）薄膜离子电导率和介电常数的静水压效应，并结合Ｘ－光物相分析，根据离子迁移通道的物理图象和高聚物的极化机构进行了初步的讨论．添加２０％的增塑剂碳酸丙烯酯，较大改进了压力下的导电性．１２０～３００ＭＰａ的离子电导率提高一个数量级