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...     

聚苯醚磺酸锂与酯类增塑剂共混物的导电性

聚苯醚磺酸锂与酯类增塑剂共混物的导电性汪传清，黄玉惠，赵树录，丛广民（中国科学院广州化学研究所广州５１０６５０）关键词　聚苯醚磺酸锂，酯类增塑剂，共混，导电性能高分子固体电解质［１］可作为高能电池、电致变色等材料。聚环氧乙烷／碱金属盐复合物与无机盐构...     

新型电荷转移复合物(BEDT-TTF)4·H2O·Fe(C2O3)3·C6H5NO2的合成、结构与物理性质

导电性的电荷转移复合物（盐）由于其特殊的物理性质和潜在的应用前景，近年来得到广泛研究［１，２］．导电电荷转移复合物主要包括基于Ｍ（ｄｍｉｔ）２（ｄｍｉｔ＝１，３－二硫－２－硫酮－４，５－二硫醇盐）阴离子自由基［３～５］和ＢＥＤＴ－ＴＴＦ（乙二硫撑四硫...     

新型单离子聚醚/聚氨酯固体电解质制备及其离子导电性

磺化聚醚;离子电导率;聚合物;新型单离子聚醚/聚氨酯固体电解质制备及其离子导电性     

多壁碳纳米管/聚醚胺复合物的制备

利用亲核加成逐步聚合法成功地制备了芘标记的聚醚胺(pePEA),并将其用于修饰多壁碳纳米管;采用透射电镜分析了pePEA修饰多壁碳纳米管的微观结构,并利用热重分析测定了聚醚胺的负载量.结果表明:聚醚胺对多壁碳纳米管具有较好的包覆作用,包覆层厚度约为1nm,复合物中聚醚胺的质量分数为20.4%.与此同时,多壁碳纳米管/聚醚胺复合物可在水中稳定地分散,分散液放置3周不分层,无聚集现象发生,稳定性较好.     

交联聚醚聚氨酯的表征及其聚集态转变和自由体积特征的正电子…

采用全反射红外光谱（ＡＴＲ－ＩＲ）对聚合物的结构进行了表征，证明其为交联聚醚聚氨酯（ＰＥＵ），且其碱金属盐络合物的导电性与其自由体积有关。在１１０～３５０Ｋ温度范围内测量了ＰＥＵ的正电子湮没寿命谱，结果表明正电子湮没寿命谱的强度关系可灵敏地反映聚合物的聚集态转变及其自由体积特性随温度的变化。得到了ＰＥＵ的次级转变、玻璃化转变及结晶相的熔融变化等方面的信息，并由实验测得的ｏ－Ｐｓ寿命计算出不同温度下     

无机盐对支状嵌段聚醚破乳作用的影响

通过阴离子聚合反应合成了一种七支状聚氧丙烯/聚氧乙烯(PPO/PEO)三嵌段聚醚;考察了不同无机盐存在时对原油乳状液的破乳效果的影响;通过界面张力、浊点和界面膨胀流变性的测定探讨了其界面聚集行为和破乳作用对无机盐的依赖性.结果表明,盐溶型无机离子存在时,能提高聚醚的破乳效果,而盐析型无机离子存在时,不利于聚醚的破乳作用;温度升高破乳速度加快,但45℃时脱出的水质最清.     

双离子AB交联型聚醚类固体电解质及其电流变液的性能

将α，ω－双甲基丙烯酰氧基封端的聚乙二醇与高氯酸锂络合，分别用溶液聚合和反相悬浮聚合合成了双离子ＡＢ交联型聚醚类高分子固体电解质（ＡＢＣＰＥ２）及其组成的无水电流变（ＥＲ）液．研究了ＡＢＣＰＥ２本身的离子导电性和含ＡＢＣＰＥ２的ＥＲ液的活性和电性能，并用扫描电镜表征了ＥＲ液中的粒子．获得了离子导电率高达８．０×１０－５Ｓ／ｃｍ（２５℃）的高分子固体电解质和活性较高的无水ＥＲ液．     

聚环氧乙烷环氧丙烷—盐复合物的结构和导电性

制备了室温电导率较高（１０＾－４Ｓ·ｃｍ＾－１），力学性能较好的环氧乙烷和环氧丙烷共聚物－Ｌｉ－ＣｌＯ４复合物薄膜，研究了共聚物组成对结晶及对复合物室温电导率的影响，考察了高氯酸锂浓度对复合物室温电导率的影响以及复合物电导的温度依赖关系，发现复合物中没有结晶配合物，其结晶度随聚合物结构和盐含不同而变化，室温下呈弹性体。     

交联聚醚聚氨酯的表征及其聚集态转变和自由体积特性的正电子湮没研究

采用全反射红外光谱（ＡＴＲ－ＩＲ）对聚合物的结构进行了表征，证明其为交联聚醚聚氨酯（ＰＥＵ），且其碱金属盐络合物的导电性与其自由体积有关。在１１０～３５０Ｋ温度范围内测量了ＰＥＵ的正电子湮没寿命谱，结果表明正电子湮没寿命谱的温度关系可灵敏地反映聚合物的聚集态转变及其自由体积特性随温度的变化。得到了ＰＥＵ的次级转变、玻璃化转变及结晶相的熔融变化等方面的信息。并由实验测得的ｏ－Ｐｓ寿命计算出不同温度下ＰＥＵ中自由体积孔洞的尺寸。     

Thermal and ionic‐conductive behaviors of liquid crystalline polymers with alkali metal salt

In order to investigate the relationship between ionic conductivity and liquid crystallinity, we prepared the main‐chain type polyester having 1,4‐bisstyrylbenzene units and ethyleneoxide chain in the repeating unit. The main‐chain type polyester with lithium salt at the ratio of 0.04 per polymer repeating unit exhibited a smectic phase. However, the polyester with lithium salt (0.11) showed a nematic phase. The ionic conductivity of the polyester with lithium salt increased with increasing lithium salt concentration. The trans‐type polyester exhibited a liquid crystalline phase, while the cis‐type polyester did not show any mesophase. We found that the ionic conductivity of the trans‐type polyester with lithium salt (0.11) was larger than that of the cis‐type polyester with lithium salt (0.11). However, a liquid crystalline phase was found in the side‐chain type polyether with alkoxy chain length of below 12. A smectic phase was induced for the non‐mesomorphic polyethers with lithium salt. The layer spacing of the smectic A phase for the non‐mesomorphic polyether with lithium salt decreased from 55 to 41 Å with increasing temperature. The ionic conductivity of the polyether with lithium salt increased with decreasing the layer spacing. Copyright © 2001 John Wiley & Sons, Ltd.     

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.     

Current Scenario and Future Prospective of Ionic-Liquid Doped Polymer Electrolyte for Energy Application

Solid polymer electrolyte (SPE) films based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF–HFP) with salt and ionic-liquid (IL) are synthesized using the solution-cast technique and summarized in this review. Doping ILs or salts increases ionic conductivity up to the device level. This is further confirmed using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements. Polarized optical microscopy (POM) affirms that enhancement in ionic conductivity is due to increase in amorphous nature of film. The complex nature of polymer electrolyte films is confirmed using Fourier transform infrared (FT-IR) spectroscopy. Overall results show that doping IL into polyether matrix is advantageous material playing a dominant role in electrochemical devices.     

Poly(ethylene oxide)-polyurethane/poly(acrylonitrile) semi-interpenetrating polymer networks for solid polymer electrolytes: vibrational spectroscopic studies in support of electrical behavior

Studies on solid polymer electrolyte systems based on semi-interpenetrating polymer networks of poly(ethylene oxide)-polyurethane and poly(acrylonitrile) (PEO-PU/PAN) doped with lithium trifluoromethanesulfonate (LiCF₃SO₃) is reported. Room temperature FT-IR analysis indicates a salt solvation process that occurs predominantly in the polyether segments of the semi-IPNs and incorporation of salt is also seen to favor a morphological change in the matrix with a transition from semi-crystalline to amorphous phase. From the relative band areas a critical concentration (C_c) of salt can be identified where concentration of ionic species, morphology and amount of transient crosslinks is optimal to impart maximum conductivity, which is in agreement with the room temperature conductivity results. Thermal analysis of the semi-IPN lends further support to this observation. The temperature dependence of conductivity is found to follow the Arrhenius behavior at low temperatures (∼ upto 328 K) and VTF dependence at higher temperatures. This crossover in temperature dependent conductivity is attributed to the change in the phase morphology of the semi-IPNs beyond the crystalline melting temperature (T_m1) of the polyether segments.     

聚醚介质中的离子传导机理

以单阳离子导体作为传导模型,通过对阳离子淌度的表征,证实了碱金属盐在聚合物介质中的负温度依赖性。发现在离子传导过程中,离子淌度对其电导率温度依赖性的影响远甚于载流离子数。并运用聚合物链段松驰理论对这种反常离解行为进行了唯象学的诠释。     

纳米复合全固态聚膦腈电解质

为了进一步提高聚合物电解质的室温离子电导率和锂离子的迁移数,通过对纳米二氧化硅的表面修饰,并采用可聚合的带氧化乙烯-氧化丙烯共聚侧链取代的聚膦腈大单体制备了纳米复合的全固态电解质.通过X射线光电子能谱,扫描电镜,差热扫描分析对纳米复合电解质的性能和形貌进行了分析,并通过交流阻抗考察了电解质与电极间的界面稳定性,用循环伏安表征了电解质的电化学稳定窗口,考察了锂盐含量对电解质离子电导率的影响,测试了电解质的离子电导率随温度的关系,并对锂离子的迁移数进行了测定.研究结果表明,通过纳米复合的方法,提高了聚合物电解质的离子电导率,降低了界面电阻,提高了锂离子迁移率.     

Anionic Conduction in Blends of Poly(Pyridinium Ethyl Methacrylate Perchloride) and Poly[Oligo(Oxyethylene) Methacrylate-Co-Acrylamide]

Abstract

Blends of poly(pyridinium ethyl methacrylate perchloride) and poly[oligo(oxyethylene) methacrylate-co-acrylamide] were prepared, and the ionic conductivity and mobility of the blends were investigated. Results indicate that both the transference of perchlorate anion and the dissociation of the polymeric salt in the comblike polyether obey the thermoactivation mechanism, and that the perchlorate anion in the blends is free.     

Synthesis and ionic conductivity of hyperbranched poly(glycidol)

A novel hyperbranched poly(glycidol) (HPG) was prepared and characterized. The synthesized HPG was used as a substrate of a polymer electrolyte. The ionic conductivity of a blend of HPG, polyurethane (PU), and salt was studied. The ionic conductivity of HPG/PU/LiClO₄ was about 6.6 × 10^?6 S · cm^?1 at 20 °C and 6.3 × 10^?4 S · cm^?1 at 60 °C. The results indicated that HPG showed higher solubility for salt than linear polyether when both had the same [O]/[Li⁺] molar ratio. The main reason was that more cavities and a lower degree of chain entanglement in HPG resulted in a lower glass‐transition temperature and were beneficial for decreasing the aggregation of salt or enhancing the ionic conductivity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2225–2230, 2001     

Highly concentrated polycarbonate‐based solid polymer electrolytes having extraordinary electrochemical stability

Solid polymer electrolytes (SPEs) are compounds of great interest as safe and flexible alternative ionics materials, particularly suitable for energy storage devices. We study an unusual dependence on the salt concentration of the ionic conductivity in an SPE system based on poly(ethylene carbonate) (PEC). Dielectric relaxation spectroscopy reveals that the ionic conductivity of PEC/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte continues to increase with increasing salt concentration because the segmental motion of the polymer chains is enhanced by the plasticizing effect of the imide anion. Fourier transfer‐infrared (FTIR) spectroscopy suggests that this unusual phenomenon arises because of a relatively loose coordination structure having moderately aggregated ions, in contrast to polyether‐based systems. Comparative FTIR study against PEC/lithium perchlorate (LiClO₄) electrolytes suggests that weak ionic interaction between Li and TFSI ions is also important. Highly concentrated electrolytes with both reasonable conductivity and high lithium transference number (t₊) can be obtained in the PEC/LiTFSI system as a result of the unusual salt concentration dependence of the conductivity and the ionic solvation structure. The resulting concentrated PEC/LiTFSI electrolytes have extraordinary oxidation stability and prevent any Al corrosion reaction in a cyclic voltammetry. These are inherent effects of the highly concentrated salt. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2442–2447     

Chemistry of crown ethers: Complexation with alkali metal trichloro(ethylene)platinum(II) salts

A novel method has been developed for the determination of the complexation constants of crown ethers with alkali salts. It comprises the equilibration of crown ether (1–7) solutions in deuterochloroform with solid trichloro(ethylene)platinum(II) salts (Na⁺, K⁺, Rb⁺, Cs⁺) and the PMR spectroscopic determination of the equilibrium ratio of complex to free crown ether from the relative intensities of the ethylene and crown ether protons. The solubility of uncomplexes salt was determined independently by atomic absorption spectrometry.The major advantages of this method over others are: (i) complexation constants in apolar solvents are obtained from a direct solid-liquid transition, (ii) the cation in the salt can be varied, and (iii) a simple detection technique can be used for monitoring the complexation.The PMR spectra indicate that there are three types of complex, depending on the ratio of the diameter of the crown ether cavity to that of the cation. If this ratio is small (<1), the aromatic ring is almost perpendicular to the flat polyether ring. With increasing ratio (～1.0) the flat polyether ring and the aromatic ring become almost coplanar in the complex. If the ratio is large (>1.0) the polyether ring is twisted around the cation.