聚环氧乙烷与聚2-乙烯基吡啶混物的导电率及高氯酸锂的增容作用

研究了聚环氧乙烷(PEO)/聚2-乙烯基吡啶(P2VP)的共混物分别经LiCLO₄、四氰基代苯醌二甲烷(TCNQ)及两者共同掺杂后其共混物的离子、电子及混合导电率。当PEO与P2VP的重量比分别为6/4、5/5及4/6时,共混物的混合导电率大于相应的离子及电子导电率的总和,呈现协同效应。从共混物外观的研究发现LiCLO₄能作为PEO/P2VP共混体系的增容剂。     

PAMPSLi/P(MMA-VAc)为基体的聚合物电解质

将聚(2-丙烯酰胺-2-甲基丙磺酸锂)(PAMPSLi)和聚(甲基丙烯酸甲酯-醋酸乙烯酯)[P(MMA-VAc)]与LiClO₄共混, 制备了复合聚合物电解质膜. 用FTIR, TG, XRD, DMA, SEM及电化学交流阻抗和机械性能测试对聚合物及其电解质膜的结构和性能进行了表征. 结果表明, PAMPSLi与P(MMA-VAc)共混后结晶状态发生变化, 交联网络变得密实, 提高了热稳定性和拉伸强度, 聚合物电解质膜含有较多微孔结构, 孔径为5~10 μm; 在20 ℃时, 当n(MMA)∶n(VAc)=2∶8, m(PAMPSLi)∶m[P(MMA-VAc)]=5∶95, m(LiClO₄)∶m(copolymer)=15∶85时, 聚合物电解质膜电导率可达到1.68×10^-3 S/cm, 且电导率未出现随LiClO₄含量的进一步增加而下降的现象. 将此电解质用于全固态电致变色显示器件表现出了优良的性能. 对加入PAMPSLi后聚合物电解质膜电导率和热稳定性提高的原因进行了初步探讨.     

四芳基卟啉锰配离子的TCNQ电荷转移盐的合成和物理性质

合成了13个四芳基卟啉锰配离子的TCNQ电荷转移盐[TAPMn][TCNQ]_n(TAPH₂=α,β,γ,δ-四芳基卟啉;A=C₆H₅,4-CH₃C₆H₄,4-CH₃OC₆H₄,4-ClC₆H₄,3-ClC₆H₄,3-FC₆H₄,4-(CH₃)₂NC₆H₄,2,4-Cl₂C₆H₃;TCNQ=7,7,8,8-四氰基对苯醌二甲烷;n=1,2).通过元素分析、IR、XPS、ESR、磁化率和电导率对其进行了表征.结果表明:这些电荷转移盐分子中存在TCNQ⁰和TCNQ^-,且TCNQ⁰和TCNQ^-之间存在相互作用,部分电荷从[TCNQ]_n^-向[TAPMn]⁺转移,导致化合物中的锰表现为混合价态.复合盐的室温电导率在10^-7～10^-10S·cm^-1,属于有机半导体,简单盐的室温电导率小于10^-11S·cm^-1.     

Li1.5Al0.5Ge1.5(PO4)3基固体复合电解质的制备及锂离子导电行为

将聚氧化乙烯(PEO)和二(三氟甲基磺酰)亚胺锂(LiTFSI)混合(固定EO/Li摩尔比为13)后, 采用溶液浇注法制备了一系列不同Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP)与PEO质量比的LAGP-PEO(LiTFSI)固体复合电解质体系. 结合电化学阻抗法、 表面形貌表征以及与惰性陶瓷填料(SiO₂, Al₂O₃) 性能的对比分析, 探讨了LAGP在固体复合电解质中的作用机理以及锂离子的导电行为. 结果表明, 在以LAGP为主相的固体复合电解质中, PEO主要处于无定形态, 整个体系主要为PEO与LiTFSI的络合相、 LAGP与PEO(LiTFSI)相互作用形成的过渡相和LAGP晶相. 其中LAGP作为主要的导电基体不仅起到降低PEO结晶度、 改善两相导电界面的作用; 同时自身也可以作为离子传输的通道, 降低锂离子迁移的活化能, 从而使离子电导率得到提高. 当LAGP与PEO的质量比为6:4时, 固体复合电解质的成膜性能最好, 离子电导率最高, 在30 ℃时为2.57×10^-5 S/cm, 接近LAGP的水平, 电化学稳定窗口超过5 V.     

过渡金属吡啶配离子的TCNQ电荷转移盐的合成和物理性质

合成了通式为[M(Py)_m][TCNQ]_n(M=Mn,m＝4;M＝Co,Ni,Cu,m＝2;TCNQ＝7,7,8,8-四氰基对苯醌二甲烷,n＝2,3)的8个过渡金属吡啶配离子的TCNQ电荷转移盐,通过元素分析、红外光谱、顺磁共振谱、光电子能谱、磁化率和电导率对这些电荷转移盐进行了表征,结果表明,在这些电荷转移盐分子中存在TCNQ^-和TCNQ⁰,且TCNQ^-与TCNQ⁰相互作用形成结构单元[TCNQ]_n^2-(n＝2,3),各个结构单元沿一维方向堆积形成分子柱,部分电荷从[TCNQ]_n^2-向[M(Py)_m]²⁺转移,导致化合物中的金属表现为混合价态.其中3个电荷转移盐具有良好的导电性.     

铝-邻苯二酚紫络合吸附波的研究

邻苯二酚紫在NH₄Ac(pH4.7)底液中还原,产生良好的示波极谱图,E_p1=-0.66V(vs.SCE).加入A1³⁺后,此波高降低,并在稍负的电位上出现一个尖峰形的新波(E_P2=-0.85V),其峰电流与铝的浓度在1×10^-6-1.2×10^-5M范围成正比,此波可用于测定铝,实验表明,该波属于络合吸附波,用连续变化法确定络合物的络合比为1:1。     

芳香查尔酮衍生物的合成、理论计算及三阶非线性光学性质

合成了2种新的具有潜在应用价值的非线性光学(NLO)有机材料芳香查尔酮衍生物1-(呋喃-2-基)-3-(4-甲氧基苯基)丙烯酮(1)和1-(噻吩-2-基)-3-(4-甲氧基苯基)丙烯酮(2),并对其进行了NMR、IR和HR-MS结构表征。 采用4f相位相干成像技术测定了化合物1和2的三阶NLO性质并确定了相关参数:脉冲宽度4 nm,激光波长440 nm,化合物1:非线性吸收系数β=5.5×10^-10 m/W,非线性折射系数n₂=-2.1×10^-17 m²/W,三阶非线性极化率χ⁽³⁾=1.58×10^-11 esu;化合物2:β=-2.4×10^-10 m/W,n₂=0.3×10^-17 m²/W,χ⁽³⁾=0.50×10^-11 esu;并测定了紫外光谱和DSC曲线。 采用密度泛函方法计算了化合物1和2的轨道能量和极化率,结果表明电子转移能在分子内部进行,说明比较易于极化,展示了良好的非线性光学性质。     

应用扫描电化学显微镜研究水/1,2-二氯乙烷界面上离子诱导的电子转移反应

应用扫描电化学显微镜和微电极技术研究了水/1,2二氯乙烷界面上的反向电子转移反应.分别以K₄Fe(CN)₆和7,7,8,8四氰代二甲基苯醌(TCNQ)作为水相和有机相的电活性物质,通过选择合理的共同离子(TPAs⁺与TBA⁺)来控制界面电位差,实现了这一在热力学上通常不可能实现的反向电子转移反应.利用扫描电化学显微镜给出的正负反馈信息,研究了界面电位差驱动的液/液界面上的电子转移反应,并进一步得到了在不同的共同离子浓度比时,此异相界面反应速率常数k_f为1.3×10^-31.8×10^-2cm/s(共同离子为TBA⁺)和2.5×10^-32.8×10^-2cm/s(共同离子为TPAs⁺).验证了此反应速率常数k_f是由界面电位差所决定的.在此实验条件下,此反应速率常数kf与界面电位差的关系遵守Butler-Volmer公式.     

以脲和硫氰酸盐为主体的高分子固体电解质的研究

在熔盐体系相图指导下研制出以脲和硫氰酸铵(钾)为主体的高分子固体电解质(PSE),其室温电导率分别为1.20×10^-2和2.65×10^-3S/cm.考察了影响该PSE电导率的因素,讨论了PSE的导电机理.结果表明,所研制的PSE为无定形固熔体,主要通过硫氰酸盐的电离导电,电导率-温度关系服从VTF方程.     

铜-丁二酮肟-四硼酸钠体系络合吸附波的研究

ΠpoxopoBa等曾研究铜-丁二酮肟(DMG)-氨缓冲溶液体系的dc极谱行为。他们认为pH9.35,铜离子浓度3.5×10^-4M,DMG浓度≤7×10^-4M时是个扩散波(E_1/2=-0.3V);当DMG浓度较大时,波呈峰形(E_p=0.5V),是个催化氢波。他们尚未研究该体系的灵敏度及其应用。我们用单扫示波极谱研究了铜-DMG-Na₂B₄O₇,体系的极谱行为。铜一DMG络合物在Na₂B₄0₇缓冲溶液(pH9.4)中还原,产生良好的示波极谱图,E_p=-0.34V(vs.SCE)。其峰电流与铜的浓度在5×10^-8-3×10^-8M范围成正比,并应用于污水中微量铜的测定。用连续变化法确定络合物的络合比Cu(II):DMG=1:2。用循环伏安法等手段研究该波的性质及其机理,并测定了不同铜浓度时体系的吸附量。实验表明,所研究体系的极谱波属于络合吸附波。     

CONDUCTING BLENDS OF POLY (2-VINYL PYRIDINE) AND POLYETHYLENE OXIDE WITH HIGH MOLECULAR WEIGHT

Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinylpyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after dopedwith LiClO_4, TCNQ or LiClO_4 and TCNQ were investigated. Effects of LiClO_4 and TCNQconcentrations on the conductivity of PEO/P2VP/LiClO_4 or TCNQ blend were studied.The ionic conductivity of PEO/P2VP/LiClO_4 blend increases with increasing PEO content.At a Li/ethylene oxide molar ratio of 0.10 and a TCNQ/2-vinyl pyridine molar ratio of 0.5,the mixed conductivity of PEO / P2VP / LiClO_4 / TCNQ is higher than the total of ionicconductivity of PEO/P2VP/LiClO_4 and electronic conductivity of PEO/P2VP/TCNQwhen the weight ratio of PEO and P2VP is 6/4 or 5/5. Scanning electron microscopy(SEM) on the broken cross-section of the PEO/P2VP/LiClO_4 blend and differential scan-ning calorimetry (DSC) results show that LiClO_4 could act as a compatibilizer in the blend.     

高分子凝胶电解质高氯酸锂 - 碳酸乙二醇酯 - 聚甲基丙烯酸甲酯体系的研究

研究了高分子凝胶电解质高氯酸锂 碳酸乙二醇酯 聚甲基丙烯酸甲酯体系（ＬｉＣｌＯ４ ＥＣ ＰＭＭＡ）的离子导电性、热稳定性和电化学稳定性．该体系的离子电导率与温度的关系服从ＶＴＦ方程．当ＬｉＣｌＯ４的浓度ＣＬｉＣｌＯ４＝１５ｍｏｌ／Ｌ、ＰＭＭＡｗｔ％（质量百分数）＝３５时，其离子电导率达极大值δ＝１９２×１０－３Ｓ／ｃｍ，光学透明度高，在空气中的稳定性较好，且具有一定的粘附性．该体系在１０２℃以下的热稳定性较高（失重率为３２８％）；电化学稳定性窗口为４５Ｖ，可满足固态电致变色“Ｓｍａｒｔ”窗的要求．     

Semiconducting polymers based on charge-transfer complexes. IV. Electrical properties and structure of polymeric charge-transfer complexes

Model electron donor molecules, 10-methylphenothiazine and 4-(methylthio)anisole, and polymeric electron donors which contained these molecules on the side chains of N-acyl-substituted polyethylenimines, were complexed with the electron acceptors, dichlorodicyanoquinone (DDQ), tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), and tetranitrofluorenone (TNF). The model donors formed 1:1 complexes with all the acceptors except TCNE. The polymeric donors formed amorphous complexes with DDQ, TCNQ, and TCNE. Crystalline complexes were formed with TNF which had low melting points (lower than the model complexes and the pure polymer). This is apparently due to poor lateral packing of the polymer chains. Electrical resistivities were lower for all the polymer complexes than for the corresponding model complexes. Electrical resistivity also decreased with increase in complex crystallinity. In the best case the polymer complex was two hundred times as conducting as the model. The concentration of unpaired electrons measured by EPR was nearly independent of temperature. Most of the electrons seen are trapped and do not participate in conduction. Thermal activation energies for conduction were in the range of 0.5–1.8 eV and were nearly equal for the model and corresponding polymeric complexes. Elongation of polymer complex with TCNQ by rolling produces a decrease in resistivity in the roll direction, although the complex is amorphous. This reinforces the hypothesis that conduction is parallel to the polymer backbone. A polymer–tetranitrofluorenone complex was photoconducting, though the photoconductivity was smaller than the dark conductivity at the level of illumination used. Dember and Seebeck effects indicated that the major carrier in the complex was holes.     

Tetranuclear complexes of [Fe(CO)2(C5H5)]+ with TCNX ligands (TCNX=TCNE, TCNQ, TCNB): intramolecular electron transfer alternatives in compounds (mu4-TCNX)[MLn]4

The complexes {(mu4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4 were prepared as light-sensitive materials from [Fe(CO)2(C5H5) (THF)](BF4) and the corresponding TCNX ligands (TCNE = tetracyanoethene, TCNQ=7,7,8,8-tetracyano-p-quinodimethane, TCNB=1,2,4,5-tetracyanobenzene). Whereas the TCNE and TCNQ complexes are extremely easily reduced species with reduction potentials>+0.3 V vs ferrocenium/ferrocene, the tetranuclear complex of TCNB exhibits a significantly more negative reduction potential at about -1.0 V. Even for the complexes with strongly pi-accepting TCNE and TCNQ, the very positive reduction potentials, the unusually high nitrile stretching frequencies>2235 cm(-1), and the high-energy charge-transfer transitions indicate negligible metal-to-ligand electron transfer in the ground state, corresponding to a largely unperturbed (TCNX degrees)(FeII)4 formulation of oxidation states as caused by orthogonality between the metal-centered HOMO and the pi* LUMO of TCNX. M?ssbauer spectroscopy confirms the low-spin iron(II) state, and DFT calculations suggest coplanar TCNE and TCNQ bridging ligands in the complex tetracations. One-electron reduction to the 3+ forms of the TCNE and TCNQ complexes produces EPR spectra which confirm the predominant ligand character of the then singly occupied MO through isotropic g values slightly below 2, in addition to a negligible g anisotropy of frozen solutions at frequencies up to 285 GHz and also through an unusually well-resolved solution X band EPR spectrum of {(mu4-TCNE)[Fe(CO)2(C5H5)]4}3+ which shows the presence of four equivalent [Fe(CO)2(C5H5)]+ moieties through 57Fe and 13C(CO) hyperfine coupling in nonenriched material. DFT calculations reproduce the experimental EPR data. A survey of discrete TCNE and TCNQ complexes [(mu4-TCNX)(MLn)4] exhibits a dichotomy between the systems {(mu4-TCNX)[Fe(CO)2(C5H5)]4}4+ and {(mu4-TCNQ)[Re(CO)3(bpy)]4}4+ with their negligible metal-to-ligand electron transfer and several other compounds of TCNE or TCNQ with Mn, Ru, Os, or Cu complex fragments which display evidence for a strong such interaction, i.e., an appreciable value delta in the formulation {(mu4-TCNXdelta-)[Mx+delta/4Ln]4}. Irreversibility of the first reduction of {(mu4-TCNB)[Fe(CO)2(C5H5)]4}(BF4)4 precluded spectroelectrochemical studies; however, the high-energy CN stretching frequencies and charge transfer absorptions of that TCNB analogue also confirm the exceptional position of the complexes {(mu4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4.     

高氯酸锂-乙酰胺/乙烯脲体系的二元熔盐电解质

制备了高氯酸锂与乙酰胺和乙烯脲形成的二元低温熔盐电解质，采用差示扫描量热法、交流阻抗法和循环伏安法分别对其热学、电化学性质进行了研究.测试结果表明,高氯酸锂-乙酰胺体系具有较好的热稳定性和高的电导性，配比n（LiClO4）:n（Acetamide）=1.0:5.5的样品室温（25 ℃）电导率为1.25×10－3 S•cm－1，80 ℃电导率为1.15×10－2 S•cm－1;其电化学稳定电位窗近3 V左右.     

阻抗虚部计算聚合物电解质电导率

用交流阻抗法研究了（PEO1）10LiClO4-Al2O3和（PEO2）16LiClO4－碳酸乙烯酯（EC）两种复合物电解质体系的电导率，给出了等效电路和各拟合元件的物理意义。当阻抗谱图发生严重变形时，提出一种比较简单的计算聚合物电解质电导率的方法－－阻抗虚部最大值法。     

含氟聚合物杂化电解质膜的结构分析

聚偏氟乙烯;共聚物;微孔膜;离子电导率;含氟聚合物杂化电解质膜的结构分析     

含有添加剂及LiClO_4的接枝聚酯网络的离子导电性能研究

研究了碳酸丙烯酯（添加量５％）与γ－丁内酯（添加量１０％）对由数均分子量为８００的聚氧化乙烯（ＰＥＯ８００）大单体交联不饱和聚酯（含ＬｉＣｌＯ４）形成的接枝聚酯网络的离子导电性能影响，发现其电导率主要取决于体系中的ＬｉＣｌＯ４浓度．当［ＥＯ链节］／［Ｌｉ＋］＝３０时，室温电导率达最大值，σ２９８Ｋ＝（４．０—４．５）×１０－５Ｓｃｍ－１．这类接枝聚酯网络的玻璃化转变温度（Ｔｇ）同样取决于盐类浓度，而与网络的交联程度无关．网络中的极性添加剂并不显著影响其交联程度与Ｔｇ，但较大幅度提高离子导电性能，这可能与极性添加剂加速载荷离子在导电通道中的迁移性有关．若在上述接枝网络中引入环氧树脂网络，形成接枝聚合物互穿网络，则成膜后的机械强度有进一步提高，同时具有优良的室温电导率，σ２９８Ｋ＝２．４×１０－５Ｓｃｍ－１。     

胺铜或镍配离子的TCNQ电荷转移盐的合成和物理性质

合成了七个胺铜或镍配离子的TCNQ电荷转移盐[ML2][TCNQ]n(TCNQ=7, 7, 8, 8-四氰基对苯二醌二甲烷; n=2, 3;M=Cu, Ni; L=tn, pn, dien, dmtade)。通过元素分析、红外光谱、电子光谱、顺磁共振谱、光电子能谱、磁化率和电导率对这些电荷转移盐进行了表征。结果表明, 这些电荷转移盐分子中存在TCNQ^0和TCNQ^-且TCNQ^0与TCNQ^-之间存在相互作用, 部分电荷从[TCNQ]n^2向[ML2]^2^+转移, 导致化合物中的金属表现为混合价态。七个样品的室温电导率在10^-^5～10^-^1^0S.cm^-^1, 属于有机半导体, 其导电性主要归结为一维TCNQ分子柱的形成。