聚甲基丙烯酸多缩乙二醇二酯—锂盐—增塑剂聚合物电解质…

合成了一系列甲基丙烯酸多缩乙二醇二酯，并且考究了溶剂含量，盐浓度，增塑剂种类对由ＰＥＤ，锂盐，溶剂组成的聚合物电解质的电导率的影响。当溶剂含量高于８０ｍｏｌ％，盐含量相同时，不同分子量的ＰＥＤ形成的电解质的电导率非常接近，表明增塑剂在盐的解离和离子迁移过程中起主导作用。     

凝胶型聚合物电解质中离子的溶剂化与缔合的研究

考察了聚（三乙二醇甲基丙烯酸二酯）－ＬｉＣｌＯ４－溶剂三组分凝胶固体电解质中离子溶剂化和缔合现象，发现电解质中自由离子摩尔百分数随ＬｉＣｌＯ４盐浓度的提高而线性下降，离子对摩尔百分数先增加后减小，而三离子摩尔百分数则随盐浓度增加而线性增加。在盐浓度为０．５ｍｏｌ／Ｌ￣１．５ｍｏｌ／Ｌ时，聚合物电解质的离子电导主要由三离子所贡献。但各离子摩尔百分数随温度变化的情况因溶剂不同而不同。以四乙二醇为增塑剂     

PAA－PEG－盐复合膜导电性能研究

研究了聚丙烯醚（ＰＡＡ）－聚乙二醇（ＰＥＧ）－盐复合膜的导电性能及其影响因素。研究结果表明，ＰＡＡ－ＰＥＧ－盐复合膜具有一定的导电能力。ＬｉＣｌ的加入量、添加剂的种类及其湿度、温度影响着复合膜的导电性能。随着ＬｉＣｌ含量的增加，电导率增大，但ＬｉＣｌ含量的增加是有限的；添加剂的加入可以大大提高电导率，而ＥＧ类的添加剂效果最好；复合膜的导电性能随着湿度、温度的升高而提高。     

Li_2SO_4－Li_2O－P_2O_5体系非晶态Li~＋离子导体的研究

本文给出了非晶态Ｌｉ￣＋离子导体Ｌｉ＿２ＳＯ＿４－Ｌｉ＿ｂＯ－Ｐ＿２Ｏ＿５体系的制备条件、导电性以及差热分析（ＤＴＡ）结果，同时还对其晶化过程进行了研究。结果表明，首先成功地制备出了以Ｌｉ＿２ＳＯ＿４为基质的非晶态离子导电材料，并且在３５０℃时组成为Ｌｉ＿２ＳＯ＿４－０．３０Ｌｉ＿２Ｏ－０．７０Ｐ＿２Ｏ＿５样品的电导率最大（σ＝６．７８×１０￣（－３）Ω￣（－１）ｃｍ￣（－１）），这一结果与ＤＴＡ测量结果取得一致，ＳＥＭ证明是由于非晶母体部分晶化造成的。采用液氮温区急冷技术已成功的将该状态稳定到了室温，稳定后的态再重测其电导率随温度变化关系，相应的电导率提高３０％左右，如果找到某种合适的稳定剂使其一直处于微晶态，将为高电导率离子导体的制备提供一条新路。     

聚(丙烯酸-丙烯酰胺)-碱金属盐复合物的离子电导性

聚（丙烯酸－丙烯酰胺）－碱金属盐复合物是一种新型高分子固体电解质。文中详细讨论了离子种类，盐浓度，增塑剂种类和用量以及温度等因素对其电导率的影响。结果表明，不同碱金属盐对电解质电导率的影响因其阳离子半径，晶格能，离子淌度以及在电解质中的溶解度的不同而不同。     

PAA—PEG—盐复合膜导电性能研究

研究了聚丙烯酸（ＰＡＡ）－聚乙二醇（ＰＥＧ）－盐复合膜的导电性能及其影响因素。研究结果表明，ＰＡＡ－ＰＥＧ－盐复合膜具有一定的导电能力。ＬｉＣｌ的加入量、添加剂的种类及其湿度、温度影响着复合膜的导电性能。随着ＬｉＣｌ含量的增加，电导率增大，但ＬｉＣｌ含量的增加是有限的；添加剂的加入可以大大提高电导率，而ＥＧ类的添加剂效果最好；复合膜的导电性能随着湿度、温度的升高而提高。     

共聚物电解质MA－Na_2／AA－Na水溶液的粘度特性

对共聚物电解质ＭＡ－Ｎａ２（顺丁烯二酸钠）／ＡＡ－Ｎａ（丙烯酸钠）水溶液ηＳＰ／Ｃ（比浓粘度）与浓度的关系、中性盐及溶液ｐＨ对ηＳＰ／Ｃ的影响进行了研究。结果表明，稀释ＭＡ－Ｎａ２／ＡＡ－Ｎａ溶液时，ηＳＰ／Ｃ急剧上升，而稀释含中性盐（ＫＣｌ或ＣａＣｌ２）的ＭＡ－Ｎａ２／ＡＡ－Ｎａ溶液体系时（中性盐含量保持０．０１ｍｏｌ／Ｌ），ηＳＰ／Ｃ的变化却不大。添加极少量（＜０．０５％）中性盐，可使ＭＡ－Ｎａ２／ＡＡ－Ｎａ溶液体系的ηＳＰ／Ｃ大幅度下降，当中性盐浓度大于０．０５％时，ηＳＰ／Ｃ趋于稳定。溶液ｐＨ＝８时，ηＳＰ／Ｃ最高，ｐＨ＜８或ｐＨ＞８时，ηＳＰ／Ｃ迅速降低。     

双甲基丙烯酰氧基聚乙二醇与甲基丙烯酸盐共聚及导电性

在合成α，ω－双甲基丙烯酰氧基封端的聚乙二醇（ＢＭＡＰＥＧ）的基础上，通过ＢＭＡＰＥＧ与甲基丙烯酸盐（ＭＡＡＭ）共聚，制备了离子导电率（σ）在３０℃时为４．０×１０－６Ｓ／ｃｍ的单离子传导的ＡＢ交联型聚醚类固体电解质（ＡＢＣＰＥ）。研究了影响ＡＢＣＰＥ离子导电率的因素。结果表明，用甲基丙烯酰氯与聚乙二醇进行酯化反应可以合成所期望结构的ＢＭＡＰＥＧ。ＡＢＣＰＥ的σ随ＰＥＧ链段长度和共聚单体浓度的增加出现最大值；降低ＢＭＡＰＥＧ的双键官能度，或升高温度，σ升高。     

K_2NbOF_5－MF_3系玻璃的结构及电性质

研制了Ｋ＿２ＮｂＯＦ＿５－ＭＦ＿３（Ｍ＝Ａｌ、Ｇａ）新体系氟化物玻璃，测定了玻璃的特征温度、Ｒａｍａｎ光谱和电导率，玻璃中Ｎｂ￣（５＋）、Ａｌ￣（３＋）、Ｇａ￣（５＋）分别以ＮｂＯＦ、ＡＩＦ、ＧａＦ八面体形式存在，玻璃的电导率随ＡｌＦ＿３含量的增加而增加，ＡｌＦ＿３含量达到３０ｍｏｌ％时，Ａｌ￣（３＋）除ＡＩＦ八面体外，还有ＡｌＦ四面体结构出现，同时电导率降低，Ｆ￣－阴离子是主要的导电离子，７５Ｋ＿２ＮｂＯＦ＿５·２５ＡｌＦ＿３玻璃的电导率在１９６℃时，σ＝１．０２×１０￣（－２）Ｓ·ｃｍ￣（－１）。     

聚丙烯酸与聚乙二醇在浓溶液中的复合作用

研究了聚丙烯酸（ＰＡＡ）与聚乙二醇（ＰＥＧ）在浓溶液中的复合作用及影响因素，发现ＰＡＡ－ＰＥＧ在很宽的ＰＨ范围内都存在着复合作用。低ＰＨ时，通过氢键作用的形式进行复合，高ＰＨ时，则通过离子－偶极作用。对ＰＡＡ－ＰＥＧ－盐以及ＰＡＡ－盐复合膜进行了ＤＳＣ和Ｘ射线衍射分析，结果表明，ＰＡＡ与ＰＥＧ进行复合，可以破坏ＰＥＧ的结晶性能。     

Conductivity behaviour of polymer gel electrolytes: Role of polymer

Polymer is an important constituent of polymer gel electrolytes along with salt and solvent. The salt provides ions for conduction and the solvent helps in the dissolution of the salt and also provides the medium for ion conduction. Although the polymer added provides mechanical stability to the electrolytes yet its effect on the conductivity behaviour of gel electrolytes as well as the interaction of polymer with salt and solvent has not been conclusively established. The conductivity of lithium ion conducting polymer gel electrolytes decreases with the addition of polymer whereas in the case of proton conducting polymer gel electrolytes an increase in conductivity has been observed with polymer addition. This has been explained to be due to the role of polymer in increasing viscosity and carrier concentration in these gel electrolytes.     

多嵌段聚醚氨酯脲类固态离子导体的动态力学性能

本文研究了以多嵌段聚乙二醇聚氨酯脲(PEUU)和高氯酸锂(LiClO_4)为原料制备的高分子固态离子导体的动态力学性能。文中讨论了 LiClO_4加入后对软段松弛的影响,利用 WLF 方程完成了贮能弹性模量 E'的频率-温度叠合曲线,并解释了造成松弛时间分布不同的原因。     

Effect of ZrO2 on conductivity of PVC-PMMA-LiBF4-DBP polymer electrolytes

The preparation and characterization of composite polymer electrolytes of PVC-PMMA-LiBF₄-DBP for different concentrations of ZrO₂ have been investigated. FTIR studies indicate complex formation between the polymers, salt and plasticizer. The electrical conductivity values measured by a.c. impedance spectroscopy is found to depend upon the ZrO₂ concentration. The temperature dependence of the conductivity of the polymer films seems to obey the VTF relation. The conductivity values are presented and results discussed.     

Chitosan-based electrolyte for secondary lithium cells

The system chitosan : ethylene carbonate : LiCF₃SO₃ was prepared by the solution cast technique. To verify that the conductivity of the material is due to the salt, the electrical conductivity at room temperature of the chitosan acetate film and that of the chitosan acetate films containing different amounts of ethylene carbonate added to it were measured. The order of magnitude of the electrical conductivity was 10^–10 S cm^–1. Films containing fixed content of chitosan and plasticizer but different amounts of salt were then prepared in the same manner and the highest electrical conductivity obtained was 1.3 × 10^–5 S cm^–1 at room temperature. These results indicate that the conductivity is due to the salt. Conductivity-temperature studies show that the ln T versus 10³/T graphs obey Arrhenius rule implying that the conductivity occurs by way of some thermally assisted mechanism. Polarization current measurement shows that the lithium ion transference number is 0.09. A LiMn₂O₄/chitosan-LiCF₃SO₃/C cell was fabricated which cycled between 1.5 to 2.5 V with fading capacity. This could be the result of LiF formation due to interaction between the salt and the fluorine in the binding agent.     

Preparation and characterization of plasticized polymer electrolytes based on the PVdF-HFP copolymer for lithium/sulfur battery

PVdF-TG-LiX polymer electrolytes comprised of polyvinylidene fluoride (PVdF)-hexafluoropropylene (HFP) copolymer, tetra(ethylene glycol) dimethyl ether as plasticizer, LiCF₃SO₃, LiBF₄ and LiPF₆ as lithium salt and acetone as solvent have been prepared by solvent casting of slurry that mixed PVdF-HFP copolymer with acetone and salt using a ball-milling technique, which was performed for 2 and 12 h with a ball-to-material ratio of 400:1, and their electrochemical and thermal properties were studied. The ball-milled PVdF-TG-LiX polymer electrolytes have higher ionic conductivity as well as lower glass transition temperature and melting points than the magnetically stirred one. The PVdF-TG-LiPF₆ polymer electrolytes prepared by ball-milling, for, 12 h, in particular, resulted in a maximum value in the ionic conductivity, which was 4.99×10^–4 S cm^–1 at room temperature. The ball-milled PVdF-TG-LiX polymer electrolytes were introduced into Li/S cells with sulfur as cathode and lithium as the anode. The first specific discharge capacities with discharge rate of 0.14 mA cm^–2 at room temperature were about 575 and 765 mA h g–cathode^–1 for magnetic stirring and 12 h ball milling.     

Impedance studies on plasticized PMMA-LiX [X: CF3SO3, N(CF3SO2)2−] polymer electrolytes

Plasticized polymer electrolytes composed of poly(methylmethacrylate) (PMMA) as the host, propylene carbonate (PC) or ethylene carbonate (EC) as a plasticizer and LiX (X: CF₃SO₃⁻ or N(CF₃SO₂)₂⁻) as a salt were prepared by the solution cast technique. Impedance spectroscopy was performed in the temperature range between 303 and 383 K. In this paper, we report the electrical properties of polymer electrolytes with different lithium salts and plasticizers. The polymer electrolytes investigated exhibited high ionic conductivity at room temperature in the range of 10^− 6 to 10^− 4 S cm^− 1. The temperature dependence studies showed that the samples were ionic conductors and seemed to obey the Vogel-Tamman-Fulcher (VTF) rule. FTIR spectroscopy studies confirmed the polymer-salt interaction.     

Impact of ethylene carbonate on ion transport characteristics of PVdF-AgCF3SO3 polymer electrolyte system

The ionic transport in thin film plasticized polymer electrolytes based on polyvinylidene fluoride (PVdF) as the polymer host, silver triflate (AgCF₃SO₃) as salt and ethylene carbonate (EC) as plasticizer prepared by solution casting technique has been reported. Addition of silver triflate has resulted in an increase in the room temperature (298 K) electrical conductivity of the polymer from 10⁻⁶ to 10⁻⁵ S cm⁻¹ whereas incorporation of EC as the plasticizer has further enhanced the conductivity value by an order of magnitude to 10⁻⁴ S cm⁻¹ owing to the possible decrease in crystallinity of the polymer matrix as revealed by the detailed temperature-dependent complex impedance, silver ionic transference number, Fourier transform infrared and X-ray diffraction measurements.     

Electrochemical properties of composite electrolytes based on poly(ethylene oxide)/poly(ethylene imine) containing the inorganic silica fillers

In this study, poly(ethylene oxide) (PEO) and poly(ethylene imine) (PEI) polymer blends containing inorganic silica fillers were studied in order to enhance the ion conductivity and interfacial properties. Lithium perchlorate (LiCIO4) as a salt, and silica (SiO2) as the inorganic filler were introduced in the polymer electrolyte composites and were examined to evaluate their use to improve the ionic conductivity. The addition of inorganic fillers in polymer electrolytes has resulted in high ionic conductivity at a room temperature. The structure and morphology of the solid polymer electrolytes were evaluated using X-ray diffraction (XRD) and scanning electron microscope (SEM). The ionic conductivity was measured by an AC impedance method. The enhanced conductivity was dependent on the decreased crystallinity and more heterogeneous morphologies.