单离子型全氟凝胶聚合物固体电解质的结构与离子导电性能

从Nafion树脂出发,制备了一系列单离子型全氟凝胶聚合物固体电解质膜,其中有机极性介质为碳酸丙烯酯(PC)。通过溶胀曲线测定、红外光谱分析、复阻抗分析等手段对材料的结构与离子导电性能进行了研究。结果表明,PC与阳离子之间存在较强的相互作用,而且PC与Li+离子之间的相互作用强于PC与H+离子之间的相互作用。PC含量对材料的离子导电性能也有较大的影响。随着PC含量的增加,材料的离子电导率呈上升趋势。当PC含量较低时,Li+型样品的室温离子电导率高于H+型样品;而PC含量较高时,Li+型样品的室温离子电导率则低于H+型样品。Li+型样品和H+型样品的室温离子电导率均可达到1.25×10-4S·cm-1。     

高固体分丙烯酸树脂相对分子质量的研究

采用溶液聚合法合成高固体分丙烯酸树脂,用凝胶渗透色谱(GPC)法分析引发剂的种类和用量、反应温度及聚合工艺对丙烯酸树脂的相对分子质量及其分布的影响。结果表明,选用偶氮二异丁腈和过氧化苯甲酰两种引发剂进行复配可提高聚合物的相对分子质量;采用“饥饿态”聚合工艺进行聚合反应可有效控制聚合物的相对分子质量,且相对分子质量分布均匀,分散度小于2;当引发剂用量为2%,在110℃的反应条件下制得的丙烯酸树脂的综合性能优异,固含量超过70%,相对分子质量可达4万。     

All‐Solid Actuator Consisting of Polyaniline Film and Solid Polymer Electrolyte

An all‐solid actuator, consisting of a polyaniline (PANI) film and a solid polymer electrolyte (SPE) of poly(ethylene oxide) derivative (STO288), clearly showed a reversible displacement in an atmosphere when a voltage was applied between the PANI film and the SPE layer. The displacement and the response rate are mainly dependent on the applied voltage and the employed supporting salt, but are influenced by the humidity and temperature of the environment. The results of the present experiments have revealed that the influences of the humidity and temperature on the performance of the actuator are predominantly through the ionic conductivity of the SPE.

All‐solid actuator consisting of PANI and SPE.     

锂离子电池用凝胶聚合电解质基体改性的研究进展

介绍了目前用于锂离子电池的凝胶聚合物电解质体系,重点介绍了凝胶聚合物电解质在离子电导率等方面的改性进展。     

PVDF-HFP型凝胶聚合物固体电解质的结构与离子导电性能

以PVDF-HFP为基体聚合物，制备了一系列凝胶聚合物固体电解质膜，其中有机极性介质为碳酸丙烯酯(PC)，电解质盐为LiClO4。通过红外光谱分析、差示扫描量热分析、复阻抗分析等手段对凝胶聚合物固体电解质的结构与离子导电性能进行了研究。结果表明，PC与阳离子之间存在较强的络合作用，PC对基体聚合物有很强的增塑作用。锂盐和PC含量对材料的离子导电性能有较大的影响。随着锂盐和PC含量的增加，材料的离子电导率呈上升趋势。     

A Review on Ionic Liquids-Based Membranes for Middle and High Temperature Polymer Electrolyte Membrane Fuel Cells (PEM FCs)

Today, the use of polymer electrolyte membranes (PEMs) possessing ionic liquids (ILs) in middle and high temperature polymer electrolyte membrane fuel cells (MT-PEMFCs and HT-PEMFCs) have been increased. ILs are the organic salts, and they are typically liquid at the temperature lower than 100 °C with high conductivity and thermal stability. The membranes containing ILs can conduct protons through the PEMs at elevated temperatures (more than 80 °C), unlike the Nafion-based membranes. A wide range of ILs have been identified, including chiral ILs, bio-ILs, basic ILs, energetic ILs, metallic ILs, and neutral ILs, that, from among them, functionalized ionic liquids (FILs) include a lot of ion exchange groups in their structure that improve and accelerate proton conduction through the polymeric membrane. In spite of positive features of using ILs, the leaching of ILs from the membranes during the operation of fuel cell is the main downside of these organic salts, which leads to reducing the performance of the membranes; however, there are some ways to diminish leaching from the membranes. The aim of this review is to provide an overview of these issues by evaluating key studies that have been undertaken in the last years in order to present objective and comprehensive updated information that presents the progress that has been made in this field. Significant information regarding the utilization of ILs in MT-PEMFCs and HT-PEMFCs, ILs structure, properties, and synthesis is given. Moreover, leaching of ILs as a challenging demerit and the possible methods to tackle this problem are approached in this paper. The present review will be of interest to chemists, electrochemists, environmentalists, and any other researchers working on sustainable energy production field.     

快冷对PEO/LiClO_4固态电解质的晶型与导电性的影响

聚合物电解质的离子电导率是电解质的一个重要参数 ,与聚合物电解质中的非晶态的存在有很大的关系。在本文中 ,以X射线衍射 (XRD)、差热分析 (DTA)和交流阻抗 (Acimpedance)为研究手段 ,研究了快冷对聚合物电解质的晶型转变和对聚合物电解质室温离子电导率的影响。在快速冷却的条件下 ,质量比为1∶1的PEO/LiClO4聚合物电解质的室温离子电导率可达 1 6 1x 10 -7S/cm ,比慢冷处理的相同体系的室温离子电导率提高了 1个数量级。实验证明 ,快速冷却可破坏聚合物的结晶性 ,提高聚合物电解质的离子电导率。     

低分子阳离子聚合物对高浓度聚驱解堵作用的评价

针对大庆油田的现状,研制出了一种低分子阳离子聚合物,能够有效改善地层堵塞状况,解堵率达到90％以上。     

减少DMC催化合成聚醚多元醇中高相对分子质量拖尾部分的研究

以双金属氰化物络合物(DMC)为催化剂,采用间歇法合成了聚醚多元醇,讨论了催化剂用量、反应温度、反应压力等因素对聚醚多元醇相对分子质量分布的影响。结果表明,硫酸质量分数为总量的0.004%、环氧丙烷预投量为起始聚醚质量分数的16%、DMC催化剂质量分数为总量的0.006%、反应温度在120～130℃和反应压力为0.1 MPa时,所制备的聚醚多元醇中高相对分子质量拖尾部分减少,相对分子质量分布窄,且其它物理性能也较好。     

溶胶-凝胶法制备NASICON型Li_(1.15)Y_(0.15)Zr_(1.85)(PO_4)_3固态电解质

以碳酸锂、硝酸锆、磷酸氢二铵和硝酸钇为原料,柠檬酸为络合剂,采用溶胶–凝胶法制备了NASICON型Li1.15Y0.15Zr1.85(PO4)3固态电解质材料,通过无压烧结和放电等离子烧结(SPS)得到固态电解质片。结果表明:采用无压烧结在1 150℃制备的电解质密度可以达到理论密度的95.2%,在室温下晶粒电导率和总电导率分别为2.19×10–4 S/cm和0.86×10–4 S/cm;采用SPS在1 150℃烧结得到的电解质片密度可达到理论密度的96.8%,在室温下样品总电导为0.97×10–4S/cm,激活能为0.44 e V。四方相Zr O2的存在是样品激活能升高的主要原因。     

超高相对分子质量聚乙烯固相挤出过程研究

采用一种新型超高相对分子质量聚乙烯成型技术—固相挤出成型。采用扫描电子显微镜观察了制品成型前后内部微观结构变化;采用差示扫描量热分析,研究了不同挤出温度与口模拉伸比对挤出制品热性能的影响。结果表明,相对熔融挤出成型,固相挤出成型制品光滑、透明、密度较大;制品内部产生大量的微纤结构,结晶度提高,分子链取向增强,拉伸强度提高了2.7～4.5倍,拉伸弹性模量提高了42倍;另外,熔点上升了3～5 ℃、熔融焓及结晶度分别提高了8~10个百分点。     

增塑剂对聚氨酯型固体电解质离子导电性能的影响

利用溶液聚合方法合成了聚醚聚氨酯,并以聚氨酯、高氯酸锂和增塑剂为组分,制备了一系列新型聚合物固体电解质。运用差示扫描量热分析、动态力学分析、交流复阻抗谱、扫描电镜和原子力显微镜对体系性能和形态进行了研究。结果表明,在聚氨酯/高氯酸锂复合物中,增塑剂的加人会导致体系玻璃化转变温度和力学性能有所下降,离子导电性能显著增加。在所研究的6种增塑剂碳酸丙烯酯、碳酸二乙酯、二乙二醇二甲醚、N,N-二甲基甲酰胺、聚乙二醇400和丙三醇中,聚乙二醇400对聚氨酯/高氯酸锂复合物的增塑效果最好,该体系室温电导率达到10-4S／cm。     

高分子在固体表面吸附的分子模拟

综述了分子模拟研究高分子在固体表面吸附的应用,简单介绍了分子模拟的基本原理及其常用的几种方法,并分别介绍了分子模拟在研究高分子吸附构象以及吸附动力学方面的应用。     

Memristive Switching Characteristics in Biomaterial Chitosan-Based Solid Polymer Electrolyte for Artificial Synapse

This study evaluated the memristive switching characteristics of a biomaterial solid polymer electrolyte (SPE) chitosan-based memristor and confirmed its artificial synaptic behavior with analog switching. Despite the potential advantages of organic memristors for high-end electronics, the unstable multilevel states and poor reliability of organic devices must be overcome. The fabricated Ti/SPE-chitosan/Pt-structured memristor has stable bipolar resistive switching (BRS) behavior due to a cation-based electrochemical reaction between a polymeric electrolyte and metal ions and exhibits excellent endurance in 5 × 10² DC cycles. In addition, we achieved multilevel per cell (MLC) BRS I-V characteristics by adjusting the set compliance current (I_cc) for analog switching. The multilevel states demonstrated uniform resistance distributions and nonvolatile retention characteristics over 10⁴ s. These stable MLC properties are explained by the laterally intensified conductive filaments in SPE-chitosan, based on the linear relationship between operating voltage margin (ΔV_switching) and I_cc. In addition, the multilevel resistance dependence on I_cc suggests the capability of continuous analog resistance switching. Chitosan-based SPE artificial synapses ensure the emulation of short- and long-term plasticity of biological synapses, including excitatory postsynaptic current, inhibitory postsynaptic current, paired-pulse facilitation, and paired-pulse depression. Furthermore, the gradual conductance modulations upon repeated stimulation by 10⁴ electric pulses were evaluated in high stability.     

新型单官能度高分子量聚醚多元醇的研究

介绍了一种丙烯醇聚醚多元醇的合成方法。采用了丙烯醇作为起始剂、环氧丙烷作为聚合单体、氢氧化钾和双金属催化剂作为双催化剂,采用二次聚合方式,通过选择适合的聚合反应条件,从而制得一种性能优异的新型单官能度高分子量丙烯醇聚醚多元醇。并对其反应条件及使用性能进行了研究。     

高相对分子质量低不饱和度聚醚多元醇技术进展

阐述了传统聚醚多元醇的技术进展、合成高相对分子质量低不饱和度聚醚多元醇的催化体系及研究进展,对高相对分子质量低不饱和度聚醚多元醇在聚氨酯泡沫、弹性体和密封胶中的应用进行概述,并就其未来发展提出建议。     

固态纳米复合聚合物电解质的离子导电性能研究

以PEO为基质,复配少量纳米无机填料及低分子乙氧化物,制备出了新型的固态纳米复合聚合物电解质膜,利用交流阻抗法测试了聚合物电解质的离子电导率,对离子导电性能进行了研究。采用CPE元件的模拟电路具有很好的适用性。结果表明当低分子乙氧化物的加入量超过80％时电解质膜的电导率大幅提高,并且PEGDME优于PEG300。电导率在LiPF6加量在O：Li为8：1时达到最大,随着LiClO4加量的增加持续增加,随无机盐加量增加电解质膜的成膜性能变差。用多微孔高比表面的纳米SiO2粒子复合有利于改善聚合物的电导率。聚合物电解质离子电导率对温度的依赖关系符合Arrhenius方程。     

凝胶色谱法测定高聚物的平均分子量及分子量分布

介绍了用凝胶色谱法测定高聚物的平均分子量及分子量分布。     

聚合工艺对低不饱和度高相对分子质量聚醚性能的影响

采用双金属氰化络合物催化剂（DMC）合成了低不饱和度高相对分子质量聚醚（DL-4000D）,讨论了聚合温度、聚合压力、低聚物脱水时间等聚合工艺条件对DL-4000D及其制品性能的影响。结果表明,聚合温度在115~125℃、低聚物脱水时间在2 h左右,聚合压力小于100 kPa等工艺条件下,制备的聚醚不饱和度低,相对分子质量分布窄,由其制得的聚氨酯制品的综合性能好。     

低单官能度高分子量聚醚多元醇的制备

使用双金属氰化物络合催化剂,制备了分子量高、分子量分布窄、不饱和度低的低单官能度聚醚多元醇。重点讨论了催化剂、溶剂、反应压力对聚醚多元醇质量的影响。