高分子固体电解质设计的新概念

高分子固体电解质是开发零释放能源－－高性能电池的关键材料。本文详细介绍了20世纪90年代以来高分子固体电解质结构设计的新概念，包括高分子凝胶电解质，两相高分子电解质，盐掺聚合物（Polymer-in-salt)，有机／无机纳米复合型电解质，悬挂柔性短聚醚侧链的网格聚合物电解质。     

锂电池用全固态聚合物电解质

随着储能电源和电子产品以及电动汽车的迅速发展,开发高能量密度的锂离子电池已经成为现阶段研究的重点方向之一。目前,较广泛使用的液态锂离子电池,由于容易发生有机液态电解质的泄漏、燃烧、爆炸和短路等问题,存在非常大的安全隐患。因此,迫切需要开发能量密度更高,安全性更加好的锂离子电池。与现有的有机液态电解质相比,全固态聚合物电解质(All-solid-state polymer electrolyte,ASPE)具有理论比容量更高、结构可设计性强、易于大规模生产制造、排除了泄漏液体等体系安全性能好的优点,是一类具有广泛应用前景的电解质。ASPEs在锂离子电池中起到了主导作用,研究者们对其进行了大量的科研工作。本文结合并比较了典型的ASPEs(聚醚、聚酯、聚氨酯、聚硅氧烷)的最新科研进展以及本课题组的工作,回顾了这几种固态聚合物的发展,对高性能锂电池全固态电解质的制备设计、新型锂电池、界面调控和制备工艺成型等方面作了阐述,并对其未来的研究做出展望。     

Development on Solid Polymer Electrolytes for Electrochemical Devices

Electrochemical devices, especially energy storage, have been around for many decades. Liquid electrolytes (LEs), which are known for their volatility and flammability, are mostly used in the fabrication of the devices. Dye-sensitized solar cells (DSSCs) and quantum dot sensitized solar cells (QDSSCs) are also using electrochemical reaction to operate. Following the demand for green and safer energy sources to replace fossil energy, this has raised the research interest in solid-state electrochemical devices. Solid polymer electrolytes (SPEs) are among the candidates to replace the LEs. Hence, understanding the mechanism of ions’ transport in SPEs is crucial to achieve similar, if not better, performance to that of LEs. In this paper, the development of SPE from basic construction to electrolyte optimization, which includes polymer blending and adding various types of additives, such as plasticizers and fillers, is discussed.     

锂电池中的凝胶聚合物电解质

锂电池目前在人们生活中已经得到广泛应用,但是传统的液体电解质沸点低且易泄漏,容易引起锂枝晶生长和安全问题。凝胶聚合物电解质(GPEs)的状态介于液态电解质和固态电解质之间,不仅可以作为电解质,还可以作为隔膜,这样可以减少液体电解质的泄漏以及改善固体电解质的界面电阻。本文综述了锂电池中制备不同类型的GPEs的方法,如溶液浇铸法、相转化法、原位聚合法、UV(紫外)固化法和静电纺丝法等,重点总结了不同纤维基的GPEs(聚(偏二氟乙烯)(PVDF)、聚(偏二氟乙烯-共六氟丙烯)(PVDF- HFP)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯腈(PAN)和聚间亚苯基间苯二甲酰胺(PMIA))在锂电池中的运用,并通过对不同基质的改性来改善电解质的离子电导率,阻碍锂枝晶的生长。最后,本文对锂电池中GPEs的未来发展前景进行了展望,讨论和提出的策略将为今后高性能锂电池的实际应用提供更多的途径。     

离子导电聚合物电解质的研究*

本文对离子导电聚合物电解质的发展史、分类、导电机理、研究方法及离子导电聚合物电解质电导率提高的途径进行了综述分析,并讨论了今后工作的发展方向。     

高分子固体电解质

本文叙述了高分子固体电解质的离子传导机理、特点及国内外近年来的研究进展和应用前景。     

含[AMIM]BF4的聚甲基丙烯酸甲酯基凝胶聚合物电解质的制备与改性

用两步法合成了离子液体1-烯丙基-3-甲基咪唑四氟硼酸盐（[AMIM]BF4）,将聚甲基丙烯酸甲酯(PMMA)引入离子液体[AMIM]BF4中,制备出含离子液体[AMIM]BF4的新型凝胶聚合物电解质,采用非质子溶剂、纳米SiO2等对其进行了改性。 用FT-IR、交流阻抗（AC）、TG、SEM等测试技术对其结构和性能进行了表征。 结果表明,非质子溶剂碳酸丙烯酯、碳酸二甲酯和纳米SiO2的加入使聚合物电解质的室温离子电导率增大,达5.25×10-3 S/cm;电导率与温度的关系符合Arrhenius方程;几种凝胶聚合物电解质的热分解温度均高于300 ℃,显示出良好的热稳定性。     

新型梳状高分子固体电解质的研究（Ⅱ）

新型梳状高分子固体电解质的研究（Ⅱ）丁黎明，林云青，梁洪泽，汪东梅，王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词梳状高分子，ＮａＣＩＯ＿４络合物，固体电解质，离子电导率聚环氧乙烷（ＰＥＯ）可以溶解多种碱金属盐并形成络合物，这种络合物具...     

复合聚合物电解质的导电行为及电导率的测定

研究了乙烯碳酸酯（EX）增塑的（PEO）16LiClO4-EC复合聚合物电解质交流阻抗谱图，提出了不锈钢电极／聚合物电解质／不锈钢电极这种结构在交流阻抗测试分析中具有普适性的模拟等效电路，并且根据等效电路中元件拟合值测定出复合聚合物电解质体系在不同EC增塑量及温度时的电导率，用复合聚合物电解质体系中各组分之间的相互作用解释了EC对聚合物电解质电行为的影响，在低EC含量的复合聚合物电解质体系中，电导率和温度的关系在低温时符合Arrhenius方程，在高温时符合Vogel-Tamman-Fulcher(VTF)方程；而当EC含量大于20％时，电导率和温度的关系在实验温度范围内符合VTF方程。     

锂/聚合物电解质电化学固/固界面的研究

综述了聚合物锂电池中锂/聚合物电解质电化学固/固界面的研究进展。通过与锂/液体电解质体系进行比较,简要介绍了在锂/聚合物电解质界面上发生的电化学反应、锂钝化层形成及其对界面反应的影响,并侧重讨论了传统电化学方法和谱学方法,特别是现场分析技术在电化学固/固界面研究中的应用。总结了锂/聚合物电解质界面的几种不同改善途径。     

聚合物固体电解质基体的研究进展

综述了聚合物固体电解质基体的设计原理、分类和研究进展，并对今后在聚合物基体设计方面的研究前景作了展望。     

固态单离子聚合物电解质的研究进展

综述了用于锂金属聚合物电池中固态单离子聚合物电解质的研究进展，从均聚、共聚、共混、杂原子链及单阴离子型聚合物电解质等方面对不同体系的组成与性质进行了概述，并对该类电解质的发展趋势进行了分析。     

高分子固体电解质材料研究进展

高分子固体电解质材料由于具有优良的成膜性和粘弹性等特点，。近年来得到了很大的发展。本文综述了高分子固体电解质材料的电性能，离子传导特性，提高其性能的途径及近期发展，并对其发展前景作了简要的探讨。     

Improved Conductivity in Gellan Gum and Montmorillonite Nanocomposites Electrolytes

Nanocomposite polymer electrolytes (NPEs) were obtained using gellan gum (GG) and 1 to 40 wt.% of montmorillonite (Na⁺SYN-1) clay. The NPEs were crosslinked with formaldehyde, plasticized with glycerol, and contained LiClO₄. The samples were characterized by impedance spectroscopy, thermal analyses (TGA and DSC), UV-vis transmittance and reflectance, X-ray diffraction (XRD), and continuous-wave electron paramagnetic resonance (CW-EPR). The NPEs of GG and 40 wt.% LiClO₄ showed the highest conductivity of 2.14 × 10⁻⁶ and 3.10 × 10⁻⁴ S/cm at 30 and 80 °C, respectively. The samples with 10 wt.% Na⁺SYN-1 had a conductivity of 1.86 × 10⁻⁵ and 3.74 × 10⁻⁴ S/cm at 30 and 80 °C, respectively. TGA analyses revealed that the samples are thermally stable up to 190 °C and this did not change with clay addition. The transparency of the samples decreased with the increase in the clay content and at the same time their reflectance increased. Finally, CW-EPR was performed to identify the coordination environment of Cu²⁺ ions in the GG NPEs. The samples doped with the lowest copper concentration exhibit the typical EPR spectra due to isolated Cu²⁺ ions in axially distorted sites. At high concentrations, the spectra become isotropic because of dipolar and exchange magnetic effects. In summary, GG/clay NPEs presented good ionic conductivity results, which qualifies them for electrochemical device applications.     

Ionic Transport in Dilute Solid Polymer Electrolytes with Amorphous Structure

The ionic structure and transport properties of amorphous solid polymer electrolytes in the system copolymer of acrylonitrile and butadiene (40 : 60)—lithium hexafluoroarsenate (SPE) is studied in the region of small salt concentrations (up to 0.37 mol dm⁻³) at 298–368 K. In conditions studied, LiAsF₆ is dissociated predominantly to ions. Macroscopic models of ion transport are used to analyze the results of measurements of transport characteristics of SPE. Transport of anions free of the polymer matrix is realized activationlessly and resembles the Stokes drift in viscous media. Transport of cations solvated by electron-donating groups of the polymer turns possible only at temperatures in excess of a critical value (T _crit ≈ 333 K), when the statistical mean of molecules in the first coordination sphere of the lithium cation becomes less than four (which is the coordination number for solvation) and requires the overcoming of an energy barrier of ∼6 kJ mol⁻¹. Below T _crit, the SPE are unipolar anionic conductors.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 537–545.Original Russian Text Copyright © 2005 by Bushkova, Sofronova, Lirova, Zhukovskii.     

聚合物固体电解质研究进展

本文概述近十几年来聚合物固体电解质材料开发研究的状况,包括线型高分子、为改进性能而发展起来的枝型、梳型及交联型高分子,并对高分子与金属盐络合的离子聚合物结构和性能作了描述。阐述了高分子固体电解质的导电行为、导电模型及导电机理。对聚合物固体电解质的各种应用作了介绍并简要讨论了高分子固体电解质的发展趋向及前景。     

锂离子电池用聚合物固体电解质的新进展

综述了锂离子电池用聚合物固体电解质方面的进展。     

Conductivity Study on PEO Based Polymer Electrolytes Containing Hexafluorophosphate Anion: Effect of Plasticizer

PEO based polymer electrolytes containing ammonium hexafluorophosphate (NH₄PF₆) and hexafluorophosphoric acid (HPF₆), both with PF anion have been studied. The effect of the addition of propylene carbonate (PC) to PEO-NH₄PF₆ and PEO-HPF₆ has been observed to increase in ionic conductivity which is attributed to an increase in free ion concentration due to the dissociation of ion aggregates present at higher acid/salt concentrations. The plasticized polymer electrolytes containing HPF₆ show relatively higher conductivity (σ_max = 1.02 × 10⁻⁴ S/cm at 10 wt% HPF₆) as compared to electrolytes containing NH₄PF₆ (σ_max = 1.09 × 10⁻⁵ S/cm at 10 wt% NH₄PF₆). Presence of free ions, ion aggregates and their dissociation with the addition of PC has been studied by Fourier Transform Infrared Spectroscopy (FTIR). The change in amorphous phase with PC content was also studied by X-Ray Diffraction (XRD). The variation of conductivity with temperature shows Vogel–Tammen–Fulcher (VTF) behavior, which is associated with the highly amorphous nature of electrolytes. ¹H Nuclear magnetic Resonance (NMR) spectra at different temperatures shows line narrowing and suggests the onset of long range ion diffusional motion. Change in surface morphology of polymer electrolytes with the addition of PC is also checked by Scanning Electron Microscopic (SEM) studies.     

用于锂离子电池聚合物电解质的组成、结构和性能

聚合物电解质是全固态锂离子电池的重要组成部分, 其电导率对电池的性能有很重要的影响.本文综述了聚合物电解质的组成、结构和性能对锂 离子电池导电率影响的最新研究进展,特别是介绍了聚合物-碱金属盐复合电解质和聚离子体电解质两个体系的研究进展.     

无机纳米粒子在复合聚合物电解质中作用的研究进展

聚合物电解质材料已经成为当前锂离子电池研究领域的热点之一。复合化是有效提高聚合物电解质材料性能的有效手段。本文从纳米粒子掺杂的角度,综述了近年来无机纳米粒子对复合聚合物电解质(CPE)体系的离子电导率、锂离子迁移数的影响,并介绍了四种初步解释了无机纳米粒子在复合聚合物电解质中的作用的机理;讨论了无机纳米粒子对CPE体系/电极界面稳定及相容性的影响;提出了无机纳米粒子掺杂的复合聚合物电解质研究的三个热点方向。