聚合物电解质的研究与进展

介绍了聚合物电解质的研究与进展，重点综述了纯固态聚合物电解质（DSPE）、凝胶聚合物电解质（GSPE）、多孔型聚合物电解质（PSPE）以及复合型聚合物电解质（CSPE），聚合物电解质的导电机理及其在锂离子二次电池中的应用。     

PEO基聚合物电解质

聚氧化乙烯（PEO）基电解质是研究最早的聚合物电解质体系，它在电池生产中已得到应用。PEO基聚合物电解质主要分为聚合物/盐型和凝胶型两大类，凝胶型聚合物电解质因具有较高的电导率而被认为是固态锂离子电池最有应用前景的临时性解质体系。对两种类型的聚合物电解质的研究进展作了较为详细的论述，在此基础上分析了PEO基聚合物电解质中离子的传输机理。PEO基聚合物电解质中离子的运动能力与链的结构。离子浓度，温度，增塑剂等因素有关。     

塑料锂离子电池用聚合物电解质性能表征

以导电聚合物作为电解质的塑料锂离子电池被认为是迄今锂电池发展最新水平，研制性能优良的聚合物电解质是生产该种锂离子电池的关键技术，因此对聚合物电解质的表征是必不可少的步骤，电导率，扩散系数，迁移数和电化学窗口是表征聚合物电解质的重要指标，文中介绍了塑料锂离子电池用聚合物电解质性能的表征方法，给出了交流阻抗，浓差极化，断电流，线性伏安扫描等实验方法，并对其作为分析和讨论。     

纳米SiO2/LiClO4/PVDF-HFP复合凝胶聚合物电解质的制备及其电化学性能

为了解决液态电解质锂离子电池存在的安全性问题,以偏氟乙烯和六氟丙烯的共聚物(PVDF-HFP)为基体,通过加入高氯酸锂(LiC1O4)、增塑剂(碳酸丙烯酯和碳酸二甲酯)、纳米二氧化硅等,制备出了具有高电导率的复合凝胶聚合物电解质.用X射线衍射仪测试聚合物电解质的结构,用交流阻抗法测定其电导率,用线性伏安扫描法研究了该聚合物电解质体系的电化学稳定性,并以其为电解质制备成锂离子电池进行充放电测试.结果表明,在20℃时复合凝胶聚合物电解质的电导率最高可达7.56×10-3S/cm,该电解质在4.6 V以下电化学窗口稳定,以其为电解质的锂离子电池具有良好的电化学性能,说明纳米SiO2/LiC1O4/PVDF-HFP复合凝胶聚合物电解质能满足锂离子电池的应用.     

锂离子电池凝胶聚合物电解质制备工艺进展

凝胶聚合物电解质的应用广泛,在化学电源方面的应用主要集中应用于聚合物锂离子电池。本文介绍了锂离子电池用凝胶聚合物电解质的制备方法、各自的优缺点以及其在电池制备中的应用,重点介绍了UV固化技术在凝胶聚合物电解质制备中的应用,展望了聚合物锂离子电池UV聚合工艺的发展前景。     

纳米 SiO 2/ LiClO 4/ PVDF2 HFP复合凝胶聚合物电解质的制备及其电化学性能

为了解决液态电解质锂离子电池存在的安全性问题 , 以偏氟乙烯和六氟丙烯的共聚物( PVDF2 HFP)为基体 , 通过加入高氯酸锂(LiClO 4) 、 增塑剂(碳酸丙烯酯和碳酸二甲酯) 、 纳米二氧化硅等 , 制备出了具有高电导率的复合凝胶聚合物电解质。用 X射线衍射仪测试聚合物电解质的结构 , 用交流阻抗法测定其电导率 , 用线性伏安扫描法研究了该聚合物电解质体系的电化学稳定性 , 并以其为电解质制备成锂离子电池进行充放电测试。结果- 3表明 , 在 20℃ 时复合凝胶聚合物电解质的电导率最高可达 7. 56×10 S/ cm , 该电解质在 41 6 V 以下电化学窗口稳定 , 以其为电解质的锂离子电池具有良好的电化学性能 , 说明纳米 SiO 2/ LiClO 4/ PVDF2 HFP复合凝胶聚合物电解质能满足锂离子电池的应用。     

锂离子电池电解质的最新研究进展

综述了近几年来电解质（即液态电解质和固态电解质）的研究进展，主要是介绍如何提高液态电解质的性能和固态电解质的性能。对液态电解质主要是电化学稳定性的提高，而对固态电解质则包括对离子电导率、电化学稳定、机械性能等的提高。虽然在锂离子电池中，对电池性能起决定作用的是电极材料，但只有对正、负极匹配合适的和性能好的电解质才能达到对锂离子电池性能的优化和提高。因而电解质性能的好坏对锂离子电池的性能有重要的影响。     

全固态锂离子电池用PEO基聚合物电解质的研究进展

锂离子电池作为重要的能量储存元件在消费类电子产品、电动汽车和可再生能源存储等领域具有广泛的应用。传统液态电解质锂离子电池受到能量密度低、安全性差等诸多缺陷的限制,采用固态电解质替代液态电解质制备新型固态锂离子电池目前备受关注。PEO基固态聚合物电解质由于其设计简单、易于制造、使用安全等优点已被认为是替代传统液体电解质的首选。介绍了当前PEO基聚合物电解质的主要研究种类、特点和性能;阐述了锂离子在PEO基聚合物电解质中的导电机制;分析了与PEO络合的锂盐种类对聚合物电解质的电导率的影响规律;在此基础上提出了几种改善PEO基聚合物电解质性能的措施和方法。     

锂离子二次电池固体电解质材料发展现状及展望

简述了锂离子二次电池的发展、组成及工作原理。重点介绍了锂离子二次电池中聚合物电解质分类,导电原理、性能以及发展方向。作为新型锂离子电池的电解质材料,聚合物电解质的性能较液体电解质有更大的发展潜力。     

用于锂离子电池的全固态聚合物电解质

用全氟醚作为增塑剂对PEO改性,并与双三氟甲烷磺酰亚胺锂复合,制备了全固态聚合物电解质。采用SEM、交流阻抗、稳态电流法及恒电流恒电压充放电等对固态聚合物电解质的性能进行了测试表征,结果表明:m(PFPE)∶m(PEO)=0.6的固态聚合物电解质膜的电导率30℃时为2.6×10-3 S·cm-1,同条件下电解质溶液电导为8.2×10-3 S·cm-1,二者处于同一个数量级;随PFPE的量增加,锂离子的迁移数增大;与液态电解质电池相比,固态聚合物电解质制成的电池具有更好的循环容量保持特性,固态聚合物电解质电池500次循环的容量保持率在88.1%,液态电解质电池循环容量保持率在64.5%左右;固态聚合电解质有很优异的耐高温安全性,在130℃和150℃下经1~2h热箱试验,用固态聚合物电解质制作的锂离子电池没出现明显体积变化,而相同条件下的液态电解质锂离子电池已发生爆裂或起火。     

SAXS/WAXS/DSC study of temperature evolution in nanopolymer electrolyte

Soft matter polymer electrolytes as nanostructured materials are very attractive components for batteries and for opto-electronic devices as a new generation of dye-sensitized solar cells. (PEO)₈ZnCl₂ polymer electrolytes were prepared from PEO and ZnCl₂. The nanocomposites (PEO)₈ZnCl₂/TiO₂ themselves contained TiO₂ nanograins. In this work, the influence of TiO₂ nanograins or the morphology and ionic conductivity of the nanocomposite was systematically studied by small-angle X-ray scattering (SAXS) simultaneously recorded with wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) at the synchrotron ELETTRA. Shown by previous impedance spectroscopy measurements (IS), the room temperature conductivity of nanocomposite polymer electrolyte increased more than two times above 65 °C, relative to pure composites of PEO and salts. The SAXS/DSC measurements yielded insight into the temperature-dependent changes of the grains of the electrolyte as well as into the effects of heating and cooling rates. The crystal structure and temperatures of melting and crystallization of the nanosize grains was revealed by the simultaneous WAXS measurements.     

Structural,thermal and electrical properties of plasticised PVA based polymer electrolyte

Polymer electrolyte films of polyvinyl alcohol as host polymer, poly(3,4-etylenedioxythiophene)/poly(styrenesulphonate), magnesium bromide were prepared using solution cast technique. Succinonitrile was used as plasticiser in the matrix at different concentrations. These films were characterised using thermogravimetric analysis, X-ray diffraction and ac impedance spectroscopy. The conductivity measurement was used to determine the ionic conductivity of the polymer electrolyte at different temperature and frequency values, giving some insight into its potential utility as a solid membrane in solid state batteries. The ionic transference number of mobile ions has been estimated by a dc polarisation method, and the results reveal that the conducting species are predominately ions. A solid state magnesium battery was fabricated and characterised.     

锂离子电池聚氨酯型凝胶态聚合物电解质的研究

采用一种自制新型超支化聚醚(PHEMO)与甲苯2,4-二异氰酸酯(MDI)在电解液中进行缩合反应,制备了一种具有交联网状结构的聚氨酯(PEU)型凝胶态聚合物电解质.利用傅立叶红外光谱(FTIR)、示差扫描量热分析(DSC)、热重分析(TGA)、交流阻抗谱等测试方法对聚合物电解质的结构、热稳定性能、离子电导率进行了研究.研究发现:上述制备的PM-1M-Z4聚合物电解质体系室温电导率可达2.53×10-3S/cm,电化学稳定窗口为2.3～4.0V,并且具有较好的热稳定性和优良的机械性能.此外,在这种新型的电解质中,电解液小分子被聚合物大分子包裹在其中,可有效防止凝胶聚合物电解质的漏液问题,从而可提高锂离子电池的安全性能.     

Molecular Design of the Solid Copolymer Electrolyte- Poly(styrene-b-ethylene oxide) for Lithium Ion Batteries

Poly(ethylene oxide) (PEO) is a commonly used electrolytic polymer in lithium ion batteries because of its high viscosity which allows fabricating thin layers. However, its inherent low ionic conductivity must be enhanced by the addition of highly conductive salt additives. Also its weak mechanical strength needs a complementary block, such as poly(styrene) (PS), to strengthen the electrolytic membrane during charging/discharging processes. PS is a strong material to complement the PEO and to create a reinforced copolymer electrolyte termed as the poly(styrene-b-ethylene oxide) (PS-PEO). In this work, molecular dynamics simulations are employed to study the effects of doping the PS constituents into the PEO based copolymer electrolyte. The results reveal that strengthening the mechanical strength increases the intra conjugation forces which penalize the ionic conductivity. Hence both ionic conductivity and mechanical strength of the copolymer have to be compromised. This paper designs the optimized molecular structure through the atomistic analysis instead of try-and-error experiments.     

Antioxidant technology for durability enhancement in polymer electrolyte membranes for fuel cell applications

While polymer electrolyte membrane fuel cells (PEMFCs) have surged in popularity due to their low environmental impact and high efficiency, their susceptibility to degradation by in-situ generated peroxide and oxygen radical species has prevented their widespread adoption. To alleviate chemical attack on components of PEMFCs, particularly on polymer electrolyte membranes (PEMs), antioxidant approaches have been the subject of enormous interest as a key solution because they can directly scavenge and remove detrimental peroxide and oxygen radical species. However, a consequence is that long-term PEMFC device operation can cause undesirable adverse degradation of antioxidant additives provoked by the distinctive chemical/electrochemical environment of low pH, electric potential, water flux, and ion exchange/concentration gradient. Moreover, changes in the physical state such as migration, agglomeration, and dissolution of antioxidants by mechanical or chemical pressures are serious problems that gradually deteriorate antioxidant activity and capacity. This review presents current opportunities for and limitations to antioxidant therapy for durability enhancement in PEMs for electrochemical device applications. We also provide a summary of advanced synthetic design strategies and in-depth analyses of antioxidants regarding optimizing activity-stability factors. This review will bring new insight into the design to realization of ideal antioxidant nanostructures for PEMs and open up new opportunities for enhancing proliferation of durable PEMFCs.     

Ionic conductive polymers as artificial solid electrolyte interphase films in Li metal batteries – A review

Lithium (Li) metal has been considered as the ultimate anode material for next-generation rechargeable batteries due to its ultra-high theoretical specific capacity (3860 mAh g⁻¹) and the lowest reduction voltage (−3.04 V vs the standard hydrogen electrode). However, the dendritic Li formation, uncontrolled interfacial reactions, and huge volume variations lead to unstable solid electrolyte interphase (SEI) layer, low Coulombic efficiency and hence short cycling lifetime. Designing artificial solid electrolyte interphase (artificial SEI) films on the Li metal electrode exhibits great potential to solve the aforementioned problems and enable Li–metal batteries with prolonged lifetime. Polymer materials with good ionic conductivity, superior processability and high flexibility are considered as ideal artificial SEI film materials. In this review, according to the ionic conductive groups, recent advances in polymeric artificial SEI films are summarized to afford a deep understanding of Li ion plating/stripping behavior and present design principles of high-performance artificial SEI films in achieving stable Li metal electrodes. Perspectives regarding to the future research directions of polymeric artificial SEI films for Li–metal electrode are also discussed. The insights and design principles of polymeric artificial SEI films gained in the current review will be definitely useful in achieving the Li–metal batteries with improved energy density, high safety and long cycling lifetime toward next-generation energy storage devices.     

Composite electrolytes of polyethylene glycol methyl ether and TiO2 for dye-sensitized solar cells—Effect of heat treatment

For solid-state dye-sensitized solar cells (DSSCs), a composite electrolyte of polyethylene glycol methyl ether (PEGME) and titania (TiO₂) nanoparticles was prepared and characterized by Fourier transform-infra red (FT-IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and Raman spectroscopy. The heat treatment on PEGME and TiO₂ composite was found to be an essential step to improve morphology, amorphicity and ionic conductivity of PEGME–TiO₂ composite electrolytes. It was attributed to the increased bond strength of OC–O–Ti between PEGME and TiO₂ and increased surface roughness of composite materials, which may help to absorb a large amount of iodide couple and effective generation of I₃⁻ ions. A DSSC fabricated with heat treated PEGME–TiO₂ composite electrolyte showed significantly enhanced overall conversion efficiency of 3.1%, which was 20% higher than that of the DSSC fabricated with bare PEGME–TiO₂ composite electrolyte.     

Measurements of water distribution in through-plane direction of PEFC by using neutron radiography

Fuel gas (hydrogen gas) and oxidant gas (air) are supplied to a polymer electrolyte fuel cell (PEFC). Protons pass through the electrolyte membrane, and combine with oxygen to form water in the cathode reaction site. The generated water must be supplied appropriately to the membrane for proton conduction. On the other hand, the generated water may affect the fuel cell performances because of the blocking of oxygen from reaching the cathode reaction site. Therefore, water management in the PEFC is important, and water distribution during the operation in the through-plane direction has been of wide concern. In order to obtain the water distributions in a membrane electrode assembly (MEA) and a gas diffusion layer (GDL), a borescope system was newly employed using neutron radiography. The system could obtain the water distribution in the MEA and the GDL, and pixel size of 6.5 μm was achieved. Furthermore, the system was applied for a tilted converter system. The pixel of 1.0 μm at an angle of 81° was achieved, and improvement of the spatial resolution was confirmed.     

感光材料用新型抗静电剂──高分子固体电解质型抗静电剂的研究

对聚乙二醇（ＰＥＧ）－碱金属盐（ＭＸ）高分子固体电解质型抗静电剂在感光材料中的应用进行了研究，并考察了ＰＥＧ的分子量、不同碱金属盐、明胶溶液的ＰＨ值和涂层厚度等对抗静电性能的影响。结果表明，ＰＥＧ—ＭＸ体系具有优良的抗静电性能，尤其是在低湿度和真空环境下。