阻燃聚氨酯基固态聚合物电解质的制备与表征

以聚己二酸-1,4-丁二醇酯二醇(PBA)、六亚甲基二异氰酸酯(HDI)和N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯(FCR-6)为主要原料合成阻燃聚氨酯(TPUP),将阻燃聚氨酯与双(三氟甲烷)磺酰亚胺锂(LiTFSI)复合得到一系列锂盐质量分数不同的阻燃聚氨酯基固态聚合物电解质(TPUP10%Li、TPUP20%Li、TPUP25%Li、TPUP30%Li)。采用红外光谱、热重分析、锥形量热、力学测试、电化学窗口、电导率和电池的充放电性能测试等对阻燃聚氨酯基固态聚合物电解质进行了表征和性能测试。结果表明,TPUP具有良好的阻燃性能,制备的阻燃电解质TPUP25%Li综合性能最佳,且拉伸强度达到2.09MPa,80℃时离子电导率为3.09×10–4S/cm,以TPUP25%Li阻燃聚氨酯基固态聚合物电解质组装的全固态锂电池,在80℃时0.2C电流密度下放电容量达到159 mA·h/g。     

荧光聚氨酯固态锂电池电解质的制备及性能

以聚碳酸酯二元醇(PCDL)和六亚甲基二异氰酸酯(HDI)为主要原料,1,4-丁二醇(BDO)和荧光小分子二元醇N,N-二羟乙基苯胺-β-三联吡啶(TPPDA)为扩链剂,制备了一种热塑性荧光聚氨酯,其与双三氟甲烷磺酰亚胺锂(LiTFSI)共混制备了荧光聚氨酯电解质(FPU)。采用傅里叶变换红外光谱仪、荧光光谱仪、拉伸测试仪、同步热分析仪、电化学工作站和电池测试仪对制备的电解质进行了结构、光学性能、力学性能、热稳定性能和电化学性能的测试与分析。结果表明,随着膜内LiTFSI质量分数的增加,荧光强度增大;LiTFSI质量分数为30%制备的荧光聚氨酯电解质膜(FPU-3)拉伸强度达到4.5 MPa,电导率达到1.03×10~(–4) S/cm;采用LiTFSI质量分数为30%的荧光聚氨酯电解质膜与磷酸铁锂正极和锂金属负极组装的全固态电池表现出良好的倍率与循环性能,在80℃、0.2 C和1.0 C倍率下首次放电比容量分别达到164和112 mA·h/g。     

硫化物固态电解质电化学稳定性研究进展

锂离子电池固态化在大幅提高安全性的同时可兼具高能量和高功率密度,在电动车、国防等领域具有重大的应用前景。在实现全固态锂电池的3种固态电解质体系中,硫化物固态电解质由于具有最高的离子电导率、较好的机械延展性以及与电极良好的界面接触等优点,成为最具潜力的技术方向。然而其空气稳定性和电化学稳定性较差,尤其是后者直接限制了其在高能量密度全固态锂电池中的应用。通过从实验及理论计算两方面总结归纳了迄今为止关于硫化物固态电解质电化学稳定性的研究进展,并对现有提升硫化物固态电解质电化学稳定性的实验思路和理论结果进行了总结。     

锂离子电池固态电解质的研究进展

固态锂离子电池具有安全性能高、能量密度大、工作温区广等优点,是锂离子电池领域的研究热点。固体电解质的研究是固态锂离子电池实现应用的先决条件,目前国内外研究较多的有晶态的LISICON结构、钙钛矿结构、石榴石结构电解质和非晶态的氧化物、硫化物、氮氧化物电解质。概述了锂离子电池固态电解质的研究进展,对各种电解质的发现过程、晶体结构、电导率等性能进行了详细的介绍。     

锂离子电池中有机-无机复合固态电解质的研究进展

在新一代储能领域中,相比于传统的有机液态电池,全固态电池具有安全性高、能量密度高和循环寿命长等优势,对其电解质的研究更是关注的重点.有机-无机复合固态电解质结合了无机固态电解质高强度、高稳定性、高离子电导率与聚合物固态电解质的质软、易加工的优势,是目前最有潜力的电解质体系.对锂离子固态电解质的基础进行了简介,并着重对有...     

锂离子电池固态电解质的研究进展

固态锂离子电池具有安全性能高、能量密度大、工作温区广等优点,是锂离子电池领域的研究热点。固体电解质的研究是固态锂离子电池实现应用的先决条件,目前国内外研究较多的有晶态的LISICON结构、钙钛矿结构、石榴石结构电解质和非晶态的氧化物、硫化物、氮氧化物电解质。概述了锂离子电池固态电解质的研究进展,对各种电解质的发现过程、晶体结构、电导率等性能进行了详细的介绍。     

锂电池固态电解质新材料问世

近日,丰田中央研发实验室开发了一种有望用于高功率和高能量的全固态锂离子电池的固体电解质新材料。该材料用于正极为钴酸锂、负极为锂单质的锂离子电池时,具有优异的充放电性能和循环性能。     

锂离子电池用固态电解质的研究现状与展望

目前商业化的锂离子电池多使用有机液态电解质,存在易燃易爆、易泄露等安全风险,而采用固态电解质替代有机液态电解质可以有效提高电池安全性。锂离子电池用固态电解质又可分为无机固态电解质和有机——即聚合物固态电解质。无机固态电解质对高温或其他腐蚀性环境适应性好,适用于在极端工作环境中刚性电池等领域;聚合物固态电解质在柔韧性和可加工性上则优势明显,适用于柔性电池等领域,但这些材料均尚有问题待解决。无机-有机复合的方式,有望综合两种材料的优势,取长补短,提高固态电解质的综合性能和实用价值。     

LLZTO复合PVDF-HFP基高盐聚合物固态电解质的制备及性能研究

本研究以钽掺杂锂镧锆氧(LLZTO)、聚偏氟乙烯-六氟丙烯(PVDF-HFP)及双三氟甲烷磺酰亚胺锂(LiTFSI)等作为原料,使用刮涂法制得一种高盐聚合物固态电解质(LSE)。采用X射线衍射仪(XRD)、交流阻抗谱(EIS)、线性扫描伏安法(LSV)、恒压极化法等手段对高盐聚合物固态电解质进行表征和测试。研究发现,在室温条件下,LLZTO含量为20%(质量分数)的LSE_0.20离子电导率可达到4.5×10^-4 S/cm,锂离子迁移数为0.48,电化学窗口可达到4.65 V。组装为LiFePO₄/LSE_0.20/Li全固态电池后,在室温条件下以0.2C充放电,电池的首次放电比容量为156.85 mAh/g。在50次充放电循环后,该电解质的放电比容量仅下降约3%,高达152.34 mAh/g,容量保持率可达到97%。     

聚合物基镁离子固态电解质的研究进展Q

镁离子电池因其比容量高、资源丰富、环境友好、安全性高(无枝晶)等优势,在储能电池领域脱颖而出.然而,镁金属负极在液态电解质中易钝化,导致其电化学性能不佳.因此,开发高效适用的固态电解质对实现高性能、实用化镁离子电池至关重要.聚合物电解质具有优异的机械稳定性、电化学稳定性、热稳定性且离子电导率高、成本低.但镁离子较高的电荷密度和较强的溶剂化作用限制了其在固态电解质中的解离与扩散.从纯固态聚合物电解质、凝胶聚合物电解质、复合聚合物电解质3个方面综述了国内外聚合物基镁离子固态电解质的离子电导率对解决镁金属负极钝化效应的贡献及其应用研究进展,指出聚合物基镁离子固态电解质当前面临的挑战并对其研究方向进行了建议和展望.     

Conductivity of composite solid polymer electrolyte made of PEO-LiClO4-fiber

The conductivity of composite solid polymer electrolyte (SPE) made of different compositions of poly(ethylene oxide) (PEO), LiClO₄ and fiber was investigated in this study. Results obtained through alternating current (AC) impedance measurements demonstrated that the conductivity of the SPE was much improved by blending fiber into it. Moreover, increasing the composition of fiber added leads, thereby increasing the conductivity of the composite SPE. The average conductivity of the composite SPE was 10⁻⁴ S/cm at 25 °C. Performance in thermal properties was also investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) experiments. Although the mechanical strength of the composite SPE was not better than that of other materials as expected, the fiber added made it more stable.     

Nanocomposite polymer electrolyte based on whisker or microfibrils polyoxyethylene nanocomposites

Nanocomposite polymer electrolytes composed of high molecular weight poly(oxyethylene) PEO as a matrix, LiTFSI as lithium salt and ramie, cotton and sisal whiskers with high aspect ratio and sisal microfibrils (MF), as reinforcing phase were prepared by casting-evaporation. The morphology of the composite electrolytes was investigated by scanning electron microscopy and their thermal behavior (characteristic temperatures, degradation temperature) were investigated by thermogravimetric analysis and differential scanning calorimetry.Nanocomposite electrolytes based on PEO reinforced by whiskers and MF sisal exhibited very high mechanical performance with a storage modulus of 160 MPa at high temperature. A weak decrease of the ionic conductivity was observed with the incorporation of 6 wt% of whiskers. The addition of microfibrils involved a larger decrease of the conductivity. This difference may be associated to the more restricted PEO mobility due to the addition of entangled nanofibers.     

High temperature operation of a composite membrane-based solid polymer electrolyte water electrolyser

The high temperature behaviour of a solid polymer electrolyte (SPE) water electrolyser based on a composite Nafion-SiO₂ membrane was investigated and compared to that of a commercial Nafion membrane. The SPE water electrolyser performance was studied from 80 to 120 °C with an operating pressure varying between 1 and 3 bar abs. IrO₂ and Pt were used as oxygen and hydrogen evolution catalysts, respectively. The assemblies were manufactured by using a catalyst-coated membrane (CCM) technique. The performance was significantly better for the composite Nafion-SiO₂ membrane than commercial Nafion 115. Furthermore, the composite membrane allowed suitable water electrolysis at high temperature under atmospheric pressure. The current densities were 2 and 1.2 A cm⁻² at a terminal voltage of 1.9 V for Nafion-SiO₂ and Nafion 115, respectively, at 100 °C and atmospheric pressure. By increasing the temperature up to 120 °C, the performance of Nafion 115 drastically decreased; whereas, the cell based on Nafion-SiO₂ membrane showed a further increase of performance, especially when the pressure was increased to 3 bar abs (2.1 A cm⁻² at 1.9 V).     

Influences of Bentonite on conductivity of composite solid alkaline polymer electrolyte PVA-Bentonite-KOH-H2O

The influence of the dopant Bentonite, on the ionic conductivity of the PVA-KOH-H₂O alkaline solid polymer electrolyte (ASPE) is studied. The results show that the addition of Bentonite has both positive and negative effects on the ionic conductivity of ASPE. At lower KOH and H₂O contents, the addition of Bentonite can break the continuous ion conducting phase of the ASPE, and therefore decrease the ASPE conductivity. However, the addition of Bentonite can also increase the KOH content in PVA matrix. This greatly increases the conductivity of the ASPE especially at higher water content. A highest ionic conductivity of 0.11 S cm⁻¹ is reached at room temperature. A maximum ionic conductivity value is observed at relative lower water content for different amount of Bentonite-doped ASPE. The temperature dependence of the ionic conductivity is of the Arrhenius type. The ion transfer activation energy Ea, in the order of 4-6 kJ mol⁻¹, heavily depends on the Bentonite content. XRD and SEM tests show that PVA in the Bentonite-doped ASPE is of amorphous structure, and there are lots of interspaces in the composite ASPE inner structure. The composite electrolyte has good electrochemical stability window and good charged-discharge property in secondary Zn-Ni cells at low charge-discharge rate.     

全固态聚合物电解质的性能研究

聚合物电解质由于本身的优点,已成为锂离子电池研究的一个热点.聚合物电解质由聚合物、锂盐及添加剂组成,本文综述了聚合物电解质研究的新体系,论述了聚合物电解质中各组分对其性能的影响.     

Electrochemical lean-deNOx catalyst using H-conducting solid polymer electrolyte

The reduction of NO to N₂/N₂O in the presence of excess O₂ has been successfully achieved at 70 °C using an electrochemical cell of the type, 0.1% NO, 0–10% O₂, Pt | NAFION | Pt, H₂O. An H⁺-conducting solid polymer electrolyte (SPE) plays a key role in evolving hydrogen on the Pt cathode, where the catalytic NO–H₂ takes place. It was revealed that the competitive H₂–O₂ reaction is suppressed because the Pt surface was covered with stable nitrate (NO₃) species, which blocks oxygen adsorption hereon. The inhibition of H₂–O₂ reaction becomes most efficient at 100 °C in agreement with the optimal operation temperature range of SPE. The reduction efficiency of NO in an excess O₂ could be improved by packing 1 wt% Pt/ZSM-5 catalyst in the cathode room. The combination between the SPE cell and Pt catalysts can broadly be applied to novel low-temperature deNO_x processes in a strongly oxidizing atmosphere.     

阻燃聚氨酯基固态聚合物电解的制备

摘要：以聚己二酸-1,4-丁二醇酯二醇( PBA) 、六亚甲基二异氰酸酯( HDI)和阻燃剂N，N阻双（2（羟乙基）胺基亚甲基磷酸二乙酯( FCR-6）为主要原料合成阻燃聚氨酯（TPUP），将阻燃聚氨酯与锂盐复合得到阻燃聚氨酯基固态聚合物电解质。采用红外光谱、热重分析、锥形量热、力学测试、电化学窗口、电导率和电池的充放电性能测试等对阻燃聚氨酯基固态聚合物电解质进行了表征和性能测试。研究表明，TPUP具有良好阻燃性能，制备的阻燃电解质TPUP25%Li综合性能最佳，且拉伸强度达到2.09MPa，80℃时离子电导率为3.09M10-4 S/cm，以阻燃电解质组装的全固态锂电池，在80℃时0.2C电流密度下放电容量达到159mA?h/g。     

New solid polymer electrolyte composites for water electrolysis

A new procedure for the preparation of SPE-electrocatalyst composites has been developed. In this procedure, noble metal cationic species are chemically reduced within a solid polymer electrolyte. The metallic particles are not homogeneously distributed across the SPE thickness but predominate near its surfaces. The structure and the distribution of the precipitates, along the membrane thickness have been investigated by scanning electron microprobe analysis and transmission electron microscopy. Application to SPE water electrolysis has been performed using Nafion membranes and platinum-group electrocatalysts. The SPE-electrocatalyst composites prepared according to this new procedure present good electrochemical properties, low catalyst loadings, long-time stability and high energetic efficiencies.     

固体聚合物电解质膜臭氧生成技术

本文对固体聚合物电解质膜生成臭氧技术进行了介绍。该技术具有装置小型化、臭氧浓度高、电流效率大等特点。由于该技术的核心部件三合一膜电极(MEA)成本较高,电催化剂效率低,本文介绍了一些改进膜电极结构的措施以提高电极性能。     

Ionic conductivity of a novel solid polymer electrolyte

A novel kind of solid polymer electrolyte, the solvation unit of which is O?CNHR, has been studied. The effects of host polymer structure, ion species, salt concentration, and plasticizers on ionic conductivity are discussed in detail. The solvability of host polymers is a very important factor that affects the ionic conductivity of electrolytes and is fully decided by the structure of solvation units and their density in polymer chain. The latter two rest with monomers structure and copolymerization ratio. Effects of alkali metal salts and divalent metal salts on ionic conductivity are different because of their different leading factor of cation radius. Salt concentration dependence of ionic conductivity appears as a double‐peak shape when alkali metal salts are added because of the total contribution of two kinds of ionic conductance modes, and appears as similar shapes when divalent metal salts are added. Different influences of plasticizers on ionic conductivity result from their different action ways. Ethylene glycol acts well because of its effective action from three different modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2176–2184, 2001