含离子液体的凝胶聚合物电解质的导电行为研究

以聚偏氟乙烯-六氟丙烯(PVDF-HFP)为聚合物基体,制备了含离子液体1-甲基-3-乙基咪唑六氟磷酸盐(EMIPF_6)和1-甲基-3-乙基咪唑二(三氟甲基磺酰)亚胺盐(EMITFSI)的凝胶聚合物电解质,测试了电解质的电导率和阳离子迁移数,并基于自由体积理论的观点对电解质的导电行为进行了研究。结果表明,EMIPF_6-PVDF-HFP与EMITFSI-PVDF-HFP两种离子液体凝胶聚合物电解质,聚合物的分子链段运动对导电离子的迁移影响微小;logσ与1/T呈线性关系,上述两种电解质的导电行为服从阿伦尼乌斯方程,电解质的电导率主要靠自由离子的迁移;离子液体EMIPF_6、EMITFSI的加入促进了Li⁺的自由移动,显著提高了电解质的锂离子电导率。     

DDBA改性纤维对PEO聚合物电解质性能的影响

针对聚环氧乙烷(PEO)基聚合物电解质室温易结晶的问题，将4-4-二羟基-α,α’-二甲基卞联氮(DDBA)改性芳纶纤维(DF)掺杂在基体中，抑制PEO结晶，提高其离子电导率。通过交流阻抗、差式扫描量热等方法进行表征。结果表明：制备的聚合物电解质在少量DF掺杂时离子电导率有所改善，其中掺杂质量分数2.0%DF的电解质电化学性能最好，在25℃下电导率达到1.5×10^-5 S/cm，离子迁移数提高至0.30。     

LLZO基夹层混合固态电解质的制备及性能研究

采用旋涂法在Li₇La₃Zr₂O₁₂(LLZO)基体上涂覆PVDF基聚合物膜，制备得到LLZO基夹层混合固态电解质，以改善LLZO与锂金属负极之间接触性差的问题。通过控制不同的旋涂转速，获得了表面光滑平整、无褶皱的聚合物膜；并从PVDF电解质溶液中双三氟甲基磺酰亚胺锂(LiTFSI)含量、夹层混合固态电解质放置时间及温度3个方面研究其对夹层混合固态电解质离子电导率的影响。结果表明：当m(PVDF)∶m(LiTFSI)=4∶1时，夹层混合固态电解质离子电导率为4.40×10^-5S/cm；室温下放置20 d后，离子电导率减小至1.70×10^-5S/cm，且离子电导率随温度的升高而增大，90℃时为7.07×10^-5S/cm。     

Li+电池固态聚合物电解质研究进展

固态聚合物电解质具有高安全性、高成膜性和黏弹性等优点,并与电极具有良好的接触性和相容性,是实现高安全性和高能量密度固态Li⁺电池的重要电解质体系。然而聚合物电解质室温离子电导率较低（10^-8~10^-6 S·cm^-1）,不能满足固态聚合物电池在常温运行的需求。因此,在提高离子电导率、机械强度和电化学稳定性等本征属性的基础上,同时探究改善电解质/电极的界面处及电极内部的离子输运是研发固态聚合物Li⁺电池面临的关键问题。主要从改性聚合物电解质用以提高Li⁺电池电化学性能的角度出发,综述了凝胶聚合物电解质、全固态聚合物电解质和复合固态电解质中的离子输运机制及其关键参数,总结了近年来聚合物电解质的最新研究进展和未来的发展方向。     

LCI-PEO/PLA固态聚合物电解质电导率的研究

针对聚氧化乙烯(PEO)聚合物电解质室温电导率较低的问题,设计掺杂液晶离聚物(LCI)改善PEO/PLA共混相结构以提高聚合物室温电导率。通过差示扫描量热分析、偏光显微镜技术、扫描电子显微镜技术、电化学阻抗测试等对其进行表征。结果表明:制备的固态聚合物电解质在较低的LCI掺杂下显示出显著的电导率改善。掺杂1.0wt.%LCI在17℃下电导率达到3.58×10~(-5) S/cm,相比于PEO电解质电导率提高了三个数量级。     

PEO基聚合物复合电解质的制备及性能研究

将不同含量的单宁酸加入到聚环氧乙烷(PEO)和双三氟甲磺酰胺亚胺锂(Li TFSI)体系中,采用流延法来制备聚合物电解质膜。在氢键的作用下破坏PEO的结晶度来提高聚合物电解质的离子电导率。通过X射线衍射、差示扫描量热仪、热重分析仪、力学性能、表面形貌以及交流阻抗法等对聚合物电解质膜进行表征。结果表明,随着单宁酸(TA)含量的增加,结晶度下降,断裂伸长率提高,最高达到了675%,热力学性能也有很大的改善。室温下,当单宁酸含量为1%时,拉伸强度达到0.22 MPa,离子电导率最大达到了3.4×10-5S/cm。     

一种双离子梳状聚合物电解质的合成与性能研究

以端基含有烯丙基侧链含有氯甲基的不饱和聚醚 (UPEO)与苯乙烯 (St)共聚 ,得到以聚烯烃为主链、PEO为侧链、侧链挂载氯甲基的梳状聚合物 (CPPC) ,CPPC与亚硫酸锂反应 ,合成了一种新型单离子梳状聚合物电解质 (CPPL)。研究发现该梳状聚合物电解质的玻璃化温度 (θg)取决于苯乙烯的配比和磺化反应效率。对比研究了CPPL和CPPL复合LiClO4而成的双离子梳状聚合物电解质(CPPL2 )的θg、热稳定性、电化学窗口和电导率。测定结果表明 :CPPL和CPPL2的室温电导率分别为1.3× 10 -4s/cm和 7.8× 10 -4s/cm。     

新型聚合物固体电解质的导电性研究

采用溶液浇铸法制得以偏二氟乙烯与六氟丙烯共聚物P(VdF-HFP)为基质的聚合物固体电解质,并测定了该类电解质的电导率。讨论了锂盐浓度、增塑剂配比、纳米SiO2粉末掺入以及温度对膜的离子电导率的影响;结果表明:以P(VdF-HFP)为基质的电解质的室温电导率最高达到2.81×10-3S·cm-1。利用红外分析对聚合物固体电解质的导电性进行分析,探讨了聚合物固体电解质膜的各组分间相互作用的规律。     

BMIMBF_4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质的合成与性能

以甲基丙烯酸甲酯(MMA)和1-乙烯基-3-丁基咪唑溴盐(VBIMBr)为单体,通过自由基溶液聚合制备了无规共聚物聚(甲基丙烯酸甲酯-1-乙烯基-3-丁基咪唑溴盐)[P(MMA-VBIMBr)],并以此聚合物为基体,离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)为增塑剂,制备了BMIMBF4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质,采用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、热重分析(TG)和电化学交流阻抗(EIS)等方法对聚合物和聚合物电解质的性质进行了研究。结果表明,聚合物电解质膜具有优良的热稳定性和机械强度;当BMIMBF4/P(MMA-VBIMBr)质量配比为2时,离子电导率高达2.77×10-3S/cm(20℃),且离子电导率随着温度的升高而迅速增加,电导率-温度曲线符合Arrhenius方程。     

安全固态锂电池室温聚合物基电解质的研究进展

目前,大多数聚合物固态电解质在室温下离子电导率较低,约为10^–8 ~10^-6 S /cm,且对温度存在着较大的依赖性,仍无法满足高性能室温固态锂电池的实际应用需要。基于此,本文先介绍了室温聚合物电解质在锂离子电池中应用的主要研究进展及其优缺点。然后,从物理调控、化学调控等多角度重点阐述了室温聚合物电解质（包括全固态聚合物电解质、准固态聚合物电解质）的制备工艺、优化与改性方法、作用机理等在电池中应用的主要研究进展和现状。最后,对锂离子电池用室温聚合物电解质存在的挑战和未来可能发展趋势进行了展望。     

聚氧化乙烯-蒙脱土复合聚合物电解质室温电导率的研究

采用溶液浇铸法对蒙脱土与聚氧乙烯、LiClO4进行复合制备了聚合物电解质膜。用X射线衍射对蒙脱土及电解质膜进行了结构表征。采用交流阻抗法对复合型电解质膜的离子电导率进行了测试。结果表明：一定量的蒙脱土可以使（PEO）16LiClO4的离子电导率提高几倍。蒙脱土对基体离子电导率提高程度的不同取决于蒙脱土的含量。     

聚氧乙烯-改性蒙脱石复合材料电性能的研究

用离子交换法对蒙脱石进行有机及无机改性制备了3种改性蒙脱石。采用溶液浇铸法分别对3种改性蒙脱石与聚氧乙烯、LiClO4进行复合制备了聚合物电解质膜。用X射线衍射对改性前后的蒙脱石及部分电解质膜进行了结构表征。采用交流阻抗法对复合型电解质膜的离子电导率进行了测试。结果表明：一定量的改性蒙脱石可以使（PEO）16LiClO4的离子电导率提高几倍到几十倍。改性蒙脱石对基体离子电导率提高程度的不同取决于改性蒙脱石的含量和结构。     

增塑剂PC掺杂（PEO）_8-LiClO_4-SiO_2电解质体系的性能研究

以增塑剂碳酸丙烯酯（PC）作为掺杂物,混于（PEO）8-LiClO4-SiO2固体电解质体系中。得到厚度约为350μm性能良好的聚合物电解质薄膜,利用交流阻抗法测定聚合物电解质的电导率,通过XRD对聚合物电解质薄膜的物相结构进行分析研究。结果表明掺杂后（PEO）8-LiClO4-SiO2-PC固体电解质的室温电导率较（PEO）8-LiClO4-SiO2体系有了进一步提高,在PC质量分数为40%时最高,达到3.083×10-6 S.cm-1;电导率与温度关系遵循Arrhenius方程。温度的升高有利于电导率的提升,在80℃时体系的离子电导率为1.180×10-5 S.cm-1。XRD分析表明,加入PC后PEO的结晶度进一步减小,体系不定形相增加,有利于离子电导率的提高。     

Effect of additives in PEO/PAA/PMAA composite solid polymer electrolytes on the ionic conductivity and Li ion battery performance

Polyethylene oxide (PEO) based-solid polymer electrolytes were prepared with low weight polymers bearing carboxylic acid groups added onto the polymer backbone, and the variation of the conductivity and performance of the resulting Li ion battery system was examined. The composite solid polymer electrolytes (CSPEs) were composed of PEO, LiClO_4, PAA (polyacrylic acid), PMAA (polymethacrylic acid), and Al₂O₃. The addition of additives to the PEO matrix enhanced the ionic conductivities of the electrolyte. The composite electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 exhibited a low polarization resistance of 881.5 ohms in its impedance spectra, while the PEO:LiClO₄ film showed a high value of 4,592 ohms. The highest ionic conductivity of 9.87 × 10⁻⁴ S cm⁻¹ was attained for the electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 at 20 °C. The cyclic voltammogram of Li⁺ recorded for the cell consisting of the PEO:LiClO₄:PAA/PMAA/Li_0.3:Al₂O₃ composite electrolyte exhibited the same diffusion process as that obtained with an ultra-microelectrode. Based on this electrolyte, the applicability of the solid polymer electrolytes to lithium batteries was examined for an Li/SPE/LiNi_0.5Co_0.5O₂ cell.     

SiO_2掺杂（PEO）_8-LiClO_4固体电解质的性能研究

通过正硅酸乙酯水解得到的SiO2溶胶,掺杂于（PEO）8-LiClO4固体电解质体系中。得到厚度约为130μm性能良好的聚合物电解质薄膜,利用交流阻抗法测定聚合物电解质的电导率,通过红外光谱对聚合物电解质薄膜的基团状态进行分析研究。结果表明掺杂SiO2后（PEO）8-LiClO4固体电解质的室温电导率有很大提高,在SiO2质量分数为10%时最高,达到2.522×10-6S/cm;温度的升高有利于电导率的提升,电导率与温度关系遵循Arrhenius方程,在lgσ-1000/T曲线上以为PEO的熔点为转折点,体现为两条斜率不同的直线,在80℃时体系的离子电导率为6.852×10-6 S/cm。红外光谱、XRD分析表明,加入SiO2后PEO的结晶度降低,体系不定形相增加,有利于离子电导率的提高。对该电解质薄膜进行了透光率测定,表明各组分下该薄膜透光率基本保持在96%以上,确定了将其应用于电致变色器件的可能性。     

Fabrication and characterization of PEO/PPC polymer electrolyte for lithium‐ion battery

A new poly(propylene carbonate)/poly(ethylene oxide) (PEO/PPC) polymer electrolytes (PEs) have been developed by solution‐casting technique using biodegradable PPC and PEO. The morphology, structure, and thermal properties of the PEO/PPC polymer electrolytes were investigated by scanning electron microscopy, X‐ray diffraction, and differential scanning calorimetry methods. The ionic conductivity and the electrochemical stability window of the PEO/PPC polymer electrolytes were also measured. The results showed that the T_g and the crystallinity of PEO decrease, and consequently, the ionic conductivity increases because of the addition of amorphous PPC. The PEO/50%PPC/10%LiClO₄ polymer electrolyte possesses good properties such as 6.83 × 10^?5 S cm^?1 of ionic conductivity at room temperature and 4.5 V of the electrochemical stability window. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigations on the enhancement mechanism of inorganic filler on ionic conductivity of PEO-based composite polymer electrolyte: The case of molecular sieves

Polarized optical microscopy (POM) and differential scanning calorimeter (DSC) techniques are used to study the effect of ZSM-5 molecular sieves on the crystallization mechanism of poly(ethylene oxide) (PEO) in composite polymer electrolyte. POM results show that ZSM-5 has great influence on both the nucleation stage and the growth stage of PEO spherulites. ZSM-5 particles can act as the nucleus of PEO spherulites and thus increase the amount of PEO spherulites. POM and DSC results show that ZSM-5 can restrain the recrystallize tendency of PEO chains through Lewis acid-base interactions and hence decrease the growth speed of PEO spherulites. Room temperature ionic conductivity of PEO-LiClO₄-based polymer electrolyte can be enhanced by more than two magnitudes during long time storage with the addition of ZSM-5.     

PEO在聚合物锂离子电池中的应用

聚氧化乙烯（PEO）可与锂盐形成具有离子导电性的络合物,但PEO的高结晶性使其与锂盐构成的固体电解质在室温下电导率很低,不能满足实际应用要求,因此需对PEO基固体电解质进行改性。简介PEO的特点和离子传导机理,重点介绍提高PEO基固体电解质室温导电性能目前所采取的措施,包括形成共聚物、生成交联聚合物、掺杂复合物盐、加入增塑剂、加入无机填料和制备侧链含PEO链段高聚物。     

Effects of polymer matrix and salt concentration on the ionic conductivity of plasticized polymer electrolytes

Two polar polymers with different dielectric constants, poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO), were each blended with a chlorine-terminated poly(ethylene ether) (PEC) and one of the two salts, LiBF₄ and LiCF₃CO₂, to form PEC plasticized polymer electrolytes. The room-temperature ionic conductivity of the PEC plasticized polymer electrolytes reached a value as high as 10^?4 S/cm. The room-temperature ionic conductivity of the PVDF-based polymer electrolytes displayed a stronger dependence on the PEC content than did the PEO-based polymer electrolytes. In PVDF/PEC/LiBF₄ polymer electrolytes, the dynamic ionic conductivity was less dependent on temperature and more dependent on the PEC content than it was in PEO/PEC/LiBF₄ polymer electrolytes. The highly plasticized PVDF-based polymer electrolyte film with a PEC content greater than CF4 (CF4 defined as the molar ratio of the repeat units of PEC to those of PVDF equal to 4) was self-supported and nonsticky, while the corresponding PEO-based polymer electrolyte film was sticky. In these highly plasticized PVDF-based polymer electrolytes, the curves of the room-temperature ionic conductivity vs. the salt concentration were convex because the number of carrier ions and the chain rigidity both increased with increase of the salt content. The maximum ionic conductivity at 30°C was independent of the PEC content, but it depended on the anion species of the lithium salts in these highly plasticized polymer electrolytes. © 1995 John Wiley & Sons, Inc.     

Study of poly(organic palygorskite-methyl methacrylate)/poly(ethylene oxide) blended gel polymer electrolyte for lithium-ion batteries

In this study, the composite polymer was prepared by blending poly(ethylene oxide) (PEO) and POPM (the copolymer of methyl methacrylate [MMA] and organically modified palygorskite), and then the composite polymer based membrane was obtained by phase-inversion method. The scanning electron microscopy results showed that the composite polymer membrane has a three-dimensional network structure. X-ray diffraction results indicated that the crystalline region of PEO is disappeared when introduction of a certain amount of the PEO. Meanwhile, the elongation of composite polymer membrane increased when increasing PEO concentration, but the value of tensile strength of PEO-POPM membrane decreased. When the mass fraction of PEO was 24%, the porosity and maximum value of ionic conductivity of the composite polymer membrane were 54% and 2.41 mS/cm, respectively. The electrochemical stability window of Li/gel composite polymer electrolyte/stainless steel batteries was close to 5.3 V (vs. Li⁺/Li), and the battery of Li/gel composite polymer electrolyte/LiFePO₄ showed good cycling performance and the discharge capacity of the battery were between 169.8 and 155 mAh/g. Meanwhile, the Coulombic efficiency of the battery maintained over 95% during the 80 cycles.