锂电池用PEO基固态聚合物电解质研究进展及应用

介绍了锂电池用聚氧化乙烯(PEO)基固态聚合物电解质的研究进展,论述了国内外在PEO改性、锂盐改进和制备PEO-无机复合聚合物电解质等三方面在提高其电导率、电化学稳定窗口和离子迁移数等性能进行的研究,综述了PEO基聚合物电解质的应用情况.     

碳量子点/聚环氧乙烷固态电解质的制备

针对聚氧化乙烷(PEO)基固态电解质室温电导率较低的问题，通过在PEO中掺杂碳量子点(CQDs)作为填料，制备出不同CQDs含量的PEO基固态电解质，通过差示扫描量热分析技术、X射线衍射技术、扫描电子显微镜(SEM)技术等对其进行表征。结果表明：与PEO基固态电解质相比，掺杂CQDs的PEO基固态电解质的结晶度有明显的下降趋势；通过电化学阻抗测试(EIS)得出，PEO-LITFSI-5%CQDs固态电解质在室温下的离子电导率为2.01×10^-5 S/cm,与PEO-LiTFSI-0%CQDs室温下的离子电导率相比，有明显的提升。     

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。     

新能源汽车固态电池中的锂枝晶抑制研究

相比于商业化的锂离子电池,固态电池具有更高的能量密度和更好的安全性。然而,固体电解质依旧面临锂枝晶生长的问题。以目前已大规模工业化的聚氧化乙烯(PEO)基电解质作为研究对象,通过将PEO与高杨氏模量的石榴石型电解质复合,抑制了锂枝晶在PEO基复合电解质中的生长,不仅使电解质膜的离子电导率从9.8×10-6S/cm增加到了3.8×10-4S/cm,还使锂/锂对称电池的临界电流密度从0.4 m A/cm²提高到1.6 mA/cm²。与此同时,组装的基于金属锂负极与传统石墨负极的软包电池可分别获得334.5 W·h/kg与218.2 W·h/kg的能量密度。其中,钴酸锂/复合电解质/石墨软包全电池循环1 000次后的容量保持率可达92.3%,能够满足新能源汽车的需求。     

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。     

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。     

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。     

固体聚合物电解质

本文介绍了固体聚合物电解质在全固体电池方面的应用及其发展,叙述了新型固体聚合物电解质——亚甲氧基连接的聚氧化乙烯的研究工作。和聚氧化乙烯-盐电解质相比,亚甲氧基连接的聚氧化乙烯经氟甲基磺酸锂掺杂后的电导率在室温下提高3个数量级。     

新型硼酸锂盐电解质在三元正极中的应用

在高能量密度的锂电池中,电解质起着重要的作用,不仅影响功率和循环性能,还影响容量和安全性。寻找新型锂盐对于高性能的锂金属电池是非常有必要的。硼是一种独特的元素。硼酸锂盐由于其独特的性质,如出色的热稳定性,良好的离子电导率,成本效益,环境友好性和良好的固体电解质界面(SEI)形成性,从而引起了广泛的关注。本文尝试了硼中心锂盐Li TFPFB搭配EC/DMC溶剂时,在高镍正极中的电化学性能。实验发现该硼中心锂盐电解质具有优异的电化学性能。     

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。     

Studies of dielectric relaxation and a.c. conductivity in [(100−<Emphasis Type="Italic">x</Emphasis>)PEO + <Emphasis Type="Italic">x</Emphasis>NH<Subscript>4</Subscript>SCN]: Al-Zn ferrite nano composite polymer electrolyte

Present work deals with findings on dielectric behaviour and a.c. conduction in a ferrite doped polymer nano composite electrolyte system, namely [(100−x) PEO + xNH₄SCN]: ferrite. The formation of nano composite and structural behavior of electrolyte was studied by XRD and SEM images. The effect of salt and ferrite on conductivity behaviour of PEO based nano composite polymer electrolyte has been investigated by the impedance spectroscopy at room temperature. The variation of dielectric permittivity and dielectric loss with frequency was carried out at ambient temperature. The a.c. conductivity seems to follow the universal power law.     

Structural and dielectric studies of amorphous and semicrystalline polymers blend‐based nanocomposite electrolytes

The solid polymeric nanocomposite electrolyte (SPNE) films based on the blend of amorphous poly(methyl methacrylate) (PMMA) and semicrystalline poly(ethylene oxide) (PEO) (PMMA:PEO = 80:20 wt %) doped with lithium perchlorate (LiClO₄) salt and montmorillonite (MMT) clay nanofiller were prepared by classical solution cast, ultrasonic assisted solution cast and ultrasonication along with microwave irradiated solution cast followed by melt‐pressing methods. The X‐ray diffraction study of these electrolytes revealed the amorphous behavior with intercalated MMT structures. The suppressed crystallinity of PEO in the blend electrolyte complexes confirmed the existence of single discrete PEO chains confined within the PMMA domains. The dielectric relaxation spectroscopy of these materials was performed over the frequency range 20 Hz to 1 MHz, at ambient temperature. The presence of a singular relaxation peak in the loss tangent and electric modulus spectra of these electrolytes confirms a coupled cooperative chain segmental dynamics of the blend polymer owing to their miscible amorphous morphology. The behavior of transient complexes formed between the polymers functional groups, lithium cations and the intercalated MMT nanoplatelets was explored. The ambient temperature ionic conductivity of these electrolytes depends on the structural dynamics and the sample preparation methods. It is revealed that the presence of PEO in the PMMA matrix mainly governs the structural, dielectric, and ionic properties of these SPNE films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41311.     

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。     

New solid polymer electrolytes based on PEO/PAN hybrids

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO₄ were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO₄‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO₄‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N₂, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006     

Suppression of crystallization in a plastic crystal electrolyte (SN/LiClO4) by a polymeric additive (polyethylene oxide) for battery applications

A basic problem with many promising solid electrolyte materials for battery applications is that crystallization in these materials at room temperature makes ionic mobilities plummet, thus compromising battery function. In the present work, we consider the use of a polymer additive (polyethylene oxide, PEO) to inhibit the crystallization of a promising battery electrolyte material, the organic crystal forming molecule succinonitrile (SN) mixed with a salt (LiClO₄). While SN spherulite formation still occurs at low PEO concentrations, the SN spherulites become progressively irregular and smaller with an increasing PEO concentration until a ‘critical’ PEO concentration (20% molar fraction PEO) is reached where SN crystallization is no longer observable by optical microscopy at room temperature. Increasing the PEO concentration further to 70% (molar fraction PEO) leads to a high PEO concentration regime where PEO spherulites become readily apparent by optical microscopy. Additional diffraction and thermodynamic measurements establish the predominantly amorphous nature of our electrolyte-polymer mixtures at intermediate PEO concentrations (20-60% molar fraction PEO) and electrical conductivity measurements confirm that these complex mixtures exhibit the phenomenology of glass-forming liquids. Importantly, the intermediate PEO concentration electrolyte-polymer mixtures retain a relatively high conductivity at room temperature in comparison to the semicrystalline materials that are obtained at low and high PEO concentrations. We have thus demonstrated an effective strategy for creating highly conductive and stable conductive polymer-electrolyte materials at room temperature that are promising for battery applications.     

Effect of grafting degree and side PEO chain length on the ionic conductivities of NBR-g-PEO based polymer electrolytes

Comb-shaped graft polymers were synthesized and complexed with a LiCF₃SO₃ salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid ⁷Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.     

Ionic conductivities of solid polymer electrolyte/salt systems for lithium secondary battery

We establish a new ionic conductivity model based on the Nernst-Einstein equation in which the diffusion coefficient is derived from modified double lattice-nonrandom-Pitzer-Debye-Hückel (MDL-NR-PDH) model. The proposed model takes into account the mobility of the salt and the motion of the polymer host simultaneously by expressing the effective chemical potential as the sum of chemical potentials of the salt and the polymer. To describe the segmental motion of the polymer chain, which is the well-known conduction mechanism for solid polymer electrolyte (SPE) systems, the effective co-ordinated unit parameter is introduced. The obtained co-ordinated unit parameter for each state is used to describe the behavior of the ionic conductivities of the given systems. Good agreement is obtained upon comparison with experimental data of various PEO and salt systems in the interested ranges.     

全固态锂离子电池的研究进展与挑战

全固态锂离子电池具有安全性高、电化学性能优异等优点,但存在电极与电解质界面相容性差、室温离子电导率低等问题。本文总结了以上问题产生的原因及解决方案。对于正极界面,可复合正极材料与固态电解质、构造三维多孔结构固态电解质或在界面处引入缓冲层。对于负极界面,可设计界面层、原位聚合生成固态电解质、构造固态电解质骨架或使用自愈合和弹性固态电解质。对于固态电解质自身,以聚氧化乙烯（PEO）固态聚合物电解质为例,可添加增塑剂、无机陶瓷填料或构造聚合物共混物与嵌段共聚物。最后,对今后的研究方向提出了建议：应注重优化电极/固态电解质界面层;探索锂离子传输机理;构建具有高离子电导率的固态电解质等。