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。     

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。     

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。     

PVDF/PEO/PS交联复合型凝胶聚合物电解质薄膜的制备及性能测试

采用相反转法和聚苯乙烯原位交联制备了一系列聚偏氟乙烯(PVDF)、聚氧化乙烯(PEO)和聚苯乙烯(PS)交联复合型凝胶聚合物电解质薄膜,测定了它们的孔隙率、吸液率、离子电导率等性能,并通过扫描电镜对其形貌进行了分析。结果表明,PVDF-30%(PEO/PS)薄膜中当PS含量达到PEO/PS总含量的25%时薄膜具有较高的孔隙率、吸液率和电导率,孔隙率达到67.4%,吸液率高达184.3%,离子电导率为4.4×10~(-3)S/cm。     

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。     

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。     

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。     

固态纳米复合聚合物电解质的离子导电性能研究

以PEO为基质,复配少量纳米无机填料及低分子乙氧化物,制备出了新型的固态纳米复合聚合物电解质膜,利用交流阻抗法测试了聚合物电解质的离子电导率,对离子导电性能进行了研究。采用CPE元件的模拟电路具有很好的适用性。结果表明当低分子乙氧化物的加入量超过80％时电解质膜的电导率大幅提高,并且PEGDME优于PEG300。电导率在LiPF6加量在O：Li为8：1时达到最大,随着LiClO4加量的增加持续增加,随无机盐加量增加电解质膜的成膜性能变差。用多微孔高比表面的纳米SiO2粒子复合有利于改善聚合物的电导率。聚合物电解质离子电导率对温度的依赖关系符合Arrhenius方程。     

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^-6 S/cm增加到了3.8×10^-4 S/cm,还使锂/锂对称电池的临界电流密度从0.4 mA/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。     

基于复合固体聚合物电解质的固态钠电池

将钠离子导体Na-β’’-Al_2O_3作为活性填料引入聚氧化乙烯(PEO)/双(三氟甲基磺酰)亚胺钠(NaTFSI)固体聚合物电解质(SPE)中,得到有机–无机复合固体聚合物电解质(CPE)。对SPE及CPE的相结构、相转变、离子电导率、离子迁移数及电化学稳定性等基础理化性质进行了表征分析,对两者在固态钠电池Na_3V_2(PO_4)_3@C||Na中的电化学性能进行了测试。结果表明:Na-β’’-Al_2O_3的引入,有效提升了钠离子迁移数(SPE为0.19,CPE为0.71)和钠离子电导率(80℃时,SPE为1.65×10~(–4) S/cm,CPE为8.19×10~(–4) S/cm)。基于CPE的固态钠电池表现出更加优异的循环稳定性,0.5 C循环100周后容量保持率为93.9%,2.0 C循环500周后容量保持率为74.0%。     

Effect of nano‐TiO2 dispersion on PEO polymer electrolyte property

Polymer electrolyte membranes based on poly(ethylene oxide) (PEO) doped with TiO₂ nanoparticles were synthesized by simple solution cast technique. Mesoporous TiO₂ film was prepared by doctor‐blade method. The modified polymer membranes and the mesoporous films were characterized by SEM, TEM, AFM, ionic conductivity, and J‐V measurements. Dye‐sensitized solar cells (DSSC) have been fabricated in which PEO‐polymer electrolyte doped with and without nano‐TiO₂ were sandwiched between porous TiO₂ and counter electrodes. The DSSC with nano‐TiO₂ doped polymer electrolyte shows better performance (1.68%) in comparison with pristine polymer electrolyte (1.07%), which is due to improved ionic conductivity value in polymer electrolyte system by nano‐TiO₂ doping. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Morphology and electrochemical and mechanical properties of polyethylene‐oxide‐based nanofibrous electrolytes applicable in lithium ion batteries

We report the synthesis of all‐solid‐state polymeric electrolytes based on electrospun nanofibers. These nanofibers are composed of polyethylene oxide (PEO) as the matrix, lithium perchlorate (LiClO₄) as the lithium salt and propylene carbonate (PC) as the plasticizer. The effects of the PEO, LiClO₄ and PC ratios on the morphological, mechanical and electrochemical characteristics were investigated using the response surface method (RSM) and analysis of variance test. The prepared nanofibrous electrolytes were characterized using SEM, Fourier transform infrared, XRD and DSC analyses. Conductivity measurements and tensile tests were conducted on the prepared electrolytes. The results show that the average diameter of the nanofibers decreased on reduction of the PEO concentration and addition of PC and LiClO₄. Fourier transport infrared analysis confirmed the complexation between PEO and the additives. The highest conductivity was 0.05 mS cm^?1 at room temperature for the nanofibrous electrolyte with the lowest PEO concentration and the highest ratio of LiClO₄. The optimum nanofibrous electrolyte showed stable cycling over 30 cycles. The conductivity of a polymer film electrolyte was 29 times lower than that of the prepared nanofibrous electrolyte with similar chemical composition. Furthermore, significant fading in mechanical properties was observed on addition of the PC plasticizer. The results obtained imply that further optimization might lead to practical uses of nanofibrous electrolytes in lithium ion batteries. © 2019 Society of Chemical Industry     

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.     

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.     

Study of a new polymer electrolyte poly(ethylene oxide): NaClO3 with several plasticizers for battery application

Sodium ion conducting thin film polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with NaClO₃ were prepared by a solution‐casting method. Characterization by XRD, IR spectroscopy and AC conductivity has been carried out on these thin film electrolytes to analyse their properties. The conductivity studies show that the conductivity value of PEO:NaClO₃ complex increases with the increase in salt concentrations. Increase in conductivity was found in the electrolyte system by the addition of low molecular weight polymer poly(ethylene glycol) (PEG) and the organic solvents dimethylformamide (DMF) and propylene carbonate (PC). Using these electrolyte systems, cell parameters were measured from the discharge study with the application of load 100 kΩ at room temperature with common cell configuration Na|electrolyte|C:I₂:electrolyte. The open circuit voltage (OCV) ranges from 2.81 to 3.23 V and the short circuit current (SCC) ranges from 340 to 1180 µA. © 2001 Society of Chemical Industry     

Studies on isomeric effects of 2- and 4-Mercapto pyridine as dopants in polymer electrolyte in dye-sensitized solar cells

In this present work, isomers like 2- and 4-Mercapto pyridine were used as dopants (additives) in Poly (ethylene oxide) based polymer electrolyte and their effects in dye-sensitized solar cells (DSC) have been investigated. Due to the coordinating and plasticizing effects of Mercapto pyridine, enhanced ionic conductivity and reduced crystallinity of PEO polymer electrolyte accompanied by a better penetration of the same into the dye coated nanocrystalline TiO₂ in order to have better performances were achieved. The 2-Mercapto pyridine doped PEO (E) shows comparatively better performance than 4-Mercapto pyridine doped one (F), is due to the fact that the π-electron donicity of 2-Mercapto pyridine is greater. These results suggests that the electron donating capacity of 2-Mercapto pyridine and 4-Mercapto pyridine would influence the interaction of nanocrystalline TiO₂ electrode and I⁻/I₃⁻ redox couple leading to radical changes in the cell performance.     

Composite polymer electrolyte incorporating WO3 nanofillers with enhanced performance for dendrite-free solid-state lithium battery

All solid-state lithium batteries (ASS-LBs) with polymer-based solid electrolytes are a prospective contender for the next-generation batteries because of their high energy density, flexibility, and safety. Among all-polymer electrolytes, PEO-based solid polymer electrolytes received huge consideration as they can dissolve various Li salts. However, the development of an ideal PEO-based solid polymer electrolyte is hindered by its insufficient tensile strength and lower ionic conductivity due to its semi-crystalline and soft chain structure. In order to lower the crystallization and improve the performance of PEO-based solid polymer electrolyte, tungsten trioxide (WO₃) nanofillers were introduced into PEO matrix. Herein, a PEO₂₀/LiTFSI/x-WO₃ (PELI-xW) (x = 0%, 2.5%, 5%, 10%) solid composite polymer electrolyte was prepared by the tape casting method. The solid composite polymer electrolyte containing 5 wt% WO₃ nanofillers achieved the highest ionic conductivity of 7.4 × 10^-4 S cm^-1 at 60 °C. It also confirms a higher Li-ion transference number of 0.42, good electrochemical stability of 4.3V, and higher tensile strength than a PEO/LiTFSI (PELI-0W) fillers-free electrolyte. Meanwhile, the LiFePO₄│PELI-xW│Li ASS-LBs demonstrated high performance and cyclability. Based on these findings, it can be considered a feasible strategy for the construction of efficient and flexible PEO-based solid polymer electrolytes for next-generation solid-state batteries.