Effect of a novel amphipathic ionic liquid on lithium deposition in gel polymer electrolytes

A novel dimeric ionic liquid based on imidazolium cation and bis(trifluoromethanesulfonyl) imide (TFSI) anion has been synthesized through a metathesis reaction. Its chemical shift values and thermal properties are identified via ¹H nuclear magnetic resonance (NMR) imaging and differential scanning calorimetry (DSC). The effect of the synthesized dimeric ionic liquid on the interfacial resistance of gel polymer electrolytes is described. Differences in the SEM images of lithium electrodes after lithium deposition with and without the 1,1′-pentyl-bis(2,3-dimethylimidazolium) bis(trifluoromethane-sulfonyl)imide (PDMITFSI) ionic liquid in gel polymer electrolytes are clearly discernible. This occurs because the PDMITFSI ionic liquid with hydrophobic moieties and polar groups modulates lithium deposit pathways onto the lithium metal anode. Moreover, high anodic stability for a gel polymer electrolyte with the PDMITFSI ionic liquid was clearly observed.     

Morphology and ionic conductivity of thermoplastic polyurethane electrolytes

Thermoplastic polyurethane (TPU) with a mixture of soft segments [poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG)], denoted TPU‐M, was prepared as an ion‐conducting polymer electrolyte. TPUs with PEG and PTMG as soft segments were also synthesized individually as polymer electrolytes. The changes in the morphology and ion conductivity of the phase‐segregated TPU‐based polymer electrolytes as a function of the lithium perchlorate concentration were determined with differential scanning calorimetry, Fourier transform infrared spectroscopy, alternating‐current impedance, and linear sweep voltammetry measurements. Both solid and gelatinous polymer electrolytes were characterized in this study. The effect of temperature on conductivity was studied. The conductivity changes revealed the combined influence of PTMG and PEG units in TPU‐M. The swelling characteristics in a liquid electrolyte and the dimensional stability were evaluated for the three TPUs. Because of its dimensional stability and ionic conductivity, the TPU system containing both PEG and PTMG as soft segments was found to be more suitable for electrolyte applications. A room‐temperature conductivity of approximately 1 × 10^?4 was found for TPU‐M containing 50 wt % liquid electrolyte. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1154–1167, 2004     

Preparation of thermally stable polymer electrolytes from imidazolium-type ionic liquid derivatives

Thermally stable polymer electrolytes based on ionic liquids were prepared and analyzed. Mono-functional ionic liquid monomers, ionic liquid cross-linkers, and ethylimidazolium-type ionic liquid salts were mixed and polymerized. The ionic liquid-type cross-linkers were effective to prepare thermally stable polymer films. In particular, the copolymerization of cross-linker and ethylimidazolium-type ionic liquid monomers were used to make polymer electrolytes with high ionic conductivities. The copolymerization in ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide gave a transparent film showing no thermal degradation up to 400 °C.     

PEO-based polymer electrolytes

Like a liquid solvent, poly(ethylene oxide) dissolves a wide variety of inorganic salts. Ionic conductivity occurs in the amorphous region of the polymer and typically both anions and cations are mobile to some extent. This paper discusses the preparation, thermal behaviour and ionic transport of thin cast films of PEO-based electrolytes containing monovalent and divalent cations. The techniques that shed light on the structure-conductivity relationship are emphasized. The temperature and composition dependence of conductivity is also considered. Finally, attention has been paid to the possible uses of these polymeric electrolytes in solid-state electrochemical devices such as primary and secondary batteries, electrochromic displays and sensors.     

二元离子液体基染料敏化太阳能电池性能的研究

对6种用于染料敏化太阳能电池的二元离子液体电解质进行了考察,电池的光电转化效率在1.39%～4.98%,其中,1-乙基-3-甲基咪唑四氟硼酸盐/碘化1-丁基-3-甲基咪唑类电解质具有最高的光电转化效率。对这种二元离子液体电解质体系进一步优化,测试了不同碘浓度下相应染料敏化太阳能电池的效率、电化学阻抗谱(EIS)和紫外-可见吸收光谱(UV-vis)。结果表明,随着碘单质浓度的增大,铂-电解质界面的传荷电阻(RPt)、TiO2-电解质表面的传荷电阻(Rct)和瓦尔堡阻抗(Zw)逐渐减小,而电解质对紫外光的吸收逐渐增大,在AM1.5的条件下,当碘单质的浓度为0.25 mol/L时电池效率最高,达到5.20%。     

聚合物及离子液体电解质在锂二次电池中的应用

系统地介绍了锂离子二次电池电解质,特别是聚合物电解质及离子液体电解质的应用研究现状。开发具有高能量密度、稳定的充放电性能、循环寿命长、可塑性、高安全性与低成本的锂离子电池是当前的研究热点。离子液体具有较高的离子电导率、宽电化窗口,且无蒸汽压,而聚合物具有良好的机械加工性能。二者的结合将为锂离子电池电解质的研究提供了新的开发思路。     

离子液体电解质在锂二次电池中的应用

锂二次电池作为动力电池,被寄予厚望。但锂二次电池面临的安全隐患也是不容忽视的,是当前亟需解决的问题,而这与电解质的性质有着紧密的联系。离子液体由于具有较宽电化学窗口、良好的导电性、高热稳定性、几乎无挥发及不燃烧等优良的特性,正在作为一种新型绿色替代溶剂被电化学领域所关注。离子液体的不燃烧特性,对于替代传统有机电解质具有十分重要的意义。本文阐述了新型溶剂“离子液体”作为电解质在锂二次电池中的应用,其中重点阐述了在碳、硅、钛酸锂(Li₄Ti₅O₁₂)、磷酸亚铁锂(LiFePO₄)、钴酸锂LiCoO₂、镍锰酸锂(LiNi_xMn_yO_z),镍钴锰锂(LiNi_xCo_yMn_zO_w)及在锂硫(Li-S)电池中的应用。     

Solid polymer electrolytes with stable electrochemical properties

In order to build solid-state ambient-temperature batteries with stable electrochemical performances over a period of months, the crystallization process in polymer electrolytes can be suppressed by the addition of an elastomer and a styrenic macromonomer of PEO to a PEO-lithium salt electrolyte. Complex impedance measurements and X-ray diffraction studies were carried out in an attempt to understand the effect of the macromonomer on the electrochemical behaviour. The conductivity was found to increase with macromonomer content and values as high as 10^?5S cm^?1 at room temperature can be obtained. X-ray, diffraction patterns have shown that addition of the elastomer and the macromonomer does not alter the monoclinic unit cell of the crystallized PEO. During ageing, the diffraction lines were found not to vary appreciably over a period of 15 months. Similarly, no appreciable change in the conductivity level was noticed within the same period. The observed behaviour was explained as a suppression of the crystallization process.     

Preparation and characterization of low environmental humidity sensitive ionic liquid polymer electrolytes

Methyl 3‐(3‐(2‐hydroxyethyl)imidazole‐1‐yl)propanoate chloride salt (IL‐Cl), methyl 3‐(3‐(2‐hydroxyethyl)imidazole‐1‐yl)propanoate bromate salt (IL‐Br), and their derivatives modified by polyethylene glycol (PEG) through ester‐exchange reaction (IL‐PEGs) were synthesized. First, the properties of those materials, especially their conductivity, have been extensively studied. Second, using the IL‐PEG with the highest conductivity as a plasticizer and electrolyte, a series of gel polymer electrolytes were successfully fabricated from polyurethane, poly‐1,4‐butylene adipate glycol 2000, and IL‐PEGs by melting blends with different mass ratios in a Haake torque rheometer. The surface morphology, thermal properties, and the surface resistivity of gel polymer electrolytes were studied by scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, and surface resistivity test, respectively. Scanning electron microscopy pictures showed that the surface of polymer electrolyte is smoother than that without added IL‐PEGs. Thermogravimetric analysis results revealed that the polymer electrolytes will not decompose when the processing temperature is below 275°C. It was found that the surface resistivity of polymer electrolytes can be below 10⁹ Ω, showing a good antistatic property, and it changes slightly as the relative humidity decreases from 40% to 0.1%, indicting that the material has low humidity sensitivity. This study is a new demonstration and development in ionic liquid based polymer electrolyte. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40675.     

Crystallinity,thermal properties,morphology and conductivity of quaternary plasticized PEO‐based polymer electrolytes

Quaternary plasticized solid polymer electrolyte (SPE) films composed of poly(ethylene oxide), LiClO₄, Li_1.3Al_0.3Ti_1.7(PO₄)₃, and either ethylene carbonate or propylene carbonate as plasticizer (over a range of 10–40 wt%) were prepared by a solution‐cast technique. X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) indicated that components such as LiClO₄ and Li_1.3Al_0.3Ti_1.7(PO₄)₃ and the plasticizers exerted important effects on the plasticized quaternary SPE systems. XRD analysis revealed the influence from each component on the crystalline phase. DSC results demonstrated the greater flexibility of the polymer chains, which favored ionic conduction. SEM examination revealed the smooth and homogeneous surface morphology of the plasticized polymer electrolyte films. EIS suggested that the temperature dependence of the films' ionic conductivity obeyed the Vogel–Tamman–Fulcher (VTF) relation, and that the segmental movement of the polymer chains was closely related to ionic conduction with increasing temperature. The pre‐exponential factor and pseudo activation energy both increased with increasing plasticizer content and were maximized at 40 wt% plasticizer content. The charge transport in all polymer electrolyte films was predominantly reliant on lithium ions. All transference numbers were less than 0.5. Copyright © 2006 Society of Chemical Industry     

A study on polyurethane/acrylate crosslinked gel polymer electrolytes

2,4‐Toluene diisocyanate, poly(propylene glycol), poly(ethylene glycol) (PEG) and 2‐hydroxyethyl methacrylate were used to synthesize PEG–UA (urethane acrylate) monomer. The crosslinked polymer and gel polymer electrolytes were prepared in dioxane by free radical polymerization. The swelling behaviour, thermal degradation properties, morphology and ionic conductivity of the gel polymer electrolytes were investigated. With decrease in the proportion of dioxane used, the synthesized polymer's network density increased, its affinity with a solution of 1 M LiClO₄ in propylene carbonate (PC) decreased, and more microgel which diffused in the network. At the same time, the conductivity increased and reached 4 × 10^?4 S cm^?1 at 25 °C. Copyright © 2003 Society of Chemical Industry     

高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展

综述了近十几年来高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展及其在高温质子交换膜燃料电池中的应用进展,指出了此类电解质目前存在的亟待解决的两个问题：咪唑类离子液体毒化Pt基催化剂和复合膜中离子液体的长期稳定性。最后对高温质子交换膜燃料电池用离子液体聚合物电解质的发展前景作了展望,即开发与Pt基催化剂相容的离子液体聚合物电解质以及预防复合膜内离子液体的流失,即提高高温质子交换膜燃料电池的性能及长期稳定性,最终提高高温燃料电池的寿命。     

Conductivity enhancement within garnet-rich polymer composite electrolytes via the addition of succinonitrile

All-solid-state lithium-ion batteries (ASSLIBs) are promising alternatives to conventional organic electrolyte-based batteries due to their higher safety and higher energy densities. Despite advantages, ASSLIBs suffer from issues like high charge transfer resistances due to the brittleness of the inorganic solid electrolyte and chemical instabilities at the lithium/electrolyte interface. Within this work, we investigate composite electrolytes (CEs) based on garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO), polyethylene oxide, and lithium bis(trifluoromethanesulfonyl)imide, prepared via a solvent-free cryo-milling approach in contrast to conventional solvent-mediated synthesis. Compositions ranging from polymer-rich to garnet-rich systems are investigated via X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy in order to determine the compatibility of the cryo-milling process toward membrane fabrication along with the possible chemical interactions between the composite membrane components. Electrochemical impedance spectroscopy is used to study the role of ceramic to polymer weight fraction on ionic conductivity. It is shown that the addition of succinonitrile (SCN) to the garnet-rich CEs can significantly improve the ionic conductivity compared to the SCN-free CEs.     

Sulfonate based ionic liquid incorporated polymer electrolytes for Magnesium secondary battery

The polymer electrolytes comprising of PVdF-HFP/PVAc/Mg(ClO₄)₂ as salt based polymer blend electrolytes derived from the addition of varying amounts of 1-ethyl – 3-methylimidazolium trifluoromethane sulfonate [EMITF], as dopant were synthesized in the form of films by solution-casting method. The XRD and FTIR patterns confirm the formation of an amorphous phase and also that complex formation between the polymers, salt and ionic liquid. The SEM images show that the polymer electrolyte exhibit a enormous pores, remarkably, the maximum ionic conductivity is obtained in the case of the typical polymer system I₃ is found to be 9.122 × 10^?4 Scm^?1at 303 K.     

Ionic liquid/poly(ionic liquid)‐based electrolytes for energy devices

Ionic liquids are organic salts with melting points generally below 100 °C. They are attracting wide attention and are used as electrolytes in electrochemical devices, such as fuel cells, lithium‐ion batteries, dye‐sensitized solar cells, supercapacitors and light‐emitting electrochemical cells, due to their negligible vapor pressure, high ionic conductivity and wide electrochemical window. This perspective article highlights the applications of ionic liquid‐ or poly(ionic liquid)‐based electrolytes in fuel cells, dye‐sensitized solar cells and supercapacitors. © 2013 Society of Chemical Industry     

离子液体改性石墨烯的制备及其对ABS复合材料导热性能的影响

合成了一种氨基功能化离子液体[HAIM]BF4,并将其应用于石墨烯的改性。通过绿色直接的球磨法,将G粉与1-己基-3-氨乙基咪唑四氟硼酸离子液体[HAIM]BF4相结合,制备出离子液体功能改性石墨烯（G@ILs）。所得G@ILs使用熔融共混法加入丙烯腈-丁二烯-苯乙烯共聚物（ABS）中,制备G@ILs/ABS复合材料。使用X射线衍射分析（XRD）,X射线光电子能谱（XPS）,扫描电子显微镜（SEM）,透射电子显微镜（TEM）和拉曼测试等多种手段对G@ILs的结构和性质进行分析。结果表明,[HAIM]BF4通过阳离子-π相互作用对石墨烯进行了有效修饰,保持了石墨烯的结构完整性。由于G@ILs的独特性能,G@ILs/ABS复合材料在机械性能方面表现出相当大的改善。加入1 wt.%G@ILs的G@ILs/ABS复合材料的拉伸强度和弯曲模量为42.4 MPa和2145.1 MPa,比ABS提高了8.36%和12.76%。此外,在加入1 wt.%G@ILs的G@ILs/ABS复合材料的导热系数为0.249 W·m-1·k-1,比纯ABS提高了21.5%。     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

聚合离子液体的研究进展

随着对离子液体研究的深入,离子液聚合物IF成为新的研究热点.简单综述了近年来聚合离子液的合成方法,主要包括自由基引发聚合、辐射聚合以及与其他物质共聚等.其中,自由基引发聚合操作简便,易于监测,是目前制备聚合离子液体的常用方法.