高分子凝胶电解质及其在电色Smart窗中的应用

研究了高分子凝胶电解质高氯酸锂－碳酸丙烯酯－聚甲基丙烯酸甲酯体系（ＬｉＣｌＯ４－ＰＣ－ＰＭＭＡ）的离子导电性、导电机理以及在电色Ｓｍａｒｔ窗中的应用．其离子电导率与温度的关系服从Ｖｏｇｅｌ－Ｔａｍｍａｎｎ－Ｆｕｌｃｈｅｒ方程，并与体系的ＰＭＭＡ质量百分数、玻璃化温度（Ｔｇ）、碱金属盐的浓度等有关．当ＬｉＣｌＯ４浓度为０．５ｍｏｌ／Ｌ，ＰＭＭＡ＝３５％时，电解质具有良好的粘附性、光学透明度及较高的室温离子电导率（σ＝８．７５×１０－４Ｓ／ｃｍ）．由其组装成的全固态电色Ｓｍａｒｔ窗具有良好的光谱特性，可见光调制范围为４０％～６０％；具有良好的光开关特性，响应时间仅为５ｓ．     

P(VAc-MA)/PMMA为基体的聚合物电解质制备及其在电致变色器件中的应用

以醋酸乙烯酯(VAc)和丙烯酸甲酯(MA)为单体, 采用半连续种子乳液聚合法制备了无规共聚物P(VAc-MA), 以PMMA与P(VAc-MA)的共混物为基体制备了聚合物电解质. 用红外光谱(FTIR)、X射线衍射(XRD)、热重分析(TG)、紫外光谱(UV)、力学性能测试及电化学交流阻抗等方法研究了聚合物、聚合物膜和聚合物电解质的性质. 结果表明, VAc与MA通过打开各自的CC键聚合生成P(VAc-MA); P(VAc-MA)与PMMA共混后结晶状态发生了变化, 增加了无定形相区, 降低了链段运动的能量壁垒, 提高了热稳定性和拉伸强度. 以P(VAc-MA)/PMMA为基体的聚合物电解质膜具有很高的透明性, 最大室温电导率达到1.17×10-3 S/cm; 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; 将此电解质用于全固态电致变色显示器件显示出优良的性能.     

水溶性共轭聚电解质的制备及在有机电致变色器件中的应用

制备了聚噻吩电解质聚[3-(1'-丙氧基-3'-磺酸)噻吩](PTH-n₃-SO₃H). 以铂线和ITO玻璃作为电极, PTH-n₃-SO₃H的水溶液作为支持电解质, 分别以齐聚噻吩衍生物5,5"'-双醛基-2,2': 5',2": 5",2"'-四噻吩(4T-2CHO)和5,5"'-双氰基-2,2': 5',2": 5",2"'-四噻吩(4T-2CN)薄膜作为电致变色活性层, 组装了有机电致变色器件. 研究了4T-2CHO和4T-2CN的电致变色性能, 同时考察了PTH-n₃-SO₃H水溶液作为支持电解质在有机电致变色器件中的应用. 研究发现, 当进行电化学掺杂和去掺杂时, 4T-2CHO膜发生从黄色到蓝绿色的可逆变化, 4T-2CN膜发生从淡黄色到蓝色的可逆变化. 结果表明, PTH-n₃-SO₃H水溶液可以作为支持电解质用于有机电致变色器件.     

一种新型凝胶态聚合物电解质的制备和性能

采用一种新型胶联剂新戊二醇二丙烯酸酯(noepentyl glycol diacrylate, NPGDA)和聚偏氟乙烯-六氟丙烯(poly(vinylidene fluoride-co-hexafluoropropylene), PVDF-HFP), 液态电解液组成电解质混合溶液, 然后加入引发剂并加热引发聚合反应制备了一种具有互穿聚合物网络结构的凝胶态聚合物电解质, 可以用于制备聚合物锂离子二次电池. 考察了不同PVDF-HFP/NPGDA质量比对凝胶态聚合物电解质性能的影响. 结果表明, PVDF-HFP/NPGDA质量比可以影响凝胶态聚合物电解质的结构形貌、电化学特性以及聚合物锂离子二次电池的性能. 研究发现, 当m(PVDF-HFP)/m(NPGDA)＝1:1时制备的凝胶态聚合物电解质具有较高的离子电导率和电化学稳定窗口, 室温下分别为6.99×10^-3 S•cm^-1和4.8 V(vs Li⁺/Li), 以其为电解质制备的聚合物锂离子二次电池具有较好的电化学性能.     

离子液体/凝胶聚合物电解质的制备及其与LiFePO_4的相容性

以1-甲基-3-乙基咪唑六氟磷酸盐(EMIPF6)、聚偏氟乙烯-六氟丙烯(P(VDF-HFP))和六氟磷酸锂(LiPF6)为原料,采用溶液浇铸法制备了离子液体/凝胶聚合物电解质(ILGPE).通过循环伏安(CV)、计时电流法、恒流充放电、电化学阻抗法(EIS)研究了该电解质的离子传输特性以及与锂离子电池正极材料LiFePO4的相容性.结果表明,离子液体/凝胶聚合物电解质的室温电导率为1.650×10-3S·cm-1,电化学稳定窗口达到5.0V.在充放电循环过程中,电极表面形成的钝化膜改善了锂离子脱、嵌可逆性和电极/电解质的界面性质.     

凝胶电解质的研究进展

本文评述了凝胶电解质－一种新型功能高人子材料的研究进展,讨论了电解质的特性,类型,关于其结构性能的研究方法,以及其在电双层电容器和锂离子二次电池方面的应用研究状况,并简要探讨了发展前景。     

Ion Conducting Polyethylene Oxide-Based Polymer Electrolyte Dopped with Ionic Liquid-Trifluoromethanesulfonic Chloride

In last few decades, polymer electrolyte is the most promising candidate for the fabrication of electrochemical devices. In current work, the influence of adding the room-temperature ionic liquid (trifluoromethanesulfonic chloride – CClF3O2S) in polyethylene oxide (PEO): ammonium iodide (NH4I) polymer electrolyte has been studied. The IL-doped polymer electrolyte films are synthesized by solution casting method with varying stoichiometric ratios. Several experimental techniques including optical polarizing microscope, impedance spectroscopy, X-ray diffraction, Linear sweep voltammetry, Ionic transference number thermal analysis, and electrical conductivity measurements at room temperature have been studied in detail. The complex material's maximum conductivity has been determined to be 3.3 × 10⁻⁵ S cm⁻¹ at room temperature. The POM images show the increase in amorphous region which further confirm the improvement in ionic conductivity. Ionic transference number 0.96 shows the system is purely ionic in nature. The ESW of the IL doped polymer electrolyte is also sawed to be 3.32 V which is suitable for the fabrication of electrochemical devices.     

Current Scenario and Future Prospective of Ionic-Liquid Doped Polymer Electrolyte for Energy Application

Solid polymer electrolyte (SPE) films based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF–HFP) with salt and ionic-liquid (IL) are synthesized using the solution-cast technique and summarized in this review. Doping ILs or salts increases ionic conductivity up to the device level. This is further confirmed using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements. Polarized optical microscopy (POM) affirms that enhancement in ionic conductivity is due to increase in amorphous nature of film. The complex nature of polymer electrolyte films is confirmed using Fourier transform infrared (FT-IR) spectroscopy. Overall results show that doping IL into polyether matrix is advantageous material playing a dominant role in electrochemical devices.     

辐照交联法制备锂离子电池用凝胶聚合物电解质及其性能

采用γ-射线辐照交联法制备了具有网络结构的聚偏氟乙烯-六氟丙烯/新戊二醇二丙烯酸酯(PVDF-HFP/NPGDA)基凝胶聚合物电解质(GPE). 考察了不同辐照剂量对凝胶电解质形貌结构、热稳定性和电化学性能的影响以及不同辐照剂量和不同温度下电导率的变化. 结果表明, 随辐照剂量的增加, 凝胶电解质的固化程度提高, 电导率下降. 电导率随温度的变化符合VTF方程. 当辐照剂量为5 kGy 时, 制备的凝胶电解质具有较高的离子电导率和电化学稳定窗口, 室温下分别为7.8×10-3 S·cm-1和4.7 V(vs Li/Li+). 以其为电解质制备的LiMn2O4∣GPE∣Li聚合物锂离子电池具有较好的循环性能.     

用于锂离子电池的凝胶聚合物电解质的制备与性能

以丙烯腈(AN)、丙烯酸甲酯(MA)和衣康酸锂(IALi)为自由基共聚反应的主要单体, 采用溶液聚合方法, 合成轻度交联的P(AN-MA-IALi)聚合物电解质膜.通过FTIR, DSC和SEM等测试方法对共聚物的结构进行了表征, 利用交流阻抗等电化学方法对该膜的导电性能进行了研究.实验结果表明, 所制备的交联聚合物的室温电导率达到10-5~10-4 S/cm, 当IALi的质量分数为3%时, 所制备的聚合物电解质膜的电导率最大可达到1.89×10-4 S/cm.     

纤维素凝胶电解质及其在超级电容器中的应用

以纸浆为原料制备得到一种粘胶液,经静置水化交联,得到一种纤维素凝胶电解质(XWD-NaOH);添加亚铁氰化钾,使获得的新型纤维素凝胶电解质(XWD-NaOH-K 4[Fe(CN)6])呈现良好的氧化还原活性,电导率达15.3 mS/cm;与XWD-NaOH相比,XWD-NaOH-K 4[Fe(CN)6]电解质超级电容器,在0.5 A/g电流密度下,比电容、功率密度和能量密度分别提高了57%、111%和214%,并且体系具有更低的内阻、电荷转移电阻及高的循环稳定性。     

PVA碱性凝胶聚合物电解质薄膜电化学稳定性研究

应用溶解—铸膜法制备聚乙烯醇(polyvinylalcohol,PVA)碱性凝胶聚合物电解质(gelpolymerelectrolyte,GPE)薄膜.交流阻抗(EIS)测试表明,随着KOH含量的增加,该薄膜的离子电导率表现为先增大而后减小的变化趋势,当KOH含量为42%(bymass,下同)时,电导率达到最大值,为2.01×10-3S/cm.X射线衍射(XRD)结果表明,当膜中KOH含量大于20%时,晶态的PVA就逐渐转变为非晶态结构.又当KOH含量增加到一定值后,由于体系中未电离的非晶态KOH量的增多而导致离子电导率下降.循环伏安(CV)和拉曼光谱(Raman)结果表明,该薄膜具有很好的电化学稳定性,可应用于碱性二次电池.     

锂电池中的凝胶聚合物电解质

锂电池目前在人们生活中已经得到广泛应用,但是传统的液体电解质沸点低且易泄漏,容易引起锂枝晶生长和安全问题。凝胶聚合物电解质(GPEs)的状态介于液态电解质和固态电解质之间,不仅可以作为电解质,还可以作为隔膜,这样可以减少液体电解质的泄漏以及改善固体电解质的界面电阻。本文综述了锂电池中制备不同类型的GPEs的方法,如溶液浇铸法、相转化法、原位聚合法、UV(紫外)固化法和静电纺丝法等,重点总结了不同纤维基的GPEs(聚(偏二氟乙烯)(PVDF)、聚(偏二氟乙烯-共六氟丙烯)(PVDF- HFP)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯腈(PAN)和聚间亚苯基间苯二甲酰胺(PMIA))在锂电池中的运用,并通过对不同基质的改性来改善电解质的离子电导率,阻碍锂枝晶的生长。最后,本文对锂电池中GPEs的未来发展前景进行了展望,讨论和提出的策略将为今后高性能锂电池的实际应用提供更多的途径。     

Review on Comparative Study of Solid Polymer Electrolyte Polyethylene Oxide (PEO) Doped with Ionic Liquid

Future demands for energy shortages have prompted a lot of effort to be put into finding alternatives. The use of renewable energies as a revolutionary energy source has gained acceptance. Due to their high flexibility and the interaction between the electrode and the electrolyte, solid polymer electrolytes are employed as a favorable electrolyte for application of electrochemical devices to storage renewable energy. As these are easy in synthesis, have much lower mass density, shows high mechanical stability, also have low binding energy with salts, and high mobility of charge carriers, polyethylene Oxide (PEO) based electrolyte has attracted a lot of interest. Configuration rectification combining PEO with ionic liquids has been introduced to enhance the low ionic conductivity and poor thermodynamic stability of the PEO materials in high-voltage devices at ambient temperature. This configuration modification can successfully validate the applications of PEO polymer electrolyte with large electro-stable voltage ranges. Solution casting method has been used for the synthesis of polymer electrolyte. The essential physical characteristics of PEO in polymer matrices work as a polymer host in SPEs has been described in this review paper, along with several modifications to overcome these limitations. It has been seen that the addition of ionic liquid increases the all over conductivity of the solid polymer electrolyte in most cases also improves the electrical stability of the electrolyte.     

含[AMIM]BF4的聚甲基丙烯酸甲酯基凝胶聚合物电解质的制备与改性

用两步法合成了离子液体1-烯丙基-3-甲基咪唑四氟硼酸盐（[AMIM]BF4）,将聚甲基丙烯酸甲酯(PMMA)引入离子液体[AMIM]BF4中,制备出含离子液体[AMIM]BF4的新型凝胶聚合物电解质,采用非质子溶剂、纳米SiO2等对其进行了改性。 用FT-IR、交流阻抗（AC）、TG、SEM等测试技术对其结构和性能进行了表征。 结果表明,非质子溶剂碳酸丙烯酯、碳酸二甲酯和纳米SiO2的加入使聚合物电解质的室温离子电导率增大,达5.25×10-3 S/cm;电导率与温度的关系符合Arrhenius方程;几种凝胶聚合物电解质的热分解温度均高于300 ℃,显示出良好的热稳定性。     

固态导电聚合物多色电致变色器件的制备

制备了基于聚3-甲基噻吩(P3MeT)和聚苯胺(PANI)的两种结构(侧面结构和垂直结构)固态导电聚合物多色电致变色器件(ECD). 采用电化学现场紫外-可见光谱法研究了侧面结构固态ECD的电致变色特性, P3MeT-ECD显示出蓝色和红色的可逆变化, PANI-ECD显示出墨绿色和黄绿色的可逆变化, 同时采用P3MeT和PANI作变色材料的P3MeT-PANI-ECD可以实现红、蓝、墨绿和草绿多色变化. 用激光雕刻微型化P3MeT-PANI变色层组装制得的侧面结构固态P3MeT-PANI-ECD控制合适电压也可多色变化. 另外, 用CeO₂-TiO₂作为P3MeT-PANI对电极的垂直结构固态P3MeT-PANI-ECD在实现红、蓝、墨绿和草绿多色变化的同时, 也可进行四色自由搭配选择.     

具有微孔结构的聚合物电解质

具有微孔结构的聚合物电解质;纳米Al2O3;离子导电率;交流阻抗;相转化     

增塑剂对PVA碱性聚合物电解质电化学性能的影响

通过溶解―铸膜法制备聚乙烯醇(PVA)-KOH-H2O碱性聚合物电解质膜。向聚合物中添加增塑剂丙三醇(GROL)和碳酸丙烯酯(PC)来提高离子电导率。X射线晶体衍射分析(XRD)结果表明,添加增塑剂未改变聚合物的物相结构,薄膜仍主要为不定形态。差示扫描热分析(DSC)结果显示,添加增塑剂后聚合物电解质膜的玻璃化转变温度降低,促进了电解质膜向不定形态转变。电解质膜室温离子电导率随增塑剂添加而增大,增塑剂超过一定量后离子电导率开始下降。PC对提高离子电导率的作用优于GROL。循环伏安测试结果显示,电解质膜的电化学稳定性窗口随增塑剂的添加而有所变窄,但仍显示了较好的电化学稳定性。     

Influence of Carbon Black on Conductivity and Structure of Polyethylene Oxide Based Polymer Electrolyte Film

The potential applications of carbon black are expected to grow as science and technology improve offering up new possibilities for innovation throughout disciplines included in the field of energy storage. The present work shows the influence of carbon black to improve the ionic conductivity of the polymer electrolyte. The synthesis of polyethylene oxide: ammonium iodide based polymer electrolyte incorporated with carbon black varying from 0.01 to 0.06 wt% with respect to PEO: NH4I system by solution casting method. Different characterizations like polarized optical microscopy (POM), impedance spectroscopy, and ionic transference number (t_ion) are studied in detail. The maximum ionic conductivity is achieved at 0.05 wt% carbon black shows 1.20 × 10⁻⁵ S cm⁻¹ at ambient temperature. In accordance with POM data, the amorphous region has increased whereas the crystalline region has shrunk which further indicated the increase in ionic conductivity . The value of (t_ion) is calculated to be 0.97 which shows the system is ionic in nature. PEO based polymer electrolyte doped carbon black can be used for the fabrication of energy storage devices.     

PEO与Li1.3Al0.3Ti1.7(PO4)3络合的离子导体聚合物电解质

将实验室经固相反应的精细Li1．3Al0．3Ti1．7(PO4)3盐与聚氧化乙烯(PEO)按照不同，nEO／nLi摩尔比，通过溶液浇铸法制备了固态聚合物电解质。红外光谱分析表明Li1．3Al0．3Ti1．7(PO4)3盐与PEO之间有络合产生。SEM照片显示PEO晶体外层为无定形相所包覆形成的胞状结构。经电化学阻抗(简称EIS)法测试发现聚合物电解质膜的室温阻抗谱图是由高频处一压缩的半圆和低频下一条直线组成，而高温时的阻抗谱主要为一条直线。离子电导率的测试结果得到：当nEO／nLi=16时，聚合物电解质室温下电导率约为10^-6／cm，343K时达到10^-4s／cm。离子迁移率的数据表明聚合物电解质为离子和电子共混的导体，但在聚合物电解质体系中电荷的迁移主要是由离子作为载流子导电造成的，由测试结果可得此电解质为离子导体。