凝胶聚合物电解质的电化学性能

用化学交联法制备了凝胶聚合物电解质.聚烯烃多孔膜支撑的凝胶聚合物电解质具有优良的电化学性能, 室温电导率为1.01×10^-3S•cm^-1,锂离子迁移数为0.41,在Al电极上的氧化起始电位达到4.2 V以上.采用聚烯烃多孔膜支撑的凝胶聚合物电解质制备了聚合物锂离子电池,并研究了工艺条件对聚合物锂离子电池电化学性能的影响.研究的工艺条件包括：单体添加量和电极组合方式.优化后的聚合物锂离子电池具有良好的电化学性能,1 C放电容量为0.2 C放电容量的93.2%,经100次1 C循环后的剩余容量仍在80%以上.     

Electrochemical properties of Li ion polymer battery with gel polymer electrolyte based on polyurethane

Gel polymer electrolyte (GPE) was prepared using polyurethane acrylate as polymer host and its performance was evaluated. LiCoO₂/GPE/graphite cells were prepared and their electrochemical performance as a function of discharge currents and temperatures was evaluated. The precursor containing a 5 vol % curable mixture had a viscosity of 4.5 mPa s. The ionic conductivity of the GPE at 20 °C was about 4.5 × 10^–3 S cm^–1. The GPE was stable electrochemically up to a potential of 4.8 V vs Li/Li⁺. LiCoO₂/GPE/graphite cells showed a good high rate and low-temperature performance. The discharge capacity of the cell was stable with charge–discharge cycling.     

Fabrication and properties of crosslinked poly(propylene carbonate maleate) gel polymer electrolyte for lithium‐ion battery

The poly(propylene carbonate maleate) (PPCMA) was synthesized by the terpolymerization of carbon dioxide, propylene oxide, and maleic anhydride. The PPCMA polymer can be readily crosslinked using dicumyl peroxide (DCP) as crosslinking agent and then actived by absorbing liquid electrolyte to fabricate a novel PPCMA gel polymer electrolyte for lithium‐ion battery. The thermal performance, electrolyte uptake, swelling ratio, ionic conductivity, and lithium ion transference number of the crosslinked PPCMA were then investigated. The results show that the T_g and the thermal stability increase, but the absorbing and swelling rates decrease with increasing DCP amount. The ionic conductivity of the PPCMA gel polymer electrolyte firstly increases and then decreases with increasing DCP ratio. The ionic conductivity of the PPCMA gel polymer electrolyte with 1.2 wt % of DCP reaches the maximum value of 8.43 × 10⁻³ S cm⁻¹ at room temperature and 1.42 × 10⁻² S cm⁻¹ at 50°C. The lithium ion transference number of PPCMA gel polymer electrolyte is 0.42. The charge/discharge tests of the Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3O₂ cell were evaluated at a current rate of 0.1C and in voltage range of 2.8–4.2 V at room temperature. The results show that the initial discharge capacity of Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3 O₂ cell is 115.3 mAh g⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

凝胶聚合物电解质在锂硫电池中的应用状况

从凝胶聚合物电解质的制备方法 (原位聚合法和溶液浇铸法)出发,对锂硫电池中凝胶聚合物电解质的应用展开了探究。     

基于互穿网络技术构筑环境友好型聚合物电解质膜与电化学性能

利用互穿网络技术通过乳液聚合法制备环境友好型聚合物电解质膜,采用FTIR、XPS、SEM、TEM和TG等技术对样品结构和形貌进行表征;通过CV、EIS和充放电测试结果分析样品的电化学性能。结果表明：当m(AMPS):m(BA):m(AA):m(AN)=1:3:2:2时,互穿网络聚合物电解质膜的离子电导率为0.88mS/cm;聚合物膜的抗拉强度为7.53MPa,断裂伸长率为90.4%;聚合物膜的吸液量为150%,热收缩率为4%,表现出最佳的力学性能和电化学性能。该互穿网络聚合物电解质膜与目前锂离子电池主流的正负极材料具有较好的相容性,普适性较好。以LiCoO₂为正极,石墨为负极,0.2C倍率下,首次放电比容量分别为141.3mAh/g和347.1mAh/g,100次循环后容量保持率分别为94.8%和85.0%;2C倍率下,放电比容量为119.8mAh/g和239.0mAh/g。关键词：聚合物电解质膜;互穿网络技术;环境友好;锂离子电池     

Electrical performance of lithium ion based polymer electrolyte with polyethylene glycol and polyvinyl alcohol network

A solid polymer electrolyte based on lithium hydroxide (LiOH) added with polyethylene glycol and polyvinyl alcohol polymers was synthesized by solution casting. The structural variation with respect to loading wt% of LiOH reveals the semicrystalline property of polymer electrolyte. The differential scanning calorimetry data shows the onset of crystalline to amorphous transition, which occurs nearly to the melting peak, for higher salt content. The structural properties and cross-linking between polymer and salt were demonstrated by polarized optical microscopy. The polymer electrolytes were subjected to AC impedance analysis spectra for obtaining the ionic conductivity at different temperature. The charge carriers relax much faster for higher lithium salt concentration based polymer electrolyte and produces higher conductivity. The highest room temperature conductivity 2.63 × 10^?5 S/cm is obtained for 8 wt% loading of lithium salt based polymer electrolyte, confirming their use in preparation of ion conducting devices.     

阻燃聚氨酯基固态聚合物电解的制备

摘要：以聚己二酸-1,4-丁二醇酯二醇( PBA) 、六亚甲基二异氰酸酯( HDI)和阻燃剂N，N阻双（2（羟乙基）胺基亚甲基磷酸二乙酯( FCR-6）为主要原料合成阻燃聚氨酯（TPUP），将阻燃聚氨酯与锂盐复合得到阻燃聚氨酯基固态聚合物电解质。采用红外光谱、热重分析、锥形量热、力学测试、电化学窗口、电导率和电池的充放电性能测试等对阻燃聚氨酯基固态聚合物电解质进行了表征和性能测试。研究表明，TPUP具有良好阻燃性能，制备的阻燃电解质TPUP25%Li综合性能最佳，且拉伸强度达到2.09MPa，80℃时离子电导率为3.09M10-4 S/cm，以阻燃电解质组装的全固态锂电池，在80℃时0.2C电流密度下放电容量达到159mA?h/g。     

Study of ion solvation and ion association in polymer gel electrolyte with polyethylene oxide-co-polypropylene oxide as a plasticizer

Using a molal conductance method, ion solvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)–LiClO₄ gel electrolytes with amorphous ethylene oxide-co-propylene oxide (EO-co-PO, M̄_n = 1750) as the plasticizer were investigated. It was found that the fraction of solute existing as single ions (α_i) and ion pairs (α_p) decreases, while that of triple ions (α_t) increases linearly with increasing salt concentration. The dependence of these fractions on molecular weight of plasticizer was also examined. It was shown that α_i and α_t increase and α_p decreases with increasing molecular weight. The result of temperature dependence of these fractions was very interesting: when the temperature is lower than 55°C, α_i increases while α_p and α_t decrease with increasing temperature; however, when the temperature is higher than 55°C, the reverse is true.     

增塑型锂离子电池聚合物电解质

从组成聚合物电解质的聚合物基材和电解液两方面进行分析,介绍了最近几年凝胶型、微孔型和复合型聚合物电解质的研究现状,比较了它们的制备方法、性能和特点,探讨了锂盐、增塑剂、离子液体和单离子导体等对聚合物电解质性能的影响,并简要评述了聚合物锂离子电池未来发展的前景趋势。     

Enhancement of electrochemical properties of hot-pressed poly(ethylene oxide)-based nanocomposite polymer electrolyte films for all-solid-state lithium polymer batteries

PEO₁₆-LiClO₄-ZnAl₂O₄ nanocomposite polymer electrolyte (NCPE) films prepared by hot-pressing method have been investigated. In order to compare with the hot-pressed NCPEs, the NCPE films have also been prepared using the conventional solution-casting method. Field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), conductivity (σ) and interface property studies have been carried out on above two kinds of films. The results show that the NCPE film prepared by hot-pressing method has smoother surface, higher interface stability, lower crystallization and melting temperature values than that prepared by solution-casting method. An all-solid-state lithium polymer battery using the hot-pressed NCPE film as electrolyte, lithium metal and LiFePO₄ as anode and cathode respectively, shows high discharge specific capacity, good rate capacity, high coulombic efficiency, and excellent cycling stability as revealed by galvanostatical charge/discharge cycling tests.     

Structure and properties of an organic rectorite/poly(methyl methacrylate) nanocomposite gel polymer electrolyte by in situ synthesis

The synthesis of organic‐modified rectorite (OREC)/polymethyl methacrylate (PMMA) nanocomposite gel polymer electrolyte (NGPE) via in situ polymerization was investigated using free radical initiator in an solution, in which organic plasticizer, propylene carbonate(PC) acted as a solvent. A serious of NGPE membranes with different OREC content were prepared and characterized. The dispersion and exfoliation statuses of the OREC in the prepared NGPE membranes were analyzed through X‐ray diffraction (XRD) and transmission electron microscope (TEM), and the results indicated that for the NGPE with 5 wt % OREC membrane, OREC was partly exfoliated and well dispersed in the gel polymer electrolyte system. The electrochemical properties of the NGPE were determined by alternating current (AC) impedance spectroscopy, which illustrated that the ionic conductivity of the nanocomposite gel polymer electrolyte firstly increased and then decreased with increasing OREC content. Meanwhile, the maximum value of ionic conductivity for nanocomposite gel polymer electrolytes was obtained when organic clay amount was 5 wt %. The interactions among the components of the NGPE were investigated by Fourier transform infrared (FTIR) spectroscopy. It was shown that there were specific interactions between OREC and the other components, which may influence the conductivity and the stability of GPEs. Finally, an thermal stability enhancement was presented by NGPE with 5 wt % OREC compared with GPE, which was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

柔性聚合物电解质的制备及其电化学性能

以不同质量比的丙烯酸甲酯(MA)和丙烯腈(AN)为单体,聚乙烯醇(PVA)为分散剂,采用绿色环保的改性乳液聚合法制得聚合物乳液,将聚合物乳液流延涂布制得柔性聚合物膜,进一步采用电解液浸润法制得系列柔性聚合物电解质膜(S1、S2、S3和S4)。通过傅里叶红外光谱仪(FTIR)、扫描电镜(SEM)、力学性能测定、热分析、交流阻抗(EIS)和充放电测试对材料的物理化学性能进行了表征。结果表明:当m(MA)∶m(AN)=23∶2(S2)时,聚合物膜的抗拉强度为14.3 MPa,断裂伸长率为248%,25℃时的离子电导率为0.95m S/cm。分别以LiCoO_2为正极、金属锂为负极,天然石墨为正极、金属锂为负极制备CR2032扣式锂离子电池并测试其循环伏安性能和充放电性能,4次循环伏安测试发现峰电位均无明显变化,0.1 C倍率下,首次放电比容量分别为142和307 mA·h/g,50次循环后分别为135和323 m A·h/g,1.0 C倍率下,LiCoO_2的放电比容量为134.3 mA·h/g,说明所制备的材料具有较好的电化学性能。     

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     

Preparation of gel polymer electrolytes using PMMA interpenetrating polymeric network and their electrochemical performances

A gel polymer electrolyte (GPE) is prepared from polymethylmethacrylate interpenetrating polymer network, benzoyl peroxide, and 1.1 M LiPF₆/EC-DEC (1:1 vol.%). The LiCoO₂/graphite cells are prepared and their electrochemical properties were evaluated at various current densities and temperatures. The viscosity of the precursor containing 5 vol.% curable mixture is around 4.6 mPa s. The ionic conductivity of the GPE at 20 °C is around 5.8×10⁻³ S cm⁻¹. The GPE has good electrochemical stability up to 4.8 V vs. Li/Li⁺. The capacity of the cell at 1.0C rate is 82% of the discharge capacity at 0.2C rate. The capacity of the cell at −10 °C is 86% of the discharge capacity at 20 °C. Discharge capacity of the cell with GPE is stable with charge-discharge cycling.     

原位构建富氟SEI的凝胶电解质用于金属锂二次电池

以六氟磷酸锂（LiPF₆）为四氢呋喃的聚合引发剂制备凝胶电解质,同时作为氟源在金属锂负极表面原位构建富含LiF的固态电解质界面层（solid electrolyte interface,SEI）来抑制锂枝晶的生长以及金属锂/电解液之间的副反应。所制备的凝胶电解质具有较高的室温离子电导率（1.33 mS·cm^-1）和较宽的电化学稳定窗口（4.5 V）。原位聚合方式组装金属锂对称电池循环后,锂负极表面没有明显的锂枝晶和被损毁的形貌出现;XPS结果表明锂负极表面生成了富含LiF的SEI。组装的LiFePO₄全电池在1 C的电流密度下,稳定循环400周后仍保持118.7 mAh·g^-1的放电比容量。得益于四氢呋喃在开环聚合反应过程中,促进了LiPF₆分解反应平衡的正向移动,在锂负极表面形成稳定的富含LiF的SEI,能够抑制锂枝晶的生长并防止其被持续性的腐蚀破坏。     

原位构建富氟SEI的凝胶电解质用于金属锂二次电池

以六氟磷酸锂（LiPF₆）为四氢呋喃的聚合引发剂制备凝胶电解质,同时作为氟源在金属锂负极表面原位构建富含LiF的固态电解质界面层（solid electrolyte interface,SEI）来抑制锂枝晶的生长以及金属锂/电解液之间的副反应。所制备的凝胶电解质具有较高的室温离子电导率（1.33 mS·cm^-1）和较宽的电化学稳定窗口（4.5 V）。原位聚合方式组装金属锂对称电池循环后,锂负极表面没有明显的锂枝晶和被损毁的形貌出现;XPS结果表明锂负极表面生成了富含LiF的SEI。组装的LiFePO₄全电池在1 C的电流密度下,稳定循环400周后仍保持118.7 mAh·g^-1的放电比容量。得益于四氢呋喃在开环聚合反应过程中,促进了LiPF₆分解反应平衡的正向移动,在锂负极表面形成稳定的富含LiF的SEI,能够抑制锂枝晶的生长并防止其被持续性的腐蚀破坏。     

Cellulose triacetate‐based polymer gel electrolytes

New composite polymer gels were obtained from cellulose triacetate (CTA), N‐methyl‐N′‐propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr_1,3TFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Analysis by differential scanning calorimeter and scanning electron microscope showed that the ionic gel consisting of CTA, Pyr_1,3TFSI, and LiTFSI formed a completely homogeneous phase at the molar ratio of CTA/Pyr_1,3TFSI/LiTFSI = 1/3/1.5. The ionic conductivity of the polymer gel was significantly enhanced by the presence of LiTFSI. FTIR study strongly implies that the interaction of lithium ion with the carbonyl group of CTA could be responsible for the increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and electrochemical performance of gel polymer electrolytes with a novel star network

Well-defined star shaped polymers with α-Cyclodextrin (α-CD) core linking PMMA-block arms were synthesized by atom transfer radical polymerization (ATRP). Gel polymer electrolytes (GPEs) were prepared by encapsulating electrolyte solution of 1 mol L⁻¹ of LiClO₄/EC-PC (volume 1:1) into the obtained star shaped polymer host. The ionic conductivity of the GPEs and the cycling characteristics of LiCoO₂/GPEs/Graphite cell were studied by electrochemical impedance spectroscopy and charge-discharge testing, respectively. The results indicate that the GPEs have a high ionic conductivity up to 1.63 × 10⁻³ S cm⁻¹ at room temperature and exhibit a high electrochemical stability potential of 4.5 V (vs. Li/Li⁺). The discharge capacity of LiCoO₂/GPEs/Graphite cell is about 98% of its initial discharge capacity after 20 cycles at 0.1 C rate. Discharge capacity of the model cell with GPEs is stable with charge-discharge cycling.     

Improved performance of solid polymer electrolytes for structural batteries utilizing plasticizing co‐solvents

This study describes the formulation, curing, and characterization of solid polymer electrolytes (SPE) based on plasticized poly(ethylene glycol)‐methacrylate, intended for use in structural batteries that utilizes carbon fibers as electrodes. The effect of crosslink density, salt concentration, and amount of plasticizer has been investigated. Adding a plasticizing solvent increases the overall performance of the SPE. Increased ionic conductivity and mechanical performance can be attained compared to similar systems without plasticizer. At ambient temperature, ionic conductivity (σ) of 3.3 × 10^?5 S cm^?1, with a corresponding storage modulus (E ′) of 20 MPa are reached. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44917.