含高氯酸锂的IPN固体电解质研究

高分子固体电解质（ｐｏｌｙｍｅｒｉｃｓｏｌｉｄｅｌｅｃ－ｔｒｏｌｙｔｅ）由于其潜在的应用价值，人们对它进行了广泛的研究［１］。目前，主要围绕如何提高室温电导率和机械强度进行研究［２］。在所有这些研究中，利用环氧树脂（ＥＲ）与低分子量聚乙二醇（ＰＥＧ）...     

环氧乙烷和环氧丙烷共聚物及其盐复合物的结晶与熔融

环氧乙烷和环氧丙烷共聚物及其盐复合物的结晶与熔融齐力，林云青，陈东霖（中国科学院长春应用化学研究所长春１３００２２）关键词环氧乙烷环氧丙烷共聚物，高分子固体电解质，结晶，熔融聚环氧乙烷（ＰＥＯ）及其盐复合物等￣［１，２］是一类高分子固体电解质，但ＰＥ...     

定电位电解法低浓度─氧化碳气体传感器的研究──Ⅰ.半固态传感器的特性

定电位电解法气体传感器由于其具有检测气体种类多、浓度范围宽、测量精度高和可用于现场检测等优点而被广泛使用．但它的使用寿命短，一般只能保证一年．这是由于该类传感器使用水溶液电解质，在干燥气氛下长期使用时，电解液干涸而使传感器失效．为了延长这类传感器的寿命，人们开始研制固体电解质传感器，研究得最多的是用Nafion膜作固体电解质［fi，因为它是一种具有良好化学稳定性和氢离子导电能力的阳离子交换膜［‘］．但膜中氢离子的迁移一定要有水的存在【’」，所以，这种用Nafion膜作固体电解质的传感器寿命更短．我们试图在用…     

脲、硫脲固体电解质导电机理分析

高分子固体电解质（ＳＰＥ）是一类很有发展前途的功能高分子材料．在高比能电池、二次电池、光电池、传感器、电显色器、电容器等方面具有广泛的应用前景,受到国内外高分子科学界和电化学界的普遍关注［１］．目前的研究方向仍是寻找室温下高电导率的固体电解质材料［２,３］．我们［４－６］以脲和硫脲为主体,添加聚乙烯醇等高分子材料制成的ＳＰＥ,室温电导率可达６．８４ × １０-３ Ｓ·ｃｍ－１,但其导电机理尚不清楚．搞清其导电机理对于认识和改进此类电解质非常有益．１实验部分１．１ＳＰＥ的制备电解质由质量分数为５１％脲…     

稀土与穴醚[2,1,1]配位反应过程中的阴离子重排现象

用电导法研究了甲醇溶液中稀土硝酸盐及氯化物与穴醚［２，１，１］的配位作用，测定了１：１配合物的稳定常数ｌｇＫ及摩尔电导ΛＭＬ。在甲醇溶液中，稀土氯化物与［２，１，１］配合物的稳定性大于硝酸盐的相应配合物。稀土硝酸盐与［２，１，１］配合物的稳定常数ｌｇＫ随镧系收缩有明显的钆断效应。电导测定表明，在甲醇溶液中，稀土硝酸盐为弱电解质。轻稀土与［２，１，１］反应后为１：１型电解质，重稀土配合物则属１：２型电解质；稀土氯化物在甲醇中为１：１型电解质，所形成的配合物均为１：２型电解质。     

新型导电高分子材料

新型导电高分子材料梁洪泽，刘振海，丁黎明，陈东霖，景遐斌，王佛松（中国科学院长春应用化学研究所，１３００２２）松全才（北京理工大学，１０００８１）１９９３年，Ａｎｇｅｌｌ设计了一种全新的具有突破意义的合成高分子固体电解质的方法［１］。其基本路线是在数...     

交替马来酸酐共聚物多缩乙二醇酯盐络合物的离子传导性

交替马来酸酐共聚物多缩乙二醇酯盐络合物的离子传导性丁黎明，林云青，周子南，王佛松（中国科学院长春应用化学研究所，长春，１３００２２）关键词高分子固体电解质，离子电导率，玻璃化转变温度，离子传输，ＶＴＦ方程１９７３年，Ｐ．Ｖ．Ｗｒｉｇｈｔ等人［１］首次...     

聚苯醚磺酸锂与酯类增塑剂共混物的导电性

聚苯醚磺酸锂与酯类增塑剂共混物的导电性汪传清，黄玉惠，赵树录，丛广民（中国科学院广州化学研究所广州５１０６５０）关键词　聚苯醚磺酸锂，酯类增塑剂，共混，导电性能高分子固体电解质［１］可作为高能电池、电致变色等材料。聚环氧乙烷／碱金属盐复合物与无机盐构...     

三取代钨硅杂多配合物的导电性和磁性

合成了α－ＮａｍＨｎ［ＳｉＷ９Ｍ３（Ｈ２Ｏ）３Ｏ３７］·１６Ｈ２Ｏ（Ｍ＝Ｃｏ（Ⅱ），Ｎｉ（Ⅱ），Ｖ（Ⅴ）杂多配合物），通过ＩＣＰ，ＩＲ，ＵＶ，ＴＧ－ＤＴＡ，ＸＰＳ，ＥＰＲ，极谱等手段进行了表征．配合物在室温下的电导率σ值达１×１０－３Ｓ·ｃｍ－１，３４３Ｋ时可达１×１０－２Ｓ·ｃｍ－１，是有实用化前景的新型固体电解质．变温磁化率结果表明α－Ｎａ１０［ＳｉＷ９Ｃｏ３（Ｈ２Ｏ）３Ｏ３７］·１６Ｈ２Ｏ和α－Ｎａ１０［ＳｉＷ９Ｎｉ３（Ｈ２Ｏ）３Ｏ３７］·１６Ｈ２Ｏ具有反铁磁性．     

全氟庚烷端基聚丙烯酸的制备及其水溶液的表面张力

高分子聚电解质既不同于简单的电解质,也不同于无离解基团的高聚物,表现出特殊的物理化学性能,其研究在理论上有重大的意义．同时,聚电解质具有重要的实用价值,如在污水处理、土壤改良、三次采油、钻井液添加剂、制药等领域有广泛的应用．在生命科学中,高分子聚电解质的研究对于正确理解生物大分子的作用（如蛋白质和脂类在生命体中的作用）是十分重要的［１］．聚丙烯酸（ＰＡＡ）是研究较多的合成聚电解质,其分子链在水溶液中离解而带有大量羧酸阴离子［２］,Ｉｓｈｉｍｕｒｏ等［３,４］较详细研究了ＰＡＡ水溶液的表面张力随其…     

聚苯并咪唑-锂盐-聚乙二醇单甲醚共混全固态聚合物电解质的制备及性能

使用共混后浇铸成膜的方法,制备了聚苯并咪唑-锂盐-聚乙二醇单甲醚组成的锂离子电池共混全固态聚合物电解质。通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、差示扫描量热(DSC)、拉伸与交流阻抗测试表征了共混全固态电解质的结构与性能。研究了不同锂盐以及各组分含量对共混全固态电解质的力学性能与电导率的影响。结果表明:聚苯并咪唑与聚乙二醇单甲醚之间存在氢键;共混全固态电解质中聚乙二醇单甲醚处于无定形态;锂盐的加入使聚乙二醇单甲醚的玻璃化转变温度下降;聚乙二醇单甲醚含量越高,共混膜强度越低,电导率越高,并且使用三氟甲磺酸锂作为锂盐时其电导率最高,室温下可以达到3.58×10~(-5) S/cm,高温下可以达到3.3×10~(-3) S/cm,高温下满足对锂离子电池的使用需求。     

交联PEO嵌段共聚物固体电解质的制备及导电性研究

利用低分子聚乙二醇 (PEG ,Mn=6 0 0 )与CH2 Cl2 在碱性条件下通过Williamson反应生成氧亚甲基连接的聚氧化乙烯嵌段聚合物 .1 H NMR表明 ,其分子平均组成以 [CH2 O(CH2 CH2 O) 1 3]为重复单元结构 .适量的2 ,4 二异氰酸甲苯酯 (TDI)与聚合物 锂盐电解质形成交联网络结构 ,具有较好的成膜性能、力学性能与热稳定性能 .在测试温度范围内 ,电导率与温度的关系很好的符合Arrhenius关系式 (σ =Ae-Ea RT) .锂盐浓度不同 ,Arrhenius曲线有一个或两个活化能 (Ea)值出现 .该聚合物掺混LiN(CF3SO2 ) 2 形成的固体电解质具有良好的导电性 ,在EO Li =2 5∶1(摩尔比 )时 ,室温下σ =1 12× 10 - 5S cm ,分解电压可达 5 0V .     

SINGLE-ION CONDUCTIVITY IN POLY (LITHIUM PROPIONATE METHYL SILOXANE)

Poly(lithium propionate methyl siloxane )as a single-ion carrier source was synthesized. The crosslinked film showed lower lithium ionic conductivity at room temperature (about 10~(-10) S/cm). However,the lithium ionic conductivity was obviously increased by blending with high polar polymers such as polyethylene oxide, poly (methylsiloxane - co- ethylene oxide) and poly (methylsiloxane- g- ethylene oxide). In the blend system a high conductivity of 10~(-7)-10~(-5) Scm~(-1) at room temperature was obtained and the single-ion conductivity was deeply influenced by the content of the poly (lithium propionate methyl siioxane). The dc ionic conductivity of the flexible crosslinked films is more stable over time.     

PEO/LiClO_4纳米SiO_2复合聚合物电解质的电化学研究

将实验室制备的纳米二氧化硅和市售纳米二氧化硅粉末与PEO LiClO4复合 ,制得了复合PEO电解质 .它们的室温离子电导率可比未复合的PEO电解质提高 1～ 2个数量级 ,最高可以达到 1 2 4× 10 - 5S cm .离子电导率的提高有两方面的原因 :一是无机二氧化硅粉末的加入抑制了PEO的结晶 ,是二氧化硅粉末和聚合物电解质之间形成的界面对电导率的提高也有一定的作用 .在进一步加入PC EC(碳酸丙烯酯 碳酸乙烯酯 )混合增塑剂后制得的复合凝胶PEO电解质 ,可使室温离子电导率再提高 2个数量 ,达到 2× 10 - 3 S cm .用这种复合凝胶PEO电解质组装了Li|compositegelelectrolyte|Li半电池 ,并测量了该半电池的交流阻抗谱图随组装后保持时间的变化 ,实验观察到在保持时间为 144h以内钝化膜的交流阻抗迅速增大 ,但在随后的时间内逐渐趋于平稳 ,表明二氧化硅粉末的加入可以有效地抑制钝化膜的生长     

Highly ion conductive poly(ethylene oxide)-based solid polymer electrolytes from hydrogen bonding layer-by-layer assembly

We report the development of a solid polymer electrolyte film from hydrogen bonding layer-by-layer (LBL) assembly that outperforms previously reported LBL assembled films and approaches battery integration capability. Films were fabricated by alternating deposition of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) layers from aqueous solutions. Film quality benefits from increasing PEO molecular weight even into the 10(6) range due to the intrinsically low PEO/PAA cross-link density. Assembly is disrupted at pH near the PAA ionization onset, and a potential mechanism for modulating PEO:PAA ratio within assembled films by manipulating pH is discussed. Ionic conductivity of 5 x 10(-5) S/cm is achievable after short exposure to 100% relative humidity (RH) for plasticization. Adding free ions by exposing PEO/ PAA films to lithium salt solutions enhanced conductivity to greater than 10(-5) S/cm at only 52% RH and tentatively greater than 10(-4) S/cm at 100% RH. The excellent stability of PEO/PAA films even when exposed to 1.0 M salt solutions led to an exploration of LBL assembly with added electrolyte present in the adsorption step. Fortuitously, the modulation of PEO/PAA assembly by ionic strength is analogous to that of electrostatic LBL assembly and can be attributed to electrolyte interactions with PEO and PAA. Dry ionic conductivity was enhanced in films assembled in the presence of salt as compared to films that were merely exposed to salt after assembly, implying different morphologies. These results reveal clear directions for the evolution of these promising solid polymer electrolytes into elements appropriate for electrochemical power storage and generation applications.     

Conductivity studies of polymer electrolytes based on aliphatic polyesters

A series of aliphatic polyesters of sebacoyl chloride and poly(ethylene glycol) containing a different number of ethylene oxide groups was synthesized and characterized. These polyesters were complexed with lithium perchlorate to obtain a new class of polymer electrolyte. The relationships between the structure and properties of these polymer electrolytes were investigated. The main factor that affects the ionic conductivity in these systems was found to be the solvating capacity of the polyester for the lithium salt. These polymer electrolytes showed ionic conductivities up to 10^?5 ? 10^?4 S/cm at 25°C. The mechanical strength was improved by cross-linking, and the cross-linked polyester complexed with a LiCIO₄ salt showed an ionic conductivity of 2 × 10^?5 S/cm at room temperature. ⁷Li NMR spin-spin relaxation and dielectric relaxation studies were also carried out to investigate the local environments and dynamics of ions in the polymer electrolytes. © 1995 John Wiley & Sons, Inc.     

Safety-enhanced Polymer Electrolytes with High Ambient-temperature Lithium-ion Conductivity Based on ABA Triblock Copolymers

Liquid electrolytes used in lithium-ion batteries suffer from leakage,flammability,and lithium dendrites,making polymer electrolyte a potential alternative.Herein,a series of ABA triblock copolymers(ABA-x)containing a mesogen-jacketed liquid crystalline polymer(MJLCP)with a polynorbornene backbone as segment A and a second polynorbornene-based polymer having poly(ethylene oxide)(PEO)side chains as segment B were synthesized through tandem ring-opening metathesis polymerizations.The block copolymers can self-assemble into ordered morphologies at 200℃.After doping of lithium salts and ionic liquid(IL),ABA-x self-assembles into cylindrical structures.The MJLCP segments with a high glass transition temperature and a stable liquid crystalline phase serve as physical crosslinking points,which significantly improve the mechanical performance of the polymer electrolytes.The ionic conductivity of ABA-x/lithium salt/IL is as high as 10-3 S·cm-1 at ambient temperature owing to the high IL uptake and the continuous phase of conducting PEO domains.The relationship between ionic conductivity and temperature fits the Vogel-Tamman-Fulcher(VTF)equation.In addition,the electrolyte films are flame retardant owing to the addition of IL.The polymer electrolytes with good safety and high ambient-temperature ionic conductivity developed in this work are potentially useful in solid lithium-ion batteries.     

梳形聚醚全固态聚合物电解质的电导率研究

应用阳离子开环聚合反应合成含二缩三乙二醇单甲醚侧链的梳形聚醚POE,并与高氯酸锂复配制成聚合物电解质.交流阻抗测试表明,当POE电解质内的氧锂比(O/L i)为20时,其电导率最高,室温下为10-4.43S/cm,80℃时则达到10-3.44S/cm.用DSC和XPS分别表征了链段运动能力和锂盐在POE中的溶解状态对电导率的影响.     

马来酸酐—醋酸乙烯酯梳状聚合物单阳离子导体的制备及表征

马来酸酐－醋酸乙烯酯交替共聚物以聚乙二醇单醚醇解，得到带有不同长度的聚醚氧侧链的羧酸型梳状聚合物，其碱金属盐在加入适当增塑剂成膜后，可作为聚合物单阳离子导体，其结构以非晶态为主，具有较低的玻璃化转变温度及较好的热稳定性，增塑后的室温电导率最高可达１０－５Ｓ／ｃｍ．研究发现，适当增加侧链的长度有利于提高聚合物膜的离子电导率．此外，还详细探讨了增塑剂、阳离子半径、温度及外加频率等因素对电导率的影响．     

Single Lithium‐Ion Conducting Polymer Electrolytes Based on a Super‐Delocalized Polyanion

A novel single lithium‐ion (Li‐ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4‐styrenesulfonyl)(trifluoromethyl(S‐trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI^?), and high‐molecular‐weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass‐transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li‐ion transference number (t_Li⁺=0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li‐ion conductivity as high as 1.35×10^?4 S cm^?1 at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries.