Poly(ether-thioethers) by Thiol-Ene Click and Their Oxidized Analogues as Lithium Polymer Electrolytes
Poly(ether-thioethers) by Thiol-Ene Click and Their Oxidized Analogues as Lithium Polymer Electrolytes
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DOI：
10.1021/acs.macromol.5b02513
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发表时间：
2016-02-23
期刊：
影响因子：
5.5
通讯作者：
Tew, Gregory N.
中科院分区：
文献类型：
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作者：
Sarapas, Joel M.;Tew, Gregory N.
通过二硫醇和二乙烯基醚的自由基偶联反应合成了一系列共九种聚醚硫醚（PETEs），以研究有机硫在固体聚合物电解质中的重要性。合成了两个系列的四种聚合物，以探测硫醚单元之间的碳间隔基长度和醚与硫醚单元的比率的影响。来自这两个系列的PETE样品具有低的T-g值，范围为-50至-75 ° C，并且除了两个PETE之外的所有PETE都显示出结晶度。所有聚合物的分子量在7和13 kg/mol之间。利用含硫官能团的优势，将单一聚合物PETE-1选择性氧化成聚醚亚砜PESO-1和聚醚砜PES-1。氧化将PETE-1的T-g从-64 ℃分别增加到PESO-1和PES-1的-36 ℃和-26 ℃，而所有三种都是无定形的。在九种新的PETE聚合物中，两种是无定形的，并且LiTFSI的加入降低了其他七种PETE样品的结晶度。对于PETE-1、PESO-1和PES-1，也观察到随着盐的添加Tg增加。具有两个、四个和六个亚甲基单元的碳间隔物的PETE样品具有大致均匀的离子电导率，在80 ℃下接近5 × 10（-5）S/cm，而具有八个亚甲基单元的样品具有较低的电导率，其在较低温度下通过结晶度进一步降低。具有不同醚和硫醚比率的样品也具有非常均匀的电导率，与具有不同碳间隔物的样品在量值上相似。在氧化系列中，PETE-1优于PES-1，PES-1又在离子迁移率方面优于PESO-1。在80 ° C下观察到的最高电导率（10（-4）S/cm）是对于具有r = 0.05的盐负载的PETE-1。这里描述的合成方法将使大量的新的聚合物结构，以控制官能团的位置和密度提供固体聚合物电解质的新材料，广泛的官能团变化，和全面的结构-活性关系。
A family of nine poly(ether-thioethers) (PETEs) were synthesized by the radical coupling of a dithiol and a divinyl ether to investigate the importance of organo-sulfur incorporation in solid polymer electrolytes. Two series of four polymers each were synthesized to probe both the effect of the carbon spacer length between thioether units and of the ratio of ether to thioether units. PETE samples from these two series had low T-g values, ranging from -50 to -75 degrees C, and all but two PETEs displayed crystallinity. Molecular weights between 7 and 13 kg/mol were obtained for all polymers. Taking advantage of the sulfur-centered functional group, a single polymer, PETE-1, was selectively oxidized to the poly(ether-sulfoxide) PESO-1 and the poly(ether-sulfone) PES-1. Oxidation increased the T-g of PETE-1 from -64 degrees C to -36 and -26 degrees C for PESO-1 and PES-1, respectively, while all three were amorphous. Of the nine new PETE polymers, two were amorphous and the addition of LiTFSI decreased the extent of crystallinity for the other seven PETE samples. An increase in Tg was also observed for PETE-1, PESO-1, and PES-1 with the addition of salt. PETE samples with carbon spacers of two, four, and six methylene units had generally uniform ion conductivity, near 5 x 10(-5) S/cm at 80 degrees C, while the sample with eight methylene units had a lower conductivity that was further decreased by crystallinity at lower temperatures. Samples with varied ether and thioether ratios also had very uniform conductivities, similar in magnitude to samples with varied carbon spacers. Within the oxidized series, PETE-1 outperformed PES-1, which in turn outperformed PESO-1 in terms of ion mobility. The highest observed conductivity (10(-4) S/cm) at 80 degrees C was for PETE-1 with a salt loading of r = 0.05. The synthetic approach described here will enable a wealth of new polymer structures to be produced with controlled functional group placement and density providing novel materials for solid polymer electrolytes, broad functional group variation, and comprehensive structure-activity relationships.