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Polyphosphonates as ionic conducting polymers
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2020-12-19 , DOI: 10.1002/pol.20200561
Timothy R. Totsch 1 , Ivan Popov 2 , Victoria L. Stanford 1 , Aaron L. Lucius 1 , Stephen H. Foulger 3 , Gary M. Gray 1
Affiliation  

Polyphosphonates, a class of polymers with the generic formula –[P(R)(X)–OR'O]n–, exhibit a high degree of modularity due to the range of R, R', and X groups that can be incorporated. As such, these polymers may be designed with a polyethylene oxide (PEO) backbone (R' group) and employed as solid polymer electrolytes (SPEs). Two PEO‐containing polyphosphonate analogs (R = Ph; X = S or Se) were doped with LiPF6 and their conductivities were measured. Conductivities were similar (X = S) to or exceeding (X = Se) those of standard PEO systems (just below 10−4 S/cm at 100°C). Binding models for Li+ were generated using 31P{1H}NMR titration experiments. Binding of Li+ by these polyphosphonates followed a positive cooperativity model, and varying the X group (S or Se) affected the observed cooperativity (Hill coefficient = 1.73 and 4.16, respectively). The presence of Se also leads to an increase in conductivity as temperature is raised above the Tg, which is likely an effect of reduced Columbic interactions. Because of their modularity and ease with which cation binding can be evaluated using 31P{1H} NMR titration experiments, polyphosphonates offer a unique approach for the modification of Li+ ion battery technology.

中文翻译:

聚膦酸酯作为离子导电聚合物

聚膦酸酯是一类通式为[[P(R)(X)–OR'O] n –的聚合物,由于可以结合的R,R'和X基团的范围,它们具有高度的模块化性。这样,这些聚合物可以设计有聚环氧乙烷(PEO)主链(R'基团)并用作固体聚合物电解质(SPE)。用LiPF 6掺杂了两个含PEO的多膦酸酯类似物(R = Ph; X = S或Se),并测量了它们的电导率。电导率与标准PEO系统的电导率相似(X = S)或超过(X = Se)(在100°C时低于10 -4 S / cm)。使用31 P { 1 H} NMR滴定实验生成Li +的结合模型。Li +的结合这些多膦酸酯的合成遵循正合作模型,改变X基团(S或Se)会影响观察到的合作性(希尔系数分别为1.73和4.16)。当温度升高到T g以上时,Se的存在也会导致电导率增加,这很可能是降低了Columbic相互作用的结果。由于它们的模块化和易于使用31 P { 1 H} NMR滴定实验评估阳离子结合的能力,聚膦酸酯为修饰Li +离子电池技术提供了独特的方法。
更新日期:2021-01-15
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