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Polyphosphonates as ionic conducting polymers
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DOI：10.1002/pol.20200561.png)
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Abstract
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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 degrees C). Binding models for Li+ were generated using P-31{H-1}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 T-g, which is likely an effect of reduced Columbic interactions. Because of their modularity and ease with which cation binding can be evaluated using P-31{H-1} NMR titration experiments, polyphosphonates offer a unique approach for the modification of Li+ ion battery technology.
Keywords:
P-31{H-1} NMR
cooperative binding
ionic conductivity
polymer electrolyte
polyphosphonate
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