Polymer chain organization in tensile-stretched poly(ethylene oxide)-based polymer electrolytes

Polymer chain orientation in tensile-stretched poly(ethylene oxide)–lithium trifluoromethanesulfonate polymer electrolytes are investigated with polarized infrared spectroscopy as a function of the degree of strain and salt composition (ether oxygen atom to lithium ion ratios of 20:1, 15:1, and 10:1). The 1359 and 1352 cm−1 bands are used to probe the crystalline PEO and P(EO)3LiCF3SO3 domains, respectively, allowing a direct comparison of chain orientation for the two phases. Two-dimensional correlation FT-IR spectroscopy indicates that the two crystalline domains align at the same rate as the polymer electrolytes are stretched. Quantitative measurements of polymer chain orientation obtained through dichroic infrared spectroscopy show that chain orientation predominantly occurs between strain values of 150% and 250%, regardless of salt composition investigated. There are few changes in chain orientation for either phase when the films are further elongated to a strain of 300%; however, the PEO domains are slightly more oriented at the high strain values. The spectroscopic data are consistent with stretching-induced melt-recrystallization of the unoriented crystalline domains in the solution-cast polymer films. Stretching the films pulls polymer chains from the crystalline domains, which subsequently recrystallize with the polymer helices parallel to the stretch direction. If lithium ion conduction in crystalline polymer electrolytes is viewed as consisting of two major components (facile intra-chain lithium ion conduction and slow helix-to-helix inter-grain hopping), then alignment of the polymer helices will affect the ion conduction pathways for these materials by reducing the number of inter-grain hops required to migrate through the polymer electrolyte.