Thermal Gradient Infrared Spectroscopy for Diffusion in Polymers

Time-resolved Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR) was used to measure diffusion in opaque and translucent samples. FTIR-ATR was used to measure the change in the absorbance near the heated ATR crystal surface. The infrared absorbance was then related to the concentration through the Beer-Lambert law. The sample used is a polymer electrolyte composed of lithium bis-trifluoromethanesulfonylimide (LiTFSI) salt in a block copolymer polystyrene-poly(ethylene oxide) (SEO). A new approach to introduce concentration gradients is presented using a temperature gradient that creates a small salt concentration gradient due to thermally driven mass diffusion (the Soret effect). This first method was compared to a second method that we reported using two laminated polymer electrolyte films of different salt concentrations. The thermal gradient study (method 1) covered three temperature differences of 10, 15, and 20 °C, while the second study (method 2) used three average molar ratios across isothermal temperatures ranging from 80 to 120 °C. The benefits and limitations of the new approach are reported, as is the activation energy for salt diffusion in this and similar SEO electrolytes. Developing new techniques to measure diffusion coefficients effectively will aid in the development of a variety of devices, including solid-state batteries and thermogalvanic cells, that are able to convert waste heat into electricity and improve the efficiency of power-generating systems. FTIR-ATR overcomes previous limitations in experimental techniques measuring diffusion coefficients. The results prove that thermal gradient FTIR-ATR is an effective and repeatable approach for determining Fickian diffusion coefficients in viscoelastic solids.