RESUMO
The Li+ ion mobility through the porous cathode is a critical aspect in the development of commercial Li-air batteries. The bulk transport properties of lithium salts in organic solvents are not reliable parameters for the design of this type of battery since confinement could significantly modify the transport properties, especially when pore diameters are below 10 nm. In this work, we studied the effect of the carbon mesostructure and surface charge on the diffusion of LiTf and LiTFSI salts dissolved in diglyme, typical electrolytes for lithium-air batteries. Interdiffusion coefficients of the salts were determined using a conductimetric method. NMR spectroscopy and relaxometry were used to explore the effect of the carbon structure and the surface charge density on the interaction between the electrolytes and the pore wall. We showed that carbon micro/mesoporous structure plays a critical role in the transport properties of the electrolyte, producing a decrease of up to 2-3 orders of magnitude in the salt interdiffusion coefficients when going from bulk solutions to pores below 4 nm in diameter. It was observed that for pores 25 nm in diameter, the reduction in the diffusion coefficient can be mainly ascribed to the porosity of the sample, giving tortuosity factors around 1. However, for smaller pore sizes (1-10 nm diameter) bigger tortuosity coefficients were observed and were related to strong ion-pore wall interactions. Moreover, it was noticed that the ratio between the diffusion coefficients of the two studied salts dissolved in diglyme, is different in bulk and under confinement, demonstrating that the interactions of the ions with the charged pore wall probably compete with the cation-anion interactions, affecting salt association under confinement.
RESUMO
In this work, we revisited the glass transition temperature (Tg) behavior of bulk and confined water-glycerol solutions as a function of the mixture composition and size of the confinement media, with the aim to shed some light on some controversies found in the literature. In the case of bulk mixtures, some discrepancies are observed due to the differences in the way of calculating Tg from the DSC experiments and differences in the protocols of cooling/reheating. However, unphysical behavior observed below the eutectic composition can be due to the crystallization of water during the cooling of the mixture. We also analyzed the effect of confinement on the glass transition of glycerol aqueous solutions, with glycerol mass fraction, wG, between 0.5 and 1.0, in silica mesoporous samples with pore diameters between 2 and 58 nm. Our results show that the the Tg dependence on pore size changes with the mixture composition. For glycerol-rich samples, Tg decreases with a decreasing pore size. This tendency changes with increasing water concentration below wG â¼ 0.6 for samples with dp between 2 and 8 nm, where two glass transition temperatures appear. We hypothesize that this effect is related to the existence of two liquid phases with different densities. The Tg composition dependence in confined glycerol-water mixtures was analyzed with the Gordon-Taylor equation modified for confined mixtures, which allowed us to calculate the Tg of the pure components as a function of the pore size. This analysis shows that for pores with dp > 20 nm, and for pure water and pure glycerol, Tg decreases with the pore size, attaining an almost constant value for samples with pore sizes between 2 and 8 nm. This Tg pore size dependence is explained considering the competition of two opposite effects: a reduction in Tg with a decreasing pore size given when the length scale of dynamics is comparable to the pore size, and an increment in Tg with a decreasing pore size as a result of increasing interactions of the confined liquid with the pore walls.