Ionogels based on protic ionic liquid - lithium salt mixtures

The effect of the addition of lithium nitrate on the liquid range and electrical conductivity of mixtures of a protic ionic liquid, ethylammonium nitrate (EAN) with LiNO3 is reported in this work. Moreover, changes in these properties upon confinement in silica-based matrices are also analysed and related to variations on the microstructure of the mixtures. Our results show that gelation of the mixtures induces amorphous behaviour in all the samples, but no significant changes in the thermal stability are detected. However, important differences on the electrical conductivity of the liquid and gel states of the mixtures were observed. While this magnitude decreases with the addition of salt in the liquid samples for all the temperatures it increases at low concentrations of LiNO3 up to a maximum in the gelled samples with the lowest concentration of added salt (0.1 mol of salt by kg of EAN). High resolution magic angle spinning (HRMAS) NMR shows that the addition of lithium nitrate increases the mobility (both rotational and translational motion) of the cation EA+ within the ionogel and the diffusion of the cation provides evidence of the presence of two different populations of the same molecules experiencing two distinct apparent diffusion coefficients (bi-exponential decay of magnetization in diffusion NMR experiments), while it is mono-exponential in the pure ionic liquid. The Li+ cation is shown to display a higher mobility (both rotational and translational motion) in the ionogel than in the neat ionic liquid. The frustration of the formation of solvation complexes due to the confinement is suspected to be behind this behaviour.