We report on the influence of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) doping on the glass transition temperature (Tg), the ionic conductivity, and Li-ion coordination of two dicationic ionic liquids (DILs) based on the TFSI anion. The results are compared to the behaviour of traditional mono-cationic ionic liquids. The cations of the DILs contain two imidazolium rings, connected by a decane hydrocarbon chain. Homogeneous mixtures of these ILs and LiTFSI can be obtained in a large concentration range. With increasing Li-salt concentration the ionic conductivity decreases whereas the glass transition temperature increases in both systems. However, the influence of the salt doping on the ionic conductivity and the glass transition temperature is low compared to typical mono-cationic ionic liquids, based on for example the pyrrolidinium cation and the TFSI anion. This behaviour is mirrored in the average coordination number of TFSI anions around Li-ions, determined by Raman spectroscopy. The coordination number is systematically lower in the DILs, suggesting a connection between the difference in the Li-ion environment and the behaviour of the glass transition and the ionic conductivity. A Tg-scaled Arrhenius plot of the ionic conductivity shows that the ionic conductivity for all LiTFSI concentrations has the same temperature dependence, i.e., the fragility of the liquid is the same. This implies that the conduction process is dominated by the viscous properties of the liquids over the entire concentration range. This provides further support for linking the local environment of the Li-ions to the glass transition and conduction process in the ionic liquid/salt mixtures.

We report on the effect of water on local structure and phase behavior of two protic ionic liquids, C2HImTFSI and C2HImTfO. Raman and infrared spectroscopy are employed to investigate the local coordination state. We find that water interacts weakly with TFSI(-) while more specifically with TfO(-) through the -SO3 group. Additionally, we observe that upon addition of water the -NH stretching frequency does not change in C2HImTFSI, while it red-shifts in C2HImTfO, indicative of different hydrogen bonding configurations. Supported by the appearance of some additional features in the 800-1000 cm(-1) frequency range where ring out-of-plane bending (γ) modes are found, we hypothesize that in C2HImTFSI water interacts only with the cation coordinating to the ring C(2)H and the N(3)H sites, while it interacts with both cation and anion in C2HImTfO forming hydrogen bonds that involve the cationic N-H site as well as the anionic -SO3 group. These different local structures also reflect in the phase behavior investigated by DSC, which reveals a more homogeneous solution when water is added to C2HImTfO, as compared to H2O/C2HImTFSI mixtures. Finally we report that the addition of water also significantly affects both Tm and Tg.

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We report on the thermal and transport properties of new dicationic ionic liquids. The new ionic liquids are based on the bis(trifluoromethanesulfonyl)imide [NTf(2)](-) anion and a cation that contains two imidazolium rings, connected by either a pentane or a decane hydrocarbon chain and different side groups. We have investigated the conductivity and the thermal properties by dielectric spectroscopy and differential scanning calorimetry, respectively. Our results show that the length of the alkyl chain on the cation has no, or weak, influence on the glass transition temperature, T(g), whereas the presence of rigid aromatic side groups has a strong influence increase T(g). The highest ionic conductivity is 5.9 x 10(-4) S cm(-1) at 298 K for an ionic liquid with a decane chain and one methyl group on each imidazolium ring. The conductivity results correlate well with the glass transition temperatures. This shows that the flexibility of the geminal cations is very important for the conductivity. However, the presence of nonflexible aromatic side groups on the imidazolium ring decreases the flexibility and hence the mobility.