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Thermo-electrochemical cells (or thermocells) represent a promising technology to convert waste heat energy into electrical energy, generating power with minimal material consumption and a limited carbon footprint. Recently, the adoption of ionic liquids has pushed both the operational temperature range and the power output of thermocells. This research discusses the design challenges and the key performance limitations that need to be addressed to deploy the thermocells in real-world applications. For this purpose, a unique up-scaled design of a thermocell is proposed, in which the materials are selected according to the techno-economic standpoint. Specifically, the electrolyte is composed of EMI-TFSI ionic liquid supplemented by [Co(ppy)]3+/2+ redox couples characterized by a positive Seebeck coefficient (1.5 mV/K), while the electrodes consist of carbon-based materials characterized by a high surface area. Such electrodes, adopted to increase the rate of the electrode reactions, lead to a thermoelectric performance one order of magnitude greater than the Pt electrode-based counterpart. However, the practical applications of thermocells are still limited by the low power density and low voltage that can be generated.

Two ethoxy containing ionic liquids (ILs) sharing the same anion, N-trimethyl-N (2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (N111(2O1)-TFSI) and N,N-diethyl-N-methyl-N (2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (N122(2O1)-TFSI), and their mixtures are studied by means of differential scanning calorimetry and infrared spectroscopy combined with DFT calculations. The two ILs, slightly differing only for the length of two short chains, diverge significantly in the thermal properties: N111(2O1)-TFSI undergoes to a crystallization upon cooling, whereas N122(2O1)-TFSI is likely to become a glass. Experimental results indicate that in N111(2O1)-TFSI the occurrence of hydrogen bonding is energetically favored, and become particularly evident in the solid phase. The comparison with computational results indicates that it could be ascribed to the CH bonds involving the C atoms directly linked to the central N atom. In N122(2O1)-TFSI, DFT calculations suggest that hydrogen bonding could take place; however, IR measurements suggest that hydrogen bonding is not energetically favored. Moreover, in N122(2O1)-TFSI there is a larger conformational disorder that prevents from the alignment of cation and anion that contributes to the detection of clear hydrogen bonding infrared active bands. The mixtures rich in N111(2O1)-TFSI crystallize at lower temperatures than the pure ionic liquid. Progressively, the energy gain due to the instauration of hydrogen bonding decreases as the concentration of N122(2O1)-TFSI increases.

Novel ionic liquid (IL) electrolytes based on the asymmetric (fluoromethylsulfonyl)(trifluoromethylsulfonyl)imide (FTFSI)− anion, combined with the N-trimethyl-N-butyl-ammonium (N1114)+ and N,N-diethyl-N-methyl-N(2-methoxyethyl)-ammonium (N122(2O1))+ cations, were successfully synthesized and investigated in terms of thermal, vibrational and electrochemical properties. Thermogravimetric measurements revealed that the ionic liquids are stable up to 300 °C (2% mass loss). Differential scanning calorimetry measurements evidenced no phase transition down to −90 °C, suggesting a transition towards a glass state at lower temperatures. Infrared spectroscopy measurements, for the first time performed on ILs containing FTFSI, could not detect any crystallization down to −140 °C. The frequency of the main absorption bands of the ILs are in good agreement with DFT calculations. The FTFSI ionic liquid electrolytes, containing 20% mol of LiTFSI, show no solid-liquid phase transition due to the asymmetry of the FTFSI− anion, increasing the −10 °C conductivity up to 10−4 S cm−1. These interesting ion transport properties remarkably extend the operative temperature range down to low temperatures. The FTFSI electrolytes exhibit remarkable electrochemical stability up to 4.8 V, this making them appealing for realizing safer and highly reliable lithium battery systems operating at high voltages.

Poly(ionic liquid)s are an innovative class of materials with promising properties in gas separation processes that can be used to boost the neat polymer performances. Nevertheless, some of their properties such as stability and mechanical strength have to be improved to render them suitable as materials for industrial applications. This work explored, on the one hand, the possibility to improve gas transport and separation properties of the block copolymer Pebax® 1657 by blending it with poly[3-ethyl-1-vinyl-imidazolium] diethyl phosphate (PEVI-DEP). On the other hand, Pebax® 1657 served as a support for the PIL and provided mechanical resistance to the samples. Pebax® 1657/PEVI-DEP composite membranes containing 20, 40, and 60 wt.% of PEVI-DEP were cast from solutions of the right proportion of the two polymers in a water/ethanol mixture. The PEVI-DEP content affected both the morphology of the dense membranes and gas transport through the membranes. These changes were revealed by scanning electron microscopy (SEM), time-lag, and gravimetric sorption measurements. Pebax® 1657 and PEVI-DEP showed similar affinity towards CO2, and its uptake or solubility was not influenced by the amount of PIL in the membrane. Therefore, the addition of the PIL did not lead to improvements in the separation of CO2 from other gases. Importantly, PEVI-DEP (40 wt.%) incorporation affected and improved permeability and selectivity by more than 50% especially for the separation of light gases, e.g., H2/CH4 and H2/CO2, but higher PEVI-DEP concentrations lead to a decline in the transport properties.