Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM+][TFSI–]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340−1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ∼1 solvent molecule. The scarcity of solvent–ion interactions explains the fact that the diffusivity of ions in the mixture significantly depends on the viscosity of the solvent

Decoupling the Electrical Conductivity and Seebeck Coefficient in the <i>RE</i>₂SbO₂ Compounds through Local Structural Perturbations

Compromise between the electrical conductivity and Seebeck coefficient limits the efficiency of chemical doping in the thermoelectric research. An alternative strategy, involving the control of a local crystal structure, is demonstrated to improve the thermoelectric performance in the <i>RE</i>₂SbO₂ system. The <i>RE</i>₂SbO₂ phases, adopting a disordered <i>anti</i>-ThCr₂Si₂-type structure (<i>I</i>4/<i>mmm</i>), were prepared for <i>RE</i> = La, Nd, Sm, Gd, Ho, and Er. By traversing the rare earth series, the lattice parameters of the <i>RE</i>₂SbO₂ phases are gradually reduced, thus increasing chemical pressure on the Sb environment. As the Sb displacements are perturbed, different charge carrier activation mechanisms dominate the transport properties of these compounds. As a result, the electrical conductivity and Seebeck coefficient are improved simultaneously, while the number of charge carriers in the series remains constant

Disorder-Controlled Electrical Properties in the Ho₂Sb_1–<i>x</i>Bi_<i>x</i>O₂ Systems

High-purity bulk samples of the Ho₂­Sb_1–<i>x</i>­Bi_<i>x</i>O₂ phases (<i>x</i> = 0, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared and subjected to structural and elemental analysis as well as physical property measurements. The Sb/Bi ratio in the Ho₂­Sb_1–<i>x</i>­Bi_<i>x</i>O₂ system could be fully traversed without disturbing the overall <i>anti</i>-Th­Cr₂Si₂ type structure (<i>I</i>4/<i>mmm</i>). The single-crystal X-ray diffraction studies revealed that the local atomic displacement on the Sb/Bi site is reduced with the increasing Bi content. Such local structural perturbations lead to a gradual semiconductor-to-metal transition in the bulk materials. The significant variations in the electrical properties without a change in the charge carrier concentration are explained within the frame of the disorder-induced Anderson localization. These experimental observations demonstrated an alternative strategy for electrical properties manipulations through the control of the local atomic disorder