A Study of the Conformers of the (Nonafluorobutanesulfonyl)imide Ion by Means of Infrared Spectroscopy and Density Functional Theory (DFT) Calculations

Pyrrolidinium-based ionic liquids with anions of the per(fluoroalkylsulfonyl)imide family are particularly interesting for their use as electrolytes in lithium batteries. These ions have several geometric isomers and the presence of different ion conformers and their distribution affects the ILs (Ionic liquids) physical and chemical properties. In the present work, we report the temperature dependence of the infrared spectra of the N-butyl-N-methyl-pyrrolidinium(trifluoromethanesulfonyl) (nonafluorobutanesulfonyl)imide (PYR14-IM14) ionic liquid; DFT (Density Functional Theory) calculations performed with different models provides indications about the IM14 conformers and their vibrational spectra. Moreover the temperature dependence of the intensity of the lines identified as markers of different conformers provide indications about the conformers’ distribution and the difference of their enthalpy in the liquid phase

Competition between Polar and Antiferrodistortive Modes and Correlated Dynamics of the Methylammonium Molecules in MAPbI3_3 from Anelastic and Dielectric Measurements

The mechanisms behind the exceptional photovoltaic properties of the metallorganic perovskites are still debated, and include a ferroelectric (FE) state from the ordering of the electric dipoles of the organic molecules. We present the first anelastic (complex Young's modulus) and new dielectric measurements on CH$_{3}$NH$_{3}$PbI$_3$, which provide new insight on the reorientation dynamics of the organic molecules, and the reason why they do not form a FE state. The permittivity is fitted within the tetragonal phase with an expression that includes the coupling between FE and octahedral tilt modes, indicating that the coupling is competitive and prevents FE ordering. The onset of the orthorhombic phase is accompanied by sharp stiffening, analogous to the drop of permittivity, due to the hindered molecular dynamics. On further cooling, an intense anelastic relaxation process without a dielectric counterpart suggests the reorientation of clusters of molecules with strong antiferroelectric correlations.Comment: accepted in J. Phys. Chem. Let

An infrared spectroscopy study of the conformational evolution of the Bis(trifluoromethanesulfonyl)imide ion in the liquid and in the glass state

We measure the far-infrared spectrum of N,N-Dimethyl-N-ethyl-N-benzylammonium (DEBA) bis(trifluoromethanesulfonyl) imide (TFSI) ionic liquid (IL) in the temperature range between 160 and 307 K. Differential scanning calorimetry measurements indicate that such IL undergoes a glass transition around 210K. DFT calculations allow us to assign all the experimental absorptions to specific vibrations of the DEBA cation or of the two conformers of the TFSI anion. We find that the vibration frequencies calculated by means of the PBE0 functional are in better agreement with the experimental ones than those calculated at the B3LYP level, largely used for the attribution of vibration lines of ionic liquids. Experimentally we show that, in the liquid state, the relative concentrations of the two conformers of TFSI depend on temperature through the Boltzmann factor and the energy separation, ΔH, is found to be ≈2 kJ/mol, in agreement with previous calculations and literature. However, in the glassy state, the concentrations of the cis-TFSI and trans-TFSI remain fixed, witnessing the frozen state of this phase

Stability of Cubic FAPbI3_3 from X-ray Diffraction, Anelastic, and Dielectric Measurements

Among the hybrid metal-organic perovskites for photovoltaic applications FAPbI_3 (FAPI) has the best performance regarding efficiency and the worst regarding stability, even though the reports on its stability are highly contradictory. In particular, since at room temperature the cubic alpha phase, black and with high photovoltaic efficiency, is metastable against the yellow hexagonal delta phase, it is believed that alpha-FAPI spontaneously transform into delta-FAPI within a relatively short time. We performed X-ray diffraction and thermogravimetric measurements on loose powder of FAPI, and present the first complete dielectric and anelastic spectra of compacted FAPI samples under various conditions. We found that alpha-FAPI is perfectly stable for at least 100 days, the duration of the experiments, unless extrinsic factors induce its degradation. In our tests, degradation was detected after exposure to humidity, strongly accelerated by grain boundaries and the presence of delta phase, but it was not noticeable on the loose powder kept in air under normal laboratory illumination. These findings have strong implications on the strategies for improving the stability of FAPI without diminishing its photovoltaic efficiency through modifications of its composition

Elastic and dielectric measurements of the structural transformations in the ferroelectric perovskite (Na1/2Bi1/2)1-xBaxTiO3

NBT is a perovskite undergoing a series of structural and polar transitions starting from the high temperature paraelectric phase: tetragonal antiferroelectric, rhombohedral and finally ferroelectric. In solid solution with BaTiO3 the ferroelectric phase changes from rhombohedral to tetragonal, at the so-called morphotropic phase boundary, and the phases at higher temperature become ill-defined, also because of the large lattice disorder induced by the coexistence of differently charged cations in the same sublattice. Combined dielectric and anelastic spectroscopy measurements are presented, which clarify some issues related to the phase transitions in NBT-BT. The influence of Ba substitution on the tetragonal antiferroelectric phase is determined for the first time, and the possibility that a monoclinic phase, although with very short coherence length, exists near the morphotropic phase boundary is discussed in view of a large maximum of the elastic complianc

Hydrogen absorption properties of amorphous (Ni0.6Nb0.4−yTay)100−xZrx membranes

Ni based amorphous materials have great potential as hydrogen purification membranes. In the present work the melt spun (Ni0.6Nb0.4−yTay)100−xZrx with y=0, 0.1 and x=20, 30 was studied. The result of X-ray diffraction spectra of the ribbons showed an amorphous nature of the alloys. Heating these ribbons below T < 400 °C, even in a hydrogen atmosphere (1−10 bar), the amorphous structure was retained. The crystallization process was characterized by differential thermal analysis and the activation energy of such process was obtained. The hydrogen absorption properties of the samples in their amorphous state were studied by the volumetric method, and the results showed that the addition of Ta did not significantly influence the absorption properties, a clear change of the hydrogen solubility was observed with the variation of the Zr content. The values of the hydrogenation enthalpy changed from ~37 kJ/mol for x=30 to ~9 kJ/mol for x=20. The analysis of the volumetric data provides the indications about the hydrogen occupation sites during hydrogenation, suggesting that at the beginning of the absorption process the deepest energy levels are occupied, while only shallower energy levels are available at higher hydrogen content, with the available interstitial sites forming a continuum of energy levels

Hydrogen induced abrupt structural expansion at high temperatures of a Ni32Nb28Zr30Cu10 membrane for H2 purification

Ni-Nb-Zr amorphous membranes, prepared by melt-spinning, show great potential for replacing crystalline Pd-based materials in the field of hydrogen purification to an ultrapure grade (>99.999%). In this study, we investigate the temperature evolution of the structure of an amorphous ribbon with the composition Ni32Nb28Zr30Cu10 (expressed in atom %) by means of XRD and DTA measurements. An abrupt structural expansion is induced between 240 and 300 °C by hydrogenation. This structural modification deeply modifies the hydrogen sorption properties of the membrane, which indeed shows a strong reduction of the hydrogen capacity above 270 °C

Influence of doping on the structural transformations of the proton conducting perovskite BaCe1 xYxO3-&#948;

From neutron diffraction it is known that the BaCeO3 perovskite undergoes a sequence of phase transformations from high temperature cubic C to rhombohedral R, to orthorhombic O1 (Imma) and to orthorhombic O2 (Pnma). Doping Y3+ on the Ce4+ site introduces charge compensating O vacancies (VO) that may be partially filled with OH complexes with exposition to H2O, so making the material an ionic conductor. Anelastic relaxation experiments have been carried out on samples doped with 2%Y and 10%Y; the real part s\u27(T) of the complex elastic compliance presents softenings at the transitions, and the loss s\u27\u27/s\u27 curves allow the content of VO and H to be monitored. Doping has a strong effect on the temperature of the Pnma/R transition: with 10%Y in the fully hydrated state TO1-R increases up to 750 K while after full outgassing falls to 500 K, meaning that the introduction of ~5% VO shifts the transition of 250 K. While the effect of cation substitution on the transitions temperature is easily explained in terms of simple arguments usually valid for perovskites based on bond length considerations, the remarkable stabilization of the R phase by VO requires to take into account the anomalous sequence of phase transitions of undoped BaCeO3, where the R structure transforms into orthorhombic Pnma on cooling with the loss of an octahedral tilt syste

Relaxational Dynamics in the PYR14-IM14 Ionic Liquid by Mechanical Spectroscopy

The anelastic spectrum of the N-butyl-N-methyl-pyrrolidinium (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl)imide (PYR14-IM14) is reported for the first time. On cooling, at 4 Kmin-1 the sample undergoes a glass transition around 190 K. In the liquid phase, a thermally activated relaxation process is measured and it is analyzed by means of a modified Debye model. The best fit results indicate that the peak is related to the ion hopping between non-equivalent configurations which are mainly defined by the anion conformer configuration