In an example of stability from instability, a Li(7)P(2)S(8)I solid-state Li-ion conductor derived from β-Li(3)PS(4) and LiI demonstrates electrochemical stability up to 10 V vs Li/Li(+). The oxidation instability of I is subverted via its incorporation into the coordinated structure. The inclusion of I also creates stability with the metallic Li anode while simultaneously enhancing the interfacial kinetics and ionic conductivity. Low-temperature membrane processability enables facile fabrication of dense membranes, making this conductor suitable for industrial adoption.
Multi-nuclear (1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, as shown by their respective activation volumes (28.8 ± 2.5 cm3/mol for TFSA vs. 14.6 ± 1.3 cm3/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis. In addition, 2H T1 data suggests increased ordering with increasing pressure, with two T1 regimes observed for the MD3 and D2 isotopologues between 0.1–100 and 100–250 MPa respectively. The activation volumes for T1 were 21 and 25 (0–100 MPa) and 11 and 12 (100–250 MPa) cm3/mol for the MD3 and D2 isotopologues, respectively.
X-ray scattering measurements were utilized to probe the effects of pressure on a series of ionic liquids, N-alkyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr-TFSI) (A = 3, 6, and 9), along with mixtures of ionic liquid and 30 mol. % lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. No evidence was found for crystallization of the pure ionic liquids or salt mixtures even at pressures up to 9.2 GPa. No phase separation or demixing was observed for the ionic liquid and salt mixtures. Shifts in the peak positions are indicative of compression of the ionic liquids and mixtures up to 2 GPa, after which samples reach a region of relative incompressibility, possibly indicative of a transition to a glassy state. With the application of pressure, the intensity of the prepeak was found to decrease significantly, indicating a reduction in cation alkyl chain aggregation. Additionally, incompressibility of the scattering peak associated with the distance between like-charges in the pure ionic liquids compared to that in mixtures with lithium salt suggests that the application of pressure could inhibit Li coordination with TFSI to form Li[TFSI] complexes. This inhibition occurs through the suppression of TFSI in the trans conformer, in favor of the smaller cis conformer, at high pressures.
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