The reaction of Li2S and P2S5 with Li4[SnS4], a recently discovered, good Li(+) ion conductor, yields Li10SnP2S12, the thiostannate analogue of the record holder Li10GeP2S12 and the second compound of this class of superionic conductors with very high values of 7 mS/cm for the grain conductivity and 4 mS/cm for the total conductivity at 27 °C. The replacement of Ge by Sn should reduce the raw material cost by a factor of ~3.
A number of basic scientific questions relating to ion conduction in homogeneously disordered solids are discussed. The questions deal with how to define the mobile ion density, what can be learned from electrode effects, what is the ion transport mechanism, the role of dimensionality, and what are the origins of the mixed-alkali effect, of time-temperature superposition, and of the nearly-constant loss. Answers are suggested to some of these questions, but the main purpose of the paper is to draw attention to the fact that this field of research still presents several fundamental challenges.
The structure and dynamics of the interfacial layers between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy measurements. The in situ scanning tunnelling microscopy measurements reveal that the Au(111) surface undergoes a reconstruction, and at -1.2 V versus Pt quasi-reference the famous (22 × √3) herringbone superstructure is probed. Atomic force microscopy measurements show that multiple ion pair layers are present at the ionic liquid/Au interface which are dependent on the electrode potential. Upon applying cathodic electrode potentials, stronger ionic liquid near surface structure is detected: both the number of near surface layers and the force required to rupture these layers increases. The electrochemical impedance spectroscopy results reveal that three distinct processes take place at the interface. The fastest process is capacitive in its low-frequency limit and is identified with electrochemical double layer formation. The differential electrochemical double layer capacitance exhibits a local maximum at -0.2 V versus Pt quasi-reference, which is most likely caused by changes in the orientation of cations in the innermost layer. In the potential range between -0.84 V and -1.04 V, a second capacitive process is observed which is slower than electrochemical double layer formation. This process seems to be related to the herringbone reconstruction. In the frequency range below 1 Hz, the onset of an ultraslow faradaic process is found. This process becomes faster when the electrode potential is shifted to more negative potentials.
The Li + transference numbers of three different liquid electrolytes for Li-ion batteries were measured in a symmetrical Li | electrolyte | Li cell by means of very-low-frequency impedance spectroscopy (VLF-IS). The electrolytes were: (i) The standard battery electrolyte LP30; (ii) an equimolar mixture of tetraglyme (G4) and lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI); (iii) Li-TFSI dissolved in the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI). We found that the Li + transference numbers of the two electrolytes LP30 and G4/Li-TFSI are much smaller than the Li + transport numbers t NMR Li + obtained from pulsed-field gradient NMR measurements. On the other hand, in the case of BMP-TFSI/Li-TFSI, the values for t current Li + and t NMR Li + are more similar. In order to rationalize the large differences between t current Li + and t NMR Li + found for LP30 and G4/Li-TFSI, we combined the Onsager reciprocal relations with linear response theory, and we derived expressions for t current Li + , which take into account all correlations between ionic movements in the electrolyte. Thereby, we show that t current Li + can be considerably smaller than t NMR Li + , if strong directional correlations exist between the movements of cations and anions. Finally, we discuss differences in Li + transference numbers obtained by VLF-IS and by potentiostatic polarization measurements.
Ion transport processes in mixtures of N-butyl- N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) were characterized by ac impedance spectroscopy and pulsed field gradient NMR. Molar ratios x = n Li-TFSI/( n Li-TFSI + n BMP-TFSI) up to 0.377 could be achieved without crystallization. From the bulk ionic conductivity and the individual diffusion coefficients of cations and anions we calculate the Haven ratio and the apparent lithium transference number. Although the Haven ratio exhibits typical values for ionic liquid electrolytes, the maximal apparent lithium transference number is higher than found in other recent studies on ionic liquid electrolytes containing lithium ions. On the basis of these results we discuss strategies for further improving the lithium transference number of such electrolytes.
A new lithium chalcogenidotetrelate, denoted as LiChT phase, with the elemental combination Li/Sn/S was synthesized as solvent-free and solvent-containing salts. We present and discuss syntheses, crystal structures, spectroscopic and thermal properties of the phases, as well as the Li + ion conductivity of Li 4 SnS 4 , which is formally related to the thio-LISICON parent system Li 4 GeS 4 , and thus represents the first member of a new thiostannate-LISICON family. The solvent-free title compound shows a very promising Li + ion conductivity of 7 × 10 −5 S·cm −1 at 20°C and 3 × 10S·cm −1 at 100°C, which is exceptionally high for a ternary compound. Activation energies for the lithium ion transport measured via impedance spectroscopy (0.41 eV) correlate reasonably well with the values (0.29 to 0.33 eV) deduced from ionic mobility studies by 7 Li solid-state NMR spectroscopy. NMR two-time correlation functions suggest the occurrence of an additional, geometrically more restricted, ultraslow-motional process down to 121 K.
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