Miriam Kunze

Enhanced lithium transference numbers in ionic liquid electrolytes.

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.

NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials.

NMR spin relaxometry is known to be a powerful tool for the investigation of Li(+) dynamics in (non-paramagnetic) crystalline and amorphous solids. As long as significant structural changes are absent in a relatively wide temperature range, with NMR spin-lattice (as well as spin-spin) relaxation measurements information on Li self-diffusion parameters such as jump rates and activation energies are accessible. Diffusion-induced NMR relaxation rates are governed by a motional correlation function describing the ion dynamics present. Besides the mean correlation rate of the dynamic process, the motional correlation function (i) reflects deviations from random motion (so-called correlation effects) and (ii) gives insights into the dimensionality of the hopping process. In favorable cases, i.e., when temperature- and frequency-dependent NMR relaxation rates are available over a large dynamic range, NMR spin relaxometry is able to provide a comprehensive picture of the relevant Li dynamic processes. In the present contribution, we exemplarily present two recent variable-temperature (7)Li NMR spin-lattice relaxation studies focussing on Li(+) dynamics in crystalline ion conductors which are of relevance for battery applications, viz. Li(7) La(3)Zr(2)O(12) and Li(12)Si(7).

Melting Behavior and Ionic Conductivity in Hydrophobic Ionic Liquids

Four room-temperature ionic liquids (RTILs) based on the N-butyl-N-methyl pyrrolidinium (Pyr(14)(+)) and N-methyl-N-propyl pyrrolidinium cations (Pyr(13)(+)) and bis(trifluoromethanesulfonyl)imide (TFSI(-)) and bis(fluorosulfonyl)imide (FSI(-)) anions were intensively investigated during their melting. The diffusion coefficients of (1)H and (19)F were determined using pulsed field gradient (PFG) NMR to study the dynamics of the cations, anions, and ion pairs. The AC conductivities were measured to detect only the motion of the charged particles. The melting points of these ionic liquids were measured by DSC and verified by the temperature-dependent full width at half-maximum (FWHM) of the (1)H and (19)F NMR peaks. The diffusion and conductivity data at low temperatures gave information about the dynamics at the melting point and allowed specifying the way of melting. In addition, the diffusion coefficients of (1)H (D(H)) and (19)F (D(F)) and conductivity were correlated using the Nernst-Einstein equation with respect to the existence of ion pairs. Our results show that in dependence on the cation different melting behaviors were identified. In the Pyr(14)-based ILs, ion pairs exist, which collapse above the melting point of the sample. This is in contrast to the Pyr(13)-based ILs where the present ion pairs in the crystal dissociate during the melting. Furthermore, the anions do not influence the melting behavior of the investigated Pyr(14) systems but affect the Pyr(13) ILs. This becomes apparent in species with a higher mobility during the breakup of the crystalline IL.

Polymerizable ionic liquid with state of the art transport properties.

The physicochemical properties of diallyldimethylammonium-bis(trifluoromethanesulfonyl)imide (DADMATFSI) and its binary mixture with LiTFSI are presented herein, also showing this novel compound as a polymerizable room temperature ionic liquid with excellent transport properties for Li(+) ions. In particular, results of pulsed field gradient (PFG)-NMR diffusion experiments and impedance measurements show that DADMATFSI exhibits state of the art properties of ionic liquids. Similar ionic diffusion coefficients and a similarly high conductivity as seen in the benchmark compound N-butyl-N-methylpyrrolidinium-bis(trifluoromethanesulfonyl)imide (PYR14TFSI) are observed. In accordance, the Li transference number in the binary mixture matches the trend seen for PYR14TFSI-LiTFSI mixtures. In addition to these impressive properties as ionic liquid, DADMATFSI was polymerized by UV treatment. The polymerization is demonstrated and the ion conducting properties of the resulting gel polymer electrolyte are investigated, showing that DADMATFSI can be transformed into an ionogel and may have applications where polymerization is desirable.

Transport Mechanisms of Ions in Graft-Copolymer Based Salt-in-Polymer Electrolytes

Abstract Salt-in-polymer electrolytes based on graft copolymers with oligoether side chains and added LiCF3SO3 (LiTf) are investigated concerning the transport and dynamics of the ionic species with respect to applications as Li ion conductors. Polymer architectures are based on polysiloxane or polyphosphazene backbones with one or two side chains per monomer, respectively. NMR methods provide information about molecular dynamics on different length scales: The mechanisms governing local dynamics and long range mass transport are studied on the basis of temperature dependent spin-lattice relaxation rates and pulsed field gradient diffusion measurements for 7Li, 19F and 1H, respectively. The correlation times characterizing local ion dynamics reflect the complexation of the cations by the oligoether side chains of the polymer. 7Li and 19F diffusion coefficients and their activation energies are rather similar, suggesting the formation of ion pairs and clusters with similar activation barriers for cation and/or anion long-range transport. Activation energies of local reorientations are generally significantly smaller than activation energies of long range diffusion. Long range transport is affected by (1) the coupling of conformational side chain reorientations to the cation movement, and (2) the correlated diffusion of cations and anions within ion pairs. Ion pairs and their dissociation play a major role in controlling the resulting conductivity of the material. Guidelines for material optimization in terms of a maximized conductivity can thus be derived by identifying a compromise between high ionic mobility and good Li complexation by the coordinating side chains.