Transport properties of ionic liquid electrolytes with organic diluents.

Ionic liquids (ILs) form a novel class of electrolytes with unique properties that make them attractive candidates for electrochemical devices. In the present study a range of electrolytes were prepared based on the IL N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl) amide ([C(3)mpyr][NTf(2)]) and LiNTf(2) salt. The traditional organic solvent diluents vinylene carbonate (VC), ethylene carbonate (EC), tetrahydrofuran (THF) and toluene were used as additives at two concentrations, 10 and 20 mol%, leading to a ratio of about 0.6 and 1.3 diluent molecules to lithium ions, respectively. Most promisingly, the lithium ions see the greatest effect in the presence of all the diluents, except toluene, producing a lithium self-diffusion coefficient of almost a factor of 2.5 times greater for THF at 20 mol%. Raman spectroscopy subtly indicates that THF may be effectively breaking up a small portion of the lithium ion-anion interaction. While comparing the measured molar conductivity to that calculated from the self-diffusion coefficients of the constituents indicates that the diluents cause an increase in the overall ion clustering. This study importantly highlights that selective ion transport enhancement is achievable in these materials.

Hydrogen-bonding and ion-ion interactions in solutions of triflic acid and 1-ethyl-3-methylimidazolium triflate.

Ion-ion and hydrogen-bonding interactions in solutions of 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C(2)mim]Tf) and triflic acid (HTf) are investigated with infrared and Raman spectroscopy. Bands indicative of highly aggregated triflate anions appear in the vibrational spectra of solutions containing a large fraction of triflic acid. These species most likely consist of triflate anions that are at least threefold coordinated by positive ions (i.e., {[C(2)mim](x)H(y)Tf}(x+y-1) where x + y > or = 3). Such coordination environments would be consistent with a larger, extended aggregate of Tf(-), [C(2)mim](+), and H(+) ions that may be charged or neutral. Evidence for hydrogen bonding between the protons and the oxygen atoms of the triflate atoms and between the hydrogen atoms of the [C(2)mim](+) and triflate anion is identified in the infrared and Raman spectra.

Aluminium speciation in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures.

Electrodeposition of aluminium is possible from solutions of AlCl(3) dissolved in the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (C(4)mpyrNTf(2)) ionic liquid. However, electrodeposition is dependant on the AlCl(3) concentration as it only occurs at concentrations >1.6 mol L(-1). At these relatively high AlCl(3) concentrations the C(4)mpyrNTf(2)/AlCl(3) mixtures exhibit biphasic behaviour. Notably, at 1.6 mol L(-1) AlCl(3), aluminium can only be electrodeposited from the upper phase. Conversely, we found that at 3.3 mol L(-1) aluminium electrodeposition can only occur from the lower phase. The complex chemistry of the C(4)mpyrNTf(2)/AlCl(3) system is described and implications of aluminium speciation in several C(4)mpyrNTf(2)/AlCl(3) mixtures, as deduced from Raman and (27)Al NMR spectroscopic data, are discussed. The (27)Al NMR spectra of the C(4)mpyrNTf(2)/AlCl(3) mixtures revealed the presence of both tetrahedrally and octahedrally coordinated aluminium species. Raman spectroscopy revealed that the level of uncoordinated NTf(2)(-) anions decreased with increasing AlCl(3) concentration. Quantum chemical calculations using density functional and ab initio theory were employed to identify plausible aluminium-containing species and to calculate their vibrational frequencies, which in turn assisted the assignment of the observed Raman bands. The data indicate that the electroactive species involved are likely to be either [AlCl(3)(NTf(2))](-) or [AlCl(2)(NTf(2))(2)](-).

New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces.

Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO2 and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)2N(-) indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.

Cation-anion interactions in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate-based ionic liquid electrolytes.

An important step in developing ionic-liquid-based electrolytes for lithium rechargeable batteries is obtaining a molecular-level understanding of the ionic interactions that occur in these systems. In this study, 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C2mim]CF3SO3) is complexed with LiCF3SO3, and the local structures of the CF3SO3- and [C2mim]+ ions are investigated with infrared and Raman spectroscopy. The isolation and subsequent refinement of a Li[C2mim](CF3SO3)2 crystal provides further insight into the structure of the [C2mim]CF3SO3-LiCF3SO3 solutions. Minor changes are observed in the infrared and Raman spectra of dilute [C2mim]CF3SO3-LiCF3SO3 solutions compared to pure [C2mim]CF3SO3. However, a suspension of very small Li[C2mim](CF3SO3)2 crystallites forms at a solution composition of [C2mim]CF3SO3:LiCF3SO3 = 10:1 (mole ratio), placing an upper limit on the solubility of LiCF3SO3. Essentially no changes are observed in the vibrational modes of the [C2mim]+ cations over the entire range of LiCF3SO3 compositions studied, suggesting that the addition of these compounds does not significantly perturb the local structure of the [C2mim]+ cations. The salt used in this study has a common anion with the ionic liquid; thus, the ion cloud surrounding the [C2mim]+ ions, which must be primarily composed of CF3SO3- anions, is not significantly altered with the addition of LiCF3SO3.

Hydrogen bonding and cation coordination effects in primary and secondary amines dissolved in carbon tetrachloride.

Raman and infrared spectroscopy were used to investigate hydrogen-bonding interactions and cation coordination effects in solutions of lithium triflate (LiCF3SO3) dissolved in two primary amines, hexylamine (HEXA) and N,N-dimethylethylenediamine (DMEDA), and in a secondary amine, dipropylamine (DPA). Strong intermolecular hydrogen-bonding interactions and weaker intramolecular hydrogen-bonding interactions that occur only in DMEDA were spectroscopically distinguished in a comparison of pure HEXA, pure DMEDA, and the dilute solutions of these amines in CCl4. The spectroscopic shifts in intensity and frequency in the NH stretching region of DPA and DPA diluted in CCl4 were similar to those of HEXA. Dilute electrolyte solutions in carbon tetrachloride were prepared to analyze specifically the cation coordination effect. In these solutions, limited intermolecular hydrogen-bonding interactions are present, and the observed spectral shifts correspond primarily to the cation-induced shifts. The symmetric SO3 stretching region of the triflate anion was investigated to probe further the coordination of the cation. The local structures of the triflate ions and the amine groups in the electrolyte solutions dissolved in CCl4 are similar to the local structures in the corresponding amine-salt crystals previously reported by us.

Crystalline and solution phases of N,N-dimethylethylenediamine complexed with lithium triflate and sodium triflate: intramolecular and intermolecular hydrogen bonding.

Infrared and Raman spectroscopy were used to study hydrogen-bonding interactions and the cation coordination effect in solutions of N,N-dimethylethylenediamine (DMEDA) with lithium triflate (LiTf) and sodium triflate (NaTf). A comparison of pure DMEDA with DMEDA dissolved in carbon tetrachloride enabled the separation of the relative contributions of intermolecular and intramolecular hydrogen-bonding interactions to the N-H stretching frequencies. The addition of LiTf and NaTf to DMEDA shifts the N-H stretching frequencies through two competing effects: the cation coordination effect lowers the frequencies, while the disruption of the hydrogen-bonding interactions increases the frequencies. These two effects were distinguished in a study of the concentration dependence of both salts dissolved in DMEDA; the differentiation was based on the difference in the spectral sensitivities of the symmetric and the antisymmetric stretch in both the Raman and infrared spectra. During this study, DMEDA-LiTf and DMEDA-NaTf crystals were discovered, and their structures were solved by X-ray diffraction techniques. The analysis of the vibrational spectra of these crystals was greatly enhanced by unambiguous knowledge of the structural details of cation-molecule and anion-cation interactions. These structure-spectra correlations were used to complement analogous spectroscopic studies in the solution phases. Analysis of spectral regions in both crystalline and solution phases particularly sensitive to the nature and strength of cation-molecule interactions clearly established that the interaction of the lithium ion with the nitrogen atoms of DMEDA was stronger than the sodium ion-DMEDA interaction, as expected from charge density arguments.

Lithium environment in dilute poly(ethylene oxide)/lithium triflate polymer electrolyte from REDOR NMR spectroscopy.

The role of the lithium ion environment is of fundamental interest regarding transport and conductivity in lithium polymer electrolytes. X-ray crystallography has been used to characterize the lithium environment in completely crystalline poly(ethylene oxide) (PEO) electrolytes, but this approach cannot be used with dilute PEO electrolytes. Here, using solid-state NMR data collected with the rotational-echo double-resonance 13C[7Li] (REDOR) pulse sequence, we have been able to characterize the crystalline microdomains of a PEO-lithium triflate sample with an oxygen/lithium ratio of 20:1. Our data clearly demonstrates that the lithium crystalline microdomains are nearly identical to those of a completely crystalline 3:1 sample, for which the crystal structure is known.

Hydrogen bonding and the inductive effect in crystalline and solution phases of hexylamine:LiCF3SO3 and Dipropylamine:LiCF3SO3: application to branched poly(ethylenimine).

Raman and infrared spectroscopy were used to study the nature of hydrogen bonding and the cation inductive effect in solutions of LiCF(3)SO(3) dissolved in hexylamine, a primary amine, and dipropylamine, a secondary amine. Comparison of pure hexylamine and hexylamine dissolved in CCl(4) established that the Raman band maximum of the symmetric stretching mode, nu(s)(NH(2)), in pure hexylamine originates in molecules undergoing no hydrogen bonding interactions. The addition of LiCF(3)SO(3) to hexylamine or dipropylamine shifts the frequencies of the solvent NH stretching modes by two effects: the breaking of hydrogen bonds and the cation inductive effect. Comparison of the infrared and Raman spectra allows (to some degree) the separation of these two effects. During these studies, crystalline compounds of hexylamine:LiCF(3)SO(3) and dipropylamine:LiCF(3)SO(3) were discovered, and their structures were solved by single-crystal X-ray diffraction techniques. Vibrational spectra of these crystals and detailed structural knowledge of the cation-solvent interactions complement analogous spectroscopic studies of the solution phases. The cation-polymer and hydrogen bonding interactions of branched poly(ethylenimine) (BPEI) complexed with LiCF(3)SO(3) were modeled by the solutions of hexylamine and dipropylamine containing dissolved LiCF(3)SO(3). Specifically, lithium ion interactions with the primary and secondary amine groups in BPEI were modeled by the solution studies with hexylamine and dipropylamine, respectively. The analysis of the hexylamine system was particularly useful because the primary amine group of BPEI dominates the NH stretching region of the spectrum.