N-methyl-N-alkylpyrrolidinium hexafluorophosphate salts : novel molten salts and plastic crystal phases

A new series of salts, based on the N-methyl-N-alkylpyrrolidinium cation and the PF₆- anion, are reported and their thermal properties described for alkyl = Me, Et, Pr, Bu, Hx, and Hp. X-ray structures of several of the salts are also reported. The N,N-dimethylpyrrolidinium hexafluorophosphate has a melting point greater than 390 °C; however, the N-methyl-N-butylpyrrolidinium derivative melts at 70 °C. Most of the PF₆- salts were observed to have lower melting points in comparison with the analogous iodide salts. Most of the salts exhibit one or more thermal transitions prior to melting and a final entropy of melting less than 20 J K^-1 mol^-1, behavior which has previously been associated with the formation of plastic crystal phases. Good crystal structure solutions were obtained at low temperatures in the case of the alkyl = propyl and heptyl derivatives. The loss of diffraction peaks and changes in symmetry at higher temperatures indicated the presence of dynamic rotational disorder, supporting the understanding that the plastic properties arise from rotational motions in the crystal.

Pyrrolidinium imides : a new family of molten salts and conductive plastic crystal phases

A new family of molten salts is reported, based on the N-alkyl, N-alkyl pyrrolidinium cation and the bis(trifluoromethane sulfonyl)imide anion. Some of the members of the family are molten at room temperature, while the smaller and more symmetrical members have melting points around 100 °C. Of the room-temperature molten salt examples, the methyl butyl derivative exhibits the highest conductivity; at 2 × 10^-3 S/cm this is the highest molten salt conductivity observed to date at room temperature among the ammonium salts. This highly conductive behavior is rationalized in terms of the role of cation planarity. The salts also exhibit multiple crystalline phase behavior below their melting points and exhibit significant conductivity in at least their higher temperature crystal phase. For example, the methyl propyl derivative (mp = 12 °C) shows ion conductivity of 1 × 10^-6 S/cm at 0 °C in its higher temperature crystalline phase.

High conductivity molten salts based on the imide ion

The bis(trifluoromethanesulfonyl)imide ion has recently been used in its lithium salt as a useful ion in solid polymer electrolytes because of the reduced degree of ion interaction its diffuse charge generates. In this work we have synthesised a number of novel salts based on the ammonium and pyrrolidinium cations of this anion. The salts all show reduced melting points compared with analogous halide salts. In some cases they are molten at room temperature. This latter group of salts have been characterized with respect to their properties as ionic liquids; the highest room temperature conductivity 2 mS cm⁻¹ being exhibited by methyl butyl pyrrolidinium imide. Many of the salts are glass forming, exhibiting glass transition temperatures in the region of −90°C.

Room-temperature molten salts based on the quaternary ammonium ion

The properties of a family of novel quaternary ammonium salts based on the bis(trifluoromethylsulfonyl)imide and triflate anions are reported. Binary phase diagrams for some of their mixtures and their electrochemical windows of stability are also reported. The highest conductivity observed in the pure salt systems at 25 °C was 7 × 10^-4 S cm^-1. An electrochemical window of stability of up to 5 V was measured on graphite electrodes. The effect of salt structure and solvent on conductivity of the salts is also discussed.

Synthesis and properties of ambient temperature molten salts based on the quaternary ammonium ion

The synthesis of 16 tetraalkyl ammonium bis(trifluoromethane sulfonyl) imide salts, (C_nH_2n+1)₄ +N -N (SO₂CF₃)₂ (n = 1, 2, 3, 4),  (C₂H₅)₂(i-C₃H₇)₂ +N -N(SO₂CF₃)₂, (C₂H₅)(CH₃)(i-C₃H₇)₂+N-N(SO₂CF₃)₂, (n-C₇H₁₅)(C₂H₅)i-C₃H₇)₂+N-N(SO₂CF₃)₂ and (C_nH_2n+1)(C_mH_2m+1)₃+N-N(SO₂CF₃)₂ (n = 6,7,8; m = 1, 2, 4) are reported in this paper. Trends in properties of these salts are discussed. The symmetrical tetraalkyl ammonium salts with the bis(trifluoromethyl sulfonyl) imide anion exhibited a lower melting point than that of corresponding ammonium halides. The salts with low symmetry ammonium cations were found to be of generally lower melting point, and many were stable liquids at room temperature. Several of these did not crystallize during cooling below room temperature and exhibited glass transition temperatures in the region of −60 °C∼−80 °C. A comparison of properties between the ammonium imide salts and corresponding trifluoromethane sulfonates is also presented.

Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts

Mixed salts of Ionic Liquids (ILs) and alkali metal salts, developed as electrolytes for lithium and sodium batteries, have shown a remarkable ability to facilitate high rate capability for lithium and sodium electrochemical cycling. It has been suggested that this may be due to a high alkali metal ion transference number at concentrations approaching 50 mol% Li(+) or Na(+), relative to lower concentrations. Computational investigations for two IL systems illustrate the formation of extended alkali-anion aggregates as the alkali metal ion concentration increases. This tends to favor the diffusion of alkali metal ions compared with other ionic species in electrolyte solutions; behavior that has recently been reported for Li(+) in a phosphonium ionic liquid, thus an increasing alkali transference number. The mechanism of alkali metal ion diffusion via this extended coordination environment present at high concentrations is explained and compared to the dynamics at lower concentrations. Heterogeneous alkali metal ion dynamics are also evident and, somewhat counter-intuitively, it appears that the faster ions are those that are generally found clustered with the anions. Furthermore these fast alkali metal ions appear to correlate with fastest ionic liquid solvent ions.

Ion diffusion in molten salt mixtures

The molten salts, 1-methyl,3-ethylimidazolium trifluoromethanesulfonate (triflate salt, MeEtImTf) and 1-methyl,3-ethylimidazolium bis(trifluoromethanesulfonimide) (imide salt, MeEtImNTf₂) are colourless ionic liquids with conductivities of the order of 10⁻² S cm⁻¹ at room temperature. DSC measurements revealed subambient melting and glass transition temperatures. Analysis of the anion and cation diffusion coefficients suggested that the cation was the dominant charge carrier and that the motion was largely independent of the anion. Haven ratios (H_Rs) of 1 and 1.6 were determined for the imide and triflate salts, respectively, at 30°C (303 K). Values greater than one imply some degree of ionic association, suggesting that aggregation is present in the triflate salt. Mixing of the salts to form binary systems resulted in enhanced conductivities which deviated from a simple law of mixtures. Thermal analysis showed no evidence of a melting point with only a glass transition observed. Corresponding diffusion measurements for the binaries appeared to show a weighted average of the diffusion coefficients of the pure components. The increased conductivity can be attributed to an increase in the number of charge carriers as a result of decreased ion association in the binary.

N-methyl-N-alkylpyrrolidinium tetrafluoroborate salts : ionic solvents and solid electrolytes

A series of N-methyl-N-alkylpyrrolidinium tetrafluoroborate salts were synthesised. The spectroscopic, physical and electrochemical characteristics of this family of salts have been investigated with respect to potential usage as ionic solvents and electrolytes. The lowest melting point among the family is 64°C for the N-methyl-N-propylpyrrolidinium tetrafluoroborate (P₁₃BF₄). This is sufficiently low to enable this salt to be useful as an ionic liquid in chemical synthesis involving reactions above 70°C. Most of the compounds exhibit one or more solid–solid transitions below the melting point, this behaviour is thought to indicate the existence of plastic crystal phases.

Novel high salt content polymer electrolytes based on high Tg polymers

Conductivities greater than or equal to 10⁻⁸ S cm⁻¹ at T_g are reported in polymer electrolytes based on lithium triflate salt and a series of polymers whose T_g is greater than 90°C. The highest conductivities were observed for poly(acrylonitrile) based systems with salt concentrations greater than 60 wt.%. The conductivity in all cases investigated increases with increasing salt concentration. ¹H-NMR T₂ relaxation measurements suggest that T_g decreases with increasing salt content and confirms that these materials are glassy at room temperature and hence that the conductivity is significantly decoupled from the structural relaxations. It appears that the nature of the polymer is important in determining the level of ionic conductivity, possibly due to differences in polymer coordinating ability or differences in T_g. Polymer-in-salt mixtures based on a tetra-alkyl ammonium imide molten salt and several high T_g polymers are also reported. The conductivities of these mixtures appear to be independent of the polymer type.

Towards a better understanding of 'delocalized charge' in ionic liquid anions

One of the main characteristics that are attributed to ionic liquids (especially those with a low melting point) is that the anions comprising the ionic liquids possess a certain degree of charge delocalization as compared to anions in traditional molten salts. Based on the proton affinity equilibrium we proposed a new energetic criterion that can be used as a measure of charge delocalization. The proposed proton affinity comparison quantifies the extent to which ionic liquid anions are delocalized. Thus it should lead to a better understanding towards the design of task-specific ionic liquids. Therefore, this criterion can be applied to newly designed anions to assure that the extent of charge delocalization falls within the same range of values on the proton affinity scale as other commonly used ionic liquid anions.

Acid–organic base swollen polymer membranes

In this work, two different polymer membrane systems based on Nafion and Teflon were investigated as proton conductors for polymer membrane fuel cells. Water-free Nafion117 membranes swollen with different non-aqueous solvents were prepared. The solvents included imidazole, imidazole–imidazolium salt solutions, room temperature molten salts and molten salt–acid solutions. Teflon films were treated with a surfactant, or a Nafion solution, to improve their surface properties, and were subsequently swollen with phosphoric acid. Conductivity measurements were carried out on both the Nafion and Teflon membranes. Conductivities in the range of 10⁻³ S cm⁻¹ at around 100°C were obtained. This is still an order of magnitude lower than the corresponding water swollen Nafion at 80°C.

Parallel developments in aprotic and protic ionic liquids : physical chemistry and applications

This Account covers research dating from the early 1960s in the field of low-melting molten salts and hydrates,which has recently become popular under the rubric of “ionic liquids”. It covers understanding gained in the principal author’s laboratories (initially in Australia, but mostly in the U.S.A.) from spectroscopic, dynamic, and thermodynamic studies and includes recent applications of this understanding in the fields of energy conversion and biopreservation. Both protic and aprotic varieties of ionic liquids are included, but recent studies have focused on the protic class because of the special applications made possible by the highly variable proton activities available in these liquids.

Anodising AA5083 aluminium alloy using ionic liquids

Aluminium, as the current collector in lithium batteries, has shown reduced corrosion susceptibility in room temperature molten salts (1, 2). Moreover, previous studies have established that corrosion mitigation is achieved on magnesium alloys using ionic liquids pretreatments (3, 4). This paper investigated the anodisation of AA5083 aluminium alloy in Trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfony) ([P6,6,6,14][NTf2]) ionic liquid by applying a constant current followed by holding at the maximum potential for a period of time. Potentiodynamic polarisation results show that the treated surfaces were more corrosion resistant in 0.1 M sodium chloride solution compared with the control specimen. The anodising treatment was effective both in shifting the free corrosion potential to more noble values and in suppressing the corrosion current. Optical microscope and optical profilometry images indicated that an anodising film was deposited onto the alloy surface, which is thought to have inhibited corrosion in chloride environment. Further characterisation of the anodising film will be carried out in future work.

Electrochemical properties and applications of ionic liquids

This book presents the latest research in electrochemical properties and applications of ionic liquids. While there is no universally agreed upon definition, an ionic liquid may be conveniently described as a compound composed entirely of ions that is a liquid at temperatures less than 100 °C. However, this is an arbitrary definition employed to distinguish ionic liquids from classically well-known molten salts. This book addresses a comprehensive overview of the area, because it is obvious that ionic liquids have the ability to offer many advantages, but also some disadvantages, over traditional molecular solvent (electrolyte) media in the field of electrochemistry.