Lithium doped N-methyl-N-ethylpyrrolidiniumbis(trifluoromethanesulfonyl)amide fast-ion conducting plastic crystals

The incorporation of dopant levels of lithium ions (0.5 to 9.3% by mole) in the N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P₁₂TFSA) plastic crystalline phase results in increases in the solid state ionic conductivity of more than 3 orders of magnitude at 298 K. Conductivities as high as 10^−-4 S cm⁻¹ at 323 K have been measured in these doped plastic crystal phases. These materials can therefore be classified as fast-ion conductors. Higher levels of Li only marginally increase the conductivity, up to around 33 mol%, followed by a slight decrease to 50 mol%. Thermal analysis behaviour has allowed the partial development of the binary phase diagram for the LiTFSA–P₁₂TFSA system between 0–50 mol% LiTFSA, which suggests the presence of a solid solution single phase at concentrations less than 9.3 mol% LiTFSA. There is also strong evidence of eutectic behaviour in this system with a eutectic transition temperature around 308 K at 33 mol% LiTFSA. A model relating ionic conduction to phase behaviour in this system is presented. The increased conductivity upon doping has been associated with lithium ion motion via⁷Li solid state NMR linewidth measurements.

Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xHx−1]−

We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine–acetic acid mixtures. The simple 1:1 acid–base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)_xH_x−1]− stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1:1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.

Analyses and comparison of counter-movement jump performance and self-rated recovery in state under-18s Australian Rules Football players during a national championship

Recovery of team sport athletes during multiple competitive games is an important area for strength and conditioning coaches to monitor as it facilitates for athletes to be ready to perform (11,13). Utilising athletic performance data in conjunction with self-rated reporting measures can help determine if in fact a player or team has recovered sufficiently or shown a trend towards recovery prior to a competitive match (11). Positive improvement in recovery variables can provide confidence in the effectiveness of recovery methods used and assist in determining the training schedule in order to positively manipulate the fitness-fatigue relationship (3).

Various methods of analysing the recovery of athletes have been reported in the literature and are available to the strength and conditioning coach. These include subjective, self-rated scales and perceived level of recovery questionnaires (11,12,13). Athletic performance measures during exercises such as the counter movement jump (CMJ) have also been analysed, predominantly utilising force plates to obtain kinetic data. (5,13,14). However, such equipment can be difficult to transport, requires continual calibration and is costly to purchase. A linear transducer can provide important information on CMJ variables in the assessment of athletic movements and due to its size and portability could serve as a valuable tool to assist strength and conditioning coaches, (8,10), and potentially enable the monitoring of recovery.

Previous studies have investigated the fatigue effects of competitive games in various sports (11,13,14) including Australian Rules Football (AFL) at the senior elite league level (5, 6). To the authors’ knowledge, however, there is yet to be a study investigating the recovery response in AFL players, specifically in players 18 years and under competing in the National Under 18s Championships. Australian Rules football is an extremely physically demanding and fatiguing sport where players participate in games time exceeding 120 minutes duration, covering large distances (~12-18km, position dependent) with many high intensity efforts performed at random times throughout the game (2,6,16). Hence, it would seem pertinent to analyse the fatigue effects of competitive matches in an Australian Rules Under-18’s National Championship and the subsequent recovery from these games.

The aim of this study was to analyse and compare two self-rated subjective measures of recovery; they being muscle soreness (MS) of the lower body, overall perceived total recovery (TR), and the performance measure of peak velocity (PV) obtained from a CMJ analysed with a linear transducer. Data collection occurred between rounds four and five of the Australian Football League Under-18’s National Championship, representing a four-day recovery analysis period between matches.

Exploring zinc coordination in novel zinc battery electrolytes

The coordination of zinc ions by tetraglyme has been investigated here to support the development of novel electrolytes for rechargeable zinc batteries. Zn(2+) reduction is electrochemically reversible from tetraglyme. The spectroscopic data, molar conductivity and thermal behavior as a function of zinc composition, between mole ratios [80 : 20] and [50 : 50] [tetraglyme : zinc chloride], all suggest that strong interactions take place between chloro-zinc complexes and tetraglyme. Varying the concentration of zinc chloride produces a range of zinc-chloro species (ZnClx)(2-x) in solution, which hinder full interaction between the zinc ion and tetraglyme. Both the [70 : 30] and [50 : 50] mixtures are promising electrolyte candidates for reversible zinc batteries, such as the zinc-air device.

Improvement of charge/discharge properties of oligoether electrolytes by zwitterions with an attached cyano group for use in lithium-ion secondary batteries

Zwitterions with a cyano group on the side chain (CZ) were synthesized. Although the addition of CZ caused a slightly negative effect on viscosity, ionic conductivity, limiting current density, and lithium transference number, the oxidation limit of PEGDME/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) composites was improved to over 5 V. For charge/discharge testing using Li|electrolyte|LiCoO2 cells, the cycle stability of PEGDME/LiTFSA with CZ in the voltage range of 3.0-4.6 V was much higher than that of PEGDME/LiTFSA. Incorporating a small mole fraction of CZ into PEGDME-based electrolytes prevented an increase in the interface resistance between the electrolyte and cathode with increasing numbers of the cycle.

Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes

Electrolytes based on bis(fluorosulfonyl)imide (FSI) with a range of LiFSI salt concentrations were characterized using physical property measurements, as well as NMR, FT-IR and Raman spectroscopy. Different from the behavior at lower concentrations, the FSI electrolyte containing 1 : 1 salt to IL mole ratio showed less deviation from the KCl line in the Walden plot, suggesting greater ionic dissociation. Diffusion measurements show higher mobility of lithium ions compared to the other ions, which suggests that the partial conductivity of Li(+) is higher at this higher composition. Changes in the FT-IR and Raman peaks indicate that the cis-FSI conformation is preferred with increasing Li salt concentration.