Lithium polyelectrolyte–ionic liquid systems

Novel lithium polyelectrolyte–ionic liquid systems, using poly(lithium 2-acrylamido-2-methyl propanesulfonate) and its copolymer with N-vinyl formamide, have been developed in this work. The ionic liquid used in this work is from a novel family of methanesulfonate ionic liquids, specifically N-hexyl-N,N,N-tributyl ammonium methanesulfonate, which is chosen because of the similarity with the anionic functionality of the polymer. The ionic liquid thereby acts as a good solvating medium for the polyelectrolyte. It was found that the copolymer-based polyelectrolyte–ionic liquid system exhibits two to three times higher conductivity than that of the homopolymer system. The results of solid-state ⁷Li-NMR have shown that lithium cations in the copolymer system are mobile whereas in the homopolymer, only a fraction appears to be mobile even at 80 °C. This supports the hypothesis that separation of the charged groups on the polymer backbone via the co-monomer encourages the dissociation of lithium cations from the sulfonate groups bonded to the polymer chains, and hence, results in an increase in conductivity of the polyelectrolyte material.

A new Lewis-base ionic liquid comprising a mono-charged diamine structure : a highly stable electrolyte for lithium electrochemistry

A new Lewis-base ionic liquid (IL) based on mono-charged 1,4-diazabicyclo[2.2.2]octane (dabco) was synthesized and its thermal and electrochemical behaviour was characterized. The dabco-based IL with bis(trifluoromethanesulfonyl)amide (TFSA) anion melts at 76 °C when the N-substituted alkyl chain length is 2. The dabco-based IL showed a wide electrochemical window of over 4 V ranging from −3.5 to +1.5 V vs. Fc/Fc⁺ and was able to deposit and strip lithium from a nickel substrate at reasonable efficiency.

On the role of cyclic unsaturated additives on the behaviour of lithium metal electrodes in ionic liquid electrolytes

Three cyclic vinyl based additives, based respectively on oxygen, sulphur and fluorine, are tested for their ability to improve the cycling of lithium in a hostile ionic liquid medium. Oxygen based vinylene carbonate is found to offer the best protection of the lithium metal whilst allowing very consistent lithium cycling to occur. The vinylene carbonate based system under study is, however, imperfect. Lithium metal is deposited in a dendritic morphology, and vinylene carbonate is rapidly consumed during lithium cycling if it is present in a small quantity. Our results suggest that ionic liquid systems critically relying on a small amount of additive to protect a lithium electrode are not viable for long cycle life secondary batteries. It is suggested that an ionic liquid which itself is lithium metal compatible be used instead.

Lithium-functionalised silica nanoparticles for enhanced ionic conductivity in an organic ionic plastic crystal

Addition of silica nanoparticles functionalised with lithium propane sulfonate to the organic ionic plastic crystal N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ([C₂mpyr][NTf₂]) results in a significant increase in ionic conductivity. Analysis of these nanocomposites by impedance spectroscopy, NMR, positron annihilation lifetime spectroscopy (PALS) and Raman spectroscopy suggests that this is the result of higher matrix mobility due to an increase in defect size and concentration. The effect of these functionalised nanoparticles is compared to that previously observed for unfunctionalised nanoparticles in the lithium-doped and pure plastic crystal.

The use of table and cooking salt in a sample of Australian adults

Dietary sodium, the major source being salt, is associated with hypertension. Australian adults consume more than the recommended amount of salt and approximately 15% of dietary sodium comes from salt added at the table and during cooking. Objective: To determine the frequency of and the demographic characteristics associated with discretionary salt use. Design: A cross sectional survey conducted in shopping centres within Metropolitan Melbourne. Participants completed a questionnaire assessing discretionary salt use and attitudes to salt intake. Outcomes: Four hundred and seventy four surveys were collected (65% female, 77% Caucasian, 64% holding a university qualification). Eighty nine percent of respondents were classified as salt users and 11% as non-salt users. Of the salt users 52% reported that they always or sometimes add salt during cooking and at the table. Those of Asian descent and younger respondents aged 18-24 years were more likely to be salt users (chi2=12.3, df=2, p<0.001; chi2=19.2, df=5, p<0.01). Conclusion: Discretionary salt use remains high. To successfully reduce population dietary salt intake public health campaigns are urgently required and need to include consumer advice to reduce discretionary salt use, whilst reducing the salt added to processed foods. Such campaigns should include younger age groups and should be appropriate for all ethnic backgrounds to raise the awareness of the risks of a high salt diet on health.

Consumer awareness and self-reported behaviours related to salt consumption in Australia

Australians are eating far more salt than is good for health. In May 2007, the Australian Division of World Action on Salt and Health (AWASH) launched a campaign to reduce population salt intake. A consumer survey was commissioned to quantify baseline aspects of awareness and behaviour related to salt and health amongst Australians. A total of 1084 individuals aged 14 years or over were surveyed by ACA Research using an established consumer panel. Participants were selected to include people of each sex, within different age bands, from major metropolitan and other areas of all Australian states and territories. Participants were invited via email to complete a brief questionnaire online. Two-thirds knew that salt was bad for health but only 14% knew the recommended maximum daily intake. Seventy percent correctly identified that most dietary salt comes from processed foods but only a quarter regularly checked food labels for salt content. Even fewer reported their food purchases were influenced by the salt level indicated (21%). The survey showed a moderate understanding of how salt effects health but there was little evidence of action to reduce salt intake. Consumer education will be one part of the effort necessary to reduce salt intake in Australia and will require government investment in a targeted campaign to achieve improvements in knowledge and behaviours.

Sequence analysis of a salt tolerant metagenomic clone

Metagenome represent an unlimited resource for discovery of novel genes. Here we report, sequence analysis of a salt tolerant metagenomic clone (6B4) from a pond water metagenomic library. Clone 6B4 had an insert of 2254 bp with G+C composition of 64.06%. DNA sequence from 6B4 showed homology to DNA sequences from proteobacteria indicating origin of 6B4 metagenomic insert from a yet uncharacterized proteobacteria. Two encoded proteins from clone 6B4 showed match with ATP-dependent Clp protease adaptor protein (ClpS) and phasin, while two truncated encoded proteins showed match with poly-3-hydroxybutyrate synthase and permease. Clp complex is known to play a role in stress tolerance. Expression of ClpS from metagenomic clone is proposed to be responsible for salt tolerance of the metagenomic clone 6B4.

Growth of V2O5 nanorods from ball-milled powders and their performance in cathodes and anodes of lithium-ion batteries

The two-stage procedure of ball milling and annealing in air represents a prospective method of preparing nanorods of V₂O₅ with electrochemical properties suitable for the application in lithium-ion batteries. Commercially purchased V₂O₅ powder is milled in a ball mill as the first step of the synthesis. The as-milled precursor is subsequently annealed in air to produce the morphology of nanorods via solid-state recrystallization. We have recently investigated intermediate stages of the formation of nanorods, and this paper summarizes the synthesis method including the description of the current understanding of the growth mechanism. The obtained V₂O₅ nanorods have been assessed as an electrode material for both anodes and cathodes of lithium-ion batteries. When used in cathodes, the nanorods demonstrate a better retention of capacity upon cycling than that of the commercially available powder of V₂O₅. When used in anodes, the performances of nanorods and the reference V₂O₅ powder are similar to a large extent, which is related to a different operating mechanism of V₂O₅ in anodes. The experimentally observed capacity of V₂O₅ nanorods in an anode has stabilized at the level of about 450 mAh/g after few cycles.

Undoing lithium ion association in ionic liquids through the complexation by oligoethers

Tetraglyme (TG) and the recently developed trimethylsilyl capped analogue (1NM3) when used as additives in a N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl) amide [C₃mpyr][NTf₂]/0.65 M LiNTf₂ electrolyte have been shown to dramatically enhance the transport properties of this electrolyte. In fact, at a concentration of 20 mol % tetraglyme (leading to a ratio of ~1:1 ether molecule per lithium ion), viscosity, conductivity, and the diffusion coefficients of the C₃mpyr⁺ and NTf₂⁻ are practically reinstated to the values observed in the absence of lithium, thereby negating the structuring effects of the lithium ion. The ⁷Li T₁ relaxation times also indicate that these additives strongly interact with the lithium ions. Furthermore, although TG has twice the viscosity of 1NM3, the greatest improvement in transport properties was observed for TG.

Lithium toxicity in yeast is due to the inhibition of RNA processing enzymes

Hal2p is an enzyme that converts pAp (adenosine 3',5' bisphosphate), a product of sulfate assimilation, into 5' AMP and Pi. Overexpression of Hal2p confers lithium resistance in yeast, and its activity is inhibited by submillimolar amounts of Li+in vitro. Here we report that pAp accumulation in HAL2 mutants inhibits the 5'3' exoribonucleases Xrn1p and Rat1p. Li+ treatment of a wild-type yeast strain also inhibits the exonucleases, as a result of pAp accumulation due to inhibition of Hal2p; 5' processing of the 5.8S rRNA and snoRNAs, degradation of pre-rRNA spacer fragments and mRNA turnover are inhibited. Lithium also inhibits the activity of RNase MRP by a mechanism which is not mediated by pAp. A mutation in the RNase MRP RNA confers Li+ hypersensitivity and is synthetically lethal with mutations in either HAL2 or XRN1. We propose that Li+ toxicity in yeast is due to synthetic lethality evoked between Xrn1p and RNase MRP. Similar mechanisms may contribute to the effects of Li+ on development and in human neurobiology.