Gel electrolytes based on lithium modified silica nano-particles

In this work lithium modified silica (Li-SiO₂) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO₂ exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]). Several gel electrolytes based on Li-SiO₂ were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10⁻³ S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.

Zwitterion effect in polyelectrolyte gels based on lithium methacrylate-N,N-dimethyl acrylamide copolymer

Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal.

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.

Gel electrolytes based on lithium macro-anion salt

Montmorillonites are composed of aluminosilicate layers stacked one above the other, and the layer thickness is approximately 1 nm. In this work lithium modified montmorillonite (Li-MMT) was prepared and used as a lithium macro-anion salt in gel electrolytes. It was found that Li-MMT exhibited good compatibility with poly(ethylene glycol), DMSO and the ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIdca), and a few of novel gel electrolytes based on Li-MMT were obtained. These gel electrolytes were investigated by X-ray powder diffraction, solid state NMR, conductivity measurements and cyclic voltammetry. High conductivities up to 10^{− 4} to 10^{− 3} S/cm at room temperature were observed with these macro-anion gel electrolytes. These gel materials were promising to be used as lithium conductive electrolytes in electrochemical devices, such as lithium batteries.

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.

Studies on the properties and the thermal decomposition kinetics of natural rubber prepared with calcium chloride

To evaluate calcium chloride coagulation technology, two kinds of raw natural rubber samples were produced by calcium chloride and acetic acid respectively. Plasticity retention index (PRI), thermal degradation process, thermal degradation kinetics and differential thermal analysis of two samples studied. Furthermore, thermal degradation activation energy, pre-exponential factor and rate constant were calculated. The results show that natural rubber produced by calcium chloride possesses good mechanical property and poor thermo-stability in comparison to natural rubber produced by acetic acid.

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 electrochemistry of lithium in ionic liquid/organic diluent mixtures

The electrochemistry of lithium is investigated in a number of electrolytes that consist of a lithium salt dissolved in a combined ionic liquid-organic diluent medium. We find that ethylene carbonate and vinylene carbonate improve electrochemical behaviour, while toluene and tetrahydrofuran are less promising.We also present insights into the electrode passivation caused by these diluents in an ionic liquid electrolyte during lithium cycling. We observe that during lithium cycling those electrolytes with carbonate based diluents are the most able to utilise their previously reported improved lithium ion diffusivities. Conversely, tetrahydrofuran, the most promising diluent of those studied in terms of its known ability to increase lithium ion diffusivity is found not to be as advantageous as a diluent. It appears that the poor electrochemical interfacial properties of the tetrahydrofuran electrolyte prevented the realisation of the benefits of the high solution lithium ion diffusivity.

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.

Surface-Enhanced Infrared Spectra of Manganese (III) Tetraphenylporphine Chloride Physisorbed on Gold Island Films

Surface-enhanced infrared absorption (SEIRA) spectra of manganese (III) tetraphenylporphine chloride (Mn(TPP)Cl) on metal island films were measured in transmission mode. Dependences of the enhancement factor of SEIRA on both the sample quantity and the type of evaporated metal were investigated by subsequently increasing the amount of Mn(TPP)Cl on gold and silver substrates. The enhancement increases nonlinearly with the amount of sample and varies slightly with the thickness of metal islands. In particular, the SEIRA transmission method presents an anomalous spectral enhancement by a factor of 579, with substantial spectral shifts, observed only for the physisorbed Mn(TPP)Cl that remained on a 3-nm-thick gold film after immersion of the substrates into acetone. A charge-transfer (CT) interaction between the porphyrinic Mn and gold islands is therefore proposed as an additional factor in the SEIRA mechanism of the porphyrin system. The number of remaining porphyrin molecules was estimated by calibration-based fluorescence spectroscopy to be 2.36×1013 molecules (i.e., ~2.910-11 mol/cm2) for a 3-nm-thick gold film, suggesting that the physisorbed molecules distributed very loosely on the metal island surface as a result of the weak van der Waals interactions. Fluorescence microscopy revealed the formation of microcrystalline porphyrin aggregates during the consecutive increase in sample solution. However, the immersion likely redistributed the porphyrin to be directly attached on the gold surface, as evidenced by an absence of porphyrinic microcrystals and the observed SEIRA enhancement. The distinctive red shift in the UV-visible spectra and the SEIRA-enhanced peaks indicate the presence of a preferred orientation in the form of the porphyrin ring inclined with respect to the gold surface.