The effect of coordinating and non-coordinating additives on the transport properties in ionic liquid electrolytes for lithium batteries

In the present study we expand our analysis of using two contrasting organic solvent additives (toluene and THF) in an ionic liquid (IL)/Li NTf 2 electrolyte. Multinuclear Pulsed-Field Gradient (PFG) NMR, spin-lattice (T1) relaxation times and conductivity measurements over a wide temperature range are discussed in terms of transport properties and structuring of the liquid. The conductivity of both additive samples is enhanced the most at low temperatures, with THF slightly more effective than toluene. Both the anion and lithium self-diffusivity are enhanced in the same order by the additives (THF > toluene) while that of the pyrrolidinium cation is marginally enhanced. 1H spin-lattice relaxation times indicate a reasonable degree of structuring and anisotropic motion within all of the samples and both 19F and 7Li highlight the effectiveness of THF at influencing the lithium coordination within these systems.

Regenerated silk fibroin using protic ionic liquids solvents : towards an all-ionic-liquid process for producing silk with tunable properties

We have shown that protic ionic liquids, pILs, are effective coagulation solvents for the regenerated of silk fibroin, RSF. We show that the choice of pIL has a dramatic effect on the composition of the RSF. Additionally the use of pILs as the coagulator eliminates the need for volatile organic solvents in silk processing.

Cellulose-based biodegradable blends and composites regenerated from ionic liquids

This thesis presents the fabrication of biodegradable polymer blends and composites with the assistance of ionic liquids. The work included preparation and characterization of cellulose/PCL blend films, cellulose/ PCL-PDMS-PCL blend films, cellulose/ PVAL blend films and cellulose/clay composite films. An efficient and feasible approach of reducing plastic pollution was developed.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

Ionic liquid electrolytes as a platform for rechargeable metal–air batteries: a perspective

Metal-air batteries are a well-established technology that can offer high energy densities, low cost and environmental responsibility. Despite these favourable characteristics and utilisation of oxygen as the cathode reactant, these devices have been limited to primary applications, due to a number of problems that occur when the cell is recharged, including electrolyte loss and poor efficiency. Overcoming these obstacles is essential to creating a rechargeable metal-air battery that can be utilised for efficiently capturing renewable energy. Despite the first metal-air battery being created over 100 years ago, the emergence of reactive metals such as lithium has reinvigorated interest in this field. However the reactivity of some of these metals has generated a number of different philosophies regarding the electrolyte of the metal-air battery. Whilst much is already known about the anode and cathode processes in aqueous and organic electrolytes, the shortcomings of these electrolytes (i.e. volatility, instability, flammability etc.) have led some of the metal-air battery community to study room temperature ionic liquids (RTILs) as non-volatile, highly stable electrolytes that have the potential to support rechargeable metal-air battery processes. In this perspective, we discuss how some of these initial studies have demonstrated the capabilities of RTILs as metal-air battery electrolytes. We will also show that much of the long-held mechanistic knowledge of the oxygen electrode processes might not be applicable in RTIL based electrolytes, allowing for creative new solutions to the traditional irreversibility of the oxygen reduction reaction. Our understanding of key factors such as the effect of catalyst chemistry and surface structure, proton activity and interfacial reactions is still in its infancy in these novel electrolytes. In this perspective we highlight the key areas that need the attention of electrochemists and battery engineers, in order to progress the understanding of the physical and electrochemical processes in RTILs as electrolytes for the various forms of rechargeable metal-air batteries.

Silver nanoparticles prepared by gamma irradiation across metal-organic framework templates

In this study, we demonstrate for the first time the successful fabrication of well-dispersed ultrafine silver nanoparticles inside metal-organic frameworks through a single step gamma irradiation at room temperature. HKUST-1 crystals are soaked in silver nitrate aqueous solution and irradiated with a Cobalt 60 source across a range of irradiation doses to synthesize highly uniformly distributed silver nano-particles. The average size of the silver nanoparticles across the Ag@HKUST-1 materials is found to vary between 1.4 and 3 nm for dose exposures between 1 and 200 kGy, respectively. The Ag@HKUST-1 hybrid crystals exhibit strong surface plasmon resonance and are highly durable and efficient catalytic materials for the reduction of 4-nitrophenol to 4-aminophenol (up to 14.46 × 10-3 s-1 for 1 kGy Ag@HKUST-1). The crystals can be easily recycled for at least five successive cycles of reaction with a conversion efficiency higher than 99.9%. The gamma irradiation is demonstrated to be an effective and environmental friendly process for the synthesis of nano-particles across confined metal-organic frameworks at room temperature with potential applications in environmental science.

Degradation of organic dyes by P25-reduced graphene oxide: influence of inorganic salts and surfactants

Treatment of coloured effluent treatment is a major issue for the textile industry. In this study, catalyst P25-graphene was prepared and applied for degrading dye from an aqueous solution. Three types of dyes were selected to determine the feasibility of the catalyst for the dye degradation, including sulphonic, azoic, and fluorescent dyes. P25-graphene catalyst showed good ability to degrade all selected dyes. The influence of inorganic salts and surfactants on the photocatalytic degradation of rhodamine B using catalyst P25-graphene was also investigated. The degradation of rhodamine B was suppressed by the presence of NaCl, but the effect of Na2SO4 was negligible. The degradation of rhodamine B was significantly suppressed by all three types of surfactant, namely anionic, cationic and non-ionic surfactants. NMR technique was used to investigate the mechanisms associated with this suppression.

Characterization of the phase behaviour of a novel polymerizable lyotropic ionic liquid crystal

The development of new polymerizable lyotropic liquid crystals (LLCs) utilizing charged amphiphilic molecules such as those based on long chain imidazolium compounds, is a relatively new design direction for producing robust membranes with controllable nano-structures. Here we have developed a novel polymerizable ionic liquid based LLC, 1-hexadecyl-3-methylimidazolium acrylate (C16mimAcr), where the acrylate anion acts as the polymerizable moiety. The phase behaviour of the C16mimAcr upon the addition of water was characterized using small and wide angle X-ray scatterings, differential scanning calorimetry and polarized optical microscopy. We compare the phase behaviour of this new polymerizable LLC to that of the well known LLC chloride analogue, 1-hexadecyl-3-methylimidazolium chloride (C16mimCl). We find that the C16mimAcr system has a more complex phase behaviour compared to the C16mimCl system. Additional lyotropic liquid crystalline mesophases such as hexagonal phase (H1) and discontinuous cubic phase (I1) are observed at 20 °C for the acrylate system at 50 and 65 wt% water respectively. The appearance of the hexagonal phase (H1) and discontinuous cubic phase (I1) for the acrylate system is likely due to the strong hydrating nature of the acrylate anion, which increases the head group area. The formation of these additional mesophases seen for the acrylate system, especially the hexagonal phase (H1), coupled with the polymerization functionality offers great potential in the design of advanced membrane materials with selective and anisotropic transport properties.

Enhancing thermal stability and mechanical properties of lyotropic liquid crystals through incorporation of a polymerizable surfactant.

We present a facile method to prepare thermally stable and mechanically robust crosslinked lyotropic liquid crystals (LLCs) through incorporation of a polymerizable amphiphile into a binary LLC system comprising commercially available surfactant Brij 97 and water. Thermal stability and mechanical properties of the polymerized LLCs were significantly enhanced after polymerization of the incorporated polymerizable surfactant. The effect of incorporating a polymerizable amphiphile on the phase behavior of the LLC system was studied in detail. In situ photo-rheology was used to monitor the change in the mechanical properties of the LLCs, namely the storage modulus, loss modulus, and viscosity, upon polymerization. The retention of the LLC nanostructures was evaluated by small angle X-ray scattering (SAXS). The ability to control the thermal stability and mechanical strength of LLCs simply by adding a polymerizable amphiphile, without tedious organic synthesis or harsh polymerization conditions, could prove highly advantageous in the preparation of robust nanomaterials with well-defined periodic structures.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.

Improved efficiency and stability of flexible dye sensitized solar cells on ITO/PEN substrates using an ionic liquid electrolyte

Flexible dye-sensitized solar cells (DSSCs) built on plastic substrates have attracted great interest as they are lightweight and can be roll-to-roll printed to accelerate production and reduce cost. However, plastic substrates such as PEN and PET are permeable to water, oxygen and volatile electrolyte solvents, which is detrimental to the cell stability. Therefore, to address this problem, in this work, an ionic liquid (IL) electrolyte is used to replace the volatile solvent electrolyte. The initial IL-based devices only achieved around 50% of the photovoltaic conversion efficiency of the cells using the solvent electrolyte. Current-voltage and electrochemical impedance spectroscopy (EIS) analysis of the cells in the dark indicated that this lower efficiency mainly originated from (i) a lack of blocking layer to reduce recombination, and (ii) a lower charge collection efficiency. To combat these problems, cells were developed using a 12 nm thick blocking layer, produced by atomic layer deposition, and 1 μm thick P25 TiO2 film sensitized with the hydrophobic MK-2 dye. These flexible DSSCs utilizing an IL electrolyte exhibit significantly improved efficiencies and a <10% drop in performance after 1000 h aging at 60°C under continuous light illumination.

Gelled ionic liquid sodium ion conductors for sodium batteries

Owing to the unique properties of certain Ionic liquids (ILs) as safe and green solvents, as well as the potential of sodium as an alternative to lithium as charge carriers, we investigate gel sodium electrolytes as safe, low cost and high performance materials with sufficient mechanical properties for application in sodium battery technologies. We investigate the effect of formation of two types of gel electrolytes on the properties of IL electrolytes known to support Na/Na⁺ electrochemistry. The ionic conductivity is only slightly decreased by 0.0005 and 0.0002 S cm^-1 in the case of 0.3 and 0.5 M NaNTf2 systems respectively as the physical properties transition from liquid to gel. We observed facile plating and stripping of Na metal around 0 V vs. Na/Na⁺ through the cyclic voltammetry. A wide-temperature range of the gelled IL state, of more than 100 K around room temperature, is achieved in the case of 0.3 and 0.5 M NaNTf2. We conclude that the formation of a gel does not significantly affect the liquid-like ion dynamics in these materials, as further evidenced by DSC and FTIR analysis.

Solvate ionic liquids as reaction media for electrocyclic transformations

Solvate ionic liquids (SILs) consisting of lithium bis(trifluoromethylsulfonyl)imide dissolved in tri-or tetraglyme have recently emerged as a novel class of ionic liquids. Herein, the first use of solvate ionic liquids as a replacement for molecular solvents in electrocyclization reactions is reported. The SILs promoted both Diels-Alder and [2+2] cycloaddition reactions, compared to an appropriate molecular solvent, and 5 M lithium perchlorate in diethyl ether. The Gutmann acceptor number (AN) of these solvate ionic liquids has also been determined by 31P NMR spectroscopy to be 26.5, thus being modest Lewis acids.