Lithium doped N,N-dimethyl pyrrolidinium tetrafluoroborate organic ionic plastic crystal electrolytes for solid state lithium batteries

The organic ionic plastic crystal material N,N-dimethyl pyrrolidinium tetrafluoroborate ([C1mpyr][BF4]) has been mixed with LiBF4 from 0 to 8 wt% and shown to exhibit enhanced ionic conductivity, especially in the higher temperature plastic crystal phases (phases II and I). The materials retain their solid state well above 100 °C with the melt not being observed up to 300 °C. Interestingly the conductivity enhancement is highest with the lowest level of LiBF4 addition in phase II, but then the order of enhancement is reversed in phase I. In all cases, a conductivity drop is observed at the II → I phase transition (105 °C) which is associated with increased order in the pure matrix, as previously reported, although the conductivity drop is least for the highest LiBF4 amount (8 wt%). The 8 wt% sample displays different conductivity behaviours compared to the lower LiBF4 concentrations, with a sharp increase above 50 °C, which is apparently not related to the formation of an amorphous phase, based on XRD data up to 120 °C. Symmetric cells, Li/OIPC/Li, were prepared and cycled at 50 °C and showed evidence of significant preconditioning with continued cycling, leading to a lower over-potential and a concomitant decrease in the cell resistivity as measured by EIS. An SEM investigation of the Li/OIPC interfaces before and after cycling suggested significant grain refinement was responsible for the decrease in cell resistance upon cycling, possibly as a result of an increased grain boundary phase.

Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres

The incorporation of polyvinylidene difluoride (PVDF) electrospun nanofibres within N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF4] was investigated with a view to fabricating self-standing membranes for various electrochemical device applications, in particular lithium metal batteries. Significant improvement in mechanical properties and ionic conduction was demonstrated in a previous study, which also demonstrated the remarkably high performance of the lithium-doped composite material in a device. We now seek a fundamental understanding of the role of fibres within the matrix of the plastic crystal, which is essential for optimizing device performance through fine-tuning of the composite material properties. The focus of the current study is therefore a thorough investigation of the phase behaviour and conduction behaviour of the pure and the lithium-doped (as LiBF4) plastic crystal, with and without incorporation of polymer nanofibres. Analysis of the structure of the plastic crystal, including the effects of lithium ions and the incorporation of PVDF fibres, was conducted by means of synchrotron XRD. Ion dynamics were evaluated using VT solid-state NMR spectroscopy. ATR-FTIR spectroscopy was employed to gain insights into the molecular interactions of doped lithium ions and/or the PVDF nanofibres in the matrix of the [C2mpyr][BF4] composites. Preliminary measurements using PALS were conducted to probe structural defects within the pure materials. It was found that ion transport within the plastic crystal was significantly altered by doping with lithium ions due to the precipitation of a second phase in the structure. The incorporation of the fibres activated more mobile sites in the systems, but restricted ion mobility with different trends being observed for each ion species in each crystalline phase. In the presence of the fibres a strong interaction observed between the Li ion and the pyrrolidinium ring disappeared and formation of the second phase was prevented. As a result, an increased number of mobile lithium ions are released into the solid solution structure of the matrix, simultaneously removing the blocking effect of the second phase. Thus, ion conduction was remarkably improved within the Li-doped composite compared to the neat Li-doped plastic crystal.

Interactions between 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and gamma-Al2O3 (100) surface calculated by density functional theory

The main aim of this work is to investigate the 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1Im]+[BF4]-) ionic liquid (IL) adsorption on the gamma-Al2O3 (100) by density functional theory calculations to try to rationalize the adsorption as an electrostatic phenomenon. Optimized geometries and interaction energies of IL one-monolayer on the gamma-Al2O3 were obtained on high surface coverage (one cationanion pair per 94.96 nm2). A study of dispersion force was made to estimate its contribution to the adsorption. Overall, the process is ruled by electrostatic interaction between ions and surface. Adsorption of the anion [BF4]- and cation [C4C1Im]+ was also studied by Bader charge analysis and charge density difference for supported and unsupported situations. It is suggested that the IL ions have their charges maintained with significant anion cloud polarization inward to the acid aluminum sites. (c) 2012 Wiley Periodicals, Inc.

Thermodynamic behavior of the binaries 1-butilpryridinium tetrafluoroborate with water and alkanols: their interpretation using 1H-NMR spectroscopy and quantum-chemistry calculations

[EN]Here we present experimental data of different properties for a set of binary mixtures composed of water or alkanols (methanol to butanol) with an ionic liquid (IL), butylpyridinium tetrafluoroborate [bpy][BF4]. Solubility data (xIL,T) are presented for each of the mixtures, including water, which is found to have a small interval of compositions in IL, xIL, with immiscibility. In each case, the upper critical solubility temperature (UCST) is determined and a correlation was observed between the UCST and the nature of the compounds in the mixtures. Miscibility curves establish the composition and temperature intervals where thermodynamic properties of the mixtures, such as enthalpies Hm E and volumes Vm E, can be determined.

catena-[μ-tris(1,2-bis(tetrazol-1-yl)ethane-N4,N4')iron(II)] bis(tetrafluoroborate): Synthesis, structure, spectroscopic and magnetic characterisation of a chain-type coordination polymer spin-crossover compound.

In analogy to a common synthesis of 1-substituted 5-H tetrazoles (Tetrahedron Lett. 36 (1995)1759; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 11 (1985) 1521; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 1 (1991) 66; BGU, Belarus. Vestsi Akad. Navuk Belarusi, Ser. Khim. Navuk 1 (1992) 73), the new bidentate ligand 1,2-bis(tetrazol-1-yl)ethane [endi] was synthesized and characterized by X-ray diffraction, NMR, IR and UV–Vis spectroscopy. By using iron(II) tetrafluoroborate hexahydrate the complexation with this ligand yields a 1-dimensional linear coordination polymer similar to the recently published chain compound (Inorg. Chem. 39 (2000) 1891) exhibiting a thermally induced spin-crossover phenomenon. Similar to the 1,2-bis(tetrazol-1-yl)propane-bridged compound, our 1,2-bis(tetrazol-1-yl)ethane-bridged compound shows a gradual spin transition, but the spin-crossover temperature T1/2≈140 K is found to be 10 K above the other T1/2. The T1/2 was determined by temperature-dependent 57Fe-Mössbauer, far FT-IR and UV–Vis spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Single crystals of the complex were grown in situ from a solution of the ligand and iron(II) tetrafluoroborate. The X-ray structure determinations of both the high spin as well as the low spin state of the compound revealed a solid state structure, which is comparable to that of catena-[Fe(1,2-bis(tetrazole-1-yl)propane)3](ClO4)2 (Inorg. Chem. 39 (2000) 1891; 2nd TMR-TOSS Meeting, 4th Spin Crossover Family Meeting, Lufthansa Training Center, Seeheim/Germany, April 30–May 2, 1999). Both the 1,2-bis(tetrazol-1-yl)propane-bridged and our compound do not show a thermal hysteresis effect (J. Am. Chem. Soc. 115 (1993) 9810; Inorg. Chim. Acta 37 (1979) 169; Chem. Phys. Lett. 93 (1982) 567). The synthesis of the complex described in the experimental section yielded a fine powdered product being poorly soluble in most common solvents. The single crystal measurements were done with crystals obtained by various diffusion methods. Most of them yielded either thin needles or small hexagonal prism crystals depending on the specific conditions.

Galvanic replacement mediated transformation of Ag nanospheres into dendritic Au--Ag nanostructures in the ionic liquid [BMIM][BF4]

We demonstrate an unusual shape transformation of Ag nanospheres into {111}-oriented Au–Ag dendritic nanostructures by a galvanic replacement reaction in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]).

An investigation of silver electrodeposition from ionic liquids : influence of atmospheric water uptake on the silver electrodeposition mechanism and film morphology

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF4] and [C4mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C4mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

Depalladation of Neutral Monoalkyne- and Dialkyne-Inserted Palladacycles and Alkyne Insertion/Depalladation Reactions of Cationic Palladacycles Derived from N,N `,N `'-Triarylguanidines as Facile Routes for Guanidine-Containing Heterocycles/Carbocycles: Synthetic, Structural, and Mechanistic Aspects

Depalladation of the monoalkyne-inserted cyclopalldated guanidines (kappa 2(C,N)Pd(2,6-Me2C5H3N)Br] (I and II) in PhCl under reflux conditions and that of the dialkyne-inserted cyclopalladated guanidine kappa(2)(C,N):eta(2)(C=C)PdBr] (III) in pyridine under reflux conditions afforded a guanidine-containing indole (1), imidaziondole (2), and benzazepine (3) in 80%, 67%, and 76%, yields, respectively. trans-L2PdBr2] species (L = 2,6-Me2C5H3N, C5H5N) were also isolated in the aforementioned reactions in 35%, 42%, and 40% yields. Further , the reaction of the cyclopalladated guanidine kappa(2)(C,N)Pd(mu-Br)](2) (IV) with AgBF4 in a CH2Cl2/MeCN mixture afforded the cationic pincer type cyclopalladated guanidine kappa(3)(C,N,O)Pd(MeCN)]BF4] (4) in 85% yield and this palladacycle upon crystallization in MeCN and the reaction of kappa(2)(C,N)Pd(mu-Br)](2) (V) with AgBf(4) in a CH2Cl2/MeCN mixture afforded the cationic palladacycles {kappa(2)(C,N)Pd(MeCN)(2)]BF4](5 and 6) in 89% and 91% yields, respectively. The separate reactions of 4 with 2 equiv of methyl phenylpropiolate (MPP) or diphenylacetylene (DPA) and the reaction of 5 with 2 equiv of MPP in PhCl at 110 degrees C afforded the guanidine-containing quinazolinium tetrafluoroborate 7 in 25-32% yields. The reaction of 6 with 2 equiv of DPA under otherwise identical conditions afforded the unsymmetrically substituted guanidinium tetrafluoroborate 8, containing a highly substituted naphthalene unit, in 82% yield. Compounds 1-8 were characterized by analytical and spectroscopic techniques, and all compounds except 4 were characterized by single-crystal X-ray diffraction. The Molecular structure of 2 and 3 are nove, as the framework in the former arises due to the formation of two C-N bonds upon depalladation while the butadienyl unit in the latter revealed cis,cis stereochemistry, a-feature unprecedented in alkyne insertion chemistry. Plausible pathways for the formation of heterocycles/carbocycles are proposed. the influence of substitutents on the aryl rings fo the cyclopalladated guanidine moiety and those on alkynes upon the nature of the products in addressed. Heterocycles 1 and 7 revealed the presence of two rotamers in about a 1.00:0.43 ratio in CDCl3 and in about a 1.00:0.14 ratio in CD3OD, respectively, as detected by H-1 NMR spectroscopy while in CD3CN and DMSO-d(6) (1) and CD3CN and CDCl3 (7), these heterocycles revealed the presence of a single rotamer. These spectral features are attributed to the restricted C-N single-bond rotation of the CN3 unit of the guanidine moiety, which possibly arises from steric constraint due to the formation of a N-H center dot center dot center dot Cl hydrogen bond with CDCl3 (1) and N-H center dot center dot center dot O and O-D center dot center dot center dot O hydrogen bonds with CD3OD (7).

Use of vertically-aligned carbon nanotube array to enhance the performance of electrochemical capacitors

In the domain of energy storage, electrochemical capacitors have numerous applications ranging from hybrid vehicles to consumer electronics, with very high power density at the cost of relatively low energy storage. Here, we report an approach that uses vertically aligned carbon nanotube arrays as electrodes in electrochemical capacitors. Different electrolytes were used and multiple parameters of carbon nanotube array were compared: carbon nanotube arrays were shown to be two to three times better than graphite in term of specific capacitance, while the surface functionalization was demonstrated to be a critical factor in both aqueous and nonaqueous solutions to increase the specific capacitance. We found that a maximum energy density of 21 Wh/kg at a power density of 1.1 kW/kg for a hydrophilic electrode, could be easily achieved by using tetraethylammonium tetrafluoroborate in propylene carbonate. These are encouraging results in the path of energy-storage devices with both high energy density and power density, using only carbon-based materials for the electrodes with a very long lifetime, of tens of thousands of cycles. © 2011 IEEE.

Dynamic mechanical properties of gel polymer electrolytes containing ionic liquid

The copolymer of acrylonitrile (AN), methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) is synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). The dynamic mechanical properties of the resulting gel polymer electrolytes containing ionic liquid are measured.

Separation of ethyl acetate-ethanol azeotropic mixture using hydrophilic ionic liquids

The separation of ethyl acetate and ethanol (EtOH) is important but difficult due to their close boiling points and formation of an azeotropic mixture. The separation of the azeotropic mixture of ethyl acetate and EtOH using the hydrophilic ionic liquids (ILs) 1-alkyl-3-methylimidazolium chloride (alkyl = butyl, hexyl, and octyl) ([C(n)mim]Cl, n = 4, 6, 8) and 1-allyl-3-methylimidazolium chloride and bromide ([Amim]Cl and [Amim]Br) has been investigated. Triangle phase diagrams of five ILs with ethyl acetate and EtOH were constructed, and the biphasic regions were found as follows: [Amim]Cl > [Amim]Br > [C(4)mim]Cl > [C(6)mim]Cl > [C(8)mim]Cl. The mechanisms of the ILs including cation, anion, and polarity effect were discussed.

Separation of ternary systems of hydrophilic ionic liquid with miscible organic compounds by RPLC with refractive index detection

A rapid and simple analytical method was developed for the simultaneous and quantitative determination and separation of hydrophilic imidazolium ionic liquids (ILs) (1-butyl-3-methylimidazolium chloride, [C(4)mim]Cl; 1-hexyl-3-methylimidazolium chloride, [C(6)mim]Cl; 1-octyl-3-methylimidazolium chloride, [C(8)mim]Cl; 1-allyl-3-methylimidazolium chloride, [Amim]Cl; or 1-allyl-3-methylimidazolium bromide, [Amim]Br) with miscible ethyl acetate and EtOH and their mixtures using reverse phase liquid chromatography coupled with refractive index detection (RPLC-RI). The influence of 60 to 100% (volume percentage) methanol in the mobile phase on the IL systems ([C(4)mim]Cl, [C(6)mim]Cl, [C(8)mim]Cl, [Amim]Br, or [Amim]Cl)-ethyl acetate-EtOH was investigated.

Synthesis and characterisation of novel imidazolium-based ionic liquid crystals with a p-nitroazobenzene moiety

A novel series of compounds with different counter anions, i.e. 1-{[4-(4-nitrophenylazo)phenyloxy]}alkyl-3-methyl-1H-imidazol-3-ium bromide salts (C-n , n=3, 6, 10) and tetrafluoroborate salts (D-n , n=3, 6, 10), were synthesised by the incorporation of an imidazolium group into paraffin side chain-terminated 4-nitroazobenzene derivatives. Their chemical structures were determined by H-1 NMR, C-13 NMR, UV spectroscopy and elemental analysis.