LiCl Salt Research Articles

Mechano-chemical synthesis of manganese borohydride (Mn(BH4)2) and inverse cubic spinel (Li2MnCl4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior

Manganese borohydride (Mn(BH4)2) was successfully synthesized by a mechano-chemical activation synthesis (MCAS) from lithium borohydride (LiBH4) and manganese chloride (MnCl2) by applying high energy ball milling for 30 min. For the first time a wide range of molar ratios n = 1, 2, 3, 5, 9 and 23 in the (nLiBH4 + MnCl2) mixture was investigated. During ball milling for 30 min the mixtures release only a very small quantity of H2 that increases with the molar ratio n but does not exceed ∼0.2 wt.% for n = 23. However, longer milling duration leads to more H2 released. For the equimolar ratio n = 1 the principal phases synthesized are Li2MnCl4, an inverse cubic spinel phase, and the Mn(BH4)2 borohydride. For n = 2 a LiCl salt is formed which coexists with Mn(BH4)2. With the n increasing from 3 to 23 LiBH4 is not completely reacted and its increasing amount is retained in the microstructure coexisting with LiCl and Mn(BH4)2. Gas mass spectrometry during Temperature Programmed Desorption (TPD) up to 450 °C shows the release of hydrogen as a principal gas with a maximum intensity around 130–150 °C accompanied by a miniscule quantity of borane B2H6. The intensity of the B2H6 peak is 200–600 times smaller than the intensity of the corresponding H2 peak. In situ heating experiments using a continuous monitoring during heating show no evidence of melting of Mn(BH4)2 up to about 270–280 °C. At 100 °C under 1 bar H2 pressure the ball milled n = 2 and 3 mixtures are capable of desorbing quite rapidly ∼4 wt.% H2 which is a very large amount of H2 considering that the mixture also contains 2 mol of LiCl salt. The H2 quantities experimentally desorbed at 100 and 200 °C do not exceed the maximum theoretical quantities of H2 expected to be desorbed from Mn(BH4)2 for various molar ratios n. It clearly confirms that the contribution from B2H6 evolved is negligibly small (if any) when desorption occurs isothermally in the practical temperature range 100–200 °C. It is found that the ball milled mixture with the molar ratio n = 3 exhibits the highest rate constant k and the lowest apparent activation energy for dehydrogenation, EA ∼ 102 kJ/mol. Decreasing or increasing the molar ratio n below or above 3 increases the apparent activation energy. Ball milled mixtures with the molar ratio n = 2 and 3 discharge slowly H2 during storage at room temperature and 40 °C. The addition of 5 wt.% nano-Ni with a specific surface area of 60.5 m2/g substantially enhances the rate of discharge at 40 °C.

Molten salt synthesis of La0.8Sr0.2MnO3 powders for SOFC cathode electrode

For La0.8Sr0.2MnO3 (LSM) perovskite, used as the cathode material for solid oxide fuel cells (SOFC), it is known that the formation of a triple-phase-boundary is restrained due to the formation of a second phase at the YSZ/electrode interface at high temperature. To decrease the 2nd phase, lowering the sintering temperature has been used. LSM powder was synthesized by molten salt synthesis method to control its particle size, shape, and agglomeration. We have characterized the phase formation, particle size, shape, and sintering behavior of LSM in the synthesis using the variation of KCl, LiCl, KF and its mixed salts as raw materials. In the case of KCl and KCl-KF salts, the particle size and shape of the LSM was well controlled and synthesized. However, in the case of LiCl and KCl-LiCl salts, LiMnOx as 2nd phase and LSM were synthesized simultaneously. In the case of the mixed salt of KCl-KF, the growth mechanism of the LSM particle was changed from ‘diffusion-controlled’ to ‘reaction-controlled’ according to the amount of mixed salt. The sintering temperature can be decreased below 1000 °C by using the synthesized LSM powder.

Distillation of LiCl from the LiCl–Li2O molten salt of the electrolytic reduction process

Electrolytic reduction of the uranium oxide in LiCl–Li2O molten salt for the treatment of spent nuclear fuel requires the separation of the residual salt from the reduced metal product, which contains about 20 wt% salt. In order to separate the residual salt and reuse it in the electrolytic reduction, a vacuum distillation process was developed. Lab-scale distillation equipment was designed and installed in an argon atmosphere glove box. The equipment consisted of an evaporator in which the reduced metal product was contained and exposed to a high temperature and reduced pressure; a receiver; and a vertically oriented condenser that operated at a temperature below the melting point of lithium chloride. We performed experiments with LiCl–Li2O salt to evaluate the evaporation rate of LiCl salt and varied the operating temperature to discern its effect on the behavior of salt evaporation. Complete removal of the LiCl salt from the evaporator was accomplished by reducing the internal pressure to <100 mTorr and heating to 900 °C. We achieved evaporation efficiency as high as 100 %.

An Experimental Study of a Flux Modulated Solid State Metathesis Reaction

AbstractA solid state metathesis (SSM) reaction was investigated with respect to the formation of rare‐earth carbodiimides, the role of the co‐produced salt (LiCl), and the eutectic flux medium (LiCl/KCl). A SSM reaction is characterized by an exothermic reaction in which a salt (often LiCl) is coproduced. When the salt melts, it can serve as a useful medium for the crystallization of a desired product. An improved crystal growth can be observed by using an eutectic flux. However, the composition of an eutectic LiCl/KCl flux is altered when LiCl is produced during the reaction. The thermal effects concerning the endothermic melting of the flux and the exothermic ingnition of the SSM reaction may compensate each other, which is not necessarily a drawback for the reaction to proceed.

Polyamide 6–wheat straw composites: Effects of additives on physical and mechanical properties of the composite

AbstractPolyamide 6 was modified with lithium chloride (LiCl) salt and N‐butyl benzenesulfonamide (N‐BBSA) plasticizer (additives). The modification was done in order to develop an environmentally friendly composite, composed of wheat straw (WS). A 15 wt% of ground WS was compounded with Polyamide 6 along with the additives. Addition of LiCl decreased the melting point of the matrix, allowing for a lower compounding temperature. However, a pseudo‐crosslinking formation upon addition of salt limited the polymer chain movement and restricted the processing temperature. LiCl addition increased the tensile and flexural modulus of the composite, but decreased the tensile and flexural strength. Decrease in the strength was found to be related to the increase in the residence time of material during extrusion causing severe WS thermal degradation. Addition of N‐BBSA eased the processing due to lubrication effect, however, when used in excess, lowered the flexural modulus and strength. Addition of WS to Polyamide 6 increased the modulus of the matrix. Matrix tensile modulus and flexural modulus were enhanced by 27%; however, a decrease in strength of the matrix was obtained. Addition of WS, LiCl, and plasticizer lowered the impact properties of Polyamide 6. It was concluded that combination of 2 wt% LiCl and of 2 wt% N‐BBSA gives the best mechanical properties. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers

Polyamide 6‐wheat straw composites: Degradation kinetics

AbstractDegradation kinetics of ground wheat straw (WS), polyamide 6, and a WS‐polyamide 6 composites obtained from extrusion were investigated. 15 wt% of ground WS was melt blended with other additives naming; lithium chloride salt (LiCl) and N‐butylbenzenesulfonamide plasticizer (N‐BBSA) as matrix treatments. The additives were added to reduce the melting point of polyamide 6 and ease of composite processing (reduction in processing temperature and time). Two commonly used non‐isothermal kinetic models were used to investigate the degradation kinetics of WS and the composite. Thermal gravimetric analysis was utilized to measure the thermal stability and degradation kinetics of different composite formulation. The activation energy of WS was identified by iso‐conversional Friedman kinetic method. Through this method, WS activation energy was found to be around 141.4 kJ/mol. Composite kinetic studies were based on the Coats and Redfern procedure. It was concluded that the composite activation energy was correlated to the residual weight percentage of the composite at the maximum thermal degradation temperature. The onset of degradation of WS was dictated by the thermal stability of its lignin content and was found to be around 188°C. WS, however, did not go through a major degradation up to 245°C at which drastic decomposition starts. This temperature range overlaps with processing temperature of Polyamide 6 and required matrix/WS treatments. Addition of salt and plasticizer individually or with each other at any level decreased the onset of degradation temperature. Addition of plasticizer at 4 wt% level, however, shifted the degradation peak to higher temperature representing a more thermally stable composite. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers

Controlled synthesis of single-crystalline Li0.44MnO2 and Li2MnO3 nanoribbons

The Li0.44MnO2 and Li2MnO3 nanoribbons have been achieved via Na0.44MnO2 nanoribbons as precursor template followed by ion-exchange to replace Na+ by Li+. The Li0.44MnO2 nanoribbons are formed when the Na+ in Na0.44MnO2 is replaced by the Li+ in the molten LiNO3 and LiCl salts and the formation of Li2MnO3 nanoribbons involves the ion-exchange between Li+ and Na+ and the oxidation process of LiNO3. The morphology of Li0.44MnO2 and Li2MnO3 preserves the 1D nanostructure of Na0.44MnO2 nanoribbons after ion-exchange reaction between Na+ and Li+. The transformation from Na0.44MnO2 nanoribbons to Li0.44MnO2 and Li2MnO3 nanoribbons can be interpreted on the basis of a self-sacrificing templating route.

Ab initio and density functional theoretical design and screening of model crown ether based ligand (host) for extraction of lithium metal ion (guest): effect of donor and electronic induction

The structures, energetic and thermodynamic parameters of model crown ethers with different donor, cavity and electron donating/ withdrawing functional group have been determined with ab initio MP2 and density functional theory in gas and solvent phase. The calculated values of binding energy/ enthalpy for lithium ion complexation are marginally higher for hard donor based aza and oxa crown compared to soft donor based thia and phospha crown. The calculated values of binding enthalpy for lithium metal ion with 12C4 at MP2 level of theory is in good agreement with the available experimental result. The binding energy is altered due to the inductive effect imparted by the electron donating/ withdrawing group in crown ether, which is well correlated with the values of electron transfer. The role of entropy for extraction of hydrated lithium metal ion by different donor and functional group based ligand has been demonstrated. The HOMO-LUMO gap is decreased and dipole moment of the ligand is increased from gas phase to organic phase because of the dielectric constant of the solvent. The gas phase binding energy is reduced in solvent phase as the solvent molecules weaken the metal-ligand binding. The theoretical values of extraction energy for LiCl salt from aqueous solution in different organic solvent is validated by the experimental trend. The study presented here should contribute to the design of model host ligand and screening of solvent for metal ion recognition and thus can contribute in planning the experiments.

Guided self-assembly of nanostructured titanium oxide

A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiOx nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiOx nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiOx nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiOx nanorods with rough surfaces are formed by the self-assembly of TiOx nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiOx nanorods shows stronger ER properties than that of the other nanostructured TiOx particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.

Formation and ionization energies of small chlorine‐doped lithium clusters by thermal ionization mass spectrometry

Theoretical calculations have shown that the first ionization energy of clusters of the type Li(n) Cl (n ≥2), with more than eight valent electrons, is lower than that of alkali metal atoms; hence they are named superalkali. Superalkali clusters can mimic the chemical behavior of alkali metals and may be used as building blocks of new cluster-assembled materials. There is currently no reliable experimental proof of this kind of clusters and such proof is required. The Li(n) Cl (n = 2-6) clusters were produced by a thermal ionization source of modified design, and mass selected by a magnetic-sector mass spectrometer. The modification pertains to the replacement of the side filaments by a cylinder in the triple-filament thermal ionization source. The sample, which is LiCl salt, was pressed into a ring and placed on the inner wall of the cylinder. It was observed that the ions of clusters with an even number of lithium atoms (Li(2) Cl(+) , Li(4) Cl(+) , Li(6) Cl(+) ) are more stable than the odd-numbered ones (Li(5) Cl(+) , Li(3) Cl(+) ). The ionization energies were determined to be 3.98 ± 0.25 eV for Li(2) Cl, 4.10 ± 0.25 eV for Li(3) Cl, 3.90 ± 0.25 eV for Li(4) Cl, 4.01 ± 0.25 eV for Li(5) Cl, and 4.09 ± 0.25 eV for Li(6) Cl. The presence of a halogen atom reduces the ionization energy of the metal clusters. The thermal ionization source of modified design presents a suitable simple way to obtaining and measuring the ionization energies of very small lithium monochloride clusters. Clusters Li(n) Cl, n = 4 to 6, were detected for the first time.

The Influence of Water and Metal Ions on the Transport Properties of Trihexyl(tetradecyl)phosphonium Chloride

A recent study indicated that the water-saturated ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]) provided a viable electrolyte for a Mg-air battery. However, there is limited literature on the properties of IL-water mixtures as battery electrolytes. The physical properties of [P6,6,6,14][Cl] were studied with the addition of both water and metal salts (MgCl2 and LiCl) using conductivity and self-diffusion coefficient measurements. The conductivity of the samples at low water concentrations is surprisingly enhanced by the addition of the metal salt, contrary to lithium IL electrolytes. It was also found that the conductivity of the IL was increased by an order of magnitude by saturation with water. NMR diffusion measurements were used to probe the behaviour of both the cation and the water in the mixtures. It was found that the addition of metal salts to the water-saturated [P6,6,6,14][Cl] did not affect the transport properties of the water or cation.

Study on the Reduction of Rare Earth Oxides by Lithium Metal in a Molten LiCl Salt for a Pyrochemical Processing of Spent Fuels

Study on the Reduction of Rare Earth Oxides by Lithium Metal in a Molten LiCl Salt for a Pyrochemical Processing of Spent Fuels

Combining piracetam and lithium salts: ionic co-crystals and co-drugs?

Mechanochemical reaction of solid piracetam with the inorganic salts LiCl and LiBr yields ionic co-crystals which are also co-drugs, characterized by markedly different thermal properties with respect to pure components, also depending on the method for preparation and/or conditions of measurements; single crystal and powder X-ray diffraction at variable temperatures, DSC, TGA, hot stage microscopy (HSM) and intrinsic dissolution rate have been used to fully characterize the solid products.

Direct electrochemical reduction of titanium dioxide in molten lithium chloride

The electrochemical reduction of TiO 2 has been carried out in a molten LiCl salt at 650 °C. The direct reduction mechanism of TiO 2 in the molten LiCl was suggested by the CV experiment and the constant voltage electrolysis. TiO 2 was electrochemically converted to the metallic titanium via various reaction intermediates such as LiTiO 2, TiO, and Ti 2O. The interrupted voltage electrolysis was demonstrated to be effective for the direct electrochemical reduction of TiO 2 to achieve a high current efficiency. The surface morphology of the produced metal was investigated by SEM and TEM.

Study on a separation method of radionuclides (Ba, Sr) from LiCl salt wastes generated from the electroreduction process of spent nuclear fuel

In this paper, a separation method of radionuclides (Ba, Sr) from LiCl salt wastes generated from the electroreduction process of spent nuclear fuel was studied to recover pure LiCl salts and reduce radioactive wastes. The method consisted of chemical conversion process of BaCl2 and SrCl2 in LiCl molten salts by using lithium compounds and vacuum distillation process of LiCl salts. In the chemical conversion, BaCl2 and SrCl2 in LiCl molten salts were mainly converted into (Ba,Sr)CO3 or (Ba,Sr)SO4. Contents of Ba and Sr in LiCl salts recovered from the vacuum distillation process were equal to about 0.01 of initial concentrations of Ba and Sr in LiCl molten salts. These results will be utilized to recycle the LiCl salt wastes.

Morphology and structure of LiNb 0.6Ti 0.5O 3 particles by molten salt synthesis

M-phase LiNb 0.6Ti 0.5O 3 (LNT) plate-like particles with large anisometric shape were firstly fabricated by molten salt synthesis (MSS) method in LiCl flux. Effects of reaction temperature, holding time and the weight ratio of LiCl salt to the original powders on the phase structure and morphology of the synthesized particles were investigated. The LiNb 0.6Ti 0.5O 3 powders generally showed a multi-layer structure, exhibiting irregular hexagonal or triangle morphology. The reaction temperature showed a strong influence on the particle growth process, and pure LNT particles are obtained at 950 °C. Further increasing the reaction temperature and holding time could increase the average size of the particles. It revealed that the thickness of the plat-like particles was increased as the contents of the chloride salts increased. The synthesis process, the relation between crystal structure and morphology of particles were also discussed.

Metastable Phase Equilibria in the Aqueous Ternary System Containing Potassium, Lithium and Chloride Ions at 298.15 K

The metastable phase equilibrium in the ternary system containing potassium, lithium and chloride ions was studied at 298.15 K using an isothermal evaporation method. The solubility, density and refractive index of the equilibrated solution were measured. The crystalloid forms of the solid phase were determined using a schreinermarks wet residue method. On the basis of the experimental data, the metastable equilibrium phase diagram and the physicochemical properties vs composition in the ternary system at 298.15 K were plotted. The experimental results show that this system is of a simple eutectic type system, no double salt or solid solution formed at 298.15 K. The phase diagram consists of one invariant point, two uninvariant curves, and two crystallization regions. The crystallization regions correspond to potassium chloride (KCl) and lithium chloride monohydrate (LiCl·H2O), respectively. Salt KCl has the largest crystallization field, whereas salt LiCl·H2O has the smallest crystallization field. Salt LiCl has strong salting-out effect on salt KCl.

Effect of alkali and alkaline-earth chloride addition on electrolytic reduction of UO 2 in LiCl salt bath

The electrolytic reduction process of actinide oxides in a LiCl salt bath at 923 K has been developed for nuclear fuel reprocessing. Since some salt-soluble fission products, such as Cs, Sr and Ba, accumulate in the LiCl salt bath, their effect on UO 2 reduction was investigated. In the experiments, UO 2 specimens were reduced by potential- or current-controlled electrolysis in various LiCl salt baths containing up to 30 mol% of KCl, CsCl, SrCl 2 or BaCl 2. The rate of UO 2 reduction in a LiCl salt bath was considerably decreased by the addition of alkali metal chlorides (KCl and CsCl) and slightly decreased by BaCl 2 addition. SrCl 2 addition had no appreciable effect. It was suggested that the diffusion of O 2− ions from the inside of UO 2 specimens to the bulk salt determined the reduction rate during the electrolysis and that the effect of salt composition was related to the solubility of O 2− ions in the salt bath.

Melt Crystallization Process Treatment of LiCl Salt Waste Generated from Electrolytic Reduction Process of Spent Oxide Fuel

The effects of operating conditions such as crystal growing rate and initial impu rity concentration on separation(or concentration) of cesiu m and strontium fission products in the LiCl waste salt generated fro m an electro lytic reduction process of spent oxides on lab-scale layer melt crystallization process were analyzed. In a layer crystallizat ion process, impurities(CsCl and SrCl2) are concentrated in a s mall part of the LiCl salt due to the difference in the solubility in the melt phase and the solid l phase. The crystal growth rate strongly affects the crystal structure, therefore the separation efficiency, but the effect of the in itial Cs and Sr concentrations in LiCl mo lten salts was nearly negligible within the experimental range.

The structure and terahertz dynamics of water confined in nanoscale pools in salt solutions

The behaviour of liquid water below its melting point is of great interest as it may hold clues to the properties of normal liquid water and of water in and on the surfaces of biomolecules. A second critical point, giving rise to a polyamorphic transition between high and low density water, may be hidden in the supercooled region but cannot be observed directly. Here it is shown that water can be locked up in nano-pools or worm-like structures using aqueous LiCl salt solutions and can be studied with terahertz spectroscopies. Very high dynamic range ultrafast femtosecond optical Kerr effect (OKE) spectroscopy is used to study the temperature-dependent behaviour of water in these nano-pools on timescales from 10 fs to 4 ns. These experiments are complemented by temperature-dependent nuclear magnetic resonance (NMR) diffusion measurements, concentration-dependent Fourier-transform infrared (FTIR) measurements, and temperature-dependent rheology. It is found that liquid water in the nanoscale pools undergoes a fragile-to-strong transition at about 220 K associated with a sharp increase in the inhomogeneity of translational dynamics.