Lithium Nitrate Solution Research Articles

Thermodynamics of Aqueous Lithium Nitrate Solutions at 298.15 to 398.15 K and 0.1 to 60 MPa

Thermodynamics of Aqueous Lithium Nitrate Solutions at 298.15 to 398.15 K and 0.1 to 60 MPa

Transformation of by-product silicon tetrachloride to an efficient and stable heterogeneous base catalyst: Valorization of glycerol into valuable glycerol carbonate

The by-product silicon tetrachloride (SiCl4) from the polysilicon industry was recycled to fabricate a highly efficient and stable lithium silicate (LS) catalyst for upgrading of oversupplied biodiesel by-product glycerol to valuable glycerol carbonate (GC). The characteristics of the LS catalyst were systematically investigated by various experimental characterization techniques and density functional theory (DFT) calculations. The experimental results showed that the hydrolysis of SiCl4 in the lithium nitrate solution helping to the solid phase synthesis of the LS catalyst as lithium could be uniformly dispersed in the silica gel. The as-synthesized LS catalyst mainly consists of lithium orthosilicate with strong basic sties, favoring the catalytic conversion of glycerol. The LS catalyst exhibited an appreciably high catalytic efficiency (turnover frequency of 2.72 min−1) and glycerol conversion (99.8±1.8 %) compared to other reported solid base catalysts. The apparent activation energy (Ea) of this reaction was calculated to be 39.51 kJ/mol. Further, benefiting from the stable silicate structure, the LS catalyst showed an enhanced catalytic stability as the glycerol conversion declined less than 5 % after five times reuse without regeneration. The LS catalyst also revealed marked resistance to the solid base catalyst poisons like water and methanol compare to that of commercial calcium-based catalyst. The temperature-programmed desorption of CO2 (CO2-TPD) and DFT results affirmed that the low-coordination lattice oxygen of the isolated SiO4 tetrahedron on the surface of the LS catalyst acting as a strong basic electron donor promoted the transesterification reaction between DMC and glycerol. As a result, the SiCl4-derived LS catalyst possessed remarkable catalytic efficiency and reusability, which could be an ideal candidate to meet the requirements for industrial application and highlight the potential application of the by-product SiCl4.

Some thermodynamic properties and computational study of DESs (choline chloride/ethylene glycol and choline chloride/malonic acid) in lithium nitrate + propylene carbonate solutions at T = 298.15 K

Deep eutectic solvents (DESs) with propylene carbonate represent an appealing alternative for organic solvents and ionic liquids to dissolve lithium salts. The present research reports the effect of deep eutectic solvents {DESs (choline chloride/ethylene glycol with the molar ratio of 1.00:2.00) and (choline chloride/malonic acid with the molar ratio of 1.00:1.00) on the thermodynamic and transport properties of solutions of lithium nitrate (LiNO3) in propylene carbonate (PC). To evaluate solute–solvent interactions in the above systems first the volumetric, ultrasonic, and viscometric properties were studied. For this purpose, the density (d), speed of sound (C) and viscosity (η) were measured for the binary solutions of (LiNO3 + PC) and quaternary solutions containing (LiNO3 + PC) and DES in different mass fraction of, w = (0.05, 0.010, 0.015 and 0.020), at 298.15 K under ambient pressure. The measured data were used for calculation of the apparent molar volume (Vφ), standard partial molar volume (Vφ0), apparent molar isentropic compressibility (κϕ), partial molar isentropic compressibility (κφ0), partial molar volumes of transfer (ΔtrVφ0) and viscosity B-coefficient of (LiNO3 + PC + DES) solutions. Then, to evaluate the interaction energies, the density functional theory (DFT) of LiNO3 with DESs in PC has also been studied. The thermodynamic and transport investigations indicated that the choline chloride/ethylene glycol interactions are more favorable than choline chloride/malonic acid with LiNO3 in the presence of PC. Generally, the additions of these DESs on the solution of LiNO3 + PC lead to enhancing of the solute–solvent interactions. Also, the DFT results revealed that the interaction between the ChCl/EG with LiNO3 in PC is stronger than ChCl/MA with LiNO3 in PC confirming the result deduced from our experimental studies.

Lithium–Oxygen Battery Exploiting Highly Concentrated Glyme-Based Electrolytes

Concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO3) salts in either diethylene-glycol dimethyl-ether (DEGDME) or triethylene-glycol dimethyl-ether (TREGDME) are herein characterized in terms of chemical and electrochemical properties in view of possible applications as the electrolyte in lithium–oxygen batteries. X-ray photoelectron spectroscopy at the lithium metal surface upon prolonged storage in lithium cells reveals the complex composition and nature of the solid electrolyte interphase (SEI) formed through the reduction of the solutions, while thermogravimetric analysis shows a stability depending on the glyme chain length. The applicability of the solutions in the lithium metal cell is investigated by means of electrochemical impedance spectroscopy (EIS), chronoamperometry, galvanostatic cycling, and voltammetry, which reveal high conductivity and lithium transference number as well as a wide electrochemical stability window of both electrolytes. However, a challenging issue ascribed to the more pronounced evaporation of the electrolyte based on DEGDME with respect to TREGDME actually limits the application of the former in the Li/O2 battery. Hence, EIS measurements reveal a very fast increase in the impedance of cells using the DEGDME-based electrolyte upon prolonged exposure to the oxygen atmosphere, which leads to a performance decay of the corresponding Li/O2 battery. Instead, cells using the TREGDME-based electrolyte reveal remarkable interphase stability and much more enhanced response with specific capacity ranging from 500 to 1000 mA h g–1 referred to the carbon mass in the positive electrode, with an associated maximum practical energy density of 450 W h kg–1. These results suggest the glyme volatility as a determining factor for allowing the use of the electrolyte media in a Li/O2 cell. Therefore, electrolytes using a glyme with sufficiently high boiling point, such as TREGDME, which is further increased by the relevant presence of salts including a lithium protecting sacrificial one (LiNO3), can allow the application of the solutions in a safe and high-performance lithium–oxygen battery.

In situ processing of fluorinated carbon—Lithium fluoride nanocomposites

Lithium fluoride (LiF) and fluoride additives in carbon-based materials are currently under research as electrode materials for energy storage applications. Herein we demonstrate a simple and novel method for the in situ fabrication of fluorinated carbon-LiF nanocomposites both as powder and as supported thin films. The starting solution of polyvinylidene fluoride (PVDF) and lithium nitrate (LiNO3) in N,N‑Dimethylformamide is poured into a mould or applied to a thermally resistant substrate as a thin film. Pre-tempering and further pyrolysis at 550 °C yield LiF doped amorphous and fluorinated carbon (AC) powder or film. The precursor solution can be additionally modified with multi-walled carbon nanotubes (MWCNT) to yield porous AC-MWCNT-LiF-nanocomposites. Structural and morphological characterization (scanning electron and energy dispersive X-ray spectroscopy, X-ray diffraction as well as solid-state 7Li magic angle spinning nuclear magnetic resonance spectroscopy) show a fine dispersion of faceted LiF-nanoparticles in the carbon matrix or decorating the MWCNTs. The formation mechanism involves the thermally activated reaction of Li-ions with the fluorine of the polymer during pyrolysis thus allowing an in situ nanocomposite to be obtained. Finally the electrochemical capacitance properties in a two-electrode set-up using LiNO3 in ethylene glycol as electrolyte are reported and discussed in comparison to LiF-free electrodes.

Effect of temperature on compressibility properties of 0.1, 0.5 and 1.0 molal solutions of alkali metal nitrates. Part 2. Aqueous solutions of lithium nitrate, sodium nitrate and potassium nitrate in the 278.15 K to 353.15 K temperature range

Sound velocities in aqueous solutions of LiNO3, NaNO3 and KNO3 were measured at 1K intervals from T=(278.15 to 353.15)K, in the 0.1mol·kg−1 0.5mol·kg−1 and 1.0mol·kg−1 solutions. Determined sound velocities and densities served to determine the isentropic and isothermal compressibilities, the apparent molar compressibilities, the apparent molar volumes, the isochoric thermal pressure coefficients, cubic expansion coefficients, changes of heat capacities with volume and with pressure, and the hydration numbers. In addition were evaluated the ultrasonic relaxation times and corresponding thermodynamic functions of the activation of the viscous process. Determined parameters are qualitatively correlated with changes in the structure of water when alkali metal nitrates are dissolved in it.

Crystal growth of titania by photocatalytic reaction

Substrate plates coated with anatase-type titania thin films were immersed in a solution of titanium (IV) chloride and lithium nitrate at 353K during UV irradiation. About 20 nm-sized anatase-type titania crystals were formed on the original titania film consisting of almost the same sized particles. Nitrate ions in the solution were reduced to nitrite ions, and water was transformed into hydroxide ions by a photocatalytic reaction on the original titania film. The pH value increased on the titania surface, which caused the titanium hydroxide formation. The titanium hydroxide was then dehydrated and transformed into titania. The titania particles formed on the substrate exhibited a photocatalytic activity similar to the original titania.

The effect of ionic liquid 1-ethyl-3-methylimidazolium hydrogen sulfate on thermodynamic properties of aqueous lithium nitrate solutions at different temperatures and ambient pressure

Some thermodynamic quantities are evaluated for the ternary ([Emim][HSO4]+LiNO3+water) mixture and their corresponding binary mixtures. For this purpose, the vapor – liquid equilibrium at T=298.15K and volumetric properties at T=293.15K – 313.15K for this mixture are considered. We evaluated these properties by using the measured osmotic coefficients, activity and density data. Then the quality of some thermodynamic models such as: Pitzer and modified - TCPC models to correlate the activity and osmotic coefficients values for studied binary systems and Scatchard model for the ternary systems have been examined. Also the polynomial equation which proposed by Redlich and Meyer is applied to correlate the apparent molar volume values. Also with helping the results which obtained from the vapor – liquid equilibrium and volumetric measurements, we described the possible interactions which are existed in the studied systems.

Stacking changes of KLi[Sb2(C4H2O6)2] homochiral layers mediated by interlayer solvent molecules

Abstract A new compound KLi[Sb2(C4H2O6)2]·4H2O, 1, was synthesized in single crystal form by slowly evaporating an aqueous solution of potassium antimony tartrate and lithium nitrate. The structure of 1 consists of homochiral layers of antimony tartrate dimers linked by LiO4 tetrahedra. The interlayer water molecules can be reversibly driven out by heating or exchanged by small alcohol molecules under ambient conditions, occurring via single-crystal to single-crystal transformations. To accommodate different interlayer molecules, the interlayer space is changed by adjusting the relative lateral shift of neighboring layers. A similar adjustment in the layer stacking also occurs in a structural phase transition caused by order-disorder transformation of the arrangement of interlayer methanol molecules at low temperature.

A new method for online measurement of the concentration of working fluids in absorption refrigeration systems

This paper proposes a new method for online measurement of the concentration of working fluids in absorption refrigeration systems: electrical conductivity is measured to determine the concentration of the solution. Compared with the common density-concentration method, electrical conductivity-concentration method has the same accuracy but helps to save cost when applied in absorption systems with ammonia–salt solutions. This novel method is also suitable for systems with traditional working fluids like water–lithium bromide solution. Electrical conductivities of ammonia–lithium nitrate, ammonia–sodium thiocyanate and water–lithium bromide solutions were measured between (293.15 and 333.15) K, using an Industrial Conductivity Meter. The ammonia mass fraction varied from 0.35 to 0.48 for ammonia–lithium nitrate solution and from 0.35 to 0.50 for ammonia–sodium thiocyanate solution. For water–lithium bromide solution, the mass fraction of lithium bromide was within the range of 40%–60%. The experimental data were correlated as a function of temperature and composition using the extended Casteel–Amis equation. In addition, correlations of refrigerant mass concentration as a function of electrical conductivity and temperature of the solution are proposed.

Development and Characterization of Li(NixMnyCo1-x-y)O2 Layered Cathode Materials for Lithium Ion Batteries

Lithium ion batteries are now widely used especially in mobile applications as a power source. In the case of Li-ion batteries, certain properties such as energy density, cycle life, safety, electrical conductivity and rate capability have great importance. LiCoO2 has been used as a cathode material for Li-ion batteries for many years. However, capacity of the currently used layered LiCoO2 cathodes is limited to perform 50% of its theoretical capacity (140 mAh/g) [1]. In this regard, novel layered Li(Ni1/3Mn1/3Co1/3)O2 cathode materials have been investigated as an alternative cathodes searching for higher capacity, cycle life, rate capability and safety. Li(Ni1/3Mn1/3Co1/3)O2 cathodes exhibit higher capacity that of close to 200 mAh/g with enhanced safety [2]. This high capacity can be associated with the improved chemical stability. However, the rate capability is the most important deficiency which should be improved for new layered Li(Ni1/3Mn1/3Co1/3)O2cathode materials. Moreover, the electrochemical performance of cathode is strongly affected by powder properties such as morphology, surface area and composition. Therefore, spray pyrolysis method was used to obtain spherical fine-sized morphology followed by heat treatment will to obtain better electrochemical activity [3]. The precursor powders were prepared using aquaous solution via spray pyrolysis. Li(NixMnyCo1-x-y)O2 cathode material was produced by using solutions of lithium nitrate (LiNO3), nickel (II) nitrate hexahydrate (N2NiO6.6H2O), manganese (II) nitrate tetrahydrate (Mn (NO3).4H2O and cobalt (II) nitrate hexahydtare (Co(NO3)2.6H2O) with the mole ratio of 1:1/3:1/3:1/3, repectively. The total concentration of the solution is 0.5 M with additives of citric acid and ethylene glycol. Spray pyrolysis was used to obtain spherical fine-sized particles which then heat treated between 800⁰C - 1000⁰C. Different time-temperature combinations were tried and an undefined peak of new layered Li(Ni1/3Mn1/3Co1/3)O2 was observed which heat treated at 1000⁰C. Therefore, temperature range between 800⁰C and 900⁰C was chosen as heat treatment temperature. X-Ray Diffraction (XRD) pattern of obtained layered Li(Ni1/3Mn1/3Co1/3)O2cathode material showed good [006]/[102] and [108]/[110] doublets indicating layered structure and good hexagonal ordering as shown in Figure 1. Figure 1. XRD spectrum of layered Li(Ni1/3Mn1/3Co1/3)O2cathode materials produced by using spray pyrolysis and then heat treated. Precursor concentration, droplet size, gas flow rate and temperature are the main parameters affecting the particle properties. Therefore, these parameters were optimized to obtain particles with spherical fine-sized and narrow size distribution. The morphology of Li(NixMnyCo1-x-y)O2 observed by scanning electron microscopy (SEM) and average particle size was between 0.4 and 0.6 μm, as shown in Figure 2. Li(NixMnyCo1-x-y)O2cathode materials will be investigated focusing on the improvement of capacity, cycle life and especially rate capability via doping elements. With proper cathode composition, experimental parameters, electrode design and doping elements, improved electrochemical properties was achieved. Figure 2. SEM images of studied layered Li(Ni1/3Mn1/3Co1/3)O2 cathode materials produced by using spray pyrolysis and then heat treated. Figure 1

Experimental assessment of vapour adiabatic absorption into solution droplets using a full cone nozzle

This work investigates experimentally the adiabatic absorption of ammonia vapour into ammonia–lithium nitrate solution using a full cone nozzle and an upstream single-pass subcooler. Data are representative of the working conditions of adiabatic absorbers in absorption chillers. The nozzle was located at three different heights inside the absorption chamber, separated 0.165, 0.205 and 0.225m from the bottom liquid surface. The diluted solution mass flow rate was modified between 0.04–0.08kg/s and the solution inlet temperature between 23.5 and 30.6°C. This paper analyzes the influence of these variables on the absorption ratio, mass transfer coefficient, outlet subcooling and approach to equilibrium factor. A linear relation between the inlet subcooling and the absorption ratio is observed. The approach to equilibrium factor for the conditions essayed is always between 0.64 and 0.87. Mass transfer coefficients and correlations for the approach to equilibrium factor and the Sherwood number are obtained. Results are compared with other ones reported in the literature.

High-rate intercalation capability of NaTi2(PO4)3/C composite in aqueous lithium and sodium nitrate solutions

The nanodispersed NaTi2(PO4)3/C composite containing 20–25 wt.% of in-situ formed carbon, was synthesized by gel combustion procedure followed by a heat treatment at 650, 700 and 750 °C. The samples calcined at 700 and 750 °C displayed crystalline nasicon structure. They were subjected to the investigation of intercalation/deintercalation kinetics in aqueous NaNO3 and LiNO3 solutions, using cyclic voltammetry and galvanostatic charging/discharging measurements. As regards to the effect of electrolyte composition, the reactions were evidenced to be roughly twice faster in sodium nitrate than in lithium nitrate solution. Among the samples treated at 700 and 750 °C, better performance was evidenced for the sample treated at lower temperature. Coulombic capacity in NaNO3 solution at charging rate 1C amounted to ∼70 mAh g−1 and ∼55 mAh g−1 for the sample calcined at 700 and 750 °C, respectively, and displayed surprisingly slight dependence on charging rate up to even 100C.

Preparation of Li4Ti5O12 electrode thin films by a mist CVD process with aqueous precursor solution

Spinel Li4Ti5O12 thin films were prepared by a mist CVD process, using an aqueous solution of lithium nitrate and a water-soluble titanium lactate complex as the source of Li and Ti, respectively. In this process, mist particles ultrasonically atomized from a source aqueous solution were transferred by nitrogen gas to a heating substrate to prepare thin films. Scanning electron microscopy observation showed that thin films obtained by this process were dense and smooth, and thin films with a thickness of about 500 nm were obtained. In the X-ray diffraction analysis, formation of Li4Ti5O12 spinel phase was confirmed in the obtained thin film sintered at 700 °C for 4 h. The cell with the thin films as an electrode exhibited a capacity of about 110 mAh g−1, and the cell showed good cycling performance during 10 cycles.

Electrochemical Properties of Li1+xCoO2 Synthesized for All-Solid-State Lithium Ion Batteries with Li2S-P2S5 Glass-Ceramics Electrolyte

The over-stoichiometric Li1+xCoO2 (x = 0.1, 0.2, and 0.3) cathode materials were synthesized from an aqueous solution of lithium nitrate (LiNO3) as an excess lithium precursor and their effects on the electrochemical properties of all-solid-state lithium batteries employing Li2S-P2S5 glass-ceramics solid electrolytes are investigated. A combination of X-ray diffraction, Fourier transform infrared spectroscopy, and inductively coupled plasma atomic emission spectroscopy reveals that the excess lithium forms a residual Li2CO3 layer on the surface of as-prepared Li1+xCoO2 particles during the synthesis process. While regarded as an impurity phase in lithium battery systems using liquid electrolytes due to its detrimental effects on electrochemical performance, the Li2CO3 formed on the surface of the over-stoichiometric Li1+xCoO2 powders is identified in all-solid-state lithium battery systems using sulfide solid electrolytes to act as an effective coating material to suppress the interfacial side reactions despite its low ionic and electronic conductivity.

Experimental assessment of an absorption cooling system operating with the ammonia/lithium nitrate mixture

This paper reports the experimental results of a single effect absorption cooling system of 3 kW of nominal cooling capacity operating with ammonia–lithium nitrate solution. The system was designed and built in the Instituto de Energías Renovables of the Universidad Nacional Autónoma de México and can be used for food conservation or air conditioning. The absorber and generator are falling film heat exchangers. The condenser, evaporator and solution heat exchanger are compact plate heat exchangers. The heat was supplied to the generator at temperatures between 85 °C and 105 °C, while the cooling water temperatures to remove the heat produced during the condensation and absorption varied between 18 °C and 36 °C. The results showed that the system can produce up to 2.7 kW of cooling capacity at heating water temperatures of 95 °C and can achieve evaporator temperatures as low as 1 °C. The experimental coefficients of performance varied between 0.45 and 0.70. Because of the developed system do not need a rectifier and reasonable good coefficients of performance were achieved, the developed system seems to be a good alternative to be used for food conservation or air conditioning.

Effect of annealing temperature on the characteristics of the modified spray deposited Li-doped NiO films and their applications in transparent heterojunction diode

Modified spray method (m-SM) was used to fabricate 8at%-lithium-doped NiO (NiO:8-Li) films using the nickel nitrate [Ni(NO3)2·6H2O] and lithium nitrate (LiNO3) solutions. The NiO:8-Li solutions were sprayed on glass substrates and annealed at various temperatures. It found that the resistivity was decreased and the optical bandgap value were increased as annealing temperature of the NiO:8-Li films was increased from 400°C to 600°C. As the annealing temperature increased, the ratio (fitting area) of Ni3+/Ni2+ in the NiO:8-Li films decreased, which was caused by the increasing in carrier concentration. When the NiO:8-Li films was deposited on ITO glass substrates, the rectifying current–voltage (I–V) properties confirmed that a p–n heterojunction diode characteristic was successfully formed in a NiO:8-Li/ITO structure. The NiO:8-Li/ITO heterojunction parameters such as ideality factor (n), barrier height (φb), and series resistance (Rs) were determined using conventional forward bias I–V characteristics, Cheung׳s and Norde׳s methods. The ideality factor of 3.3, barrier height of ~0.72eV, and the series resistance of ~0.21kΩ were estimated using I–V characteristics.

Solvation of Lithium Salts in Protic Ionic Liquids: A Molecular Dynamics Study

The structure of solutions of lithium nitrate in a protic ionic liquid with a common anion, ethylammonium nitrate, at room temperature is investigated by means of molecular dynamics simulations. Several structural properties, such as density, radial distribution functions, hydrogen bonds, spatial distribution functions, and coordination numbers, are analyzed in order to get a picture of the solvation of lithium cations in this hydrogen-bonded, amphiphilically nanostructured environment. The results reveal that the ionic liquid mainly retains its structure upon salt addition, the interaction between the ammonium group of the cation and the nitrate anion being only slightly perturbed by the addition of the salt. Lithium cations are solvated by embedding them in the polar nanodomains of the solution formed by the anions, where they coordinate with the latter in a solid-like fashion reminiscent of a pseudolattice structure. Furthermore, it is shown that the average coordination number of [Li](+) with the anions is 4, nitrate coordinating [Li](+) in both monodentate and bidentate ways, and that in the second coordination layer both ethylammonium cations and other lithiums are also found. Additionally, the rattling motion of lithium ions inside the cages formed by their neighboring anions, indicative of the so-called caging effect, is confirmed by the analysis of the [Li](+) velocity autocorrelation functions. The overall picture indicates that the solvation of [Li](+) cations in this amphiphilically nanostructured environment takes place by means of a sort of inhomogeneous nanostructural solvation, which we could refer to as nanostructured solvation, and which could be a universal solvation mechanism in ionic liquids.

Biodiesel production over lithium modified lime catalysts: Activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca=0.3 atomic ratio). The catalysts were calcined at 575°C and 800°C, for 5h, to remove nitrate ions before reaction.The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)2. The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO.In the tested condition (wcat/woil=5%; CH3OH/oil=12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability.

리튬용액 침투방법에 의한 Li2TiO3페블 제조

To fabricate spherical lithium titanate (Li₂TiO₃) pebbles which are used for a breeder material in fusion reactor, titanium oxide (TiO₂) granules were used as a starting material. The granules were pre-sintered, and then aqueous lithium nitrate solution infiltrated into the granules at vacuum condition. The granules were crystallized to Li₂TiO₃ after sintering under the control of process parameters. In this study, the concentration of lithium in the solution, as well as the number of penetration times and sintering temperature affected the final crystallite phase and the microstructure of the pebbles. In particular, the sphericity and size of the pebbles were effectively controlled by a technical rolling process. The useful spherical Li₂TiO₃ pebbles which have 10 ~ 20% porosity and 60 ~ 120 N compressive strength were obtained through the sintering at 1000 ~ 1100℃ in the multi-times infiltration process with 50 wt% solution. The physical properties of pebbles such as density, porosity and strength, can be controlled by a selection of TiO₂ powders and control of processing parameters. It can be thought that the lithium penetration method is a useful method for the fabrication of mass product of spherical Li₂TiO₃ pebbles.