WO2017168386A1 - Chemical preparation of lithium sulfide nanoparticles - Google Patents

Chemical preparation of lithium sulfide nanoparticles Download PDF

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WO2017168386A1
WO2017168386A1 PCT/IB2017/051863 IB2017051863W WO2017168386A1 WO 2017168386 A1 WO2017168386 A1 WO 2017168386A1 IB 2017051863 W IB2017051863 W IB 2017051863W WO 2017168386 A1 WO2017168386 A1 WO 2017168386A1
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lithium
sulfide nanoparticles
nps
nanoparticles
lithium sulfide
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PCT/IB2017/051863
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French (fr)
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José Manuel PÉREZ-DONOSO
Bernardo COLLAO ABARCA
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Universidad Andrés Bello
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention refers to a method for synthesizing lithium sulfide nanoparticles, from now on Li 2 S NPs. This method allows synthesizing lithium sulfide nanoparticles with electrochemical properties, which can be used for battery construction.
  • the method proposed consists in mixing a solution of a lithium salt (lithium hydroxide, chloride, carbonate, phosphate and acetate), a solution of glutathione (GSH) or mercapto succinic acid (MSA) in a buffer solution of borate-citrate 10.7 mM at 8.0 pH, and incubating at a temperature of 50-170°C, in an aerobic or anaerobic atmosphere. The reaction time will depend on the reaction volume. Finally, incubation temperature is reduced to 2-10°C for 2-6 hours in order to stop the formation of Li 2 S NPs.
  • a lithium salt lithium hydroxide, chloride, carbonate, phosphate and acetate
  • GSH glutathione
  • MSA mercapto succinic acid
  • NPs created by means of the proposed method have a particle size between 15 and 30 nm and an absorbance pattern with maximum absorbance between 400 and 410 nm.
  • Rechargeable batteries produce energy based on their components reversible electrochemical reaction.
  • Batteries are comprised of different chemical elements combinations. Among most commonly used combinations we shall mention nickel-cadmium (NiCd), nickel- metal hydride (NiMH) and lithium-ion (Li-ion).
  • lithium-ion batteries are formed by cathodes and anodes made up of different types of materials.
  • lithium-ion batteries lithium- sulphur batteries (Li-S or Li/S) are the most known because of their effectiveness and energy high density.
  • This type of batteries is formed by one positive electrode made up of sulphur and one negative electrode made up of lithium. To produce and accumulate energy, the following chemical reduction-oxidation reaction takes place in the battery:
  • Reaction reversibility determines battery charge and discharge.
  • the charge process is determined by lithium dissolution on the anode surface
  • the discharge process is determined by lithium deposit in the anode and by the reduction of polysufides in the cathode (Tudron, F.B., Akridge, J.R., and Puglisi, V.J. Arlington, AZ; Sion Power. 2004).
  • lithium ions are alternated both in the anode and cathode, and their maximum reaction capacity is dependent on the number of sulphur atoms (Bullis, Kevin. Revisiting Lithium-Sulfur Batteries. Technology Review. May 22 nd , 2009). This makes existent lithium-ion cells have a limited charge and discharge, which is lower than that of Li-S batteries, since they can produce a higher energy density due to lithium storage.
  • Li-S batteries are an interesting and powerful alternative of energy, these batteries still have certain disadvantages.
  • the main problem of Li-S batteries is that they have lower specific theoretical energy due to low Li 2 S ionic and electrical conductivity (Shim, J. et al, J. Electrochem. Soc. 2002 149(10):A1321- A1325; Gao, L. et al., Adv. Mater. 2011, 23, 4679-4683).
  • To solve the problem of ionic and electrical conductivity it has been proposed the construction of Li-S batteries by means of covered Li 2 S nanoparticles. In this way, Lin et al. work presents the synthesis of nanoparticles with a Li 2 S core and an external or coated shell of L1 3 PS 4 .
  • the synthesis method involves reacting elemental sulphur (S) with lithium triethylborohydride (LiEt 3 BH) in tetrahydrofuran (THF). Nanoparticles synthesized by this method are 30-50 nm in diameter, and diffraction maximums of X-rays corresponding to 27.2°, 31.6°, 45.1°, 53.5° and 56.0° (Lin, Z., Zengcai, L., Dudney, N. and Liang, C; ACS Nano. 2013 Mar 26;7(3):2829-33).
  • compositions may include nanoparticles of lithium/metal type and/or lithium core alloys, and lithium nitrate or other material shell capable of conducting lithium ions.
  • the method described in this document involves exposing lithium to metal material or half-metallic alloy to form an alloy, vaporizing the alloy to form an alloy vapor, and directing a cooling gas over the alloy vapor to form alloy nanoscale particles.
  • Document WO 2014074150 Al discloses a method for synthesizing nanoparticles made up of a lithium sulphur core and shell, comprising at least one of carbon, polyanaline or a transition metal sulfide. Within method stages, a particular method is described to synthesize the internal layer of lithium sulfide nanoparticles. This methodology involves dissolving or resuspending sulphur particles in an organic solvent until a solution or suspension is formed; adding a lithium reduction agent to the solution to reacting with sulphur particles and produce precipitates comprising a plurality of lithium sulfide nanoparticles; and separating lithium sulfide nanoparticles from the solution.
  • Document CN 1794495 discloses an active material like Li 2 S/Co nanocomposite for use in lithium-ion battery electrodes and its preparation method.
  • the preparation method disclosed mainly consists in depositing a Li 2 S compound and the cobalt metallic element by means of laser pulse.
  • Li/S nanoparticles synthesis comprise complex stages and use of specialized materials and instruments to achieve the appropriate conditions of alloy and precipitation, such as the use of argon atmospheres for reaction, or the use of laser for material deposit.
  • proposed methodology for synthesizing Li2S nanoparticles is a simple and effective procedure that can be performed in aerobic and anaerobic environments, with no need of applying an atmosphere of elements such as argon, or the use of complex instruments such as a laser to achieve nano structures deposit. Even when proposed synthesis methodology is simple, nanoparticles generated through this method present physical-chemical characteristics recommended for use as composition material of li-ion batteries.
  • document PCT/CL2014/000073 refers to a method for chemical synthesis of fluorescent semiconductor nanoparticles of copper sulphur, where said method involves using biological reagents (such as cysteine, glutathione, mercapto succinic acid, phosphate), to produce nanoparticles of copper sulphur in the presence of oxygen and low reaction temperatures.
  • biological reagents such as cysteine, glutathione, mercapto succinic acid, phosphate
  • Document PCT/CL2014/000074 presents a microbiological method to produce fluorescent semiconductor nanoparticles of copper sulphur, which comprises the following stages: a) making microorganism grow, which is resistant to selected copper salt; b) resuspending microorganism sediment in phosphate buffer and treat with at least one of the selected copper salts, until the microorganism acquires fluorescent characteristics; c) evaluating production of copper fluorescent semiconductor nanoparticles, exposing bacterial cells to UV light (360nm); and d) purifying copper semiconductor nanoparticles.
  • Document PCT/CL2014/000075 discloses a method to synthesize CdS fluorescent semiconductor nanoparticles, which comprises the following: mixing a buffer that allows the reaction mixture to be at 7-10 pH with a thiol as sulphur source and wrapping agent; adding a cadmium salt solution; adding a compound as phosphate source to the reaction mixture; incubating at 37°C until achieving fluorescence; and evaluating fluorescence by exposing reaction tubes to UV light (365nm).
  • the present invention contemplates the chemical preparation of lithium sulfide nanoparticles with particular physical and chemical characteristics for use in the manufacture of batteries, rechargeable batteries, supercapacitors and energy storage devices in general.
  • This invention refers to a synthesis method of lithium sulfide nanoparticles, which comprises the following stages:
  • stage (b) Incubating the solution obtained in stage (a) at a temperature between 50- 170°C in an aerobic or anaerobic atmosphere during 1-8 hours, until lithium sulfide nanoparticles are formed.
  • stage (b) Reducing incubation temperature of stage (b) to 2-10°C during 2-6 hours, preferably to 4°C during 2 hours.
  • concentration ranges are:
  • Lithium salts 50-200 mM
  • Citrate-borax buffer 10.7 mM
  • the mixture obtained in stage (a) is incubated at 50-170°C in an aerobic or anaerobic atmosphere. After incubation period, which varies from 1 to 8 hours, incubation temperature of above-mentioned solution is reduced to 2-10°C during 2-6 hours, preferably to 4°C for 2 hours, stopping synthesis reaction of Li 2 S nanoparticles.
  • stage (b) mixture will depend on the final reaction volume, which may vary from 1 hour for a total volume of lmL to 8 hours for a total volume of 50mL. This is without limiting to the possibility of mixing with other reaction volumes and, thus, other periods of incubation.
  • lithium salts correspond, without limitation, to lithium hydroxide, lithium carbonate, lithium phosphate, and lithium acetate or lithium chloride.
  • the thiol compound corresponds to the sulphur source for nanoparticle configuration.
  • thiol makes reference to compounds whose functional group is formed by one atom of sulphur and one atom of hydrogen (-SH).
  • the thiol compound corresponds preferably to mercaptosuccinic acid or glutathione.
  • stage (b) of the method the solution obtained in stage (a) is incubated at a temperature between 50 and 170°C, being 90°C a preferable temperature of incubation.
  • Li/S nanoparticles with physical and chemical characteristics typical of their nature. Since they are characterized by spectrophotometry, Li/S nanoparticles have a plasmon (absorbance pattern) between 400-410 nm. On the other hand, when they are evaluated by means of transmission electron microscopy (TEM), nanoparticles size ranges from 15 to 30 nm.
  • TEM transmission electron microscopy
  • the XRD analysis of nanoparticles shows diffractograms with characteristic diffraction peaks to Li 2 S. The width of the diffraction peaks (greater thickness) confirms that the formulation corresponds to nanometric particles.
  • this invention refers to the use of Li/S nanoparticles obtained by means of the proposed method for the manufacture of batteries, rechargeable batteries, supercapacitors and energy storage devices in general.
  • incubation temperature is reduced to 4°C for 2 hours in order to stop reaction.
  • the production of nanoparticles in the solution is determined by analyzing spectroscopic properties characteristics of Li 2 S nanoparticles (peak of absorbance between 400 and 410 nm, and size ranging from 15 and 30 nm).
  • incubation temperature is reduced to 4°C for 2 hours in order to stop reaction.
  • the production of nanoparticles in the solution is determined by analyzing spectroscopic properties characteristics of Li 2 S nanoparticles (peak of absorbance between 400 and 410 nm, and size ranging from 15 and 30 nm).

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) comprising: a) Mixing an aqueous solution of a lithium salt with an aqueous solution of a compound such as thiol in a citrate-borax buffer solution at pH 8.0. 5 b) Incubating the solution obtained in stage (a) at a temperature between 50- 170°C in an aerobic or anaerobic atmosphere during 1-8 hours, until lithium sulfide nanoparticles are formed. c) Reducing incubation temperature of stage (b) to 2-10°C during 2-6 hours. d) Stopping the reaction once stage (c) incubation time has passed. NPs created by means of the proposed method have a particle size between 15 and 30 nm and an absorbance pattern with maximum absorbance between 400 and 410 nm. Use of NPs obtained by the proposed method in the manufacture of batteries, rechargeable batteries, supercapacitors and energy storage devices.

Description

CHEMICAL PREPARATION OF LITHIUM SULFIDE
NANOPARTICLES
The present invention refers to a method for synthesizing lithium sulfide nanoparticles, from now on Li2S NPs. This method allows synthesizing lithium sulfide nanoparticles with electrochemical properties, which can be used for battery construction.
The method proposed consists in mixing a solution of a lithium salt (lithium hydroxide, chloride, carbonate, phosphate and acetate), a solution of glutathione (GSH) or mercapto succinic acid (MSA) in a buffer solution of borate-citrate 10.7 mM at 8.0 pH, and incubating at a temperature of 50-170°C, in an aerobic or anaerobic atmosphere. The reaction time will depend on the reaction volume. Finally, incubation temperature is reduced to 2-10°C for 2-6 hours in order to stop the formation of Li2S NPs.
NPs created by means of the proposed method have a particle size between 15 and 30 nm and an absorbance pattern with maximum absorbance between 400 and 410 nm.
Background Art
Rechargeable batteries produce energy based on their components reversible electrochemical reaction. Batteries are comprised of different chemical elements combinations. Among most commonly used combinations we shall mention nickel-cadmium (NiCd), nickel- metal hydride (NiMH) and lithium-ion (Li-ion).
Particularly, lithium-ion batteries are formed by cathodes and anodes made up of different types of materials. Among lithium-ion batteries, lithium- sulphur batteries (Li-S or Li/S) are the most known because of their effectiveness and energy high density. This type of batteries is formed by one positive electrode made up of sulphur and one negative electrode made up of lithium. To produce and accumulate energy, the following chemical reduction-oxidation reaction takes place in the battery:
1€U S» eibS The chemical process in the Li-S battery allows producing a specific theoretical energy of 2500 Wh/kg, which is more than 5 times higher than the energy density of conventional Lithium-ion batteries (Ji, X. et al., Nat Mater. 2009 Jun; 8(6):500- 6; Jayaprakash, N. et al., Angew. Chem. Int. Ed. 2011, 50, 5904-5908; Bruce, P. et al, Angew. Chem. Int. Ed. 2012, 2-33, 2012; Lin, Z., Liu, Z., Dudney, NJ., Liang, C. ACS Nano. 2013 Mar 26;7(3):2829-33). Reaction reversibility determines battery charge and discharge. The charge process is determined by lithium dissolution on the anode surface, and the discharge process is determined by lithium deposit in the anode and by the reduction of polysufides in the cathode (Tudron, F.B., Akridge, J.R., and Puglisi, V.J. Tucson, AZ; Sion Power. 2004). In conventional lithium-ion batteries, lithium ions are alternated both in the anode and cathode, and their maximum reaction capacity is dependent on the number of sulphur atoms (Bullis, Kevin. Revisiting Lithium-Sulfur Batteries. Technology Review. May 22nd, 2009). This makes existent lithium-ion cells have a limited charge and discharge, which is lower than that of Li-S batteries, since they can produce a higher energy density due to lithium storage.
While Li-S batteries are an interesting and powerful alternative of energy, these batteries still have certain disadvantages. The main problem of Li-S batteries is that they have lower specific theoretical energy due to low Li2S ionic and electrical conductivity (Shim, J. et al, J. Electrochem. Soc. 2002 149(10):A1321- A1325; Gao, L. et al., Adv. Mater. 2011, 23, 4679-4683). To solve the problem of ionic and electrical conductivity, it has been proposed the construction of Li-S batteries by means of covered Li2S nanoparticles. In this way, Lin et al. work presents the synthesis of nanoparticles with a Li2S core and an external or coated shell of L13PS4. Adding this new material of nanoparticles allows the formation of a superionic lithium sulphur cathode, with energy efficiency and conductivity at 25°C significantly higher than a cell that is using Li-S (Lin, Z., Dudney, NJ., Liang, C. ACS Nano. 2013 Mar 26;7(3):2829-33).Nowadays, there are methods described to prepare potentially useful Li-S nanoparticles in battery formation. Particularly, scientific articles have described the study of synthesis procedures of this type of nanoparticles and its application in cells. According to Lin Z. et al description, it is possible to obtain Li2S core-shell nanoparticles with Li2S core and L13PS4 external shell. The synthesis method involves reacting elemental sulphur (S) with lithium triethylborohydride (LiEt3BH) in tetrahydrofuran (THF). Nanoparticles synthesized by this method are 30-50 nm in diameter, and diffraction maximums of X-rays corresponding to 27.2°, 31.6°, 45.1°, 53.5° and 56.0° (Lin, Z., Zengcai, L., Dudney, N. and Liang, C; ACS Nano. 2013 Mar 26;7(3):2829-33).
According to Zhang K. et al, it is possible to synthesize graphene2Li2s nanoparticles in-situ (in-situ TG2Li2S) for use as cathode material in batteries. The synthesis procedure described in this document involves the chemical reduction of sulphur mixed with graphene by addition of triethylborohydride (LiEt3BH) in argon atmosphere. As a result, Li2S nanoparticles are obtained, which are homogenously anchored to graphene nanolaminates. Additionally, a Li2S/Si cell was formed and evaluated with produced nanoparticles, obtaining high conductivity and efficient ionic electrical transport (Zhang, K., Scientific Reports 4, Article number:6467, September 25, 2014).
Moreover, there are patent documents describing methods for synthesizing lithium compositions and lithium nanoparticles to be included in electrodes and/or batteries. Document US20100156353 Al discloses a method to prepare lithium compositions that can be included in electrochemical applications, such as electrodes or batteries. Compositions may include nanoparticles of lithium/metal type and/or lithium core alloys, and lithium nitrate or other material shell capable of conducting lithium ions. The method described in this document involves exposing lithium to metal material or half-metallic alloy to form an alloy, vaporizing the alloy to form an alloy vapor, and directing a cooling gas over the alloy vapor to form alloy nanoscale particles.
Document WO 2014074150 Al discloses a method for synthesizing nanoparticles made up of a lithium sulphur core and shell, comprising at least one of carbon, polyanaline or a transition metal sulfide. Within method stages, a particular method is described to synthesize the internal layer of lithium sulfide nanoparticles. This methodology involves dissolving or resuspending sulphur particles in an organic solvent until a solution or suspension is formed; adding a lithium reduction agent to the solution to reacting with sulphur particles and produce precipitates comprising a plurality of lithium sulfide nanoparticles; and separating lithium sulfide nanoparticles from the solution.
Document CN 1794495 discloses an active material like Li2S/Co nanocomposite for use in lithium-ion battery electrodes and its preparation method. The preparation method disclosed mainly consists in depositing a Li2S compound and the cobalt metallic element by means of laser pulse.
All above-mentioned methods allows synthesizing Li2S nanoparticles anchored to other chemical structures or external layers such as graphene, carbon structures or inorganic elements such as L13PS4 and cobalt. The present invention provides a method for synthesizing stable Li2S nanoparticles with no need of adding other type of element. Li2S nanoparticles synthesized by the method suggested have totally different structural and physical-chemical characteristics from similar nanoparticles described to date.
Moreover, methods proposed to date for Li/S nanoparticles synthesis comprise complex stages and use of specialized materials and instruments to achieve the appropriate conditions of alloy and precipitation, such as the use of argon atmospheres for reaction, or the use of laser for material deposit. On the contrary, proposed methodology for synthesizing Li2S nanoparticles is a simple and effective procedure that can be performed in aerobic and anaerobic environments, with no need of applying an atmosphere of elements such as argon, or the use of complex instruments such as a laser to achieve nano structures deposit. Even when proposed synthesis methodology is simple, nanoparticles generated through this method present physical-chemical characteristics recommended for use as composition material of li-ion batteries.
Besides, document PCT/CL2014/000073 refers to a method for chemical synthesis of fluorescent semiconductor nanoparticles of copper sulphur, where said method involves using biological reagents (such as cysteine, glutathione, mercapto succinic acid, phosphate), to produce nanoparticles of copper sulphur in the presence of oxygen and low reaction temperatures. Document PCT/CL2014/000074 presents a microbiological method to produce fluorescent semiconductor nanoparticles of copper sulphur, which comprises the following stages: a) making microorganism grow, which is resistant to selected copper salt; b) resuspending microorganism sediment in phosphate buffer and treat with at least one of the selected copper salts, until the microorganism acquires fluorescent characteristics; c) evaluating production of copper fluorescent semiconductor nanoparticles, exposing bacterial cells to UV light (360nm); and d) purifying copper semiconductor nanoparticles.
Document PCT/CL2014/000075 discloses a method to synthesize CdS fluorescent semiconductor nanoparticles, which comprises the following: mixing a buffer that allows the reaction mixture to be at 7-10 pH with a thiol as sulphur source and wrapping agent; adding a cadmium salt solution; adding a compound as phosphate source to the reaction mixture; incubating at 37°C until achieving fluorescence; and evaluating fluorescence by exposing reaction tubes to UV light (365nm). While these documents present methods for producing metallic- sulphur nanoparticles, each type of metal and of application, particularly of nanoparticles, entails refining the process in a way that nanoparticles with unique physical- chemical characteristics are obtained, in order to satisfy the needs relevant to each application. Thus, the present invention contemplates the chemical preparation of lithium sulfide nanoparticles with particular physical and chemical characteristics for use in the manufacture of batteries, rechargeable batteries, supercapacitors and energy storage devices in general.
DESCRIPTION OF THE INVENTION
This invention refers to a synthesis method of lithium sulfide nanoparticles, which comprises the following stages:
a) Mixing an aqueous solution of a lithium salt with an aqueous solution of a compound such as thiol in a citrate-borax buffer solution at pH 8.0.
b) Incubating the solution obtained in stage (a) at a temperature between 50- 170°C in an aerobic or anaerobic atmosphere during 1-8 hours, until lithium sulfide nanoparticles are formed.
c) Reducing incubation temperature of stage (b) to 2-10°C during 2-6 hours, preferably to 4°C during 2 hours.
d) Stopping the reaction once stage (c) incubation time has passed.
In one embodiment of the invention, concentration ranges are:
Lithium salts: 50-200 mM
Compound such as thiol: 100-400 mM
Citrate-borax buffer: 10.7 mM The mixture obtained in stage (a) is incubated at 50-170°C in an aerobic or anaerobic atmosphere. After incubation period, which varies from 1 to 8 hours, incubation temperature of above-mentioned solution is reduced to 2-10°C during 2-6 hours, preferably to 4°C for 2 hours, stopping synthesis reaction of Li2S nanoparticles.
Incubation periods of stage (b) mixture will depend on the final reaction volume, which may vary from 1 hour for a total volume of lmL to 8 hours for a total volume of 50mL. This is without limiting to the possibility of mixing with other reaction volumes and, thus, other periods of incubation.
In this invention, lithium salts correspond, without limitation, to lithium hydroxide, lithium carbonate, lithium phosphate, and lithium acetate or lithium chloride.
In the method proposed herein, the thiol compound corresponds to the sulphur source for nanoparticle configuration. Referring to thiol makes reference to compounds whose functional group is formed by one atom of sulphur and one atom of hydrogen (-SH). In this invention, the thiol compound corresponds preferably to mercaptosuccinic acid or glutathione.
In stage (b) of the method, the solution obtained in stage (a) is incubated at a temperature between 50 and 170°C, being 90°C a preferable temperature of incubation.
The proposed method allows producing Li/S nanoparticles with physical and chemical characteristics typical of their nature. Since they are characterized by spectrophotometry, Li/S nanoparticles have a plasmon (absorbance pattern) between 400-410 nm. On the other hand, when they are evaluated by means of transmission electron microscopy (TEM), nanoparticles size ranges from 15 to 30 nm. The XRD analysis of nanoparticles shows diffractograms with characteristic diffraction peaks to Li2S. The width of the diffraction peaks (greater thickness) confirms that the formulation corresponds to nanometric particles.
In addition, this invention refers to the use of Li/S nanoparticles obtained by means of the proposed method for the manufacture of batteries, rechargeable batteries, supercapacitors and energy storage devices in general.
Example 1 (aerobic conditions):
Prepare a mixture with lithium chloride solution (100 mM) and mercaptosuccinic acid (200 mM) in a citrate-borax buffer (10.7 mM) at 8.0 pH.
Incubate the mixture obtained at 90°C in an aerobic atmosphere during 8 hours.
After that time, incubation temperature is reduced to 4°C for 2 hours in order to stop reaction. The production of nanoparticles in the solution is determined by analyzing spectroscopic properties characteristics of Li2S nanoparticles (peak of absorbance between 400 and 410 nm, and size ranging from 15 and 30 nm).
Example 2 (anaerobic conditions):
Prepare a mixture with lithium chloride solution (100 mM) and mercapto succinic acid (200 mM) in a citrate-borax buffer (10.7 mM) at 8.0 pH.
Incubate the mixture obtained at 90°C in an anaerobic atmosphere during 8 hours.
After that time, incubation temperature is reduced to 4°C for 2 hours in order to stop reaction.
The production of nanoparticles in the solution is determined by analyzing spectroscopic properties characteristics of Li2S nanoparticles (peak of absorbance between 400 and 410 nm, and size ranging from 15 and 30 nm).

Claims

1. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) CHARACTERIZED because it entails:
a) Mixing an aqueous solution of a lithium salt with an aqueous solution of a compound such as thiol in a citrate-borax buffer solution at pH 8.0.
b) Incubating the solution obtained in stage (a) at a temperature between 50- 170°C in an aerobic or anaerobic atmosphere during 1-8 hours, until lithium sulfide nanoparticles are formed.
c) Reducing incubation temperature of stage (b) to 2-10°C during 2-6 hours, d) Stopping the reaction once stage (c) incubation time has passed.
2. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1, CHARACTERIZED because lithium salt is selected from the group of: lithium hydroxide, lithium carbonate, lithium phosphate, lithium acetate and lithium chloride.
3. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1 and 2, CHARACTERIZED because lithium salt concentration ranges from 50 to 200 mM.
4. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1, CHARACTERIZED because the thiol compound is selected from the group of: mercaptosuccinic acid and glutathione.
5. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1 and 4, CHARACTERIZED because thiol compound concentration ranges from 100-400 mM.
6.- Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1, CHARACTERIZED because incubation temperature is preferably 90 °C in stage b).
7. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1, CHARACTERIZED because in stage b) the incubation time will depend on the reaction volume, that is 1 hour for a total volume of lmL and 8 hours for a total volume of 50mL.
8. - Method for chemical preparation of lithium sulfide nanoparticles (Li2S NPs) according to claim 1, CHARACTERIZED because in stage c) incubation temperature is reduced preferably to 4°C for 2 hours.
9.- Lithium sulfide nanoparticles obtained using the method referred in these claims, CHARACTERIZED because they have an absorbance pattern with maximum absorbance between 400 and 410 nm, and the size of nanoparticles ranging from 15 to 30 nm.
10.- Use of lithium sulfide nanoparticles obtained by the method referred in claims 1 to 8, CHARACTERIZED because they can be used to manufacture batteries, rechargeable batteries, supercapacitors and energy storage devices.
PCT/IB2017/051863 2016-03-31 2017-03-31 Chemical preparation of lithium sulfide nanoparticles WO2017168386A1 (en)

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HOSSEINI ET AL.: "Recent achievements in the micorbial synthesis of semiconductor metal sulfide nanoparticles", MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING, vol. 40, 2015, pages 293 - 301, XP029284154 *

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