Method for producing lithium halide compounds

Abstract

Provided is a method for producing a lithium halide compound, the method involving producing lithium halide compounds, especially lithium bromide and lithium iodide, having little water content without a step for removing water directly, said compounds being produced at high reaction efficiency and in an industrially advantageous manner, and the method including: mixing lithium sulfide, halogen molecules of bromine and / or iodine, and a first solvent; and removing the first solvent, the first solvent being a solvent that dissolves lithium halide including the halogen element of the halogen molecules.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a lithium halide compound. [Background technology]

[0002] With the recent rapid spread of information-related devices and communication devices such as personal computers, video cameras, and mobile phones, the development of batteries to be used as their power sources has become increasingly important. Conventionally, batteries used for such applications have used electrolytes containing flammable organic solvents, but by making batteries all-solid-state, flammable organic solvents are not used in the battery, safety devices can be simplified, and manufacturing costs and productivity are excellent. Therefore, batteries in which the electrolyte is replaced with a solid electrolyte layer are being developed.

[0003] Sulfide solid electrolytes have been known for some time as solid electrolytes used in solid electrolyte layers, and it is known that a glass-ceramic electrolyte with high ionic conductivity can be obtained by, for example, reacting lithium sulfide with phosphorus sulfide to produce sulfide glass and then subjecting this sulfide glass to heat treatment (see, for example, Patent Document 1). In addition, in response to demand for higher ionic conductivity, a manufacturing method using lithium halide as a sulfide solid electrolyte containing halogen atoms is also known (see, for example, Patent Document 2).

[0004] Lithium halides used as raw materials in the production of sulfide solid electrolytes containing halogen atoms are generally produced as hydrates because aqueous solutions of the raw materials are used in the synthesis process or the reaction is carried out in water (see, for example, Patent Documents 3 and 4). If lithium halides contain moisture, the ionic conductivity of the sulfide solid electrolyte may decrease. Therefore, it is necessary to remove moisture from the lithium halides. Methods of removing moisture from the lithium halides include azeotropic distillation with organic solvents and drying (see, for example, Patent Document 4), and methods of removing moisture by heating under reduced pressure (see, for example, Patent Documents 5 and 6). However, in any case, removing moisture from lithium halide hydrates is not easy.

[0005] Therefore, methods for producing lithium halides such as anhydrous lithium halides without removing water have been investigated. For example, a method has been disclosed in which lithium sulfide is reacted with halogen molecules using a grinder in a solvent such as an aromatic hydrocarbon in which alkali metal sulfides are poorly soluble (see, for example, Patent Document 7). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-228570 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-201110 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-103851 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-256416 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-65637 [Patent Document 6] Japanese Patent Application Laid-Open No. 2014-65638 [Patent Document 7] International Publication No. 2017 / 159665 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing lithium halide compounds, particularly lithium bromide and lithium iodide, having low water contents, with high reaction efficiency and in an industrially advantageous manner without involving a step of directly removing water. [Means for solving the problem]

[0008] The method for producing a lithium halide compound according to the present invention comprises the steps of: mixing lithium sulfide, at least one halogen molecule of bromine and iodine, and a first solvent; and removing the solvent; Including, the first solvent is a solvent that dissolves lithium halide containing a halogen element of the halogen molecule; A method for producing a lithium halide compound. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing lithium halide compounds, particularly lithium bromide and lithium iodide, having low water contents, with high reaction efficiency and in an industrially advantageous manner without involving a step of directly removing water. [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows X-ray diffraction spectra of lithium sulfide used in Example 1 and lithium iodide obtained in Example 1. [Figure 2] 1 shows X-ray diffraction spectra of the lithium halide complex and lithium iodide obtained in Example 2. [Figure 3] 1 shows X-ray diffraction spectra of lithium bromide and lithium iodide obtained in Example 3. [Figure 4] 1 shows X-ray diffraction spectra of the lithium iodide complex obtained in Example 4 and lithium iodide. [Figure 5] 1 is an X-ray diffraction spectrum of lithium iodide obtained in Example 5. [Figure 6] 1 is a SEM (scanning electron microscope) image of the sample obtained in Comparative Example 1. [Figure 7] 1 is an EDS image of the sulfur element constituting the sample obtained in Comparative Example 1. [Figure 8] 1 is an EDS image of iodine element constituting the sample obtained in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the upper and lower limit values ​​of a range of values ​​expressed as "greater than or equal to," "less than or equal to," and "to" can be arbitrarily combined, and the numerical values ​​in the examples can also be used as the upper and lower limit values.

[0012] (Findings gained by the inventors to arrive at the present invention) As a result of extensive research aimed at solving the above problems, the present inventors have discovered the following and have completed the present invention. As described in paragraph

[0013] of Patent Document 7, when reacting an alkali metal sulfide with a halogen molecule, it is known that by using a method of pulverizing the alkali metal sulfide using a pulverizer, the surface of the alkali metal sulfide is scraped off, making the halogen molecule more reactive. However, this method requires the use of a pulverizer to promote the reaction, and if a pulverizer is not used, the reaction will be significantly delayed. After extensive investigation into this phenomenon, the present inventors found that the cause is that lithium halide, a reaction product of the primary reaction between the alkali metal sulfide and the halogen molecule, is precipitated on the surface of the alkali metal sulfide.

[0013] Therefore, the present inventors considered that, as a method for avoiding or minimizing the use of a pulverizer, dissolving the produced lithium halide in a solvent might expose a newly produced surface of lithium sulfide and promote the reaction with halogen molecules, and investigated changing the type of solvent. The solvent used must have the ability to dissolve lithium halides, particularly lithium bromide and lithium iodide, in order to reduce the deposition of lithium halides on the surface of the alkali metal sulfide. On the other hand, it is empirically known that solvents capable of dissolving lithium bromide and lithium iodide have difficulty dissolving iodine, which is a solid. Therefore, we investigated the use of a solvent that specifically dissolves iodine. Based on the above investigations, it was found that by selecting a solvent that dissolves lithium halide as the solvent and mixing lithium sulfide and halogen molecules in the solvent, the reaction between lithium sulfide and halogen molecules can proceed smoothly without using a pulverizer.

[0014] [Method for producing lithium halide compounds] The method for producing a lithium halide compound according to the first aspect of this embodiment includes the steps of: mixing lithium sulfide, at least one halogen molecule of bromine and iodine, and a first solvent; and removing the first solvent; Including, the first solvent is a solvent that dissolves lithium halide containing a halogen element of the halogen molecule; A method for producing a lithium halide compound.

[0015] In Patent Document 7, lithium halides such as anhydrous lithium halide can be produced without removing water by reacting lithium sulfide with halogen molecules in a solvent such as an aromatic hydrocarbon in which alkali metal sulfides are poorly soluble. In this respect, lithium halides can be produced more easily than the conventional methods described in Patent Documents 3 to 6. However, as mentioned above, this method requires the use of a pulverizer and is not suitable for mass production, making it an industrially advantageous method. In addition, if a pulverizer is not used, lithium halide precipitates on the surface of the alkali metal sulfide, significantly slowing down the reaction.

[0016] According to the first aspect, by employing a solvent capable of dissolving lithium halide corresponding to the halogen molecules used as a raw material, lithium halide obtained by the reaction between lithium sulfide and halogen molecules and precipitated on the surface of lithium sulfide can be dissolved in the solvent, thereby suppressing the precipitation of lithium halide on the surface of lithium sulfide and allowing the reaction between the newly exposed lithium sulfide surface and halogen molecules to occur at all times, thereby accelerating the reaction. Furthermore, by accelerating the reaction, the reaction between lithium sulfide and halogen molecules can proceed simply by mixing without pulverization, making pulverization unnecessary, making this an industrially advantageous production method.

[0017] In the first embodiment, the halogen element of the halogen molecule used as the raw material, the halogen element in the lithium halide in which the first solvent can dissolve, and the halogen element in the obtained lithium halide compound correspond to each other, i.e., are the same element. When bromine is used as the halogen molecule, the lithium halide that can be dissolved in the first solvent is lithium bromide, and the resulting lithium halide compound is a lithium bromide compound. When iodine is used as the halogen molecule, the same applies as for bromine molecules. Furthermore, when bromine and iodine atoms are used as the halogen molecules, the lithium halide that can be dissolved in the first solvent is lithium bromide and lithium iodide, and the resulting lithium halide compounds are lithium bromide and lithium iodide compounds.

[0018] The method for producing a lithium halide compound according to the second aspect of this embodiment includes the steps of: mixing lithium sulfide, halogen molecules, and a second solvent; further adding and mixing the first solvent; and removing the second solvent; wherein the second solvent is a solvent that does not dissolve lithium halide containing a halogen element of the halogen molecule. A method for producing a lithium halide compound. The second embodiment is characterized in that, before using the first solvent in the first embodiment, lithium sulfide and halogen molecules are mixed using a second solvent, then the first solvent is added and mixed, and the second solvent is removed. As in the first embodiment, the halogen elements of the halogen molecules, the halogen elements of the lithium halide in which the second solvent does not dissolve, and the halogen elements of the resulting lithium halide compound are the same species.

[0019] According to the second aspect, by using a second solvent before using the first solvent, it is possible to improve the reactivity of halogen molecules, particularly iodine, which are poorly soluble in the first solvent. If the first solvent can dissolve even a small amount of iodine, there is no need to use a second solvent. However, as mentioned above, there is empirical evidence that a solvent that easily dissolves lithium halide also has the property of poorly dissolving halogen molecules, particularly iodine. In other words, a solvent that does not dissolve lithium halide also has the property of dissolving halogen molecules, particularly iodine. Furthermore, by using a second solvent that dissolves halogen molecules, particularly iodine, the reaction with lithium sulfide can easily proceed, even when iodine, a solid raw material with low reactivity, is used, making it possible to improve reaction efficiency. Considering the above findings, the use of the second solvent has an advantageous effect in that it improves the reactivity of halogen molecules, especially iodine, and improves the reaction efficiency. Furthermore, the use of the second solvent increases the dispersibility of lithium sulfide and halogen molecules used as raw materials, and the addition of the first solvent to the resulting mixture also has the secondary effect of improving the reactivity.

[0020] Regarding the removal of the solvent, in the second embodiment, the second solvent is removed, but in the first embodiment, the first solvent is removed, and therefore, as a result, all of the solvent used in the manufacturing method of this embodiment is removed.

[0021] A method for producing a lithium halide compound according to a third aspect of this embodiment includes the steps of: The lithium halide compound includes a lithium halide complex. A method for producing a lithium halide compound. The lithium halide complex is not only a lithium halide, i.e., lithium bromide or lithium iodide, but also a complex thereof formed with a solvent. The first solvent has the property of dissolving lithium halide, and as a solvent having such a property, a solvent having a heteroatom such as a nitrogen atom in its molecule is preferably used, as described below. In this case, it is specified that the heteroatom can form a complex (also called a "lithium halide complex") coordinated (bonded) with an atom constituting the lithium halide, particularly a lithium atom. Inclusion of a lithium halide complex in the third aspect means that use of such a first solvent improves the contribution of the halogen molecules in the reaction between lithium sulfide and the halogen molecules, and thus the reaction is promoted and the amount of residual halogen molecules can be further reduced, thereby improving the reaction efficiency and achieving high reaction efficiency.

[0022] A method for producing a lithium halide compound according to a fourth aspect of this embodiment includes the steps of: The first solvent has a solubility of lithium bromide and lithium iodide of 1 g / L or more. This is a method for producing lithium halide compounds. The property of not dissolving lithium halides specifically stipulates that the solubility of lithium halides in lithium bromide and lithium iodide is 1 g / L or more. When the first solvent has such properties, it is possible to suppress deposition of lithium halide on the surface of lithium sulfide, and to always cause a reaction between lithium sulfide whose newly exposed surface is present and halogen molecules, thereby accelerating the reaction, thereby improving the reaction efficiency.

[0023] A method for producing a lithium halide compound according to a fifth aspect of this embodiment includes the steps of: The second solvent has a solubility of lithium bromide and lithium iodide of less than 1 g / L. This is a method for producing lithium halide compounds. The property of dissolving lithium halides specifically specifies that the solubility of lithium halides, such as lithium bromide and lithium iodide, is less than 1 g / L. The second solvent having such properties is likely to have the effect of improving the reactivity of halogen molecules, particularly iodine, which are poorly soluble in the first solvent, and as a result, the reaction between lithium sulfide and halogen molecules is accelerated, improving the reaction efficiency.

[0024] A method for producing a lithium halide compound according to a sixth aspect of this embodiment includes the steps of: Further, the method includes washing and removing sulfur molecules. This is a method for producing a lithium halide compound. The reaction between lithium sulfide and halogen molecules produces sulfur molecules as a by-product along with the lithium halide. According to the sixth aspect, the by-product sulfur molecules are removed by washing, thereby making it possible to produce a lithium halide compound with high purity.

[0025] A method for producing a lithium halide compound according to a seventh aspect of this embodiment includes the steps of: a third solvent is used in the washing and removing; A method for producing a lithium halide compound. The method for producing a lithium halide compound according to the eighth aspect includes the steps of: The removal of the third solvent is carried out by at least one treatment selected from filtration and heating under reduced pressure. A method for producing a lithium halide compound. The sulfur molecules can be washed and removed by washing with a third solvent, and the third solvent used for washing can be removed by a process such as filtration. Both of these methods are easy to use, and therefore, the sulfur molecules that are by-products can be easily removed.

[0026] A method for producing a lithium halide compound according to a ninth aspect of this embodiment includes the steps of: the first solvent is an aprotic solvent having at least one functional group selected from an ester group, an ether group, and an amino group; This is a method for producing a lithium halide compound. As described above, by employing a solvent containing a heteroatom such as a nitrogen atom or an oxygen atom, more specifically an aprotic solvent having a functional group containing such a heteroatom, as the first solvent, a lithium halide complex can be formed. Furthermore, by improving the contribution of the halogen molecules in the reaction between lithium sulfide and halogen molecules, the reaction can be accelerated and the amount of residual halogen molecules can be further reduced, thereby improving the reaction efficiency and achieving high reaction efficiency.

[0027] A method for producing a lithium halide compound according to a tenth aspect of this embodiment includes the steps of: The second solvent is at least one of an aromatic hydrocarbon and an aliphatic hydrocarbon. A method for producing a lithium halide compound, and the method for producing a lithium halide compound according to an eleventh aspect of the present invention comprises the steps of: The second solvent has a boiling point of 150°C or less. A method for producing a lithium halide compound. As described above, the second solvent is likely to have the effect of improving the reactivity of halogen molecules, particularly iodine, which are poorly soluble in the first solvent, and aromatic hydrocarbons, aliphatic hydrocarbons, and solvents with a boiling point of 150° C. or higher are advantageous because they are likely to exhibit this effect. By using such a second solvent, the reaction between lithium sulfide and halogen molecules is promoted, and the reaction efficiency is improved.

[0028] A method for producing a lithium halide compound according to a twelfth aspect of this embodiment includes the steps of: The third solvent has a solubility of sulfur molecules of 0.1 g / L or more. A method for producing a lithium halide compound, and a method for producing a lithium halide compound according to a thirteenth aspect, At least one of the aromatic hydrocarbon and the aliphatic hydrocarbon, A method for producing a lithium halide compound. The third solvent is used to wash and remove sulfur molecules that are by-produced in the reaction between lithium sulfide and halogen molecules. By using a solvent having the above-described solubility, specifically, an aromatic hydrocarbon, an aliphatic hydrocarbon, or the like, a good washing and removal effect can be obtained, and lithium halide with high product purity can be easily obtained.

[0029] A method for producing a lithium halide compound according to a fourteenth aspect of this embodiment includes the steps of: the second solvent and the third solvent are the same; A method for producing a lithium halide compound. As in the above-mentioned tenth and thirteenth embodiments, aromatic hydrocarbons and aliphatic hydrocarbons are preferably used as the second and third solvents. Using the same type of solvent is easier to process than using different types of solvents, and is also more efficient in terms of production management.

[0030] The manufacturing method of this embodiment will be described in more detail below in accordance with the above-described embodiment.

[0031] (lithium sulfide) The lithium sulfide used in the manufacturing method of this embodiment is usually in particulate form and may be a commercially available product, or may be manufactured by a known method. Lithium sulfide is an alkali metal sulfide, and the ionic conductivity of a sulfide solid electrolyte tends to be improved by using a light alkali metal. Therefore, the lithium halide obtained by the manufacturing method of this embodiment using lithium sulfide as a raw material is a light metal among alkali metals and is an effective compound in terms of improving ionic conductivity. Known methods for obtaining lithium sulfide include, for example, a method in which lithium hydroxide and hydrogen sulfide are reacted in a hydrocarbon organic solvent at 70°C to 300°C to produce lithium hydrosulfide, and then this reaction solution is dehydrosulfided to synthesize lithium sulfide (Japanese Patent Laid-Open No. 2010-163356), and a method in which lithium hydroxide and hydrogen sulfide are reacted at 130°C or higher and 445°C or lower to synthesize lithium sulfide (Japanese Patent Laid-Open No. 9-278423).

[0032] The average particle size (D 50 ) is preferably 10 μm or more and 2000 μm or less, more preferably 30 μm or more and 1500 μm or less, and even more preferably 50 μm or more and 1000 μm or less. 50 ) is the particle size at which 50% of the total particle size is reached when the particle size distribution curve is plotted and accumulated from the smallest particle size. The volume distribution is the average particle size that can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer.

[0033] Lithium sulfide preferably contains a small amount of water as an impurity, in order to reduce the amount of water in the resulting lithium halide, and further, when using lithium halide as a raw material for a sulfide solid electrolyte, to prevent a decrease in ionic conductivity and a decrease in battery performance due to water. The amount of water contained in lithium sulfide is preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. The lower limit is not particularly limited, as the lower the better, but is typically about 0.1% by mass. In this specification, the water content in lithium sulfide is a value measured using a Karl Fischer moisture meter under conditions of vaporization at 280°C.

[0034] (halogen molecules) The halogen molecule used in the production method of this embodiment is at least one of bromine and iodine, and is a molecule represented by the following general formula (1). X2...(1) (In general formula (1), X is a bromine element or an iodine element.)

[0035] Generally, preferred examples of halogen molecules include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), with bromine (Br) and iodine (I) being particularly preferred. In the production method of this embodiment, the halogen molecules can be used alone or in combination. That is, bromine can be used alone, iodine can be used alone, or bromine and iodine can be used in combination. Note that, although the production method of this embodiment targets at least one of bromine and iodine as halogen molecules, it can also be applied to other halogen molecules such as fluorine and chlorine.

[0036] In the production method of this embodiment, lithium sulfide and halogen molecules react with each other according to the following reaction formula (2): Therefore, the amount of halogen molecules used should be the same molar amount as that of lithium sulfide, and when multiple types of halogen molecules are used, the total number of moles of the multiple types of halogen molecules should be the same molar amount.

[0037] Li2S+X2→2LiX+S (2) (In formula (2), X2 is a halogen molecule of bromine or iodine.)

[0038] As described above and as shown in the above reaction formula (2), lithium halide is produced by the reaction of lithium sulfide with halogen molecules, but the lithium halide is produced in such a way that it precipitates on the surface of the lithium sulfide, making it difficult for the lithium sulfide to further react. According to the production method of this embodiment, since the first solvent that dissolves lithium halide is used, lithium halide is not precipitated on the surface of the lithium sulfide, and a newly formed surface is always exposed, thereby accelerating the reaction.

[0039] Furthermore, as shown in the above reaction formula (2), sulfur is produced as a by-product. In addition to the methods described in Patent Documents 3 and 4, lithium halide can also be obtained, for example, by the reaction of lithium hydroxide with hydrogen halide, but water is produced as a by-product. By selecting lithium sulfide and halogen molecules as raw materials, which are easily available and suitable for mass production, water is not obtained as a by-product and the process can be adapted to industrial scale. In these respects, the combination of lithium sulfide and halogen molecules is extremely useful.

[0040] (First Solvent) The first solvent used in the production method of this embodiment is a solvent that dissolves lithium halides. The lithium halides vary depending on the type of halogen molecules used together with lithium sulfide, and specifically may include lithium bromide and lithium iodide. That is, the first solvent has the property of dissolving these lithium halides. The first solvent is not particularly limited as long as it can dissolve the lithium halides, such as lithium bromide and lithium iodide, and examples thereof include those having a solubility (at 20°C) of preferably 1 g / L or more, more preferably 3 g / L or more, and even more preferably 5 g / L or more. If the solubility of lithium halide is within the above range, the lithium halide produced by the reaction between lithium sulfide and halogen molecules quickly dissolves in the first solvent without depositing on the surface of the lithium sulfide, thereby further suppressing the deposition. Furthermore, there is no particular limit to the upper limit of the solubility, and it is usually about 1000 g / L or less.

[0041] In this specification, the solubility of lithium halide is measured by the following method. Lithium halide was added to a solvent and thoroughly mixed at 20°C. The presence of lithium halide that was not dissolved in the solvent in the solution was visually confirmed. Next, the resulting solution was subjected to inductively coupled plasma (ICP) atomic emission spectroscopy using an inductively coupled plasma (ICP) atomic emission spectroscopy analyzer. The content of lithium in the resulting solution, i.e., the lithium dissolved in the solvent, was measured, and the solubility (g / L) of lithium halide was calculated.

[0042] A preferred example of such a first solvent is a complexing agent. The complexing agent is capable of forming a complex (also referred to as a "lithium halide complex") by coordinating (bonding) with the lithium atom, sulfur atom, and halogen atom, particularly lithium atom, contained in the lithium sulfide, halogen molecules, or lithium halide used in the production method of this embodiment, which is obtained by the reaction of these. The complexing agent can be used without any particular limitation as long as it has such properties. In particular, a compound containing an atom having a high affinity with lithium atoms, such as a nitrogen atom, an oxygen atom, or a chlorine atom, is preferred, and a compound having a group containing these heteroatoms is more preferred. The use of a complexing agent as the first solvent promotes the reaction between lithium sulfide and halogen molecules, further reducing the amount of residual halogen molecules, thereby improving the reaction efficiency and achieving high reaction efficiency. Furthermore, the use of a complexing agent as the first solvent allows the lithium halide obtained by the reaction between lithium sulfide and halogen atoms to dissolve as a complex in the solvent, and the lithium halide obtained becomes porous by removing the solvent, making it easier to obtain a sulfide solid electrolyte with higher ionic conductivity.

[0043] In the production method of this embodiment, when a complexing agent is used as the first solvent, what is obtained by mixing and removing the solvent is a complex composed of lithium halide and the complexing agent, which is generated by the above-mentioned coordination (bonding), and strictly speaking, is not lithium halide. In other words, the lithium halide compound obtained by the production method of this embodiment may include not only lithium halide but also lithium halide complexes, and when multiple types of halogen molecules are used, it may also include what is called a lithium halide composite containing halogen atoms derived from the multiple types of halogen molecules. Furthermore, since any of these can be suitably used as a raw material for a sulfide solid electrolyte, the lithium halide compound obtained by the production method of this embodiment may be any of lithium halide, lithium halide complexes, and lithium halide composites.

[0044] As the heteroatom, a nitrogen atom or an oxygen atom is more preferred, and as a group containing these heteroatoms, a nitrogen atom-containing group is preferably an amino group, an amide group, a nitro group, or a nitrile group, with an amino group being more preferred. Furthermore, as a group containing an oxygen atom, an ester group or an ether group is preferred, with an ester group being more preferred. Therefore, in the production method of this embodiment, a solvent that is particularly preferably used as the first solvent is a complexing agent, particularly an aprotic solvent having at least one functional group selected from an ester group, an ether group, and an amino group.

[0045] Examples of the complexing agent having an amino group include amine compounds such as aliphatic amines, alicyclic amines, heterocyclic amines, and aromatic amines, and these can be used alone or in combination.

[0046] Representative and preferred examples of the aliphatic amine include aliphatic primary diamines such as ethylenediamine, diaminopropane, and diaminobutane; aliphatic secondary diamines such as N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyldiaminopropane, and N,N'-diethyldiaminopropane; and aliphatic tertiary diamines such as N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetramethyldiaminopropane, N,N,N',N'-tetraethyldiaminopropane, N,N,N',N'-tetramethyldiaminobutane, N,N,N',N'-tetramethyldiaminopentane, and N,N,N',N'-tetramethyldiaminohexane. In the examples given in this specification, for example, in the case of diaminobutane, unless otherwise specified, all isomers of butane, such as linear and branched isomers, are included, in addition to isomers relating to the position of the amino group, such as 1,2-diaminobutane, 1,3-diaminobutane, and 1,4-diaminobutane.

[0047] The number of carbon atoms in the aliphatic amine is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more, with the upper limit being preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less. The number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic amine is preferably 2 or more, and the upper limit being preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0048] Typical preferred examples of the alicyclic amine include alicyclic primary diamines such as cyclopropanediamine and cyclohexanediamine; alicyclic secondary diamines such as bisaminomethylcyclohexane; and alicyclic tertiary diamines such as N,N,N',N'-tetramethyl-cyclohexanediamine and bis(ethylmethylamino)cyclohexane. Typical preferred examples of the heterocyclic amine include heterocyclic primary diamines such as isophoronediamine; heterocyclic secondary diamines such as piperazine and dipiperidylpropane; and heterocyclic tertiary diamines such as N,N-dimethylpiperazine and bismethylpiperidylpropane. The number of carbon atoms in the alicyclic amine and heterocyclic amine is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.

[0049] Representative preferred examples of the aromatic amine include aromatic primary diamines such as phenyldiamine, tolylenediamine, and naphthalenediamine; aromatic secondary diamines such as N-methylphenylenediamine, N,N'-dimethylphenylenediamine, N,N'-bismethylphenylphenylenediamine, N,N'-dimethylnaphthalenediamine, and N-naphthylethylenediamine; and aromatic tertiary diamines such as N,N-dimethylphenylenediamine, N,N,N',N'-tetramethylphenylenediamine, N,N,N',N'-tetramethyldiaminodiphenylmethane, and N,N,N',N'-tetramethylnaphthalenediamine. The aromatic amine preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, and even more preferably 8 or more carbon atoms, and the upper limit is preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms.

[0050] The amine compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, or a cyano group, or with a halogen atom. Although diamines have been given as specific examples, it goes without saying that the amine compounds that can be used in this embodiment are not limited to diamines, and examples thereof include aliphatic monoamines corresponding to various diamines such as trimethylamine, triethylamine, ethyldimethylamine, and the above-mentioned aliphatic diamines; piperidine compounds such as piperidine, methylpiperidine, and tetramethylpiperidine; pyridine compounds such as pyridine and picoline; morpholine compounds such as morpholine, methylmorpholine, and thiomorpholine; imidazole compounds such as imidazole and methylimidazole; and the above-mentioned alicyclic diamines. In addition to monoamines such as alicyclic monoamines such as the corresponding monoamines; heterocyclic monoamines corresponding to the above heterocyclic diamines; and aromatic monoamines corresponding to the above aromatic diamines, polyamines having three or more amino groups, such as diethylenetriamine, N,N',N''-trimethyldiethylenetriamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, triethylenetetramine, N,N'-bis[(dimethylamino)ethyl]-N,N'-dimethylethylenediamine, hexamethylenetetramine, and tetraethylenepentamine, can also be used.

[0051] Among the above, from the viewpoints of promoting the reaction between lithium sulfide and halogen molecules to improve reaction efficiency, rapidly dissolving the lithium halide, and suppressing precipitation of lithium sulfide on the surface, tertiary amines having a tertiary amino group as the amino group are preferred, tertiary diamines having two tertiary amino groups are more preferred, tertiary diamines having two tertiary amino groups at both ends are even more preferred, and aliphatic tertiary diamines having tertiary amino groups at both ends are even more preferred. Among the above amine compounds, preferred aliphatic tertiary diamines having tertiary amino groups at both ends are tetramethylethylenediamine, tetraethylethylenediamine, tetramethyldiaminopropane, and tetraethyldiaminopropane, and taking into consideration ease of availability, etc., tetramethylethylenediamine (also referred to as "TMEDA") and tetramethyldiaminopropane (also referred to as "TMPDA") are preferred.

[0052] Although not specifically exemplified, compounds having a nitrogen atom as a heteroatom and a group other than an amino group, such as an amide group, a nitro group, or a nitrile group, can also provide the same effects as compounds containing an amino group.

[0053] Next, examples of the complexing agent having the above-described ether group as the group containing an oxygen atom include ether compounds such as aliphatic ethers, alicyclic ethers, heterocyclic ethers, and aromatic ethers, and these can be used alone or in combination of two or more types.

[0054] Examples of aliphatic ethers include monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and tert-butyl methyl ether; diethers such as dimethoxymethane, dimethoxyethane, diethoxymethane, and diethoxyethane; polyethers having three or more ether groups such as diethylene glycol dimethyl ether (diglyme) and triethylene oxide glycol dimethyl ether (triglyme); and ethers containing hydroxyl groups such as diethylene glycol and triethylene glycol. The aliphatic ether preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and even more preferably 4 or more carbon atoms, and the upper limit is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less carbon atoms. The number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic ether is preferably 1 or more, and the upper limit is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0055] Examples of alicyclic ethers include ethylene oxide, propylene oxide, tetrahydrofuran, tetrahydropyran, dimethoxytetrahydrofuran, cyclopentyl methyl ether, dioxane, and dioxolane. Examples of heterocyclic ethers include furan, benzofuran, benzopyran, dioxene, dioxin, morpholine, methoxyindole, and hydroxymethyldimethoxypyridine. The number of carbon atoms in the alicyclic ether and heterocyclic ether is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.

[0056] Examples of aromatic ethers include methyl phenyl ether (anisole), ethyl phenyl ether, dibenzyl ether, diphenyl ether, benzyl phenyl ether, and naphthyl ether. The aromatic ether preferably has 7 or more carbon atoms, more preferably 8 or more carbon atoms, and the upper limit is preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms.

[0057] The ether compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, or a cyano group, or with a halogen atom.

[0058] The ether compound used in the present embodiment is preferably an aliphatic ether, and more preferably dimethoxyethane or tetrahydrofuran, from the viewpoints of improving the reaction efficiency by promoting the reaction between lithium sulfide and halogen molecules, and of quickly dissolving lithium halide and suppressing precipitation of lithium sulfide on the surface.

[0059] Furthermore, examples of the complexing agent having the above-described ester group as the group containing an oxygen atom include ester compounds such as aliphatic esters, alicyclic esters, heterocyclic esters, and aromatic esters, and these can be used alone or in combination of two or more types.

[0060] Examples of aliphatic esters include formate esters such as methyl formate, ethyl formate, and triethyl formate; acetate esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; propionate esters such as methyl propionate, ethyl propionate, propyl propionate, and butyl propionate; oxalate esters such as dimethyl oxalate and diethyl oxalate; malonate esters such as dimethyl malonate and diethyl malonate; and succinate esters such as dimethyl succinate and diethyl succinate. The number of carbon atoms in the aliphatic ester is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more, with the upper limit being preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less. The number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic ester is preferably 1 or more, more preferably 2 or more, and the upper limit being preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0061] Examples of alicyclic esters include methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, dimethyl cyclohexanedicarboxylate, dibutyl cyclohexanedicarboxylate, and dibutyl cyclohexenedicarboxylate. Examples of heterocyclic esters include methyl pyridinecarboxylate, ethyl pyridinecarboxylate, propyl pyridinecarboxylate, methyl pyrimidinecarboxylate, ethyl pyrimidinecarboxylate, and lactones such as acetolactone, propiolactone, butyrolactone, and valerolactone. The number of carbon atoms in the alicyclic ester and heterocyclic ester is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.

[0062] Examples of aromatic esters include benzoic acid esters such as methyl benzoate, ethyl benzoate, propyl benzoate, and butyl benzoate; phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, and dicyclohexyl phthalate; and trimellitic acid esters such as trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, and trioctyl trimellitate. The aromatic ester preferably has 8 or more carbon atoms, more preferably 9 or more carbon atoms, and the upper limit is preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms.

[0063] The ester compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, or a cyano group, or with a halogen element.

[0064] The ester compound used in the present embodiment is preferably an aliphatic ester, more preferably an acetic acid ester, and particularly preferably ethyl acetate, from the viewpoints of improving the reaction efficiency by promoting the reaction between lithium sulfide and halogen molecules, and of quickly dissolving lithium halide and suppressing precipitation of lithium sulfide on the surface.

[0065] The complexing agents preferably used as the first solvent generally form a lithium halide complex in which the heteroatom of the complexing agent is coordinated (bonded) with the lithium atom of the lithium sulfide. Some do not form such a complex, and those having an oxygen atom as a heteroatom as an ester group tend to have difficulty in forming a complex. However, the effect of improving the reaction efficiency is not inhibited even if the complex is not formed. This is because the complexing agent has the property of dissolving lithium halide and halogen molecules, particularly iodine, and therefore can reduce the amount of residual halogen molecules, thereby improving the reaction efficiency.

[0066] In the production method of this embodiment, the amount of the first solvent used is preferably 100 mL or more, more preferably 200 mL or more, even more preferably 250 mL or more, and still more preferably 300 mL or more, relative to 1 kg of the total amount of lithium sulfide and halogen molecules, and the upper limit is preferably 3000 mL or less, more preferably 2500 mL or less, even more preferably 2000 mL or less, and still more preferably 1550 mL or less. When the amount of the first solvent used is within the above range, lithium halide is quickly dissolved, and precipitation of lithium sulfide on the surface is easily suppressed.

[0067] (Mixing) The production method of this embodiment includes mixing the lithium sulfide, halogen molecules, and a first solvent that dissolves the lithium halide. By mixing, lithium halide is obtained by a reaction between the lithium sulfide and the halogen molecules, and the obtained lithium halide is dissolved in the first solvent without depositing on the surface of the lithium sulfide. Therefore, the newly formed surface of the lithium sulfide is always in contact with the halogen molecules, thereby accelerating the reaction.

[0068] When lithium sulfide, halogen molecules, and the first solvent capable of dissolving lithium halide are mixed, there is no particular limitation on the mixing method, and lithium sulfide, halogen molecules, and the first solvent may be mixed by being charged into an apparatus capable of mixing these substances. Here, since halogen molecules are, for example, at room temperature and normal pressure, fluorine and chlorine are gaseous, bromine is liquid, and iodine is solid, they may be supplied and mixed in a manner appropriate for the state of the halogen molecules. For example, when the halogen molecules are liquid, they may be supplied into the tank together with the first solvent, when the halogen molecules are gaseous, they may be supplied by being blown into a mixture of a complexing agent and lithium sulfide, and when the halogen molecules are solid, they may be supplied into the tank together with lithium sulfide.

[0069] The production method of this embodiment is characterized by including mixing lithium sulfide, halogen molecules, and a first solvent. Therefore, lithium halide can be efficiently produced without using equipment generally referred to as a mill, such as a media-type mill (e.g., a ball mill or a bead mill) (without pulverization). In the production method of this embodiment, "mixing" refers to a process such as stirring, which does not result in "pulverization" of the solid raw materials, lithium sulfide and halogen molecules (iodine). While the raw materials may be pulverized using a mill to shorten the mixing time or to achieve finer powder to obtain a complex, it is preferable from the viewpoint of industrialization not to use a mill, i.e., not to perform pulverization. One of the features of the production method of this embodiment is that lithium halide can be produced without pulverization.

[0070] The device for mixing lithium sulfide, halogen molecules, and the first solvent may be appropriately selected depending on the scale. For example, in the case of a small-scale system, a device such as a Schlenk system equipped with a stirring bar may be used, and in the case of a medium to large-scale system, a mechanical stirring mixer equipped with a stirring blade in a tank may be used. Examples of mechanical agitation mixers include high-speed agitation mixers and double-arm mixers, and from the viewpoint of improving the uniformity of the raw materials in the mixture of the raw materials and the complexing agent and obtaining higher ionic conductivity, high-speed agitation mixers are preferably used. Examples of high-speed agitation mixers include vertical-axis rotary mixers and horizontal-axis rotary mixers, and either type of mixer may be used.

[0071] Examples of the shape of the stirring blade used in the mechanical stirring mixer include a blade type, an arm type, an anchor type, a paddle type, a full zone type, a ribbon type, a multi-stage blade type, a double arm type, a shovel type, a double-shaft blade type, a flat blade type, and a C-shaped blade type. From the viewpoints of efficiently promoting the reaction between lithium sulfide and halogen molecules, quickly dissolving the resulting lithium halide, and easily suppressing precipitation of lithium sulfide on the surface, the shovel type, flat blade type, C-shaped blade type, anchor type, paddle type, and full zone type are preferred, with the anchor type, paddle type, and full zone type being more preferred.

[0072] The temperature conditions during mixing are not particularly limited, and are, for example, usually −30 to 100° C., preferably 5 to 50° C., more preferably 10 to 30° C., and even more preferably about room temperature (23° C.) (for example, about room temperature ±5° C.). The mixing time is usually 0.1 to 500 hours, and from the viewpoint of efficiently and sufficiently proceeding the reaction between lithium sulfide and halogen atoms, is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, even more preferably 2 to 25 hours, and even more preferably 3 to 10 hours.

[0073] (Second Solvent) In the manufacturing method of this embodiment, in addition to the first solvent, a second solvent that does not dissolve lithium halide can be used as a solvent other than the first solvent. As described above, the first solvent has the property of dissolving lithium halide, but empirically has the property of poorly dissolving halogen molecules, particularly iodine. In contrast, the second solvent has the property of not dissolving lithium halide, but has the property of easily dissolving halogen molecules, particularly iodine. Therefore, it can be said that the second solvent is preferably used to improve the reactivity of iodine, which is poorly soluble in the first solvent. Furthermore, using the second solvent before using the first solvent can promote the reaction between lithium sulfide and halogen molecules, particularly iodine, thereby improving reaction efficiency. When bromine is used as the halogen molecule, bromine is liquid at room temperature and can be dispersed without the use of a second solvent, so the second solvent is not necessarily required. Therefore, the second solvent is particularly effective when iodine is used as the halogen molecule.

[0074] The second solvent is a solvent that does not dissolve lithium halide, and is not particularly limited as long as it does not dissolve lithium halide. Examples of the second solvent include those having a solubility (20°C) of preferably less than 1 g / L, more preferably 0.5 g / L or less, even more preferably 0.1 g / L or less, and still more preferably 0.07 g / L or less. When the solubility of lithium halide is within the above range, the dispersion state of lithium sulfide and halogen molecules is improved, and the lithium halide produced by the reaction between lithium sulfide and halogen molecules is quickly dissolved in the first solvent without being deposited on the surface of lithium sulfide, thereby further suppressing the deposition. There is no particular lower limit, and the solubility is usually 0.01 mg / L or more.

[0075] The second solvent is preferably a solvent that dissolves halogen molecules, particularly iodine. Its solubility (at 25°C) is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. There is no upper limit, but examples of the solubility include 60% by mass or less, 55% by mass or less, and 10% by mass or less. When the iodine solubility in the second solvent is within the above range, the effect of using the second solvent can be efficiently obtained, and similar effects can be obtained even when bromine is used as another halogen molecule.

[0076] In this specification, the solubility of halogen molecules is measured by the following method. Iodine (2 g) was added to 3 mL of solvent and stirred at 25°C for 20 minutes. 0.1 g of the supernatant was weighed out, and 1 g of sodium thiosulfate aqueous solution (10% by mass, NaSO) was added to the supernatant. The solution was shaken for approximately 1 minute, and it was confirmed that the color of the solution had disappeared. The iodine concentration of the above solution was quantified using inductively coupled plasma (ICP) atomic emission spectroscopy, and the iodine solubility was calculated.

[0077] Preferred examples of the second solvent having such properties include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; and solvents containing carbon atoms, such as solvents containing carbon atoms and hetero atoms.

[0078] Examples of aliphatic hydrocarbons include hexane, pentane, 2-ethylhexane, heptane, octane, decane, undecane, dodecane, and tridecane. Examples of alicyclic hydrocarbons include cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, tert-butylbenzene, trifluoromethylbenzene, and nitrobenzene. Examples of solvents containing carbon atoms and heteroatoms include carbon disulfide, diethyl ether, dibutyl ether, and tetrahydrofuran. The second solvent may be used alone or in combination of two or more of the above.

[0079] Among these, from the viewpoint of quickly dissolving lithium halide and suppressing precipitation of lithium sulfide on the surface, hydrocarbon solvents are preferred, aromatic hydrocarbons and aliphatic hydrocarbons are more preferred, and toluene is preferred as the aromatic hydrocarbon. Furthermore, the aliphatic hydrocarbon preferably has a carbon number of 2 to 8, more preferably 3 to 7, and even more preferably 4 to 6. Furthermore, alicyclic hydrocarbons are preferred, and the number of carbon atoms in the cyclic portion is preferably 3 to 8, more preferably 4 to 7, and even more preferably 4 to 6, with 6 being particularly preferred. As the alicyclic hydrocarbon, cyclohexane is particularly preferred.

[0080] The second solvent preferably has a boiling point of 150° C. or less, more preferably 140° C. or less, and although there is no particular lower limit, it may be 90° C. or more. When the boiling point is within the above range, the second solvent has an appropriate viscosity, and a good dispersion state of lithium sulfide and halogen molecules can be obtained.

[0081] The second solvent has the property of not dissolving lithium halide, but also has the property of readily dissolving sulfur molecules. In the production method of this embodiment, lithium sulfide and halogen molecules react according to the reaction formula (2) above, producing sulfur molecules as a by-product along with lithium halide. That is, the mixture obtained by mixing lithium sulfide, halogen molecules, the first solvent, and the second solvent also contains sulfur molecules. To obtain lithium halide, it is necessary to remove the sulfur molecules as a by-product. Since the second solvent has the property of dissolving sulfur molecules, removing the second solvent by removing the solvent described below can also remove the sulfur molecules dissolved in the solvent. Therefore, removing the solvent described below can also be expected to have the effect of removing sulfur molecules by washing. Note that, from the viewpoint of improving the quality of the resulting lithium halide compound, it is preferable to remove the sulfur molecules by washing, as described below.

[0082] Regarding the property of the second solvent that it easily dissolves sulfur molecules, specifically, the second solvent preferably has a sulfur solubility (25°C) of 1 g / L or more, more preferably 0.3 g / L or more, even more preferably 0.5 g / L or more, and particularly preferably 10 g / L or more. There is no particular upper limit to the sulfur solubility, but it may be, for example, 600 g / L or less, 550 g / L or less, or 100 g / L or less. In this specification, the sulfur solubility is measured as follows. (Measurement of sulfur solubility) 50 ml of solvent was added to 10 g of sulfur, the temperature was adjusted to 25°C in an oil bath, and the mixture was stirred for two hours. The supernatant was then separated using a cannula (transport tube) equipped with a glass filter. The separated supernatant was evacuated to obtain dry sulfur. The solubility of sulfur (mass%) was calculated from the mass of the dry sulfur and the mass of the solvent in which the dry sulfur was dissolved.

[0083] When using a second solvent, it is preferable to mix lithium sulfide, halogen molecules, and the second solvent, and then add the first solvent and mix them. That is, before mixing using the first solvent, lithium sulfide and halogen molecules are mixed in the second solvent, and then the first solvent is added to mix the lithium sulfide, halogen molecules, first solvent, and second solvent. By mixing lithium sulfide and halogen molecules in the second solvent before mixing using the first solvent, halogen molecules, especially iodine, are dissolved in the second solvent, improving reactivity, thereby accelerating the reaction between lithium sulfide and halogen molecules and improving reaction efficiency. Furthermore, by improving the dispersibility of lithium sulfide and halogen molecules in the second solvent in advance, when a complexing agent is used as the first solvent, lithium halide complexes are easily formed. As described above, residual halogen molecules can be further reduced, improving reaction efficiency and achieving high reaction efficiency.

[0084] The mixing time of lithium sulfide and halogen molecules in the second solvent is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 1.5 hours or more, and the upper limit is preferably 4 hours or less, more preferably 3 hours or less, and even more preferably 2.5 hours or less. When the mixing time in the second solvent is within the above range, it is possible to improve the dispersion state of lithium sulfide and halogen molecules while suppressing the precipitation of lithium halide on the surface of lithium sulfide.

[0085] When the second solvent is used, the amount of the second solvent used is preferably 2000 mL or more, more preferably 3500 mL or more, even more preferably 5000 mL or more, and still more preferably 6000 mL or more, relative to 1 kg of the total amount of lithium sulfide and halogen molecules, and the upper limit is preferably 10000 mL or less, more preferably 9000 mL or less, even more preferably 8000 mL or less, and still more preferably 7500 mL or less. When the amount of the second solvent used is within the above range, it is possible to suppress the deposition of lithium halide on the surface of lithium sulfide while improving the dispersion state of lithium sulfide and halogen molecules.

[0086] (Removing the solvent) The manufacturing method of this embodiment includes removing the solvent. Removing the solvent results in the production of a lithium halide compound. Removing the solvent includes removing the solvent present as a liquid from a mixture of lithium sulfide, halogen molecules, a first solvent, and an optional second solvent, and removing the first solvent from a lithium halide complex incorporating the first solvent. The type of solvent removal can be adjusted by the solvent removal method. For the former removal, solid-liquid separation methods such as filtration and decantation can be used, while for the latter removal, drying methods can be used. These methods will be described later.

[0087] As described above, the lithium halide compound may include lithium halide, lithium halide complex, lithium halide composite containing multiple types of halogen atoms, etc. More specifically, when a complexing agent is used as the first solvent, the lithium halide compound may include lithium halide and lithium halide complex, when multiple types of halogen molecules are used, the lithium halide and lithium halide composite containing multiple types of halogen atoms, and when a complexing agent is used as the first solvent and multiple types of halogen molecules are used, the lithium halide compound may include lithium halide and lithium halide complex and lithium halide composite. Therefore, for example, when a complexing agent is used as the first solvent and multiple types of halogen molecules are used, removing the solvent by filtration will yield lithium halide, a lithium halide complex, and a lithium halide composite, and removing the solvent by drying will yield lithium halide and a lithium halide composite.

[0088] When the first solvent alone is used, the first solvent is removed, and when the first solvent and the second solvent are used in combination, both the first solvent and the second solvent are removed. As described above, when the second solvent is used, the second solvent can dissolve sulfur molecules, which are by-products, so that removing the solvent also makes it possible to remove the sulfur molecules.

[0089] As will be described later, when the lithium halide compound and sulfur molecules are washed using a third solvent, the third solvent is also a solvent that is removed by removing the solvent, and like the second solvent, it is possible to remove the sulfur molecules together. In this case, the solvent may be removed once after the mixing and again after washing, i.e., twice. This point will also be described in detail when explaining washing.

[0090] As a method for removing the solvent, filtration, drying, etc., as described above, are preferably used, and these may be used in combination. Filtration is a method used to remove solvents present as a liquid, and can be carried out using, for example, a glass filter. The glass filter to be used has a pore size of, for example, about 10 to 200 μm, preferably 20 to 150 μm.

[0091] Drying is a method that can remove the solvent present as a liquid as well as the first solvent (complexing agent) incorporated into the lithium halide complex. Drying can be performed by drying under reduced pressure, drying by heating, or the like. For example, drying under reduced pressure can be followed by drying by heating, or drying by heating under reduced pressure can also be performed. When the solvent is removed by drying, the solvent is removed by volatilization, etc., so when a lithium halide complex is contained in the lithium halide compound, the first solvent is volatilized and removed from the complex, resulting in lithium halide. Therefore, when a first solvent is used and it is desired to convert the lithium halide complex into lithium halide, the solvent can be removed by drying.

[0092] As described above, drying is a method capable of removing the first solvent incorporated into the lithium halide complex, but by adjusting the heating temperature so as not to remove the incorporated first solvent, it is possible to leave the lithium halide complex as it is, or by further drying by heating under temperature conditions so as to remove the first solvent, it is possible to remove the first solvent from the lithium halide complex and obtain lithium halide. In drying by heating, the heating temperature can be adjusted as desired.

[0093] Drying under reduced pressure can be carried out using, for example, a vacuum pump, and drying under vacuum is preferred from the viewpoint of shortening the drying time. When drying is carried out by heating, the temperature can be determined depending on the type of the first solvent and the second and third solvents used as needed, for example, at a temperature equal to or higher than the boiling points of these solvents. In this case, the heating temperature is usually 5 to 100°C, preferably 10 to 85°C, more preferably 15 to 70°C, and even more preferably 20 to 60°C, although it cannot be generalized because it also depends on the degree of reduced pressure.

[0094] Another preferred drying method is solid-liquid separation, which can be carried out by decantation or by using a centrifuge. Specifically, decantation can be performed by transferring a mixture of lithium sulfide, halogen molecules, a first solvent, and a second solvent used as needed, and a mixture containing a third solvent used in washing as needed, into a container, and after solids have precipitated, removing the first solvent, the second solvent, and the third solvent that become supernatants.

[0095] (Washing and removing sulfur molecules) The production method of this embodiment may further include washing and removing sulfur molecules. In this embodiment, as shown in the above reaction formula (2), sulfur molecules are produced as by-products by the reaction of lithium sulfide with halogen molecules. By removing these sulfur molecules, it becomes possible to produce a lithium halide compound with high purity. When a second solvent is used, sulfur molecules are usually dissolved in the second solvent, and therefore, the sulfur molecules can be removed by removing the second solvent. Therefore, washing and removing the sulfur molecules can be essentially performed by removing the solvent. When a second solvent is not used, or even when a second solvent is used, it is preferable to perform washing and removal separately from the removal of the solvent, from the viewpoint of further removing the sulfur molecules to obtain a lithium halide compound with higher purity.

[0096] The washing may be carried out after or before the removal of the solvent. However, from the viewpoint of more efficiently removing sulfur molecules, it is preferable to carry out the washing after the removal of the solvent, that is, to carry out the washing on the mixture containing the lithium halide compound and sulfur molecules obtained by removing the first solvent and the second solvent from the mixture containing the lithium halide compound, sulfur molecules, the first solvent, and the second solvent used as needed, obtained by the mixing.

[0097] The washing method is preferably a third solvent because it facilitates washing. As the third solvent, a solvent capable of dissolving sulfur molecules is preferred because it facilitates the removal of sulfur molecules. The solvent capable of dissolving sulfur molecules preferably has a sulfur solubility (20°C) of 0.1 g / L or more, more preferably 0.3 g / L or more, even more preferably 0.5 g / L or more, and particularly preferably 1 g / L or more. While there is no upper limit, examples include solvents with a sulfur solubility of 600 g / L or less, 550 g / L or less, and 100 g / L or less. That is, the third solvent can be appropriately selected from the solvents exemplified as the second solvent above. Examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; and solvents containing carbon atoms, such as solvents containing carbon atoms and heteroatoms. Hydrocarbon solvents are preferred, with aromatic hydrocarbons and aliphatic hydrocarbons being more preferred, and aromatic hydrocarbons being even more preferred, with toluene being particularly preferred, as with the second solvent. Therefore, it is preferable to use the same (same type of) solvent as the second solvent and the third solvent.

[0098] When washing is carried out using a third solvent, the mixture of lithium halide and sulfur molecules may be washed by a process similar to the decantation described above, in which the third solvent is added to a mixture of the lithium halide compound reactant and the sulfur molecules by-product, which is obtained by removing the solvent from the mixture of lithium sulfide obtained by the above-mentioned mixing, halogen molecules, the first solvent, and the second solvent used as needed, and after the solid lithium halide compound precipitates, the supernatant solvent is discarded, and the above process may be carried out repeatedly.

[0099] When washing is performed after removing the solvent, and when washing is performed using a third solvent, it is preferable to further remove the solvent after washing. This allows sulfur molecules to be removed together with the third solvent, thereby further reducing the content of sulfur molecules in the lithium halide compound. In this case, the solvent can be removed by any method appropriately selected from the above-mentioned methods for removing the solvent. In this manner, in the production method of this embodiment, solvent removal may be performed twice. In this case, the first solvent removal is performed by removing the first solvent and the second solvent from the mixture containing the lithium halide compound, sulfur molecules, the first solvent, and the second solvent used as needed, as well as removing the sulfur molecules contained in the second solvent. The second solvent removal is performed by removing the third solvent from the mixture containing the lithium halide compound, sulfur molecules, and the third solvent after washing with the third solvent, as well as removing the sulfur molecules contained in the third solvent.

[0100] As described above, the lithium halide compounds obtained by the production method of this embodiment include lithium halide, lithium halide complexes, and lithium halide composites. These lithium halide compounds are of high quality and have low water content, even though no water removal is performed, and are therefore suitable for use as raw materials for sulfide solid electrolytes. The water content of the lithium halide compound obtained by the production method of this embodiment is 1% by mass or less, further 0.5% by mass or less, or 0.3% by mass or less. The lower limit is usually about 0.01% by mass. In this specification, the water content of the lithium halide compound is a value measured using a Karl Fischer moisture meter under the vaporization method at 280°C, similar to the water content of lithium sulfide.

[0101] The lithium halide compound obtained by the manufacturing method of this embodiment is porous as described above, and has a specific surface area of ​​1.0 m2 measured by the BET method. 2 / g or more, even 5.0m 2 / g or more, 10.0m 2 / g or more. The upper limit is usually 80.0 m 2 / g or less. In this specification, the specific surface area is a value measured by the BET method (gas adsorption method), and either nitrogen (nitrogen method) or krypton (krypton method) may be used as the gas, and the measurement is performed by selecting an appropriate gas depending on the size of the specific surface area. The specific surface area can be measured using, for example, a commercially available gas adsorption measuring device (e.g., AUTOSORB6 (manufactured by Sysmex Corporation)).

[0102] (Method of manufacturing sulfide solid electrolyte) The lithium halide compound obtained by the production method of this embodiment is suitable for use as a raw material for a sulfide solid electrolyte, as described above. The sulfide solid electrolyte can be obtained, for example, by a production method including reacting the lithium halide compound obtained by the production method of this embodiment with a lithium compound other than lithium halide and a phosphorus compound. The production method including reacting the lithium halide compound with a lithium compound other than lithium halide and a phosphorus compound is a known method, and specific treatments, operations, etc. may be performed in accordance with known methods.

[0103] The lithium halide compound may be lithium fluoride, lithium chloride, lithium bromide, lithium iodide, etc. depending on the halogen molecule used, with lithium bromide and lithium iodide being preferred. Preferred examples of lithium compounds other than lithium halide compounds include lithium sulfide (Li2S), lithium oxide (Li2O), and lithium carbonate (Li2CO3), and among these, lithium sulfide is preferred from the viewpoint of ionic conductivity.

[0104] Preferred examples of phosphorus compounds include phosphorus sulfides such as diphosphorus trisulfide (P2S3) and diphosphorus pentasulfide (P2S5), and phosphate compounds such as sodium phosphate (Na3PO4) and lithium phosphate (Li3PO4). Among these, phosphorus sulfide is preferred, and diphosphorus pentasulfide (P2S5) is more preferred. Phosphorus compounds such as diphosphorus pentasulfide (P2S5) can be used without any particular limitation as long as they are industrially produced and commercially available. These phosphorus compounds can be used alone or in combination of two or more.

[0105] Furthermore, as a compound containing a halogen atom other than a lithium halide compound, a halogen molecule, i.e., fluorine (F2), chlorine (Cl2), bromine (Br2), or iodine (I2), preferably chlorine (Cl2), bromine (Br2), or iodine (I2), more preferably bromine (Br2) or iodine (I2), can also be used.

[0106] Among the above, combinations of lithium sulfide, diphosphorus pentasulfide and a lithium halide compound, and combinations of lithium sulfide, diphosphorus pentasulfide, a lithium halide compound and a halogen molecule are preferred.

[0107] When lithium sulfide, diphosphorus pentasulfide, and lithium halide are used as raw materials, the ratio of lithium sulfide to the total of lithium sulfide and diphosphorus pentasulfide is preferably 70 to 80 mol%, more preferably 72 to 78 mol%, and even more preferably 74 to 78 mol%, from the viewpoint of obtaining higher chemical stability and higher ionic conductivity. Furthermore, when lithium bromide and lithium iodide are used in combination as the lithium halide, from the viewpoint of improving ionic conductivity, the proportion of lithium bromide to the total of lithium bromide and lithium iodide is preferably 1 to 99 mol%, more preferably 20 to 90 mol%, still more preferably 40 to 80 mol%, and particularly preferably 50 to 70 mol%.

[0108] When lithium bromide and lithium iodide are used in combination as the lithium halide, from the viewpoint of improving ionic conductivity, the proportion of lithium bromide to the total of lithium bromide and lithium iodide is preferably 1 to 99 mol%, more preferably 20 to 90 mol%, still more preferably 40 to 80 mol%, and particularly preferably 50 to 70 mol%.

[0109] When lithium sulfide, diphosphorus pentasulfide, an elemental halogen, and a lithium halide are used, the content of the elemental halogen (α mol %) and the content of the lithium halide (β mol %) relative to the total amount of these preferably satisfy the following mathematical formula (2), more preferably satisfy the following mathematical formula (3), even more preferably satisfy the following mathematical formula (4), and even more preferably satisfy the following mathematical formula (5). 2≦2α+β≦100…(2) 4≦2α+β≦80 …(3) 6≦2α+β≦50 …(4) 6≦2α+β≦30 …(5)

[0110] In reacting a lithium halide compound, a lithium compound other than lithium halide, and a phosphorus compound, the reaction can be carried out by mixing, stirring, pulverizing, etc. For example, when mixing or stirring, a mechanical stirring mixer used in mixing in the production method of this embodiment can be used, and when pulverizing, a device generally referred to as a pulverizer, such as a media-type pulverizer such as a ball mill or a bead mill, can be used.

[0111] Furthermore, when reacting by mixing and stirring, it is preferable to stir (mix) the complexing agent exemplified as a preferred first solvent above with various solvents (e.g., the solvents exemplified as the second solvent above) as needed, and raw materials for a lithium halide compound, a lithium compound other than lithium halide, and a phosphorus compound, since this allows a solid electrolyte to be obtained without pulverization. In this case, stirring (mixing) produces a slurry containing an electrolyte precursor composed of the raw materials and the complexing agent, a liquid complexing agent, and a solvent, which is dried to remove the liquid complexing agent and solvent, and further heated to produce a sulfide solid electrolyte. The drying can be performed by any of the methods that can be used to perform drying in the manufacturing method of this embodiment, and the temperature conditions, etc., when drying by heating are the same as those for drying by heating in the manufacturing method of this embodiment, because the solvent used is the same as that used in the manufacturing method of this embodiment.

[0112] The sulfide solid electrolyte obtained by the above method contains lithium, sulfur, phosphorus, and a halogen element, and is basically an amorphous sulfide solid electrolyte. In this specification, the amorphous sulfide solid electrolyte refers to an X-ray diffraction pattern obtained by X-ray diffraction measurement that shows a halo pattern in which peaks other than those derived from the material are substantially not observed, regardless of whether or not peaks derived from the raw materials of the solid electrolyte are present. Representative examples of amorphous sulfide solid electrolytes obtained using lithium halide compounds obtained by the manufacturing method of this embodiment include solid electrolytes composed of lithium sulfide, phosphorus sulfide, and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, and Li2S-P2S5-LiI-LiBr; and solid electrolytes further containing other elements such as oxygen and silicon, such as Li2S-P2S5-Li2O-LiI and Li2S-SiS2-P2S5-LiI. From the viewpoint of obtaining higher ionic conductivity, solid electrolytes composed of lithium sulfide, phosphorus sulfide, and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, and Li2S-P2S5-LiI-LiBr, are preferred. The types of elements constituting the amorphous solid electrolyte can be confirmed, for example, by an ICP emission spectroscopic analyzer.

[0113] Furthermore, the above-mentioned amorphous sulfide solid electrolyte can be converted into a crystalline sulfide solid electrolyte by further heating. In this specification, a crystalline solid electrolyte is a solid electrolyte in which a peak derived from the solid electrolyte is observed in an X-ray diffraction pattern in X-ray diffraction measurement, regardless of whether or not a peak derived from the raw material of the solid electrolyte is present. That is, the crystalline solid electrolyte contains a crystalline structure derived from the solid electrolyte, and a part of the crystalline structure may be derived from the solid electrolyte, or the entire crystalline structure may be derived from the solid electrolyte. Furthermore, as long as the crystalline solid electrolyte has the above-mentioned X-ray diffraction pattern, it may contain an amorphous solid electrolyte in part. Therefore, the crystalline solid electrolyte includes so-called glass ceramics obtained by heating an amorphous solid electrolyte to a temperature equal to or higher than the crystallization temperature.

[0114] The heating temperature can be selected appropriately depending on the structure of the amorphous sulfide solid electrolyte, so it cannot be generalized. For example, using a differential thermal analyzer (DTA device), differential thermal analysis (DTA) is performed under a heating condition of 10 ° C. / min. Starting from the temperature of the peak top of the exothermic peak observed on the lowest temperature side, the temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and even more preferably 20 ° C. or higher. There is no particular limit to the upper limit, but it should be about 40 ° C. or lower. Specifically, usually, 130 ° C. or higher is preferred, 135 ° C. or higher is more preferred, and 140 ° C. or higher is even more preferred. There is no particular limit to the upper limit, but it is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and even more preferably 250 ° C. or lower.

[0115] The heating time is not particularly limited as long as it is a time that allows a desired crystalline sulfide solid electrolyte to be obtained, but is preferably 1 minute or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and even more preferably 1 hour or more. The upper limit of the heating time is not particularly limited, but is preferably 24 hours or less, more preferably 10 hours or less, even more preferably 5 hours or less, and even more preferably 3 hours or less.

[0116] Furthermore, heating is preferably carried out in an inert gas atmosphere (e.g., a nitrogen atmosphere or an argon atmosphere) or a reduced pressure atmosphere (particularly in a vacuum), as this can prevent deterioration (e.g., oxidation) of the crystalline solid electrolyte. The heating method is not particularly limited, and examples thereof include methods using a hot plate, a vacuum heating device, an argon gas atmosphere furnace, and a baking furnace. Furthermore, industrially, a horizontal dryer or a horizontal vibration fluidized dryer having a heating means and a feeding mechanism can also be used, and the method may be selected depending on the amount of heat to be processed.

[0117] The crystalline sulfide solid electrolyte obtained using the lithium halide compound obtained by the manufacturing method of this embodiment includes a Li3PS4 crystal structure, a Li4P2S6 crystal structure, a Li7PS6 crystal structure, a Li7P3S 11Examples of such a sulfide solid electrolyte include a sulfide solid electrolyte having a crystal structure, a crystal structure having peaks at 2θ=approximately 20.2° and 23.6° (for example, JP 2013-16423 A).

[0118] Also, Li 4-x Ge 1-x P x S4-type thio-LISICON Region II crystal structure (Kanno et al., Journal of the Electrochemical Society, 148(7)A742-746(2001)), Li 4-x Ge 1-x P x Examples include a crystal structure similar to the S4-based thio-LISICON Region II type (see Solid State Ionics, 177 (2006), 2721-2725). From the viewpoint of ionic conductivity, the thio-LISICON Region II type crystal structure is preferred. Here, the "thio-LISICON Region II type crystal structure" refers to a structure in which Li 4-x Ge 1-x P x S4-type thio-LISICON Region II crystal structure, Li 4-x Ge 1-x P x This indicates that the crystal structure is either S4-type thio-LISICON Region II type or similar.

[0119] The sulfide solid electrolyte thus obtained is obtained from a water-free lithium halide compound as a raw material, and therefore has low water content, high ionic conductivity, and excellent battery performance. Therefore, the sulfide solid electrolyte obtained using the lithium halide compound obtained by the production method of this embodiment can be used in any application requiring Li ion conductivity, and is particularly suitable for use in batteries. The sulfide solid electrolyte may be used in a positive electrode layer, a negative electrode layer, or an electrolyte layer. Each layer can be produced by a known method. The battery preferably includes a current collector in addition to the positive electrode layer, electrolyte layer, and negative electrode layer, and a known current collector can be used. For example, a layer of a material that reacts with a sulfide solid electrolyte, such as Au, Pt, Al, Ti, or Cu, coated with Au or the like can be used. [Example]

[0120] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples in any way.

[0121] (Manufacturing example: manufacturing lithium sulfide (Li2S)) Toluene (manufactured by Sumitomo Corporation) was used as a non-aqueous medium and was dehydrated. When the moisture content reached 100 ppm as measured using a Karl Fischer moisture meter, 303.8 kg of the dehydrated mixture was added to a 500 L stainless steel reactor under a nitrogen stream. Subsequently, 33.8 kg of anhydrous lithium hydroxide (manufactured by Honjo Chemical Co., Ltd.) was added, and the mixture was maintained at 95°C while stirring with a Twin Star stirring blade at 131 rpm. The temperature was raised to 104°C while hydrogen sulfide (Sumitomo Seika Chemicals Co., Ltd.) was blown into the slurry at a supply rate of 100 L / min. Azeotropic gas of water and toluene was continuously discharged from the reaction vessel. This azeotropic gas was dehydrated by condensing it in a condenser outside the system. During this time, toluene in an amount equal to the toluene distilled out was continuously supplied to maintain a constant reaction liquid level. The amount of water in the condensate gradually decreased, and 24 hours after the introduction of hydrogen sulfide, distillation of water was no longer observed. During the reaction, the solid was dispersed in the toluene and was stirred, and no water separated from the toluene. Thereafter, the hydrogen sulfide was replaced with nitrogen, which was circulated at 100 L / min for 1 hour.

[0122] Example 1 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a Schlenk tube (volume: 100 mL) equipped with a stir bar under a nitrogen atmosphere. 20 mL of toluene was added as the second solvent, and after rotating the stir bar, 2.76 g (10.9 mmol) of iodine was added as a halogen molecule. The lithium sulfide and iodine were mixed in the second solvent for 2 hours. 4 mL of dehydrated ethyl acetate was added as the first solvent, and the mixture was further mixed for 2 hours. After visually confirming that the supernatant was not colored by iodine, the toluene and ethyl acetate used as the solvent were removed under vacuum. The mixture was then heated to 100°C for 2 hours to dry. After drying, 50 mL of toluene was added and the mixture was stirred for 10 minutes. After stirring, the mixture was allowed to settle, and 40 mL of the supernatant was removed. This decantation process was repeated three times. After decantation, the mixture was heated to 100°C under vacuum for 2 hours to obtain a powder. The obtained powder was subjected to powder X-ray diffraction (XRD) measurement by the following method. Furthermore, using the same method, XRD measurement was also performed on the lithium sulfide used as the raw material. The results of these XRD measurements are shown in Figure 1. As shown in Figure 1, the obtained powder had disappeared from the peaks of lithium sulfide and had peaks due to lithium iodide, confirming that it was lithium iodide powder.

[0123] In this specification, powder X-ray diffraction (XRD) measurements were carried out as follows. The powders obtained in the examples and comparative examples were filled into a groove 20 mm in diameter and 0.2 mm deep, and leveled with glass to prepare a sample. This sample was sealed in Kapton film for XRD and measured under the following conditions without exposing it to air. Measurement equipment: D2 PHASER, manufactured by Bruker Tube voltage: 30kV Tube current: 10mA X-ray wavelength: Cu-Kα ray (1.5418Å) Optical system: Concentration method Slit configuration: Soller slit 4°, divergence slit 1 mm, Kβ filter (Ni plate) Detector: Semiconductor detector Measurement range: 2θ=10-60deg Step width, scan speed: 0.05deg, 0.05deg / sec

[0124] Example 2 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a Schlenk tube (volume: 100 mL) equipped with a stir bar under a nitrogen atmosphere. 20 mL of toluene was added as a second solvent, and after rotating the stir bar, 2.76 g (10.9 mmol) of iodine was added as a halogen molecule. The lithium sulfide and iodine were mixed in the second solvent for 2 hours. 4 mL of tetramethylethylenediamine (TMEDA) was added as a first solvent, and mixing was continued for another 2 hours. After mixing, the toluene and tetramethylethylenediamine used as solvents were removed under vacuum, and the mixture was further dried by heating at 100 °C for 2 hours to obtain a powder. The obtained powder was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. The results of the XRD measurement of the powder are shown in Figure 2. Although the lithium sulfide peak disappeared from the powder, a peak different from the lithium iodide peak in Example 1 was observed, and it is believed that the powder is neither lithium sulfide nor lithium iodide, that is, a lithium iodide complex formed from lithium iodide and tetramethylethylenediamine. The powder was then dried by heating at 200°C for 2 hours. The powder obtained by this drying was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. The results of the XRD measurement of the powder are shown in Figure 2. The powder had the same peak as the powder obtained in Example 1, i.e., lithium iodide, and was therefore confirmed to be lithium iodide.

[0125] Example 3 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a 100 mL Schlenk tube equipped with a stir bar under a nitrogen atmosphere. 20 mL of toluene was added as the second solvent, and after rotating the stir bar, 0.87 g (5.44 mmol) of bromine and 1.38 g (5.44 mmol) of iodine were added as halogen molecules. The lithium sulfide, bromine, and iodine were mixed in the second solvent for 2 hours. 4 mL of dehydrated ethyl acetate was added as the first solvent, and the mixture was mixed for another 2 hours. After mixing, the toluene and ethyl acetate used as solvents were removed under vacuum, and the mixture was further dried by heating at 100 °C for 2 hours to obtain a powder. The obtained powder was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. As shown in Fig. 3, the obtained powder had no peak of lithium sulfide and had peaks due to lithium bromide and lithium iodide, and was confirmed to be a powder of lithium bromide and lithium iodide.

[0126] Example 4 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a Schlenk tube (volume: 100 mL) equipped with a stir bar under a nitrogen atmosphere. 20 mL of toluene was added as the second solvent, and after rotating the stir bar, 2.76 g (10.9 mmol) of iodine was added as a halogen molecule. The lithium sulfide and iodine were mixed in the second solvent for 2 hours. 4 mL of dehydrated tetrahydrofuran (THF) was added as the first solvent, and the mixture was mixed for another 2 hours. After mixing, the toluene and tetrahydrofuran used as solvents were removed under vacuum at room temperature (23 °C), yielding a powder. The obtained powder was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. The results of the XRD measurement of the powder are shown in Figure 4. Although the lithium sulfide peak disappeared from the powder, a peak different from the lithium iodide peak in Example 1 was observed, and it is believed that the powder is neither lithium sulfide nor lithium iodide, that is, a lithium iodide complex formed from lithium iodide and tetrahydrofuran. The powder was then dried by heating at 100°C for 2 hours. The powder obtained by this drying was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. The results of the XRD measurement of the powder are shown in Figure 4. The powder had the same peak as the powder obtained in Example 1, i.e., lithium iodide, and was therefore confirmed to be lithium iodide.

[0127] Example 5 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a 100 mL Schlenk tube equipped with a stir bar under a nitrogen atmosphere. 20 mL of cyclohexane was added as the second solvent, and after rotating the stir bar, 2.76 g (10.9 mmol) of iodine was added as a halogen molecule. The lithium sulfide and iodine were mixed in the second solvent for 2 hours. 4 mL of dehydrated tetrahydrofuran (THF) was added as the first solvent, and the mixture was mixed for another 2 hours. After mixing, the toluene and tetrahydrofuran used as solvents were removed under vacuum at room temperature (23 °C), yielding a powder. The powder was then dried by heating at 100°C for 2 hours. The powder obtained by this drying was subjected to powder X-ray diffraction (XRD) measurement in the same manner as in Example 1. The results of the XRD measurement of the powder are shown in Figure 5. The powder had the same peak as the powder obtained in Example 1, i.e., lithium iodide, and was therefore confirmed to be lithium iodide.

[0128] (Comparative Example 1) 0.50 g (10.9 mmol) of lithium sulfide (LiS) was introduced into a 100 mL Schlenk tube equipped with a stir bar under a nitrogen atmosphere. 20 mL of toluene was added as a second solvent, and after rotating the stir bar, 2.76 g (10.9 mmol) of iodine was added as a halogen molecule. The lithium sulfide and iodine were mixed in the second solvent for 50 hours. After mixing, the mixture was left to stand until a powder precipitated. The supernatant was removed and treated with an aqueous sodium thiosulfate solution. Composition analysis by ICP analysis (inductively coupled plasma atomic emission spectroscopy) confirmed that 28% of the 2.76 g of iodine used as the raw material remained unreacted.

[0129] The sample obtained in Comparative Example 1 was photographed using a scanning electron microscope (SEM), and elemental analysis was performed using an energy dispersive X-ray spectrometer (EDS). The SEM image taken with the scanning electron microscope (SEM) is shown in FIG. 6. As can be seen from FIG. 6, lithium iodide (the lighter region indicated by LiI in the figure) is formed around lithium sulfide (the darker region indicated by LiS in the figure). Thus, it was confirmed that unreacted lithium sulfide remains in the method of Comparative Example 1. 7 and 8 show EDS images of the results of elemental analysis of sulfur and iodine elements in the sample using an energy dispersive X-ray spectrometer (EDS device). The EDS images also show that sulfur element is present in the region where lithium sulfide is present, and iodine element is present in the region where lithium iodide is present, confirming that sulfur element remains due to unreacted lithium sulfide. [Industrial Applicability]

[0130] According to the production method of the present invention, lithium halide compounds, particularly lithium bromide and lithium iodide, having low water contents can be produced with high reaction efficiency and industrially advantageously without a step of directly removing water. The obtained lithium halide compounds have low water contents and can therefore be suitably used as raw materials for sulfide solid electrolytes.

Claims

1. Mixing lithium sulfide, at least one halogen molecule of bromine and iodine, and a second solvent, and further adding and mixing the first solvent; and removing the first solvent and the second solvent; Including, the first solvent is a solvent capable of dissolving lithium halide containing a halogen element of the halogen molecule, and the solubility of the lithium halide in the first solvent (at 20°C) is 1 g / L or more; the second solvent is a solvent that does not dissolve lithium halide containing a halogen element of the halogen molecule, and the solubility of the lithium halide in the second solvent (20°C) is less than 1 g / L; Method for producing lithium halide compounds.

2. 2. The method for producing a lithium halide compound according to claim 1, wherein the second solvent has a solubility (at 20° C.) of lithium bromide and lithium iodide of less than 1 g / L.

3. 3. The method for producing a lithium halide compound according to claim 1, wherein the second solvent is at least one selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons.

4. 4. The method for producing a lithium halide compound according to claim 1, wherein the second solvent has a boiling point of 150° C. or lower.

5. The method for producing a lithium halide compound according to any one of claims 1 to 4, further comprising washing and removing sulfur molecules with a third solvent, wherein the second solvent and the third solvent are the same.

6. The method for producing a lithium halide compound according to any one of claims 1 to 5, further comprising washing to remove sulfur molecules.

7. 7. The method for producing a lithium halide compound according to claim 6, wherein a third solvent is used in the washing and removing.

8. 8. The method for producing a lithium halide compound according to claim 5 or 7, wherein the removal of the third solvent is carried out by at least one treatment selected from the group consisting of filtration and heating under reduced pressure.

9. 9. The method for producing a lithium halide compound according to claim 7, wherein the third solvent has a solubility of sulfur molecules (at 25° C.) of 0.1 g / L or more.

10. 10. The method for producing a lithium halide compound according to claim 7, wherein the third solvent is at least one selected from aromatic hydrocarbons and aliphatic hydrocarbons.

11. The method for producing a lithium halide compound according to any one of claims 1 to 10, wherein the lithium halide compound comprises a lithium halide complex.

12. 12. The method for producing a lithium halide compound according to claim 1, wherein the first solvent has a solubility (20° C.) of lithium bromide and lithium iodide of 1 g / L or more.

13. 13. The method for producing a lithium halide compound according to any one of claims 1 to 12, wherein the first solvent is an aprotic solvent having at least one functional group selected from an ester group, an ether group, and an amino group.

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