CN115775657A - Method and apparatus for producing ion conductor - Google Patents
Method and apparatus for producing ion conductor Download PDFInfo
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- CN115775657A CN115775657A CN202211514408.1A CN202211514408A CN115775657A CN 115775657 A CN115775657 A CN 115775657A CN 202211514408 A CN202211514408 A CN 202211514408A CN 115775657 A CN115775657 A CN 115775657A
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Abstract
The invention provides a preparation method and a preparation device of an ion conductor with high ionic conductivity. The production method is characterized in that a 1 st compound having a 1 st cation and a 1 st anion as a counter ion thereof is dissolved in a solvent to form a 1 st solution; exchanging at least a portion of the 1 st cation or the 1 st anion in the 1 st compound with a2 nd cation or a2 nd anion using an ion exchange method to obtain a2 nd compound, and dissolving the 2 nd compound in the above solvent to obtain a2 nd solution containing an ionic conductor. The solvent may be a deoxygenated solvent or a solvent containing a deoxygenated solvent. The preparation process is carried out in a closed preparation device under the condition of not contacting with air.
Description
Technical Field
The present invention relates to a method and an apparatus for producing a sulfide solid ion conductor, and a sulfide solid ion conductor produced by the method, particularly to a technique for producing a sulfide solid ion conductor in an all-solid secondary battery using lithium.
Background
In recent years, as a battery for achieving a high energy density, development of a multivalent ion battery typified by a lithium ion battery, a sodium ion battery, and a magnesium secondary battery has been actively advanced. The lithium ion battery has the characteristics of high energy density, long service life and the like. Therefore, the lithium ion battery is widely used as a power source for personal computers, household electric appliances (such as cameras), portable electronic devices and communication devices (such as mobile phones), and electric power tools, in general. In recent years, lithium ion batteries have been widely used in large-sized batteries such as electric vehicles, hybrid electric vehicles, and stationary storage batteries. In these kinds of lithium ion batteries, when a solid electrolyte is used instead of an electrolyte containing a combustible organic solvent, not only can the safety device be simplified, but also the production cost and production efficiency are excellent. Various methods for preparing solid electrolytes have been actively studied.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open publication No. 2019-102355
Disclosure of Invention
Technical problem to be solved by the invention
However, the present inventors prepared Li by the method described in patent document 1 4 SnS 4 Due to Li obtained 4 SnS 4 The ionic conductivity was not as expected, the preparation thereof required a long time, and we found that it had not reached a practical level.
Accordingly, the present invention is directed to a method and an apparatus for producing an ion conductor, which can obtain an ion conductor having high ion conductivity.
Means for solving the problems
The invention provides a method for preparing an ion conductor, which comprises the steps of dissolving a 1 st compound at least having a 1 st cation and a 1 st anion serving as a counter ion of the 1 st cation in a solvent to form a 1 st solution, exchanging at least a part of the 1 st cation or the 1 st anion in the 1 st compound into a2 nd cation or a2 nd anion by using an ion exchange method to obtain a2 nd compound, dissolving the 2 nd compound in the solvent to obtain a2 nd solution containing the ion conductor, wherein the solvent comprises a deoxygenated solvent, and the preparation of the ion conductor is carried out under the condition of not contacting with air.
In the method for producing an ion conductor of the present invention, the solvent preferably contains water.
In the method for producing an ion conductor of the present invention, the dissolved oxygen concentration of the solvent is preferably less than 8mg-O/L.
The method for producing an ion conductor of the present invention preferably further comprises a drying step of removing the solvent from the 2 nd solution to obtain an ion conductor.
In the method for producing an ion conductor of the present invention, it is preferable to use a material containing CO in an amount of less than 1000ppm in oxygen 2 An inert atmosphere in an amount of less than 100 ppm.
The invention also provides the ion conductor prepared by the preparation method, wherein the median particle diameter D50 of the ion conductor is 0.05-500 mu m.
The present invention also provides a manufacturing apparatus for manufacturing the ion conductor, comprising:
an ultrapure water apparatus for preparing ultrapure water as a deoxygenating solvent;
a first closed reaction vessel in fluid communication with the ultrapure water device for introducing SnCl 4 ·5H 2 O is dissolved by the deoxidizing solvent, and SnCl is prepared 4 A solution;
a second closed reaction vessel which is respectively in fluid communication with the first closed reaction vessel and the ultrapure water device and is used for introducing Na 2 S is dissolved by the deoxygenated solvent to obtain Na 2 S solution, and adding the SnCl 4 The solution is mixed with the Na 2 S solutionPreparation of SnS by mixing 2 Suspension of + NaCl;
a third closed reaction vessel in fluid communication with the ultrapure water device for reacting Na 2 S is dissolved by the deoxidizing solvent to obtain Na 2 S solution;
a separation membrane unit in fluid communication with the ultrapure water device, the second closed reaction vessel and the third closed reaction vessel, respectively, for pairing SnS 2 Filtering and separating NaCl suspension and preparing SnS 2 The dispersion liquid is also used for adding Na in the third closed reaction vessel 2 Introducing S solution into the reactor and mixing with SnS 2 Reaction to prepare Na 4 SnS 4 Taking the solution as a 1 st solution;
a fourth closed reaction vessel in fluid communication with the ultrapure water device and the separation membrane unit, respectively, for storing the 1 st solution to prevent the 1 st solution from deteriorating;
a closed ion exchange column in fluid communication with the ultrapure water device and the fourth closed reaction vessel, respectively, for reacting Na 4 SnS 4 Na ions in the solution are exchanged for Li ions, and Li is prepared under the action of Li type ion exchange resin 4 SnS 4 The solution is used as a2 nd solution;
a closed recovery vessel in fluid communication with the closed ion exchange column for Li-rejection 4 SnS 4 Li obtained after drying of the solution 4 SnS 4 Solid powders or granules are stored.
By adopting the technical scheme, li is prepared 4 SnS 4 In the process, snCl is respectively put into the first closed reaction vessel and the second closed reaction vessel 4 ·5H 2 O and Na 2 S, because the first closed reaction vessel and the second closed reaction vessel are both in fluid communication with the ultrapure water device, in the first closed reaction vessel, the deoxygenation solvent and SnCl prepared by the ultrapure water device are utilized 4 ·5H 2 Obtaining SnCl from O 4 A solution; in a second closed reaction vessel, using a deoxygenated solvent and Na prepared by an ultrapure water apparatus 2 S to Na 2 S solution, then SnCl is added into a second closed reaction vessel 4 The solution is mixed with the Na 2 The S solution is stirred to react into SnS 2 Suspension of + NaCl; in a third closed reaction vessel, using a deoxygenated solvent and Na prepared by an ultrapure water device 2 S to Na 2 S solution; snS in separation membrane unit 2 Filtering and separating NaCl aqueous solution in NaCl suspension to obtain SnS 2 Dispersion of SnS 2 The dispersion was dissolved in Na 2 Preparation of Na in S solution 4 SnS 4 A solution; storing Na in a fourth closed reaction vessel 4 SnS 4 A solution; in a closed ion exchange column, adding Na 4 SnS 4 Na ions in the solution are replaced by Li ions to obtain Li 4 SnS 4 Solution, finally to Li 4 SnS 4 Drying the solution to obtain Li 4 SnS 4 Solid powders or granules. In the above process, the preparation device is more convenient to use, and Li element, sn element and S element are exposed to O 2 The time in (2) is short, and the amounts of oxygen and carbon dioxide (preparation atmosphere, use solvent, oxygen and carbon dioxide contained in the ion exchange resin) which are contacted during the preparation of the ion conductor are reduced. Further, the combination of Li element, sn element, S element and O element can be inhibited, and Li can be improved 4 SnS 4 Thereby improving the ionic conductivity.
Therefore, the preparation device of the ion conductor provided by the embodiment can reduce the interference of external factors, is more convenient to use and is beneficial to improving Li 4 SnS 4 The preparation efficiency of (2).
Preferably, the ultrapure water apparatus comprises an ultrapure water storage section and a deoxidation filter; the system comprises an ultrapure water storage component, a first closed reaction vessel, a second closed reaction vessel, a third closed reaction vessel, a separation membrane unit, a fourth closed reaction vessel and a closed ion exchange tower, wherein the outlet end of the ultrapure water storage component is connected with a connecting pipeline; the deoxygenation filter is connected to the connection line at the outlet of the ultrapure water storage section.
Preferably, the preparation device of the ionic conductor further comprises an inert gas tank, and the first closed reaction vessel, the second closed reaction vessel, the third closed reaction vessel, the separation membrane unit and the fourth closed reaction vessel are respectively connected with the inert gas tank through pipelines.
Preferably, the preparation device of the ionic conductor further comprises a vacuum pump, and the first closed reaction vessel, the second closed reaction vessel, the third closed reaction vessel, the separation membrane unit and the fourth closed reaction vessel are respectively connected with a vacuum pump pipeline.
Advantageous technical effects
According to the present invention, a solid ion conductor having high ion conductivity can be obtained in a short time.
Drawings
FIG. 1 is a schematic diagram of an apparatus for use in an ion exchange process according to an embodiment of the present invention.
[ description of symbols ]
W-1 ultrapure water equipment
V-1 vacuum pump
V-2 vacuum pump
OF deoxidation filter
G-1 inert gas tank
1-a closed reaction vessel
1-b closed reaction vessel
2-a separation membrane unit
3-a closed reaction container
3-b closed reaction vessel
4-a closed ion exchange tower
4-b closed recovery container
P1-4 inert gas supply pipe
R1-5 degassing water supply pipe
C1-2 circulating transfusion tube
TP-1 high-pressure liquid feeding pump
TP-2 liquid feeding pump
TP-3 liquid feed pump
TP-4 liquid feeding pump
E-1 sealed drain pipe
ST non-penetrating stirring device
Detailed Description
< preparation method of ion conductor >
The method for preparing an ion conductor according to the present invention has the following processes. A process for preparing a 1 st compound having at least a 1 st cation and a 1 st anion as a counter ion thereof, and dissolving in a solvent to obtain a 1 st solution. A process of exchanging at least a portion of said 1 st cation or said 1 st anion in said 1 st compound for a2 nd compound having a2 nd cation or 2 nd anion using an ion exchange method. And (3) a process of dissolving the 2 nd compound in the solvent to obtain a2 nd solution. A drying process for preparing a solid ionic conductor by removing the solvent from the 2 nd solution. Each process is described in detail below.
[ Process for producing the 1 st solution ]
In the process of producing the 1 st solution, a 1 st compound having a 1 st cation and a 1 st anion as a counter ion thereof is dissolved in a solvent to obtain a 1 st solution. In this process, it is also possible to dissolve and mix a compound having a 1 st cation and another compound having a 1 st anion as its counter ion, respectively, in a solvent to obtain a 1 st solution. In the process of preparing the solution 1, if an anion compound containing an unexchanged anion is generated by ion exchange to be performed later, a step of separating the unexchanged anion in the process of preparing the solution 1 may be included.
[ ion exchange Process ]
In the ion exchange process, at least a part of the 1 st cation or 1 st anion of the 1 st compound in the 1 st solution is exchanged with the 2 nd cation or 2 nd anion by using an ion exchange method. Thus, at least a portion of the 1 st cations or 1 st anions in the 1 st solution are exchanged for the 2 nd cations or 2 nd anions in the 2 nd solution. In the ion exchange process, at least a part of the cations (1 st cations) possessed by the 1 st compound may be ion-exchanged with the 2 nd cations using a cation exchange method. Further, at least a part of the anions (1 st anions) of the 1 st compound may be ion-exchanged with the 2 nd anions by an anion exchange method.
(ion exchange method)
The ion exchange method may be a cation exchange method or an anion exchange method.
[ method of cation exchange ]
When the ion exchange process is performed using a cation exchange method, a cation exchange resin having a2 nd cation is contacted with the 1 st solution. Thus, at least a portion of the 1 st cations in the 1 st compound contained in the 1 st solution are exchanged with the 2 nd cations in the cation exchange resin to produce a2 nd solution of the 2 nd compound containing the 2 nd cations and the 1 st anions. The 1 st and 2 nd compounds when the ion exchange process is performed using the cation exchange method will be described below.
(Compound No. 1)
The 1 st compound has at least a 1 st cation, and has a 1 st anion as its counter ion. The 1 st cation is not particularly limited and may be a monoatomic ion or a molecular ion which loses an electron and has a positive charge. Specifically, the monoatomic ions include hydrogen ions, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, aluminum ions, silver ions, zinc ions, and the like. The molecular ions include ammonium ion and pH 4+ Ion, H 3 O + Ion, H 2 F + Ions, mercury ions, cycloheptatriene cations, and the like.
Among them, the 1 st cation is preferably a sodium ion from the viewpoint of versatility.
The 1 st compound having the 1 st cation is a compound containing an electrolyte that is ionized into a cation (1 st cation) and an anion (1 st anion) when dissolved in a solvent, and is preferably a compound containing an S element. The S element-containing compound is preferably a 1 st anion S element-containing compound, and more preferably a sulfide. From the viewpoint of the ion conductivity of the ion conductor containing the 2 nd compound obtained after the ion exchange process, it is particularly preferable that the 1 st anion contains both the S element and can form a trivalent or tetravalent cationThe elements of the son (may take the valence of three or four). The element which can form a trivalent or tetravalent cation is not particularly limited and may be Sn, as, bi, ge, sb, or the like. The 1 st anion is preferably SnS 4 Ions, snS 3 Ion, asS 4 Ions, geS 4 Ion, sbS 4 Ions, sn 2 S 6 Ion, biS 2 Ion, asS 3 Ion, sbS 3 Ions and Sbs 2 Ions.
(Compound No. 2)
The 2 nd compound in the 2 nd solution is obtained by an ion exchange process using a cation exchange device, wherein at least a portion of the 1 st cations in the 1 st compound are ion exchanged with the 2 nd cations provided by the cation exchange device. That is, the 2 nd compound is a compound containing the 2 nd cation and the 1 st anion. The 2 nd cation is a different cation from the 1 st cation. The 2 nd cation is not limited to any cation other than the 1 st cation, and may be a monoatomic ion or a molecular ion which loses electrons and has a positive charge. Specifically, the monoatomic ions include hydrogen ions, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, aluminum ions, silver ions, and zinc ions. The molecular ions include ammonium ion, pH 4+ Ion, H 3 O + Ion, H 2 F + Ions, mercury ions, cycloheptatriene cations, and the like. From the above ions, according to the 1 st cation of the 1 st compound, an ion different from the 1 st cation is selected. If the cation exchange process is a cation exchange resin, the 2 nd cation may be selected in consideration of the affinity of the ion for the cation exchange resin. For example, if the affinity of the 1 st cation for the cation exchange resin is greater than that of the 2 nd cation, the ion exchange reaction between the 1 st and 2 nd cations can be efficiently performed. In the present invention, for example, when the 1 st cation is a sodium ion, the 2 nd cation is preferably a lithium ion.
Cation exchange methods include cation exchange resins. Cation exchange resins of both strong and weak acidityThe preparation is used. Strong-acid cation exchange resins are preferred because the residual amount or volume change of the H-type strong-acid cation exchange resin is small and easy to handle. Therefore, the cation exchange resin more preferably contains sulfonic acid groups (-SO) 3 -) and a2 nd cation. In some cases, chelating resins may also be used. The cation exchange resins may be used alone, or two or more kinds of cation exchange resins may be used in combination.
Styrene and acrylic resins are organic polymers that can be used as the matrix for the cation exchange resin.
In the present specification, "styrene resin" refers to a resin formed by homopolymerization or copolymerization of styrene or a styrene derivative, and its structural unit includes 50wt% or more of styrene or a styrene derivative. The styrene derivatives include alpha-methylstyrene, vinyltoluenes, chlorostyrenes, ethylbenzene ethylenes, cumene ethylenes, dimethyl styrenes, bromostyrenes, and the like. The styrene resin may be copolymerized with other copolymerizable vinyl monomers as long as the main component is a homo-or copolymer of styrene or a styrene derivative. Such vinyl monomers, preferably, for example, divinylbenzene (o-divinylbenzene, m-divinylbenzene, p-divinylbenzene); a polyfunctional monomer such as an alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate or polyethylene glycol di (meth) acrylate; (meth) acrylonitrile; and methyl (meth) acrylate. Preferably divinylbenzene, ethylene glycol di (meth) acrylate or polyethylene glycol di (meth) acrylate, and the degree of polymerization of ethylene is 4 to 16. Divinylbenzene or ethylene glycol di (meth) acrylate is more preferred, divinylbenzene being particularly preferred.
In the present specification, the "acrylic resin" is a resin in which one or more of acrylic acid, methacrylic acid, acrylate ester and methacrylate ester is contained in a polymer monomer, and the total content of an acrylic acid structural unit, a methacrylic acid structural unit, an acrylate ester structural unit and a methacrylate ester structural unit is 50wt% or more. The acrylic resin may be an acrylic acid homopolymer, a methacrylic acid homopolymer, an acrylic acid ester homopolymer, a methacrylic acid ester homopolymer, a copolymer of acrylic acid and other monomers (e.g., acrylic acid ester, methacrylic acid ester, alpha-olefin (e.g., ethylene, divinylbenzene, etc.), a copolymer of methacrylic acid and other monomers (e.g., acrylic acid ester, methacrylic acid ester, alpha-olefin (e.g., ethylene, divinylbenzene, etc.), a copolymer of acrylic acid ester and other monomers (e.g., acrylic acid, methacrylic acid ester, alpha-olefin (e.g., ethylene, divinylbenzene, etc.)), and copolymers of methacrylic acid esters with other monomers such as acrylic acid, acrylic acid esters, methacrylic acid, alpha-olefins (e.g., ethylene, divinyl benzene, etc.), and the like. Among them, a methacrylic acid-divinylbenzene copolymer or an acrylic acid-divinylbenzene copolymer is most preferable.
The acrylic acid ester is preferably an alkyl acrylate, more preferably a linear or branched alkyl acrylate, and still more preferably a linear alkyl acrylate. The carbon number of the alkyl ester group is preferably 1 to 4. It is particularly preferred that the acrylate is methyl acrylate or ethyl acrylate.
The methacrylate is preferably an alkyl ester of methacrylic acid, more preferably a linear or branched alkyl ester of methacrylic acid, and still more preferably a linear alkyl ester of methacrylic acid. The carbon number of the alkyl ester group is preferably 1 to 4. It is particularly preferred that the alkyl ester of methacrylic acid is methyl methacrylate or ethyl methacrylate.
The matrix of the cation exchange resin may be either a transparent gel-type resin having a small pore diameter or a macroporous (also called porous, or high-porosity) resin having a large pore diameter. In addition to this, the average pore diameter and specific surface area of the cation exchange resin are not limited.
[ anion exchange method ]
When the anion exchange process is performed using an anion exchange method, an anion exchange resin providing the 2 nd anion is brought into contact with the 1 st solution. This causes at least a portion of the 1 st anion in the 1 st compound contained in the 1 st solution to exchange with the 2 nd anion in the anion exchange resin to produce a2 nd solution of the 2 nd compound containing the 1 st cation and the 2 nd anion. In the case of performing an ion exchange process using an anion exchange method, the 1 st and 2 nd compounds will be described hereinafter.
(Compound No. 1)
The 1 st compound has at least a 1 st cation and a 1 st anion as its counter ion. The 1 st anion is not limited to monoatomic ions or molecular ions that gain electrons and are negatively charged. Specifically, the monoatomic ion includes a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a sulfide ion, a nitrogen ion, and a phosphate ion. The molecular ions include polystyrene sulfonate ion, acetate ion, bicarbonate ion, carbonate ion, cyanide ion, hydroxide ion, nitrate ion, phosphate ion, sulfate ion, snS 4 Ions, snS 3 Ion, asS 4 Ions, snS 4 Ions, sn 2 S 6 Ion, biS 2 Ion, asS 3 Ion, sbs 4 Ion AsS 3 Ion, sbS 3 Ion, sbS 2 Ion, sbS 2 Ions, and the like.
Among them, from the viewpoint of versatility, the 1 st anion is preferably a polystyrene sulfonate ion.
The 1 st compound having the 1 st anion is a compound containing an electrolyte, and when dissolved in a solvent, is ionized into a cation (1 st cation) and an anion (1 st anion). The 1 st cation is not limited to a single atom or molecular ion that loses an electron and has a positive charge. Specifically, the monoatomic ions include hydrogen ions, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, aluminum ions, silver ions, and zinc ions. The molecular ions include ammonium ion, pH 4+ Ion, H 3 O + Ion, H 2 F + Ions, mercury ions, cycloheptatriene cations, and the like. Among them, the 1 st cation is preferably a lithium ion from the viewpoint of versatility.
(Compound No. 2)
Anion exchange resins are anion exchange processes. Both strongly basic anion exchange resins with quaternary ammonium bases and weakly basic anion exchange resins with primary to tertiary amino groups can be used as anion exchange resins. However, from the viewpoint of the efficiency of the ion exchange reaction, it is preferable to use a strongly basic anion exchange resin. Thus, the anion exchange resin preferably contains trimethylammonium groups (-N (CH) 3 ) 3 ) And exchange combination of anion No. 2. In some casesIn this case, a chelate resin may be used. The anion exchange resins may be used alone, or two or more kinds of anion exchange resins may be used in combination.
Like the cation exchange resin, styrene and acrylic acid can be used as organic polymer monomers for the anion exchange resin matrix. The matrix of the anion exchange resin may be either a transparent gel type resin having a small pore diameter or a macroporous type (also referred to as porous type, or high pore type) resin having a large pore diameter. In addition to this, the average pore size and specific surface area of the anion exchange resin are not limited.
The ion exchange process may be repeated. A combination of cation and anion exchange methods may be used as the ion exchange method. For example, if an ion exchange process is performed using a strong acid cation exchange resin, polystyrene sulfonate derived from the resin matrix eluted from the strong acid cation exchange resin may enter the 2 nd solution as an impurity. Therefore, in the ion exchange process, the resulting 2 nd solution is used again as the 1 st solution, and impurities are removed through an anion exchange resin charged with the target anion (2 nd anion). The anions (1 st anion) in the polystyrene sulfonate are exchanged with the 2 nd anion to obtain the ion conductor with higher purity.
(solvent)
In the process for preparing the compound 1, the process for preparing the solution 1 and the ion exchange process, the solvent used in the solution 1 and the solution 2 can be water, alcohols such as methanol and ethanol, water-soluble organic solvents such as acetone, and combinations of one or more of the above solvents. Among them, the solvent preferably contains water, and the 1 st solution and the 2 nd solution preferably are aqueous solutions. The water is preferably pure water or ultrapure water.
In the present invention, the solvent is preferably a deoxygenated solvent or a deoxygenated solvent-containing solvent. In other words, the dissolved oxygen concentration of the solvent is less than the saturated dissolved oxygen concentration of the solvent. Here, for example, at a water temperature of 15 ℃, the saturated dissolved oxygen concentration is 9.76 mg/L. And the saturated dissolved oxygen concentration at 25 ℃ was 8.11mg/L (see JIS K0102: 2013). Therefore, if the solvent contains water, the dissolved oxygen concentration of the solvent (preferably water) should preferably be less than 8mg/L, more preferably less than 5mg/L, and still more preferably less than 3mg/L. Most preferably less than 1mg/L.
The method for deoxidizing the solvent is not limited, and known methods may be used. Specifically, methods such as film degassing, replacement of oxygen with He, ne, ar, kr, xe, and Rn gases, use of an oxygen absorber, and the like, and combinations of these methods.
The method of adjusting the atmosphere is not limited, and known methods may be used. Specifically, instead of oxygen, he, ne, ar, kr, xe, or Rn gas, an oxygen adsorbent, a carbon dioxide adsorbent, a vacuum atmosphere, or the like, or a combination thereof is used.
The concentration of the 1 st compound in the 1 st solution is not particularly limited, as long as it is necessary to ensure that the ion exchange process can be efficiently carried out. For example, the concentration of the 1 st compound in the 1 st solution may be 1 to 30% by weight, preferably 15 to 20% by weight. However, as described above, when the ion exchange process is repeatedly performed, if the ion exchange process is performed again in order to remove impurities generated in the ion exchange process, the concentration of the impurities (1 st compound) is not limited to the above range.
The specific operation of the ion exchange process is not limited and conventional, known methods may be employed. FIG. 1 shows a schematic diagram of an apparatus for an ion exchange process in one embodiment of the present invention. For example, the 1 st solution in the tank 1 is supplied to an ion exchange resin column 2 filled with the above-mentioned ion exchange resin. The solution 1 is passed through the ion exchange resin using a pump P. The 1 st solution is then passed through an ion exchange resin. This allows at least a portion of the 1 st cation or 1 st anion in the 1 st compound in the 1 st solution to be exchanged for a2 nd cation or 2 nd anion. The 2 nd solution flows out from the outlet of the ion exchange resin column 2, wherein at least part of the 1 st cation or 1 st anion in the 1 st compound in the 1 st solution is exchanged for the 2 nd cation or 2 nd anion. The effluent 2 nd solution is collected in the storage tank 3. The ion exchange process may also be performed in a batch system. The 1 st solution used in the ion exchange process is preferably an aqueous solution, in which case the 2 nd solution produced is also an aqueous solution.
The temperature at which the ion exchange process is carried out is not limited, and may be, for example, between 10 ℃ and 50 ℃. From the viewpoint of exchange efficiency, SV (Space velocity: volume of liquid flowing per hour divided by volume of ion exchange resin) is preferably 5h -1 Or less, more preferably 2h -1 Or less. Further, BV (Bed volume: a value obtained by dividing the total volume of the liquid stream by the volume of the ion exchange resin) may be, for example, 0.5L/L-R to 20L/L-R. However, the above range is an example of the liquid passing condition and can be adjusted as appropriate. After the 1 st solution is passed, an appropriate amount of water is preferably passed through the ion exchange resin to discharge the remaining 1 st solution from the ion exchange resin.
When the ion exchange process is carried out using a cation exchange device, as described above, the cation exchange device preferably has the 2 nd cation (hereinafter simply referred to as the element "M 2 ") strong acid cation exchange resin. For example, a sulfur-containing compound (composed of a metal element M1, an S element, and an element forming a cation having a valence of 3 or 4 (hereinafter, abbreviated as M) 3 ) Composition) was subjected to the ion exchange process, the following reaction was performed. Thus, M 2 x M 3 y S z As the 2 nd compound (containing M) 2 Compound (ii) is formed. x, y and z represent the molar ratio of each element required to form the compound. R is the matrix of the ion exchange resin.
M 1 x M 3 y S z +R-SO 3 M 2 →M 2 x M 3 y S z +R-SO 3 M 1
In the present invention, the above cation exchange method is particularly preferably provided with Li ions as M 2 An ionic strong acid cation exchange resin. For example, the 1 st compound includes a metal element M 1 S element and metal element M 3 A sulfur-containing compound. M in the above reaction equation when the solution 1 is subjected to an ion exchange process using a strongly acidic cation exchange resin loaded with lithium ions 2 Is lithium and is ion exchanged to obtain a lithium-containing compound Li x M 3 y S z . As described above, M-containing compounds can be obtained by an ion exchange process 2 A compound such as a2 nd solution containing a lithium compound, and if necessary, the 2 nd solution may be subjected to the above-described ion exchange process again. In this case, the ion exchange process may use either a cation exchange method or an anion exchange method.
More specifically, for example, the catalyst will contain an element consisting of Na (M) 1 ) S element and Sn element (M) 3 ) Na of constitution 4 SnS 4 As the 1 st compound, the 1 st solution was prepared using a solution containing Li (M) 2 ) When the ion strong acid cation exchange resin is used in the ion exchange process, the obtained product contains Li 4 SnS 4 As the 2 nd compound. In addition, the 1 st compound can be prepared by a known method. For example, if the 1 st compound is Na 4 SnS 4 Then Na can be prepared by the following two processes 4 SnS 4 。
2Na 2 S+SnCl 4 →SnS 2 +4NaCl
SnS 2 +2Na 2 S→Na 4 SnS 4
The raw materials used for the production of the compound 1 may contain no water or crystal water, or may be hydrates. When the raw materials are solid, they may be used as they are, or they may be dissolved in water or in an aqueous solution of a water-soluble organic solvent as described above. The solvent constituting the 1 st solution containing the 1 st compound may be a solvent containing an aqueous solution of a raw material for producing the 1 st compound. Therefore, as for the solvent containing the aqueous solution of the raw material for producing the 1 st compound, it is preferable to include a deoxygenated solvent. In addition, the dissolved oxygen concentration of the solvent (preferably water) containing the aqueous solution used for producing the starting material of the compound No. 1 is preferably less than 8mg/L, more preferably less than 5mg/L, still more preferably less than 3mg/L, and particularly preferably less than 1mg/L.
[ drying Process ]
The method for preparing an ion conductor according to the present invention may include a drying process, i.e., a process of removing a solvent from the 2 nd solution obtained in the ion exchange process to obtain an ion conductor. By removing the solvent in the drying process, the ion conductor mainly containing the 2 nd compound can be isolated.
The specific operation of the drying process is not particularly limited, and a known method can be generally applied. That is, the dried ionic conductor (compound No. 2) can be recovered by freeze drying (a method of freezing the solution No. 2 first, and then, in vacuum, reducing the boiling point of the freeze-dried product to sublimate the moisture of the dried product), heat drying under reduced pressure (a method of reducing the boiling point by a reduced-pressure heating apparatus to promote the removal of the solvent from the solution No. 2), spray drying (a method of obtaining a dried powder by spraying the solution No. 2 into a gas using a spray dryer to rapidly dry the solution), or the like. These methods may be used in combination. Further, drying under reduced pressure may be performed without heating, or drying under reduced pressure may be performed without heating. In addition, in the case of obtaining a dried powder by spray drying, the recovered compound 2 may be subjected to thermal drying, if necessary, in addition to freeze drying. In the heating, the heating condition is not particularly limited, and the heating temperature may be set to, for example, 50 to 300 ℃. In both cases, it is preferable to set appropriate conditions according to the type of the solvent contained in the 2 nd solution (1 st solution).
(Process atmosphere)
In the present invention, the atmosphere in the process for preparing the 1 st compound, the process for preparing the 1 st solution, the ion exchange process for obtaining the 2 nd solution by ion exchange of the 1 st solution, and the drying process for removing the solvent from the 2 nd solution to solidify the ion conductor is preferably an atmosphere in which the compound does not undergo a side reaction with an element or a molecule present in the atmosphere in the above processes. The oxygen content in air was about 210,000ppm 2 The content was about 400ppm. Therefore, the atmosphere of the process for preparing the 1 st compound, the process for preparing the 1 st solution, the ion exchange process for obtaining the 2 nd solution by ion exchange of the 1 st solution, and the drying process for removing the solvent from the 2 nd solution to solidify the ion conductor is preferably an atmosphere containing CO in an amount of less than 1000ppm in oxygen 2 An atmosphere having a content of less than 100ppm, particularly preferably less than 10ppm, CO 2 Gas content less than 1ppmAn atmosphere.
(ion conductor)
The ion conductor obtained according to the present invention is based on the 2 nd compound. However, depending on the treatment conditions in the ion exchange process, components derived from the 1 st compound contained in the 1 st solution may be mixed and present. Specifically, when the cation exchange method is used, a component derived from the 1 st compound (1 st cation) may be mixed in the 2 nd solution. In the ion conductor produced by the method of the present invention, the mass fraction of the 1 st compound component contained in the 1 st solution is usually 10ppm or less, preferably 1ppm or less.
The ionic conductors prepared according to the present invention can be identified, for example, by measuring and analyzing X-ray diffraction patterns.
The ion conductor (compound 2) prepared according to the invention is a sulfide, preferably a lithium-containing sulfide, more preferably a sulfide containing Li, S and M 3 (M 3 May be one or more of Sn, as, bi, ge, sb). Specifically, li is exemplified 4 SnS 4 、Li 2 SnS 3 、Li 3 AsS 4 、Li 3 GeS 4 、Li 3 SbS 4 、Li 4 Sn 2 S 6 、LiBiS 2 、Li 3 AsS 3 And Li 3 SbS 3 And the like. An ion conductor containing such a sulfide is suitable as a solid electrolyte. The ion conductor showed 1.0X 10 at 25 deg.C -4 Ion conductivity of S/cm or higher, and is suitable for use as a material for lithium ion batteries, such as an electrode material for positive electrodes and the like, and an electrolyte layer material and the like.
[ example 1]
(preparation of the solution 1)
Mixing Na 2 S·9H 2 After O was placed in the closed vessel 1-a, the pressure was reduced to-0.1 MPa or less by the vacuum pump V-2, and Ar gas (purity 99.99%) was filled from the inert gas tank G-1 through the gas line P-1. Water (dissolved oxygen concentration: less than 1mg-O/L, electric conductivity: less than 1. Mu.S/cm) was fed from a pipe R-1 connected to an ultrapure water apparatus W-1 to 1-a by reducing the pressure by a vacuum pump V-2, and Na was dissolved 2 S·9H 2 And O. By this operation, 12wt% of Na was prepared under a deoxygenated atmosphere by stirring with deoxygenated water 2 S aqueous solution (A). Then, snCl was charged into the closed vessel 1-b 4 ·5H 2 O, reduced in pressure to-0.1 MPa or less by a vacuum pump V-2, and Ar gas (purity 99.99%) was filled from an inert gas tank G-1 through a gas line P-2. Here, water (dissolved oxygen concentration: less than 1mg-O/L, electric conductivity: less than 1. Mu.S/cm) is fed from a pipe R-2 connected to the ultrapure water apparatus W-1 by the pressure reduction of the vacuum pump V-2, and Na is dissolved 2 S·9H 2 And O. By this operation, 28wt% of Na was prepared by stirring with deoxygenated water under deoxygenated atmosphere 2 An S aqueous solution (B). Subsequently, in the closed vessel 1-B, the solution A was fed into the vessel 1-B under the pressure of Ar gas fed from the inert gas tank G-1 through the gas line P-1, and mixed with the solution B by stirring until Na was formed 2 S：SnCl 4 1 (molar ratio), thereby obtaining SnS containing 8wt% of NaCl impurities 2 A dispersion (C). The inside of the separation membrane 2-a was depressurized to-0.1 MPa or less by a vacuum pump V-2, and Ar gas (purity 99.99%) was filled from an inert gas tank G-1 through a gas pipe P-3. The dispersion C was fed to a separation membrane 2-a by Ar gas pressure of P-2, and SnS containing NaCl was deposited on the separation membrane 2 Pressurizing the dispersion liquid through a separation filter to generate SnS containing NaCl 2 And (4) precipitating. Here, water is fed from a pipe R-3 connected to the ultrapure water device W-1 by a high-pressure liquid feed pump TP-1 at a pressure of 0.1 to 1.0MPa (dissolved oxygen concentration: less than 1mg-O/L, electric conductivity: less than 1. Mu.S/cm), and the liquid passing operation is repeated to obtain purified SnS having a low NaCl content in the separation membrane 2-a 2 An aggregate (E). Here, water (dissolved oxygen concentration: less than 1mg-O/L, electric conductivity: less than 1. Mu.S/cm) is fed from a pipe R-4 connected to the ultrapure water apparatus W-1 by the pressure reduction of the vacuum pump V-2, and Na is dissolved 2 S·9H 2 And O. By this operation, 12wt% of Na was prepared under a deoxygenated atmosphere by stirring with deoxygenated water 2 An aqueous S solution (F). For E in the separation membrane, liquid F is fed up to SnS 2 ：Na 2 S =1 (molar ratio), and repeated liquid feeding-recovery was performed through the circulation line between 2-a and 3-a, and this operation was continued until E in the separation membrane 2-a was completely dissolved, to prepare as a 1 st solution15-20 wt% of Na in the solution 4 SnS 4 An aqueous solution (G). The solution G was fed to a closed vessel 3-b previously placed under vacuum (-0.1 MPa or less) and connected to an ion exchange resin column 4-a.
(preparation of Li type cation exchange resin)
In a closed type ion exchange resin column 4-a filled with an H type cation exchange resin, the prepared 1mol/L aqueous LiOH solution (dissolved oxygen concentration of the solvent water used: less than 1mg-O/L, conductivity: less than 1. Mu.S/cm) was treated at SV =4H -1 And BV =6L/L-R, and carrying out ion exchange. Then, SV =4h first -1 And BV =1L/L-R, the residual solution was squeezed out by passing water (dissolved oxygen concentration: less than 1mg-O/L, conductivity: less than 1. Mu.S/cm). Finally SV =10h -1 And washing with water (dissolved oxygen concentration: lower than 1mg-O/L, conductivity: lower than 1 mu S/cm) under the condition of BV =10L/L-R to prepare the Li-type cation exchange resin. At this time, water (dissolved oxygen concentration: less than 1mg-O/L, conductivity: less than 1. Mu.S/cm) was always kept in a water-full state by feeding water from R-5 to the ion exchange column 4-a through the liquid feed pump TP-3, thereby preventing air from being mixed.
(ion exchange Process)
Water (dissolved oxygen concentration: less than 1mg-O/L, conductivity: less than 1. Mu.S/cm) was passed through a liquid feed pump TP-3 through a pipe R-5 into an ion exchange resin column 4-a of the Li type cation exchange resin. Thereafter, by means of the liquid feed pump TP-4, at SV =1h -1 BV =0.6L/L-R, adding Na 4 SnS 4 And (C) introducing the aqueous solution (G) for ion exchange. Then, at SV =1h -1 And BV =2L/L-R, the residual solution was squeezed out by passing water (dissolved oxygen concentration: less than 1mg-O/L, conductivity: less than 1. Mu.S/cm), and Li as a2 nd solution was recovered in a vacuum vessel 4-b connected to an ion exchange resin column 4-a (below 0.1 MPa) 4 SnS 4 An aqueous solution (H).
(drying Process)
Using warp N 2 Sealed spray dryer (trade name: GAS-410/GB210, manufactured by YAMATO Co., ltd.) for Li after GAS replacement 4 SnS 4 Aqueous solution (H)Drying and granulating, primary drying in Ar gas atmosphere at 80-150 ℃, and further drying under reduced pressure while stirring at 240 ℃ to obtain Li 4 SnS 4 Powder (I).
A disk-shaped test piece having a radius of 12mm X a height of 0.6mm was prepared by pressing I, and the ionic conductivity was measured at a set temperature (25 ℃, 50 ℃, 90 ℃) by the AC impedance method. The results are shown in Table 1.
[ example 2]
Li was produced in the same manner as in example 1, except that undeoxygenated water (dissolved oxygen concentration: 8 mg-O/L) was used as the water used in the first solution preparation and ion exchange step 1, and that 1-a, 1-b, 2-a, 3-b, 4-a, 4-b were not subjected to vacuum or gas substitution 4 SnS 4 Powder (I). For the prepared I, the ionic conductivity was measured in the same manner as in example 1. The results are shown in Table 1.
[ example 3]
Li was prepared in the same manner as in example 1 except that undeoxygenated water (dissolved oxygen concentration: 8 mg-O/L) was used as the water used in the first solution preparation and ion exchange step, and that 1-a, 1-b, 2-a, 3-b, 4-a, 4-b were not subjected to vacuum or gas substitution, and that the ion exchange step was carried out by removing the water from the ion exchange resin column 4-a after preparation of the Li-type cation exchange resin and contacting the water with air for 24 hours and then returning the water to the ion exchange resin column 4-a 4 SnS 4 Powder (I). For the prepared I, the ionic conductivity was measured in the same manner as in example 1. The results are shown in Table 1.
Comparative example 1
The comparative examples were carried out according to the methods of examples JP 2019-102355.
(preparation of the No. 1 solution)
Na is mixed with 2 S·9H 2 O was dissolved in water (dissolved oxygen concentration: 8 mg-O/L) to prepare 12wt% Na 2 S aqueous solution (A). Then SnCl is added 4 ·5H 2 O was dissolved in water (dissolved oxygen concentration: 8 mg-O/L) to prepare 28% by weight of SnCl 4 An aqueous solution (B). Stirring A while cooling, adding B dropwise and mixing until mixingNa in liquid 2 S：SnCl 4 =2:1 (molar ratio) to obtain SnS containing 8wt% of NaCl impurity 2 A dispersion (C). Placing C into a centrifuge tube, rotating a centrifuge (trade name: superma 21, manufactured by TOMY) at 3000-10000 rpm for 5 min, and SnS 2 The polymer settled to the bottom of the centrifuge tube. Subsequently, by removing the supernatant (including NaCl), snS was obtained 2 A polymer (E). After adding water (dissolved oxygen concentration: 8 mg-O/L) to E, pulverization was performed using an ultrasonic homogenizer to prepare 8wt% SnS 2 And (3) dispersing the mixture. Obtained SnS 2 Refining the dispersion with the above centrifuge repeatedly (5 times total) to reduce NaCl content to obtain refined SnS 2 A polymer (F). Adding A into F until SnS in the mixed solution 2 ：Na 2 S =1:2 (molar ratio), preparing 15-20 wt% Na as the 1 st solution 4 SnS 4 An aqueous solution (G).
(preparation of Li-type cation exchange resin)
In an ion exchange resin column filled with an H-type cation exchange resin, liOH & H is introduced 2 1mol/L aqueous LiOH solution prepared by dissolving O in water (dissolved oxygen concentration: 8 mg-O/L) at SV =4h -1 And BV =6L/L-R, and then carrying out ion exchange by passing through the solution. Then, water (dissolved oxygen concentration: 8 mg-O/L) was added at SV =1h -1 BV =1L/L-R, and then SV =10h -1 And feeding and washing the solution under the condition of BV =10L/L-R to prepare the Li-type cation exchange resin.
(ion exchange Process)
By charging an ion exchange resin column packed with the Li type cation exchange resin after replacement with water (dissolved oxygen concentration: 8 mg-O/L), SV =1h -1 And Na is added under the condition of BV =0.6L/L-R 4 SnS 4 The aqueous solution (G) is ion-exchanged. Then, at SV =1h -1 And (3) introducing water (dissolved oxygen concentration: 8 mg-O/L) into the column under BV =2L/L-R, extruding the residual solution, and recovering Li as a second solution from an outlet of the ion exchange resin column 4 SnS 4 An aqueous solution (H).
(drying Process)
Li 4 SnS 4 After the aqueous solution (H) was concentrated in an evaporator, it was frozen and freeze-dried at-40 ℃ for 60 hours, and then dried under reduced pressure at 150 ℃ for 1 hour to prepare Li 4 SnS 4 Powder (I).
TABLE 1
As shown in Table 1, the ion conductor (Li) prepared by the method of example 4 SnS 4 ) The ion conductivity is improved as compared with the ion conductor in the comparative example prepared in air using non-deoxidized water as described in patent document 1, and the mechanism is not clear. As can be seen from the comparative examples in which a solvent having a high dissolved oxygen concentration is used in air, oxygen, carbon dioxide, or oxygen in the solvent in the reaction atmosphere is a factor that inhibits ion conduction of the ion conductor, and even after the ion conductor is solidified, the oxygen remains or binds to any one of the elements constituting the ion conductor, thereby lowering the ion conductivity. Further, comparing examples 1, 2 and 3, the contact time of the cation exchange resin used in example 3 with oxygen in the air was longer and the ionic conductivity of the ionic conductor became lower than that of the cation exchange resin used in examples 1 and 2. From the above results, it is understood that in the production of an ion conductor, the amounts of oxygen and carbon dioxide (production atmosphere, use of a solvent, oxygen and carbon dioxide contained in an ion exchange resin) which are brought into contact during the production have a great influence on the ion conductivity of the obtained ion conductor.
[ example 4]
An embodiment of the present invention provides an apparatus for preparing an ion conductor, as shown in fig. 1, including: comprises an ultrapure water device W-1, a first closed reaction vessel 1-a, a second closed reaction vessel 1-b, a third closed reaction vessel 3-a, a separation membrane unit 2-a, a fourth closed reaction vessel 3-b, a closed ion exchange tower 4-a and a closed recovery vessel 4-b.
Specifically, in the present embodiment, the ultrapure water apparatus W-1 is used for preparing ultrapure water as a deoxygenating solvent;the first closed reaction vessel 1-a is in fluid communication with the ultrapure water device W-1 for the formation of the element M which can form cations of valence 3 or 4 3 Is dissolved by the deoxygenated solvent and is prepared as M 3 A solution of the chloride of (a); the second closed reaction vessel 1-b is in fluid communication with the first closed reaction vessel 1-a and the ultrapure water device W-1, respectively, for introducing the element M 1 The sulfide of (2) is dissolved in the deoxygenating solvent to obtain M 1 And the sulfide solution of (2), and the M 3 With the M 1 Preparation of M by mixing with sulfide solution 3 Sulfide of (A) and M 1 A suspension of chloride of (a); the third closed reaction vessel 3-a is in fluid communication with the ultrapure water device W-1 for placing M 1 The sulfide of (A) is dissolved by the deoxygenating solvent to obtain M 1 A solution of the sulfide of (a); the separation membrane unit 2-a is respectively in fluid communication with the ultrapure water device W-1, the second closed reaction vessel 1-b and the third closed reaction vessel 3-a and is used for M 3 Sulfide of (A) and M 1 The suspension of chloride of (A) is subjected to solid-liquid separation, and M is prepared 3 And a sulfide dispersion of (2) and further used for mixing M 3 The sulfide dispersion of (2) is dissolved in M 1 And preparing a solution containing the element M 1 Element M 3 1, a 1 st solution of the 1 st compound; the fourth closed reaction vessel 3-b is respectively in fluid communication with the ultrapure water device W-1 and the separation membrane unit 2-a for storing the 1 st solution to prevent the 1 st solution from deteriorating; the closed ion exchange tower 4-a is respectively communicated with the ultrapure water device W-1 and the fourth closed reaction vessel 3-b in fluid, and is used for leading the 1 st cation M in the 1 st solution to be acted by cation exchange resin 1 Exchanging for 2 nd cation to prepare 2 nd solution; the closed recovery vessel 4-b is in fluid communication with the closed ion exchange column 4-a for drying the 2 nd solution to obtain an ionic conductor.
The resin used in this example was a cation exchange resin, and an anion exchange resin may be used.
Element M 1 May be an atom or molecule that is capable of losing a monoatomic ion or molecular ion of an electron that has a positive charge. In particular, sheetThe atomic ions include hydrogen ions, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, aluminum ions, silver ions, zinc ions, and the like. The molecular ions include ammonium ion and pH 4+ Ion, H 3 O + Ion, H 2 F + Ions, mercury ions, cycloheptatriene cations, and the like. Wherein, element M of this embodiment 1 Preferably Na.
Elements M which can form cations of valency 3 or 4 3 May be one or more of Sn, as, bi, ge and Sb, and the element M in the embodiment 3 Preferably Sn.
The ion conductor in the present embodiment is preferably Li 4 SnS 4 。
The following preparation of Li by using cation exchange resin 4 SnS 4 The ionic conductor is taken as an example for explanation:
preparation system adopting ion conductor for preparing Li 4 SnS 4 In the process of ion conductor, snCl is respectively put into the first closed reaction vessel 1-a and the second closed reaction vessel 1-b 4 ·5H 2 O and Na 2 S, because the first closed reaction vessel 1-a and the second closed reaction vessel 1-b are both in fluid communication with the ultrapure water device W-1, in the first closed reaction vessel 1-a, the deoxygenated solvent and SnCl prepared by the ultrapure water device W-1 are utilized 4 ·5H 2 Obtaining SnCl from O 4 A solution of Na and a deoxygenated solvent prepared by an ultrapure water apparatus W-1 in a second closed reaction vessel 1-b 2 S to Na 2 S solution, then the SnCl is put in a second closed reaction vessel 1-b 4 The solution is mixed with the Na 2 Stirring and reacting the S solution to obtain SnS 2 Suspension of + NaCl; in a third closed reaction vessel, using a deoxygenated solvent and Na prepared by an ultrapure water apparatus 2 S to Na 2 S solution, snS is separated in the separation membrane unit 2-a 2 Filtering and separating NaCl aqueous solution in NaCl suspension to obtain SnS 2 Dispersing the obtained dispersion, and adding SnS 2 The dispersion is dissolved in Na 2 Preparation of Na in S solution 4 SnS 4 The solution is stored with Na in a fourth closed reaction vessel 4 SnS 4 Solution preventionStopping deterioration, adding Na in a sealed ion exchange column 4-a 4 SnS 4 Replacing Na ions in the solution with Li ions to obtain Li 4 SnS 4 Solution, finally to Li 4 SnS 4 Drying the solution to obtain Li 4 SnS 4 Solid powders or granules. In the above process, the preparation device is more convenient to use, and Li element, sn element and S element are exposed to O 2 The time in (2) is short, and the amounts of oxygen and carbon dioxide (preparation atmosphere, use solvent, oxygen and carbon dioxide contained in the ion exchange resin) which are contacted during the preparation of the ion conductor are reduced. Further, the combination of Li element, sn element, S element and O element can be inhibited, and Li can be increased 4 SnS 4 Thereby improving the ionic conductivity.
Specifically, in the preparation process, the first closed reaction vessel 1-a and the second closed reaction vessel 1-b are respectively charged with SnCl with a molar ratio of 1 4 ·5H 2 O and Na 2 And S, after the first closed reaction vessel 1-a and the second closed reaction vessel 1-b were evacuated and replaced with Ar gas (purity 99.99%), 80ml of ultrapure water, which was a deoxygenation solvent prepared by an ultrapure water apparatus W-1, was injected. Pressurizing the SnCl of the first closed reaction vessel 1-a by Ar gas 4 The solution is slowly conveyed to a second closed reaction vessel 1-b and stirred in the second closed reaction vessel 1-b to generate SnS 2 + NaCl suspension;
the resulting suspension liquid was transferred to the separation membrane unit 2-a of a closed vessel by Ar gas pressurization and depressurization of the separation membrane unit 2-a, and the NaCl separation unit was cleaned with deoxygenated ultrapure water supplied from an ultrapure water apparatus W-1 to obtain SnS 2 The dispersion of (4). At this time, the separated aqueous NaCl solution was discharged.
Na was charged into the third closed reaction vessel 3-a in a molar ratio of 2 2 S, after the inside of the vessel was evacuated, ar gas was replaced, and 80ml of deoxygenated ultrapure water was fed from the ultrapure water device W-1 to the 3-a, and stirred and dissolved. Transferring the solution to a 2-a container to dissolve SnS 2 Dispersing to obtain Na 4 SnS 4 And (3) solution.
Mixing Na 4 SnS 4 The solution was transferred to a fourth closed reaction vessel 3-b which had been subjected to Ar gas substitution in advance.
Na was added to the fourth closed reaction vessel 3-b 4 SnS 4 Feeding the aqueous solution into a closed ion exchange tower 4-a, and reacting the aqueous solution with Li type ion exchange resin through the closed ion exchange tower 4-a to obtain Li 4 SnS 4 An aqueous solution. Li obtained by ion exchange 4 SnS 4 The aqueous solution was recovered into a vacuum bag.
Connecting the closed recovery vessel 4-b to N 2 GAS displacement type spray dryer (Yamato science GB210+ GAS 410) and dry granulation to obtain light yellow Li 4 SnS 4 And (3) powder. The median diameter D50 in this case is about 1 μm.
Heating the obtained powder to 80-150 deg.C under Ar gas flow, drying in stages, reducing pressure, heating at 240 deg.C, stirring for 10 hr to obtain Li 4 SnS 4 An ion conductor.
Therefore, the preparation device of the ion conductor provided by the embodiment can reduce the interference of external factors, is more convenient to use, and is beneficial to improving Li 4 SnS 4 Efficiency and purity of the ion conductor.
Preferably, in the present embodiment, the ultrapure water apparatus W-1 comprises an ultrapure water storage section, a deoxidation filter OF. Specifically, the outlet end of the ultrapure water storage component is connected with a connecting pipeline, and the ultrapure water storage component is respectively in fluid communication with the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, the fourth closed reaction vessel 3-b and the closed ion exchange column 4-a through the connecting pipeline.
More specifically, the deoxidation filter OF is connected to the connection piping at the outlet OF the ultrapure water storage part in order in the flow direction OF the deoxidation solvent.
More specifically, the deoxidation filter OF is arranged at the outlet OF the ultrapure water storage component, so that the oxygen removal OF the ultrapure water can be realized, and the preparation efficiency OF the deoxidation solvent can be improved. The deoxidation filter OF is also equipped with a vacuum pump V-1.
Preferably, in this embodiment, the connection line includes a main line and a plurality of connection branch lines.
Specifically, in this embodiment, the main pipeline is communicated with the ultrapure water storage component, and the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, the fourth closed reaction vessel 3-b and the closed ion exchange column 4-a are respectively connected to the main pipeline through the corresponding connecting branch pipes.
More specifically, the number of the connecting branch pipes can be 5, and specifically as shown in FIG. 1, the connecting branch pipes comprise a branch pipe R-1, a branch pipe R-2, a branch pipe R-3, a branch pipe R-4 and a branch pipe R-5.
More specifically, the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, the fourth closed reaction vessel 3-b and the closed ion exchange column 4-a are respectively connected to the main pipeline through the corresponding connecting branch pipes, so that the interference of the backflow of reactants in the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, the fourth closed reaction vessel 3-b and the closed ion exchange column 4-a caused by the interference of Li can be avoided 4 SnS 4 The preparation process of (1).
Preferably, in this embodiment, the deoxygenating filter OF is provided with a first filter connected to the main line.
By adopting the technical scheme, the deoxidation filter OF is provided with the first filter connected with the main pipeline, so that the deoxidation work can be realized by utilizing the filter, and the use is more convenient.
Preferably, in this embodiment, at least the connection branch of the separation membrane unit 2-a, the closed ion exchange column 4-a is provided with a pressure pump TP-3 therein.
By adopting the technical scheme, the pressure pump TP-3 is arranged in the connecting branch pipe of the separation membrane unit 2-a and the closed ion exchange tower 4-a, so that the flow of fluid among the reaction units is facilitated, and the Li is further accelerated 4 SnS 4 The preparation process of (1).
Preferably, in the present embodiment, the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, and the fourth closed reaction vessel 3-b are equipped with a stirrer ST.
By adopting the technical scheme, the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a and the fourth closed reaction vessel 3-b are respectively provided with the stirrer ST, so that reactants in the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a and the fourth closed reaction vessel 3-b are uniformly mixed, and the preparation efficiency is improved.
Preferably, in this embodiment, the closed recovery vessel 4-b includes a dryer for drying Li 4 SnS 4 Drying the solution to obtain Li 4 SnS 4 And (3) powder.
Preferably, in this embodiment, the closed recovery vessel 4-b further comprises a heating means and a storage means; the heating member is used for heating Li 4 SnS 4 Heating the powder to obtain Li 4 SnS 4 An ion conductor; the storage part is of vacuum structure and is used for storing Li 4 SnS 4 The ion conductor stores.
Specifically, li is stored by setting the storage part to a vacuum structure 4 SnS 4 Ion conductors so as to avoid Li 4 SnS 4 The ion conductor is oxidized.
More specifically, in this embodiment, the storage component is provided as a vacuum bag.
In this embodiment, the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, the separation membrane unit 2-a, and the fourth closed reaction vessel 3-b may be provided as containers.
More specifically, in the embodiment, a first closed reaction vessel 1-a, a second closed reaction vessel 1-b, a third closed reaction vessel 3-a, a separation membrane unit 2-a, and a fourth closed reaction vessel 3-b are all subjected to a vacuum pumping process, and then injected into ultrapure water prepared by an ultrapure water apparatus W-1.
More specifically, in this embodiment, the first closed reaction vessel 1-a, the second closed reaction vessel 1-b, the third closed reaction vessel 3-a, and the separation membrane unit 2-a are reaction vessels, and the fourth closed reaction vessel 3-b is a storage vessel.
Preparation system adopting ion conductor for preparing Li 4 SnS 4 The ion conductor comprises the following steps:
the first step is as follows: snS 2 Preparation of
The user will add 0.01mol of SnCl 4 ·5H 2 O was charged into the first closed reaction vessel 1-a, and 0.02mol of Na was added 2 S is put into a second closed reaction vessel 1-b, and the inside of the first closed reaction vessel 1-a and the second closed reaction vessel 1-b are evacuated and replaced with Ar gas (purity 99.99%). The ultrapure water was deoxidized by an ultrapure water apparatus W-1 to obtain deoxidized ultrapure water. Respectively conveying 80ml of unit deoxygenation solvent into a first closed reaction vessel 1-a and a second closed reaction vessel 1-b, stirring to make SnCl 4 、Na 2 And S is dissolved. Pressurizing SnCl in a first closed reaction vessel 1-a by Ar gas 4 The solution is slowly conveyed to a second closed reaction vessel 1-b and stirred in the second closed reaction vessel 1-b to generate SnS 2 + NaCl suspension. SnS is pressurized by Ar gas and depressurized by the container separation membrane unit 2-a 2 The suspension of NaCl is sent to the separation membrane unit 2-a in a closed vessel to carry out the liquid phase synthesis reaction. A second filter is arranged in the separation membrane unit 2-a of the closed container, and after the reaction is finished, a reaction product in the second filter is cleaned by using a deoxygenation solvent to obtain SnS 2 The dispersion of (4). The aqueous NaCl solution separated from the filter was removed.
In the NaCl separation step, the filter washing method of the present invention can reduce the variation in the mixture ratio and the amount of residual chloride by such adjustment, and can suppress the change in the chlorine content of Li and Sn and the change in the ion exchange into Li 4 SnS 4 Residual Cl - 。
The second step: na (Na) 4 SnS 4 Preparation of the solution
0.02mol of Na was charged into the reaction vessel 3-a 2 And S, vacuumizing the reaction container 3-a, and then performing Ar gas replacement. 80ml of the deoxygenated solvent was supplied from the ultrapure water device W-1 to the reaction vessel 3-a and dissolved therein with stirring. Transferring the solution to a separation membrane unit 2-a container to dissolve SnS 2 Dispersing to obtain Na 4 SnS 4 Solution of Na sufficiently dissolved 4 SnS 4 The solution was transferred to the storage container 3-b previously subjected to Ar gas substitution.
The third step: li 4 SnS 4 Preparation of the aqueous solution
Storing the container in Na in the container 3-b 4 SnS 4 Feeding the aqueous solution into a closed ion exchange column 4-a, and performing ion exchange reaction with Li type ion exchange resin to obtain Li 4 SnS 4 An aqueous solution. Li obtained by ion exchange 4 SnS 4 The aqueous solution was recovered into a vacuum bag.
The fourth step: li 4 SnS 4 Preparation of the powder
Connecting a vacuum bag to N 2 Drying and granulating in a GAS displacement spray dryer (GB 210+ GAS410, manufactured by Yamato science) to obtain light yellow Li 4 SnS 4 And (3) powder. The median diameter D50 at this time was 1 μm.
The fifth step: li 4 SnS 4 Preparation of ion conductor
The obtained Li 4 SnS 4 Heating the powder to 80-150 deg.C under Ar gas flow, drying in stages, reducing pressure, and heating at 240 deg.C under stirring for 10 hr to obtain Li 4 SnS 4 An ion conductor.
Prior art JP 2019-102355, li after ion exchange 4 SnS 4 The solution is concentrated, freeze-dried and powdered, but this process usually takes about 60 hours. In the present invention, the ion-exchanged solution is treated with N 2 Spray drying granulation is directly carried out in the air atmosphere, so that the time is shortened to about 2 hours.
By usingThe preparation system of the ion conductor is used for preparing Li 4 SnS 4 In the case of an ion conductor, the following may be used: li was prepared in the same manner as in the above example except that only ultrapure water was subjected to deoxidation treatment and the vessel was not replaced with an inert gas 4 SnS 4 An ion conductor.
Li may be produced in the same manner as in the above-mentioned examples, except that the inert gas is replaced only in the vessel and that the deoxidation treatment is not performed on ultrapure water 4 SnS 4 An ion conductor.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more detailed description of the invention, taken in conjunction with the specific embodiments thereof, and that no limitation of the invention is intended thereby. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention, which also falls within the part of the invention.
Claims (10)
1. A method for producing an ion conductor, characterized in that a 1 st compound having a 1 st cation and a 1 st anion as a counter ion thereof is dissolved in a solvent to form a 1 st solution, at least a part of the 1 st cation or the 1 st anion in the 1 st compound is exchanged with a2 nd cation or a2 nd anion by an ion exchange method to obtain a2 nd compound, the 2 nd compound is dissolved in the solvent to obtain a2 nd solution containing an ion conductor, the solvent contains a deoxygenated solvent, and the production of the ion conductor is carried out without contacting air.
2. The method for producing an ion conductor according to claim 1, wherein the solvent contains water.
3. The method of claim 2, wherein the solvent has a dissolved oxygen concentration of less than 8mg-O/L.
4. The method for producing an ion conductor according to any one of claims 1 to 3, further comprising a drying step of removing the solvent from the 2 nd solution to obtain an ion conductor.
5. The method for producing an ion conductor according to any one of claims 1 to 4, which uses CO containing less than 1000ppm of oxygen 2 An inert atmosphere in an amount of less than 100 ppm.
6. The ion conductor prepared by the preparation method according to any one of claims 1 to 5, having a median particle diameter D50 of 0.05 to 500 μm.
7. An apparatus for preparing an ionic conductor, comprising:
an ultrapure water apparatus for preparing ultrapure water as a deoxygenation solvent;
a first closed reaction vessel in fluid communication with the ultrapure water device for carrying out SnCl 4 ·5H 2 O is dissolved by the deoxidizing solvent, and SnCl is prepared 4 A solution;
a second closed reaction vessel, which is respectively in fluid communication with the first closed reaction vessel and the ultrapure water device and is used for introducing Na 2 S is dissolved by the deoxygenated solvent to obtain Na 2 S solution, and adding the SnCl 4 Solution with said Na 2 S solution mixing preparation SnS 2 Suspension of + NaCl;
a third closed reaction vessel in fluid communication with the ultrapure water device for reacting Na 2 S is dissolved by the deoxidizing solvent to obtain Na 2 S solution;
a separation membrane unit in fluid communication with the ultrapure water device, the second closed reaction vessel and the third closed reaction vessel, respectively, for pairing SnS 2 Filtering and separating NaCl suspensionDissociating and preparing SnS 2 A dispersion liquid for adding Na in the third closed reaction vessel 2 Introducing S solution into the reactor and mixing with SnS 2 Reaction to prepare Na 4 SnS 4 Taking the solution as a 1 st solution;
a fourth closed reaction vessel, which is respectively in fluid communication with the ultrapure water device and the separation membrane unit, and is used for storing the 1 st solution and preventing the 1 st solution from deteriorating;
a closed ion exchange column in fluid communication with the ultrapure water device and the fourth closed reaction vessel, respectively, for reacting Na 4 SnS 4 Na ions in the solution are exchanged for Li ions, and Li is prepared under the action of Li type ion exchange resin 4 SnS 4 The solution is used as a2 nd solution;
a closed recovery vessel in fluid communication with the closed ion exchange column for Li-rejection 4 SnS 4 Li obtained after drying of the solution 4 SnS 4 Solid powders or granules are stored.
8. The apparatus for preparing an ionic conductor according to claim 7, wherein the ultrapure water device comprises an ultrapure water storage section and a deoxidation filter; wherein the content of the first and second substances,
the outlet end of the ultrapure water storage component is connected with a connecting pipeline, and the ultrapure water storage component is respectively in fluid communication with the first closed reaction vessel, the second closed reaction vessel, the third closed reaction vessel, the separation membrane unit, the fourth closed reaction vessel and the closed ion exchange tower through the connecting pipeline;
the deoxidation filter is connected to the connecting pipeline at the outlet of the ultrapure water storage component.
9. The apparatus for preparing an ionic conductor according to claim 8, further comprising an inert gas tank; wherein the content of the first and second substances,
the first closed reaction container, the second closed reaction container, the third closed reaction container, the separation membrane unit and the fourth closed reaction container are respectively connected with the inert gas tank through pipelines.
10. The apparatus for preparing an ionic conductor according to claim 8, further comprising a vacuum pump,
the first closed reaction vessel, the second closed reaction vessel, the third closed reaction vessel, the separation membrane unit and the fourth closed reaction vessel are respectively connected with the vacuum pump pipeline.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024116887A1 (en) * | 2022-11-30 | 2024-06-06 | オルガノ株式会社 | Sns2 production method and use method |
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| WO2024116887A1 (en) * | 2022-11-30 | 2024-06-06 | オルガノ株式会社 | Sns2 production method and use method |
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