WO2021241479A1 - Procédé de production de phosphate de lithium-germanium - Google Patents

Procédé de production de phosphate de lithium-germanium Download PDF

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WO2021241479A1
WO2021241479A1 PCT/JP2021/019533 JP2021019533W WO2021241479A1 WO 2021241479 A1 WO2021241479 A1 WO 2021241479A1 JP 2021019533 W JP2021019533 W JP 2021019533W WO 2021241479 A1 WO2021241479 A1 WO 2021241479A1
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source
germanium
solvent
phosphate
firing
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PCT/JP2021/019533
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Japanese (ja)
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純也 深沢
透 畠
拓馬 加藤
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日本化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing lithium germanium phosphate, which is useful as a solid electrolyte.
  • oxide-based solid electrolyte for example, garnet type oxide, NASICON type oxide, perovskite type oxide and the like are being studied.
  • Phosphate-based oxides having a NASICON structure are stable in the atmosphere, and in particular, lithium aluminum phosphate (LAGP) in which a part of germanium of lithium germanium phosphate is replaced with an Al element is lithium. It is one of the materials attracting attention as a solid electrolyte because of its high ionic conductivity (see, for example, Patent Documents 1 to 3).
  • LAGP lithium aluminum phosphate
  • a method for producing LAGP for example, a method of mixing lithium carbonate, germanium dioxide, aluminum oxide and ammonium phosphate and firing the mixture in the air to obtain LAGP by a solid phase reaction (for example, Patent Documents 1 to 3). ) Is disclosed. Further, the following Patent Document 4, as the germanium source, with GeO 2, the GeO 2 are dissolved in water with ammonia or the like, water-soluble Li source solution, obtained by containing Al source and P source A method of removing a solvent from a raw material mixed solution, then performing heat treatment to obtain amorphous LAGP, and then firing to crystallize LAGP and the like is disclosed.
  • JP-A-2019-149298 claim 1, paragraphs 0019-0020 Japanese Unexamined Patent Publication No. 2013-157195, claim 1, paragraph 0042 JP-A-2009-140911, claim 6, paragraph 0044 JP-A-2019-46559, claim 1
  • Patent Documents 1 to 3 it is difficult to obtain a raw material mixture in which a germanium source and a phosphorus source are uniformly mixed. There is a problem that it is difficult to obtain an advantage. Further, the method of Patent Document 4 is not industrially advantageous because the process tends to be complicated and problems of waste liquid and waste gas treatment are likely to occur.
  • an object of the present invention is to provide a method for producing lithium germanium phosphate capable of obtaining single-phase germanium phosphate lithium by X-ray diffraction by an industrially advantageous method.
  • the present inventors have used phosphorous acid as the P source, and the Li source, the M source, the Ge source and the P source are dissolved or dispersed in the solvent.
  • phosphorous acid as the P source
  • the Li source, the M source, the Ge source and the P source are dissolved or dispersed in the solvent.
  • monophasic germanium-lithium phosphate can be easily obtained by X-ray diffraction.
  • germanium lithium phosphate when phosphoric acid is used as the P source, rapid volume expansion occurs during firing, but when phosphoric acid is used as the P source, rapid volume expansion occurs during firing. It is possible to obtain monophasic germanium-lithium phosphate by a mild firing reaction without any volume expansion.
  • it has been found that the strong adhesion of lithium germanium phosphate after firing to the crucible can be suppressed and recovery can be facilitated depending on the firing conditions. It came to be completed.
  • the present invention (1) has the following general formula (1): Li 1 + x M x Ge 2-x (PO 4 ) 3 (1) (In the formula, 0.0 ⁇ x ⁇ 1.0, M is one or more than two selected from Al, Ga, Sc, Y, La, Fe, Cr, Ni, Mn, In and Co. Indicates a valent or trivalent metal element.) It is a method for producing germanium lithium phosphate having a NASICON structure represented by. The first step of preparing a raw material mixture in which the Li source, the M source, the Ge source, and the P source are dissolved or dispersed in a solvent, and the raw material mixture is heat-treated to prepare the solvent in the raw material mixture.
  • the present invention provides a method for producing lithium germanium phosphate, which is characterized by the above.
  • the present invention (2) provides the method for producing lithium germanium phosphate according to (1), wherein the Ge source is germanium dioxide.
  • a dissolution step of heating a slurry containing germanium dioxide, an organic acid, and a solvent to obtain a solution of germanium dioxide is performed, and then the solution of germanium dioxide is used.
  • the present invention (4) provides the method for producing germanium lithium phosphate of (3), which is characterized in that the organic acid is a carboxylic acid.
  • the present invention (5) is characterized in that, in the third step, at least the reaction precursor is fired at 600 to 1000 ° C., according to any one of (1) to (4). It provides a manufacturing method of.
  • the reaction precursor in the third step, is calcinated at 350 to 550 ° C., and then the calcination is performed at 600 to 1000 ° C.
  • the present invention provides the method for producing germanium lithium phosphate according to any one of (1) to (4).
  • the present invention (7) is characterized in that M in the formula of the general formula (1) is Al and the M source is an Al source, according to any one of (1) to (6). It provides a method for producing lithium germanium acid.
  • the present invention (8) provides the method for producing germanium lithium phosphate (7), which is characterized in that the Al source is alumina.
  • the method for producing lithium germanium phosphate of the present invention is described in the following general formula (1): Li 1 + x M x Ge 2-x (PO 4 ) 3 (1) (In the formula, 0.0 ⁇ x ⁇ 1.0, M is one or more than two selected from Al, Ga, Sc, Y, La, Fe, Cr, Ni, Mn, In and Co. Indicates a valent or trivalent metal element.) It is a method for producing germanium lithium phosphate having a NASICON structure represented by.
  • That the P source is phosphorous acid, It is a method for producing lithium germanium phosphate, which is characterized by the above.
  • the germanium lithium phosphate obtained by the method for producing lithium germanium phosphate of the present invention has the following general formula (1) :. Li 1 + x M x Ge 2-x (PO 4 ) 3 (1) (In the formula, 0.0 ⁇ x ⁇ 1.0, M is one or more than two selected from Al, Ga, Sc, Y, La, Fe, Cr, Ni, Mn, In and Co. Indicates a valent or trivalent metal element.) It is a germanium lithium phosphate having a NASICON structure represented by.
  • x is 0.0 ⁇ x ⁇ 1.0, preferably 0.1 ⁇ x ⁇ 0.5, and particularly preferably 0.2 ⁇ x ⁇ 0.4.
  • M in the formula of the general formula (1) is a metal element contained for the purpose of improving the performance such as lithium ion conductivity.
  • M is a divalent or trivalent metal element, and represents one or more metal elements selected from Al, Ga, Sc, Y, La, Fe, Cr, Ni, Mn, In and Co.
  • Al is particularly preferable.
  • a Li source, an M source, a Ge source and a P source are mixed with a solvent and stirred to obtain a Li source, an M source, a Ge source and a P source.
  • a step of preparing a raw material mixture by dissolving or dispersing in a solvent is not particularly limited.
  • Li source according to the first step examples include lithium hydroxide, lithium carbonate, lithium oxide, lithium organic acid and the like, and among these, lithium hydroxide can be present in a state of being dissolved in an aqueous solvent. , Preferable from the viewpoint of industrial availability.
  • Examples of the M source according to the first step include oxides containing M elements, hydroxides, carbonates, organic acid salts, nitrates, phosphates and the like.
  • the M element is Al
  • the Al source is alumina (Al 2 O 3 ), which is industrially easily available, has excellent reactivity, and there is little concern about residual impurities. Is preferable.
  • Examples of the Ge source according to the first step include germanium sulfate, germanium chloride, germanium nitrate, potassium germanium acid, germanium dioxide and the like.
  • Germanium dioxide is particularly industrially available, has excellent reactivity, and is also excellent in reactivity. It is preferable from the viewpoint that there is little concern about residual impurities.
  • the P source related to the first step is phosphorous acid.
  • Phosphorous acid is not particularly limited as long as it is industrially available.
  • Phosphorous acid may be an aqueous solution.
  • the production history of the Li source, the M source, the Ge source and the P source does not matter, but in order to produce high-purity germanium lithium phosphate, it is preferable that the impurity content is as low as possible.
  • those insoluble in the solvent preferably have an average particle size of 10 ⁇ m or less obtained by the laser diffraction method in order to enhance the reactivity of the reaction precursor, preferably 0.1. It is particularly preferably ⁇ 5 ⁇ m.
  • the solvent according to the first step may be a water solvent or a mixed solvent of water and a hydrophilic organic solvent.
  • the hydrophilic organic solvent is not particularly limited as long as it is inert to the raw material, and examples thereof include alcohols such as ethanol, propanol and butanol, and methyl ethyl ketone.
  • the mixing ratio of water and the hydrophilic organic solvent is appropriately selected.
  • the concentration of phosphorous acid in the raw material mixture is 1.4 to 1.8 mol / L, preferably 1.5 to 1.7 mol / L in terms of P atom. Further, by adjusting the contents of the Li source, the M source and the Ge source in the raw material mixture so as to have the composition of the general formula (1), the Li atom in the Li source and the M atom in the M source can be adjusted. It is preferable to appropriately adjust the molar ratio of Ge atoms in the Ge source and P atoms in the P source.
  • the Li source, M source, Ge source and P source are dissolved or dispersed in a solvent.
  • the raw material mixture may be in the form of a slurry or in the form of a solution in which each raw material is dissolved in a solvent.
  • the concentration of the solid content in the raw material mixture is preferably 30 to 70% by mass, particularly preferably 40 to 60% by mass. Since the concentration of the solid content in the raw material mixture is in the above range, the reaction efficiency is high and the viscosity of the slurry is not too high.
  • germanium dioxide is used as the Ge source in the method for producing lithium germanium phosphate of the present invention
  • germanium dioxide is dissolved in an aqueous solvent or an aqueous solvent, and a solution in which the Ge source is dissolved in the solvent is used. It is particularly preferable to use it from the viewpoint that a reaction precursor having further excellent reactivity can be obtained.
  • the first step as a method of using a solution in which the Ge source is dissolved in an aqueous solvent, a dissolution step of dissolving germanium dioxide in an aqueous solvent or an aqueous solvent to obtain a solution of germanium dioxide is performed, and then germanium dioxide is obtained.
  • a method of performing the first step by mixing a Li source, an M source and a P source with an aqueous solution to prepare a raw material mixed solution can be mentioned.
  • the method for producing lithium germanium phosphate of the present invention using a solution in which germanium dioxide obtained in the dissolution step is dissolved in an aqueous solvent or an aqueous solvent is less likely to cause problems in the treatment of waste water and waste gas, and this It is particularly preferable to use a solution in which the Ge source is dissolved in an aqueous solvent from the viewpoint that a reaction precursor having further enhanced reactivity of the Ge source can be obtained.
  • the first step as a method of using a solution in which the Ge source is dissolved in an aqueous solvent or an aqueous solvent, a slurry containing germanium dioxide, an organic acid, and a solvent is heated to obtain a solution of germanium dioxide.
  • a slurry containing germanium dioxide, an organic acid, and a solvent is heated to obtain a solution of germanium dioxide.
  • the first step is carried out by performing the obtaining dissolution step and then mixing the Li source, the M source and the P source with the solution of germanium dioxide to prepare a raw material mixture.
  • Examples of the organic acid involved in the dissolution step include monocarboxylic acids such as formic acid, acetic acid, glycolic acid, lactic acid and gluconic acid, dicarboxylic acids such as oxalic acid, maleic acid, malonic acid, malic acid, tartrate acid and succinic acid, and carboxyl.
  • Carous acids such as citric acid having 3 groups can be mentioned, and these may be used alone or in combination of two or more.
  • oxalic acid has excellent solubility in an aqueous solvent, has a high ability to dissolve germanium dioxide, and is easily decomposed by firing in the third step described later, and can be easily removed from the reaction system. Is preferable.
  • the amount of the organic acid added is 4 to 8, preferably 5 to 7, in terms of the molar ratio of C atoms in the organic acid to germanium dioxide (C / GeO 2 ), which rapidly dissolves germanium dioxide in an aqueous solvent. It can also be preferable from the viewpoint of economic efficiency.
  • the solvent involved in the dissolution step may be a water solvent or a mixed solvent of water and a hydrophilic organic solvent (also referred to as an aqueous solvent).
  • the hydrophilic organic solvent is not particularly limited as long as it is inert to the raw material, and examples thereof include alcohols such as ethanol, propanol and butanol, and methyl ethyl ketone.
  • an aqueous solvent a mixed solvent of water and a hydrophilic organic solvent
  • the mixing ratio of water and the hydrophilic organic solvent is appropriately selected.
  • the amount of germanium dioxide added in the dissolution step is 10 to 40 parts by mass, preferably 20 to 30 parts by mass with respect to 100 parts by mass of the solvent, from the viewpoint of preventing the reaction efficiency and the viscosity increase of the slurry. preferable.
  • the heating temperature in the melting step is preferably 40 to 90 ° C, preferably 50 to 80 ° C, from the viewpoint of increasing the melting rate. Further, the heating time in the melting step is not critical in the melting step, but preferably 1 hour or more, particularly preferably 1 to 3 hours, and germanium dioxide having various physical properties is dissolved in an aqueous solvent. It is preferable in that the dissolved solution can be obtained.
  • the dissolution step is performed in the first step according to the method for producing lithium germanium phosphate of the present invention
  • the "dissolution solution in which germanium dioxide is dissolved in an aqueous solvent or an aqueous solvent" obtained in the dissolution step after the dissolution step is performed.
  • a predetermined amount of Li source, M source and P source are added and stirred, or the like, to prepare a raw material mixed solution.
  • the temperature at which the Li source, the M source, and the P source are added to the solution in which the germanium dioxide obtained in the dissolution step is dissolved in an aqueous solvent or an aqueous solvent is not particularly limited and may be room temperature. Further, in the melting step, the Li source, the M source and the P source may be added in a state where the temperature is maintained as it is without cooling the solution, or up to the temperature of the heat treatment in the second step described later. After raising the temperature of the solution, or in the process of raising the temperature, Li source, M source and P source may be added.
  • the second step is a step of preparing a reaction precursor by heat-treating the raw material mixture obtained in the first step to remove at least a part of the solvent in the raw material mixture.
  • the raw material mixture obtained in the first step is heat-treated to remove at least a part of the solvent in the raw material mixture to obtain a paste-like reaction precursor.
  • the pasty state means a viscous state. Therefore, in the present invention, it is not necessary to remove all the solvents in the reaction precursor in the second step.
  • the content of the solvent in the reaction precursor is 30% by mass or less, preferably 20% by mass or less, a paste-like reaction precursor having satisfactory physical properties can be obtained.
  • the heating temperature in the heat treatment according to the second step is not particularly limited as long as the solvent can be removed, but usually 100 to 150 ° C., preferably 110 to 140 ° C., efficiently removes the water solvent. It is preferable from the viewpoint of
  • the heating time in the heat treatment in the second step is not particularly limited, and may be performed until the raw material mixture becomes a paste. Although it depends on the raw material concentration of the raw material mixture and the heating temperature in the heat treatment, for example, when the raw material concentration of the raw material mixture is 40 to 60% by mass and the heating temperature in the heat treatment is 120 to 130 ° C., heating is performed.
  • the time is preferably 1 hour or more, preferably 1 to 4 hours, so that a paste-like reaction precursor having satisfactory physical properties can be obtained.
  • the third step is a step of calcining the reaction precursor obtained in the second step to obtain germanium lithium phosphate.
  • the reaction precursor is calcined at 600 to 1000 ° C., preferably 650 to 850 ° C., which facilitates obtaining single-phase germanium lithium phosphate represented by the general formula (1).
  • the reaction precursor is calcined at 600 to 1000 ° C., preferably 650 to 850 ° C., which facilitates obtaining single-phase germanium lithium phosphate represented by the general formula (1).
  • the reason for this is that when the firing temperature is lower than the above temperature, the synthesis of germanium lithium phosphate represented by the general formula (1) tends to be insufficient, and when the temperature exceeds the above temperature, the general formula ( This is because the particle growth of germanium lithium phosphate represented by 1) progresses, and it tends to be difficult to obtain fine particles.
  • the calcination time for calcination of the reaction precursor is not particularly limited, and calcination is performed for a sufficient time to generate germanium lithium phosphate represented by the general formula (1) by X-ray diffraction. ..
  • the time for firing the reaction precursor at 600 to 1000 ° C., preferably 650 to 850 ° C. is 3 hours or more, preferably 3 to 10 hours, which is satisfactory.
  • a fired product having various physical properties can be obtained.
  • the firing atmosphere for firing the reaction precursor is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the atmosphere.
  • firing may be performed once, or may be performed a plurality of times if desired.
  • firing for the purpose of making the powder characteristics uniform, what has been fired once may be crushed and then fired again.
  • lithium germanium phosphate may adhere to the pit during firing in the third step, making it difficult to recover the target product.
  • the reaction precursor in the third step, is fired at a low temperature and then at a high temperature, so that the lithium germanium phosphate adheres to the pit during firing. It is industrially advantageous because it can be suppressed and the target germanium-lithium phosphate can be easily recovered from a pit or the like.
  • a third step (hereinafter referred to as a third step) of performing a temporary firing in which the reaction precursor is fired at 350 to 550 ° C. and then a main firing in which the reaction precursor is fired at 600 to 1000 ° C. It is also described as the first form of.).
  • the firing temperature of the temporary firing in the first embodiment of the third step is 350 to 550 ° C, preferably 400 to 550 ° C, particularly preferably 450 to 550 ° C, so that the paste-like reaction precursor can be solidified. Moreover, it is preferable from the viewpoint that it does not firmly adhere to the container and can maintain peelability. Further, the firing time of the temporary firing in the first embodiment of the third step is not particularly limited, and the firing time is 3 hours or more, preferably 3 to 10 hours, so that a temporary firing product having various physical properties can be obtained. It is preferable in that it can be done.
  • the firing atmosphere of the temporary firing in the first embodiment of the third step is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the atmosphere.
  • the compound contained in the calcination product has a complicated reaction and is unknown, but at least when the calcination product is subjected to X-ray diffraction analysis, some crystalline product is obtained. Diffraction peaks are observed.
  • the crystals detected by the X-ray diffraction analysis differ depending on the temperature of the calcination, but in the first embodiment of the third step, when the calcination is performed within a preferable temperature range of the calcination, the above general formula ( other phosphate germanium lithium represented by 1), GEP 2 O 7, Li -M- composite oxide of phosphorus (e.g., crystalline material such as LIMP 2 O 7, etc.) is contained.
  • the calcination product is cooled to room temperature and the obtained calcination product is pulverized or crushed to make each component uniform. It is preferable in that it is easy to be fired.
  • the method of crushing treatment and crushing treatment is not particularly limited, and a conventional method can be used.
  • the crushing treatment and the crushing treatment may be a dry treatment or a wet treatment.
  • the wet pulverizer include a ball mill and a bead mill.
  • the dry crushing device include known crushing or crushing devices such as jet mills, pin mills, roll mills, ball mills, and bead mills. Further, at the laboratory level, crushing or crushing with a household mixer, a mortar, or the like is sufficient.
  • the main firing is performed after the temporary firing.
  • the temporarily fired product is mainly fired at 600 to 1000 ° C., preferably 650 to 850 ° C., which is a single-phase phosphoric acid represented by the general formula (1). It is preferable in that it becomes easy to obtain germanium lithium.
  • the reason for this is that if the firing temperature in the main firing is lower than the above range, the synthesis of germanium lithium phosphate represented by the general formula (1) tends to be insufficient, and if it exceeds the above range, it tends to be insufficient. This is because the growth of particles of germanium lithium phosphate represented by the general formula (1) progresses, and it tends to be difficult to obtain fine particles.
  • the calcination time of the main calcination in the first embodiment of the third step is not particularly limited, and it is necessary to sufficiently carry out until the single-phase lithium germanium phosphate represented by the general formula (1) is obtained. ..
  • the firing time is 600 to 1000 ° C., preferably 650 to 850 ° C., and the firing time is 3 hours or more, preferably 3 to 10 hours.
  • the firing atmosphere of the main firing in the first embodiment of the third step is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the atmosphere.
  • the temporary firing and the main firing may be performed once, or may be performed a plurality of times if desired.
  • the one that has been main-baked once may be crushed and then the main-baking may be performed again.
  • the third step after firing, it is appropriately cooled and crushed, crushed, classified, etc. as necessary to obtain the desired germanium lithium phosphate represented by the general formula (1).
  • One of the features of the method for producing germanium lithium phosphate of the present invention is that phosphorous acid is used as a P source.
  • phosphoric acid is used as the P source, phosphoric acid is easily dehydrated and condensed by heating, and is preferentially dehydrated and condensed over the reaction with each raw material. Therefore, for example, it is prepared using phosphoric acid as the P source.
  • the reaction precursor is heat-treated at, for example, 210 ° C or 500 ° C, a substantially amorphous one is obtained (see FIGS. 2 and 4).
  • the reaction precursor prepared by using phosphorous acid as the P source is heat-treated at, for example, 210 ° C.
  • the volume expansion of the heat-treated product is suppressed when the reaction precursor is heat-treated, as compared with the case where phosphoric acid is used as the P source.
  • the dehydration reaction proceeds by heat treatment to generate polyphosphoric acid, which is a viscous liquid. Is confined in the highly viscous liquid of polyphosphoric acid and becomes a foaming state, and it is considered that rapid volume expansion occurs.
  • the germanium lithium phosphate represented by the general formula (1) obtained by the method for producing lithium germanium phosphate of the present invention is X-ray diffractically monophasic. Further, the germanium lithium phosphate represented by the general formula (1) obtained by the method for producing lithium germanium phosphate of the present invention has an average particle size of preferably 0.5 to 10 ⁇ m, which is particularly preferably obtained by a laser diffraction method. Is 1 to 5 ⁇ m, and the BET specific surface area is preferably 1 to 15 m 2 / g, particularly preferably 2 to 10 m 2 / g, from the viewpoint of excellent powder properties and easy handling.
  • the germanium lithium phosphate obtained by the method for producing lithium germanium phosphate of the present invention is suitably used as a solid electrolyte, a positive electrode, or a negative electrode material for a secondary battery.
  • Alumina was wet pulverized by a ball mill to prepare an alumina slurry used in Examples.
  • the prepared alumina slurry had a solid content concentration of 8% by mass, and the average particle size of the solid content determined by the laser diffraction method was 1.3 ⁇ m.
  • LAGP Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 (hereinafter referred to as "LAGP") having a NASICON structure>
  • LAGP ⁇ Adjustment of Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 (hereinafter referred to as "LAGP") having a NASICON structure>
  • LAGP NASICON structure
  • Example 2 This fired product was obtained in the same manner as in Example 1 except that the temperature of the temporary firing in the third step was set to 250 ° C. No volume expansion was observed in the temporarily fired product.
  • the heat-resistant container was inverted and scraped out with a spatula, so that the tentatively fired product could be easily recovered.
  • the whole sticking to the alumina crucible was observed after the main firing, the whole amount of the main fired product was recovered by scraping off with a spatula, and the main fired product was obtained by crushing with a mortar.
  • the presence of a different phase such as GeP 2 O 7 was not confirmed, and it was confirmed that it was a single-phase LAGP.
  • Example 3 This fired product was obtained in the same manner as in Example 1 except that the temperature of the temporary firing in the third step was set to 400 ° C. No volume expansion was observed in the temporarily fired product.
  • the heat-resistant container was inverted and scraped out with a spatula, so that the tentatively fired product could be easily recovered.
  • the whole amount of the main fired product was recovered by scraping off the fixed portion with a spatula, and the main fired product was obtained by crushing with a mortar.
  • a different phase such as GeP 2 O 7 was not confirmed, and it was confirmed that it was a single-phase LAGP.
  • Example 4 This fired product was obtained in the same manner as in Example 1 except that the temperature of the temporary firing in the third step was set to 500 ° C.
  • the calcined product could be easily recovered by reversing the heat-resistant container. No volume expansion was observed in the temporarily fired product. Further, the recovered calcined product was crushed in a mortar to obtain a crushed product.
  • the X-ray diffraction diagram of the obtained pulverized product is shown in FIG. Diffraction peaks of GeP 2 O 7 and LiAlP 2 O 7 were confirmed in the calcined product in addition to LATP as crystalline products.
  • the entire contents could be easily recovered by reversing the alumina crucible and scraping it with a spatula. Then, it was pulverized in a mortar to obtain this baked product.
  • a different phase such as GeP 2 O 7 was not confirmed, and it was confirmed that it was a single-phase LAGP.
  • Example 5 A main fired product was obtained in the same manner as in Example 1 except that the temperature of the temporary firing in the third step was 500 ° C. and the temperature of the main firing was 700 ° C. No volume expansion was observed in the temporarily fired product.
  • the heat-resistant container was inverted and scraped out with a spatula, so that the tentatively fired product could be easily recovered.
  • the contents could be easily recovered by reversing the alumina crucible for recovery after the main firing. Then, it was pulverized in a mortar to obtain this baked product.
  • a different phase such as GeP 2 O 7 was not confirmed, and it was confirmed that it was a single-phase LAGP.
  • ⁇ Second step> After the addition of the raw material, the heater output was increased as it was, and heating was continued, and the mixture was concentrated until the liquid temperature reached 120 ° C. to obtain 200 g of a paste-like reaction precursor. It took 3 hours for the liquid temperature to reach 120 ° C. The solvent content of the paste-like reaction precursor was measured by the dry weight loss method and found to be 17% by mass.
  • the calcined product could be easily recovered by reversing the heat-resistant container.
  • the recovered calcined product was crushed in a mortar to obtain a crushed product.
  • the X-ray diffraction pattern of the obtained pulverized product is shown in FIG.
  • the calcined product was amorphous.
  • 5 g of the obtained pulverized product was placed in an alumina crucible and subjected to main firing in an electric furnace at an atmospheric atmosphere at 800 ° C. for 4 hours to obtain a main fired product. Further, in the recovery after the main firing, the entire contents could be easily recovered by reversing the alumina crucible. Then, it was pulverized in a mortar to obtain this baked product.
  • a diffraction peak of GeP 2 O 7 was confirmed in addition to LAGP (see FIG. 3).
  • Comparative Example 2 In Comparative Example 1, the main fired product was obtained in the same manner as in Comparative Example 1 except that the temperature of the temporary firing was set to 500 ° C. After the calcining, the calcined product was recovered by natural cooling to room temperature. Volume expansion was observed in the temporarily fired product. For recovery, the calcined product could be easily recovered by reversing the heat-resistant container. Next, the recovered calcined product was crushed in a mortar to obtain a crushed product. The X-ray diffraction pattern of the obtained pulverized product is shown in FIG. The calcined product was almost amorphous.

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Abstract

L'objet de la présente invention est de fournir un procédé industriellement avantageux pour produire du phosphate de lithium-germanium qui peut donner un phosphate de lithium-germanium qui est une phase unique conformément à la diffraction par rayons X.　La présente invention concerne un procédé de production de phosphate de lithium-germanium ayant une structure NASICON et donnée par la formule générale (1) : Li1+xMxGe2-x(PO4)3 (dans la formule, 0,0 < x ≤ 1,0 et M représente un ou deux ou plusieurs éléments métalliques divalents ou trivalents sélectionnés parmi Al, Ga, Sc, Y, La, Fe, Cr, Ni, Mn, In et Co), le procédé de production de phosphate de lithium-germanium étant caractérisé en ce qu'il comprend une première étape destinée à préparer une solution mixte de produits de départ dans laquelle une source de Li, une source de M, une source de Ge et une source de P sont dissoutes ou dispersées dans un solvant ; une deuxième étape destinée à préparer un précurseur de réaction par traitement thermique de la solution mixte de produits de départ pour éliminer au moins une partie du solvant dans la solution mixte de produits de départ ; et une troisième étape destinée à cuire le précurseur de réaction, la source de P étant de l'acide phosphoreux.
PCT/JP2021/019533 2020-05-28 2021-05-24 Procédé de production de phosphate de lithium-germanium WO2021241479A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013077563A (ja) * 2011-09-16 2013-04-25 Toyota Central R&D Labs Inc リチウム二次電池用電極材、その製造方法、およびそれを備えるリチウム二次電池
JP2013125750A (ja) * 2011-12-13 2013-06-24 Samsung Electronics Co Ltd 保護負極、これを含むリチウム空気電池及びこれを含む全固体電池
JP2019085275A (ja) * 2017-11-01 2019-06-06 スズキ株式会社 固体電解質及び固体電解質の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013077563A (ja) * 2011-09-16 2013-04-25 Toyota Central R&D Labs Inc リチウム二次電池用電極材、その製造方法、およびそれを備えるリチウム二次電池
JP2013125750A (ja) * 2011-12-13 2013-06-24 Samsung Electronics Co Ltd 保護負極、これを含むリチウム空気電池及びこれを含む全固体電池
JP2019085275A (ja) * 2017-11-01 2019-06-06 スズキ株式会社 固体電解質及び固体電解質の製造方法

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