WO2025197831A1 - Procédé de production d'électrolyte solide au sulfure, procédé de production de batterie rechargeable au lithium-ion et électrolyte solide au sulfure - Google Patents

Procédé de production d'électrolyte solide au sulfure, procédé de production de batterie rechargeable au lithium-ion et électrolyte solide au sulfure

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Publication number
WO2025197831A1
WO2025197831A1 PCT/JP2025/010117 JP2025010117W WO2025197831A1 WO 2025197831 A1 WO2025197831 A1 WO 2025197831A1 JP 2025010117 W JP2025010117 W JP 2025010117W WO 2025197831 A1 WO2025197831 A1 WO 2025197831A1
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WO
WIPO (PCT)
Prior art keywords
solid electrolyte
sulfide solid
producing
electrolyte according
heat treatment
Prior art date
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Pending
Application number
PCT/JP2025/010117
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English (en)
Japanese (ja)
Inventor
秀悦 関
佑輝 福冨
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2025197831A1 publication Critical patent/WO2025197831A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • 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 sulfide solid electrolyte, a method for manufacturing a lithium-ion secondary battery, and a sulfide solid electrolyte.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and laptop computers. While liquid electrolytes have traditionally been used in lithium-ion secondary batteries, all-solid-state lithium-ion secondary batteries, which use solid electrolytes as the electrolyte, have been attracting attention due to their potential for improved safety, high-speed charging and discharging, and smaller casings.
  • a solid electrolyte used in all-solid-state lithium-ion secondary batteries is a sulfide solid electrolyte. While sulfide solid electrolytes exhibit high lithium ion conductivity, they are prone to generating hydrogen sulfide when in contact with water.
  • Patent Document 1 discloses that the generation of hydrogen sulfide can be suppressed by using a crystalline material containing a predetermined proportion of N.
  • the document discloses a sulfide solid electrolyte that is a crystalline material and has a composition represented by the general formula xLi 2 S-25P 2 S 5 -yLi 3 N (10 ⁇ y ⁇ 15, 67.5 ⁇ x+y ⁇ 85).
  • Patent Document 2 discloses that a sulfide solid electrolyte in which N is suppressed from being discharged outside the system can be produced by reacting Li 3 N with AlN to obtain a stable intermediate, and then mixing the intermediate with other raw materials and calcining the mixture.
  • Li 3 N is highly reactive and is classified as a hazardous material that reacts with water and becomes flammable. Therefore, special care must be taken when handling it. Furthermore, when using Li 3 N, if one tries to suppress the volatilization of N, it is necessary to go through an intermediate as described in Patent Document 2, which increases the number of steps and reduces efficiency.
  • a method for producing a sulfide solid electrolyte containing Li, P, M, S, and N comprising: The method includes, in order, heat-treating raw materials containing Li, P, and S, and a nitride represented by the formula M ⁇ N ⁇ to obtain a melt; and cooling the melt to precipitate a solid,
  • the element represented by M is at least one selected from the group consisting of metal elements and metalloid elements of Groups 2 to 14 of the periodic table,
  • the sulfide solid electrolyte further contains Ha
  • the raw materials further include a raw material containing Ha
  • [5] The method for producing a sulfide solid electrolyte according to any one of [1] to [4], wherein the element represented by M is at least one selected from the group consisting of Si, Al, and B.
  • [6] The method for producing a sulfide solid electrolyte according to any one of [1] to [5], wherein the nitride represented by the formula M ⁇ N ⁇ includes Si 3 N 4 .
  • [7] The method for producing a sulfide solid electrolyte according to any one of [1] to [6], wherein the nitride represented by the formula M ⁇ N ⁇ is a powder having a specific surface area of 30 m 2 /g or more.
  • [15] The method for producing a sulfide solid electrolyte according to any one of [1] to [14], further comprising performing a post-heat treatment by heating after precipitating the solid.
  • [16] The method for producing a sulfide solid electrolyte according to [15], wherein the post-heat treatment is performed at 150 to 400°C.
  • [17] The method for producing a sulfide solid electrolyte according to [15] or [16], wherein the post-heat treatment is performed in an atmosphere with a dew point of ⁇ 20° C. or lower.
  • the sulfide solid electrolyte further contains Ha as the constituent element, The sulfide solid electrolyte according to [20], wherein the element represented by Ha is a halogen element.
  • the sulfide solid electrolyte is represented by the composition formula: Li a PSi b Sc N d Ha e , The sulfide solid electrolyte according to [20] or [21], wherein 3.00 ⁇ a ⁇ 3.60, 0.07 ⁇ b ⁇ 0.33, 3.40 ⁇ c ⁇ 3.60, 0.10 ⁇ d ⁇ 0.45, and 0 ⁇ e ⁇ 0.53 are satisfied.
  • the element represented by Ha is Br and I
  • the sulfide solid electrolyte is represented by the composition formula: Li a PSi b Sc N d Br e1 I e2
  • a desired sulfide solid electrolyte can be efficiently produced with a reduced number of steps while suppressing volatilization of N, without using Li 3 N as a source of N.
  • the obtained sulfide solid electrolyte can achieve high lithium ion conductivity and good water resistance due to the introduction of nitrogen element.
  • FIG. 1 is a flow diagram showing one embodiment of the method for producing a sulfide solid electrolyte according to the present embodiment.
  • FIG. 2 is a flow diagram showing one aspect of the method for producing a sulfide solid electrolyte according to this embodiment.
  • FIG. 3 is a flow diagram showing one aspect of the method for producing a sulfide solid electrolyte according to this embodiment.
  • FIG. 4 is an XRD pattern of the solid obtained in Example 5.
  • FIG. 5 shows the DSC curves of the solids obtained in Examples 5 and 6.
  • the production method is a method for producing a sulfide solid electrolyte containing Li, P, M, S, and N, and includes the following steps in order, as shown in FIG. 1 .
  • Step S1 A process of heat-treating raw materials containing Li, P, and S, and a nitride represented by the formula M ⁇ N ⁇ to obtain a melt.
  • Step S2 A process of cooling the melt obtained in step S1 to precipitate a solid.
  • the element represented by M is at least one selected from the group consisting of metal elements and metalloid elements of groups 2 to 14 of the periodic table.
  • ⁇ and ⁇ in the above formula M ⁇ N ⁇ respectively correspond to the stoichiometric ratio of M and N in the nitride represented by the formula M ⁇ N ⁇ .
  • step S1 may include the following steps S1a and S1b.
  • Step S1a A process of mixing raw materials containing Li, P, and S, and a nitride represented by the formula M ⁇ N ⁇ to obtain a raw material mixture.
  • Step S1b A process of heat-treating the raw material mixture obtained in step S1a to obtain a melt.
  • the resulting sulfide solid electrolyte may further contain Ha.
  • the raw materials in step S1 include raw materials containing Li, P, and S, as well as raw materials containing Ha.
  • Ha refers to a halogen element, and examples include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).
  • the manufacturing method according to this embodiment may further include the following step S3 after the above step S2.
  • Step S3 After the solid is precipitated in step S2, a post-heat treatment is further performed by heating.
  • Step S1 in this embodiment is a process of obtaining a melt by heat-treating raw materials containing Li, P, and S, and a nitride represented by the formula M ⁇ N ⁇ .
  • the raw materials may further contain a raw material containing Ha from the viewpoint of improving lithium ion conductivity, etc.
  • each of the raw materials containing Li, P, and S includes one or more raw materials containing one or more elements selected from the group consisting of Li, P, and S.
  • a raw material containing Ha may also be included.
  • the element represented by M is at least one selected from the group consisting of metal elements or metalloid elements of Groups 2 to 14 of the periodic table, and ⁇ and ⁇ in the formula M ⁇ N ⁇ respectively correspond to the stoichiometric ratio of M and N in the nitride represented by the formula M ⁇ N ⁇ .
  • Ha is a halogen element, and examples thereof include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).
  • raw materials containing lithium element (Li) include lithium compounds such as lithium sulfide ( Li2S ), lithium iodide (LiI), lithium carbonate ( Li2CO3 ), lithium sulfate ( Li2SO4 ), lithium oxide (Li2O ) , and lithium hydroxide (LiOH), as well as metallic lithium, etc.
  • Li2S lithium sulfide
  • LiI lithium iodide
  • Li2CO3 lithium carbonate
  • Li2SO4 lithium sulfate
  • Li2O lithium oxide
  • LiOH lithium hydroxide
  • One type of raw material containing lithium element (Li) may be used, or two or more types may be used in combination.
  • lithium sulfide As a raw material containing lithium element (Li), it is preferable to use lithium sulfide from the viewpoint of obtaining a sulfide material. Furthermore, if the resulting sulfide solid electrolyte contains a halogen element (Ha), it is also preferable to use lithium halide (LiHa) as a raw material containing lithium element (Li). Lithium halide will be described later.
  • raw materials containing phosphorus P
  • substances containing P such as elemental P or compounds containing P
  • P can be used in appropriate combinations.
  • One type of raw material containing phosphorus (P) can be used, or two or more types can be used in combination.
  • raw materials containing phosphorus (P) include phosphorus sulfides such as diphosphorus pentasulfide ( P2S5 ) and diphosphorus trisulfide ( P2S3 ), phosphorus compounds such as sodium phosphate ( Na3PO4 ), and elemental phosphorus, etc. From the viewpoint of obtaining a sulfide material , it is preferable to use phosphorus sulfide as the raw material containing phosphorus (P), and it is more preferable to use diphosphorus pentasulfide.
  • P2S5 diphosphorus pentasulfide
  • P2S3 diphosphorus trisulfide
  • phosphorus compounds such as sodium phosphate ( Na3PO4 )
  • elemental phosphorus etc. From the viewpoint of obtaining a sulfide material , it is preferable to use phosphorus sulfide as the raw material containing phosphorus (P), and it is more preferable to use diphosphorus pent
  • raw material containing elemental sulfur As the raw material containing elemental sulfur (S), an appropriate combination of substances containing S, such as simple S or compounds containing S, can be used.
  • the raw material containing elemental sulfur (S) may be used alone or in combination of two or more.
  • Examples of raw materials containing elemental sulfur (S) include phosphorus sulfides such as diphosphorus pentasulfide (P 2 S 5 ) and diphosphorus trisulfide (P 2 S 3 ), alkali metal sulfides such as Li 2 S, other phosphorus-containing sulfur compounds, elemental sulfur, and compounds containing sulfur.
  • Examples of compounds containing sulfur include H 2 S, CS 2 , iron sulfides (FeS, Fe 2 S 3 , FeS 2 , Fe 1-x S, etc.), bismuth sulfide (Bi 2 S 3 ), and copper sulfides (CuS, Cu 2 S, Cu 1-x S, etc.).
  • Li 2 S is a compound that serves as both a raw material containing sulfur element (S) and the above-mentioned raw material containing lithium element (Li).
  • P 2 S 5 is a compound that serves as both a raw material containing sulfur element (S) and the above-mentioned raw material containing phosphorus element (P).
  • Examples of raw materials containing a halogen element (Ha) that can be used optionally include lithium halides (LiHa) such as lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), and lithium iodide (LiI), phosphorus halides, phosphoryl halides, sulfur halides, sodium halides, and boron halides.
  • lithium halides are preferred from the viewpoint of preventing the inclusion of elements other than those constituting the target sulfide solid electrolyte. These compounds may be used alone or in combination of two or more.
  • the halogen element may be introduced as a hydrogen halide or halogen gas, or when Ha is Br or I, it may be introduced as Br2 or I2 .
  • Ha preferably contains at least one of Br and I, and preferably contains both.
  • the element represented by M in the nitride represented by the formula M ⁇ N ⁇ is at least one selected from the group consisting of metal elements or metalloid elements of Groups 2 to 14 of the periodic table.
  • the element represented by M is preferably at least one selected from the group consisting of metal elements or metalloid elements of Groups 3 to 14 of the periodic table, more preferably at least one selected from the group consisting of metal elements or metalloid elements of Groups 4 to 14 of the periodic table, and even more preferably at least one selected from the group consisting of metal elements or metalloid elements of Groups 13 to 14 of the periodic table.
  • at least one selected from the group consisting of Si, Al, and B is even more preferable, and Si is particularly preferable.
  • M ⁇ N ⁇ , ⁇ and ⁇ are values that correspond to the stoichiometric ratio of M and N in the nitride.
  • the nitride is silicon nitride, represented by Si 3 N 4 , where ⁇ is 3 and ⁇ is 4.
  • M silicon
  • Al the nitride is aluminum nitride, represented by AlN, where ⁇ is 1 and ⁇ is 1.
  • M is B
  • the nitride is boron nitride, represented by BN, where ⁇ is 1 and ⁇ is 1.
  • the nitride represented by the formula M ⁇ N ⁇ is more preferably at least one selected from the group consisting of Si 3 N 4 , AlN and BN, and particularly preferably Si 3 N 4 .
  • Patent Document 1 uses an intermediate obtained by reacting Li 3 N with a highly stable nitride such as AlN.
  • the present invention has discovered that the effect of improving water resistance by introducing N can be suitably obtained by obtaining a sulfide solid electrolyte through a melt produced by heating, even when a nitride represented by the above formula M ⁇ N ⁇ , which has high chemical stability, is used instead of Li 3 N, which is highly reactive and difficult to handle.
  • a nitride represented by the above formula M ⁇ N ⁇ which has high chemical stability
  • Li 3 N which is highly reactive and difficult to handle.
  • N is not introduced due to its high chemical stability.
  • the specific surface area of the nitride represented by the formula M ⁇ N ⁇ is preferably 15 to 50 m 2 /g, more preferably 25 to 40 m 2 /g. From the viewpoint of preventing the nitride from remaining unmelted during heating, increasing reactivity, and obtaining a sulfide solid electrolyte of a desired composition, the specific surface area is preferably 15 m 2 /g or more, more preferably 25 m 2 /g or more, and even more preferably 35 m 2 /g or more. Furthermore, from the viewpoint of suppressing raw material scattering, the specific surface area is preferably 50 m 2 /g or less, more preferably 40 m 2 /g or less. In this specification, the specific surface area of the nitride refers to the specific surface area determined by the nitrogen adsorption BET multipoint method.
  • the raw materials of the sulfide solid electrolyte in this embodiment contain Li 2 S and P 2 S 5 , and the nitride contains Si 3 N 4 , and it is more preferable that the raw materials contain Li 2 S, P 2 S 5 , and at least one of LiBr and LiI, and the nitride contains Si 3 N 4 .
  • each raw material may further contain a raw material containing an element other than the above-mentioned Li, P, S, and optionally Ha, as long as the effect of the present invention is not impaired.
  • the above-mentioned other element may be an element represented by M, i.e., a metal element or semimetal element from Groups 2 to 14 of the periodic table.
  • Other elements include, for example, tin (Sn), antimony (Sb), germanium (Ge), indium (In), copper (Cu), silicon (Si), aluminum (Al), boron (B), etc. Conventional raw materials containing these elements can be used.
  • the sulfide solid electrolyte obtained by the manufacturing method according to this embodiment is used in lithium-ion secondary batteries.
  • sodium (Na) or potassium (K) may be used instead of lithium (Li).
  • conventionally known raw materials containing Na or K can be used.
  • the raw materials containing Li, P, and S and the nitride represented by the formula M ⁇ N ⁇ may be mixed to obtain a raw material mixture in step S1a as described above.
  • the raw materials can be mixed with the nitride by any conventional method known in the art. For example, mixing in a mortar, mixing using media such as a planetary ball mill, or medialess mixing such as a pin mill, powder mixer, or airflow mixing can be used.
  • the raw materials may be made amorphous by mixing as described above.
  • the mixed raw materials and nitride may be added to the container sequentially or simultaneously.
  • a melt is obtained by the heat treatment in step S1 or step S1b.
  • the specific method for obtaining a melt by heat treatment is not particularly limited.
  • the raw materials and the nitride, or a mixture of these raw materials are placed in a heat-resistant container and heated in a heating furnace.
  • the heat-resistant container may be a heat-resistant container made of carbon, a heat-resistant container containing an oxide such as quartz, quartz glass, borosilicate glass, aluminosilicate glass, alumina, zirconia, or mullite, a heat-resistant container containing a nitride such as silicon nitride or boron nitride, or a heat-resistant container containing a carbide such as silicon carbide.
  • These heat-resistant containers may be made of the above materials in bulk, or may be containers with a layer of carbon, oxide, nitride, carbide, or the like, such as a carbon-coated quartz tube.
  • the furnace body used in the heating process can be any conventionally known furnace with a heating section, and the material and size of the furnace body can be selected as desired.
  • the temperature of the heat treatment is not particularly limited as long as the raw materials and nitrides, or raw material mixture, are melted and a melt is obtained, but is preferably 600 ° C or higher, more preferably 600 to 1000 ° C, even more preferably 630 to 950 ° C, even more preferably 650 ° C or higher but less than 900 ° C, even more preferably 650 to 850 ° C, and particularly preferably 650 ° C or higher but less than 850 ° C.
  • the melt consisting of components other than the nitride to be melted becomes liquid, and the temperature of the heat treatment is preferably 600 ° C or higher, more preferably 630 ° C or higher, and even more preferably 650 ° C or higher.
  • the temperature of heat melting is preferably 1000 ° C or lower, more preferably 950 ° C or lower, even more preferably less than 900 ° C, even more preferably 850 ° C or lower, and particularly preferably less than 850 ° C.
  • the temperature of the heat treatment is the temperature of the molten material produced in the furnace, and can be adjusted by a heating unit provided in the furnace.
  • the heat treatment is preferably performed in an inert atmosphere.
  • inert atmospheres include a nitrogen gas atmosphere, an argon gas atmosphere, and a helium gas atmosphere.
  • the heat treatment may be performed in a gas atmosphere containing sulfur (S).
  • gas atmosphere containing sulfur element (S) include a mixed gas atmosphere of a gas containing sulfur element (S), such as sulfur gas, hydrogen sulfide gas, or sulfur dioxide gas, and an inert gas.
  • the dew point during the heat treatment is preferably -20°C or lower in order to prevent side reactions between the melt and water vapor, oxygen, etc.
  • the lower limit of the dew point is not particularly limited, but is usually about -80°C.
  • the oxygen concentration during the heat treatment is preferably 1000 ppm by volume or less.
  • the pressure during the heat treatment is not particularly limited as long as the raw materials and nitrides, or the raw material mixture, are melted, but atmospheric pressure or slight pressure is preferred, with atmospheric pressure being more preferred.
  • the heat treatment is preferably carried out under one or more of the following conditions: an atmosphere containing S; a heating temperature of 600 to 1000°C; a heating time of 10 to 600 minutes; an atmosphere with a dew point of -20°C or lower; and an atmosphere with an oxygen concentration of 1000 ppm by volume or lower; more preferably under two or more of these conditions; even more preferably under three or more of these conditions; still more preferably under four or more of these conditions; and particularly preferably under all five of these conditions. It is also more preferable to carry out heating at 600 to 1000° C. for 10 to 600 minutes.
  • step S1 or step S1b whether each raw material and nitride, or the raw material mixture, is completely melted can be confirmed by the absence of peaks derived from crystals in high-temperature X-ray diffraction measurement.
  • the melt may contain a compound that will become a crystal nucleus in order to facilitate precipitation of a solid in the subsequent step S2.
  • the method for incorporating a compound that will become a crystal nucleus into a melt is not particularly limited, but examples thereof include a method of adding a compound that will become a crystal nucleus to raw materials, and a method of directly adding the compound that will become a crystal nucleus to a melt that is being heat-treated.
  • Compounds that can serve as crystal nuclei include oxides, oxynitrides, nitrides, carbides, other chalcogen compounds, and halides.
  • Compounds that can serve as crystal nuclei are preferably compounds that have a certain degree of compatibility with the melt. Compounds that are completely incompatible with the melt cannot serve as crystal nuclei.
  • Step S2 in this embodiment is a step of cooling the melt obtained in step S1 or step S1b to precipitate a solid.
  • the solid obtained in step S2 may be used as the sulfide solid electrolyte, or the solid obtained by the subsequent post-heat treatment in step S3 may be used as the sulfide solid electrolyte.
  • the solid precipitated by the cooling in step S2 may be a crystalline phase or an amorphous phase, or may contain both a crystalline phase and an amorphous phase.
  • the solid phase state is determined by the ratio of each raw material and nitride added, that is, the target composition, the cooling rate, and the like.
  • the solid obtained by the manufacturing method according to this embodiment varies depending on the raw materials and nitride, but when raw materials containing Li, P, S, and Ha and a nitride represented by the formula M ⁇ N ⁇ are used, a solid represented by the composition formula Li a' PM b' S c' N d' Ha e' is obtained, where a' to e' are the content ratios (atomic ratios) of Li, M, S, N, and Ha, respectively, based on the content ratio of P.
  • M may be one element or two or more elements.
  • Ha is optional, and when Ha is contained, it may be one element or two or more elements.
  • step S2 the molten material obtained in step S1 or step S1b is discharged at any time, for example, from an outlet provided in the furnace body, and the process proceeds to cooling and solidifying.
  • Any known method can be used to cool the molten material, and there are no particular restrictions. For example, from the perspective of increasing the cooling rate, cooling using twin rollers, which is generally considered to have the fastest rapid cooling rate, is preferred.
  • the cooling rate is preferably 1,000 to 100,000°C/sec. From the perspective of improving compositional homogeneity and minimizing quality variation, the cooling rate is preferably 1,000°C/sec or higher, more preferably 3,000°C/sec or higher, and even more preferably 5,000°C/sec or higher. There are no particular restrictions on the upper limit of the cooling rate, but taking into account the cooling rate of twin rollers, which are generally said to have the fastest quenching rate, the upper limit is 1,000,000°C/sec or lower. From the perspective of practical production, the cooling rate is more preferably 100,000°C/sec or lower, even more preferably 80,000°C/sec or lower, and even more preferably 50,000°C/sec or lower.
  • the atmosphere during cooling is preferably a low-moisture, inert atmosphere, similar to that during the heat treatment in step S1 or step S1b.
  • under atmospheric pressure means that the pressure is not controlled during cooling. Specifically, it is about 0.8 to 1.2 atm.
  • Step S3 in this embodiment is an optional step of performing post-heat treatment by heating again after the solid is precipitated in step S2.
  • the post-heat treatment can improve the lithium ion conductivity of the resulting sulfide solid electrolyte.
  • the post-heat treatment in step S3 promotes crystallization if the solid obtained in step S2 contains an amorphous phase.
  • the post-heat treatment may also rearrange the ions within the crystal structure to increase lithium ion conductivity.
  • the post-heat treatment refers to at least one of a heat treatment for crystallizing the obtained solid and a heat treatment for rearranging ions within the crystal structure.
  • the temperature for post-heat treatment is preferably 150 to 400°C, more preferably 150 to 350°C, and even more preferably 180 to 300°C. From the perspective of optimally obtaining the effects of post-heat treatment and shortening the time for post-heat treatment, the temperature for post-heat treatment is preferably 150°C or higher, and more preferably 180°C or higher. Furthermore, from the perspective of preventing unintended crystal precipitation, the temperature for post-heat treatment is preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.
  • the post-heat treatment time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 5 hours, and even more preferably 10 minutes to 1 hour.
  • the post-heat treatment time is preferably 10 minutes or more, and is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 1 hour or less.
  • the post-heat treatment is preferably carried out in an inert atmosphere, such as a nitrogen gas atmosphere, an argon gas atmosphere, or a helium gas atmosphere.
  • the dew point during post-heat treatment is preferably -20°C or lower, and although there is no particular lower limit, it is usually about -80°C.
  • the oxygen concentration during the post-heat treatment is preferably 1000 ppm by volume or less.
  • the post-heat treatment is preferably carried out under one or more of the following conditions: a heating temperature of 150 to 400°C, a heating time of 10 minutes to 10 hours, in an atmosphere with a dew point of -20°C or lower, and in an atmosphere with an oxygen concentration of 1000 ppm by volume or lower; more preferably under two or more of these conditions; even more preferably under three or more of these conditions; and particularly preferably under all four of these conditions. It is also more preferable to heat the mixture at 150 to 400° C. for 10 minutes to 10 hours.
  • the method for manufacturing a lithium ion secondary battery according to this embodiment includes a step of interposing a sulfide solid electrolyte between a positive electrode and a negative electrode.
  • the sulfide solid electrolyte may be one obtained by the method described in "Method of Producing a Sulfide Solid Electrolyte.”
  • a sulfide solid electrolyte that has undergone post-heat treatment in step S3 may be preferably used.
  • the positive and negative electrodes each consist of an active material, a current collector, and optionally a conductive additive and binder, but may also contain an electrode mixture containing a sulfide solid electrolyte.
  • a conventional method can be used to interpose the sulfide solid electrolyte between the positive and negative electrodes.
  • an additive such as a binder can be added to the sulfide solid electrolyte to form a sulfide solid electrolyte layer, which can then be interposed between the positive and negative electrodes.
  • the binder may be any conventionally known material, such as butadiene rubber, acrylate butadiene rubber, styrene butadiene rubber, polyvinylidene fluoride, or polytetrafluoroethylene.
  • the amount of binder contained in the sulfide solid electrolyte layer is not particularly limited, and can be within the range of conventionally known binders.
  • the sulfide solid electrolyte according to this embodiment contains Li, P, S, M, and N as constituent elements.
  • the constituent elements may further contain Ha, and may further contain other elements.
  • Ha refers to a halogen element, such as fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • a sulfide solid electrolyte By manufacturing using the method described above in "Method for manufacturing sulfide solid electrolyte," a sulfide solid electrolyte can be obtained in which the ratio of M to N among the constituent elements is higher than in conventional cases.
  • the ratio of the content proportions represented by b'/d' is higher than that of conventionally known sulfide solid electrolytes.
  • This ratio can be, for example, 0.5 or more, and may be 0.5 to 1.
  • the ratio may be 0.5 or more, 0.6 or more, 0.7 or more, or 0.75 or more.
  • the upper limit is not particularly limited, but may be, for example, 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, or 0.8 or less.
  • the element represented by M is two or more kinds, the total content ratio of these elements is defined as b'.
  • the resulting sulfide solid electrolyte is represented by the composition formula: Li a PSi b Sc N d Ha e , where Ha is optional.
  • the atomic ratio of P among the constituent elements of the sulfide solid electrolyte is taken to be 1, with the Si content represented by b and the N content represented by d.
  • the ratio of the content proportions represented by b/d can be, for example, 0.5 to 1, and the ratio may be 0.6 to 0.95, or 0.65 to 0.9.
  • the ratio may be 0.5 or more, 0.6 or more, 0.65 or more, 0.7 or more, 1 or less, 0.95 or less, or 0.9 or less.
  • the sulfide solid electrolyte represented by the composition formula: Li a PSi b Sc N d Ha e preferably contains Ha, that is, the content ratio represented by e is preferably greater than 0, from the viewpoint of increasing lithium ion conductivity.
  • Ha is preferably at least one selected from the group consisting of Cl, Br, and I, more preferably Br or I, and even more preferably contains both Br and I.
  • the content ratio of each constituent element in the sulfide solid electrolyte represented by the composition formula: Li a PSi b Sc N d Ha e is, for example, 2.00 ⁇ a ⁇ 4.50, or 2.50 ⁇ a ⁇ 4.00, or 3.00 ⁇ a ⁇ 3.60 for Li.
  • a is, for example, 2.00 or more, 2.50 or more, or 3.00 or more, or 4.50 or less, 4.00 or less, or 3.60 or less.
  • Si for example, 0.01 ⁇ b ⁇ 1.00, 0.05 ⁇ b ⁇ 0.50, 0.07 ⁇ b ⁇ 0.35, or 0.07 ⁇ b ⁇ 0.33 may be satisfied.
  • d is, for example, 0.01 or more, 0.07 or more, 0.09 or more, or 0.10 or more, or 1.33 or less, 0.67 or less, 0.47 or less, or 0.45 or less.
  • Ha for example, 0 ⁇ e ⁇ 0.60, 0 ⁇ e ⁇ 0.58, 0.50 ⁇ e ⁇ 0.55, 0 ⁇ e ⁇ 0.53, or 0.50 ⁇ e ⁇ 0.53, where e is, for example, 0 or more, more than 0, 0.50 or more, 0.60 or less, 0.58 or less, 0.55 or less, or 0.53 or less.
  • Li a PSi b Sc N d Ha e may satisfy, for example, 2.00 ⁇ a ⁇ 4.50, 0.01 ⁇ b ⁇ 1.00, 3.00 ⁇ c ⁇ 4.20, 0.01 ⁇ d ⁇ 1.33, and 0 ⁇ e ⁇ 0.60, and may satisfy, for example, 2.50 ⁇ a ⁇ 4.00, 0.05 ⁇ b ⁇ 0.50, 3.20 ⁇ c ⁇ 4.00, 0.07 ⁇ d ⁇ 0.67, and , 0 ⁇ e ⁇ 0.58, 3.00 ⁇ a ⁇ 3.60, 0.07 ⁇ b ⁇ 0.35, 3.40 ⁇ c ⁇ 3.80, 0.09 ⁇ d ⁇ 0.47, and 0.50 ⁇ e ⁇ 0.55, or 3.00 ⁇ a ⁇ 3.60, 0.07 ⁇ b ⁇ 0.33, 3.40 ⁇ c ⁇ 3.60, 0.10 ⁇ d ⁇ 0.45, and 0 ⁇ e ⁇ 0.53.
  • the composition formula Li a PSi b Sc N d Ha e
  • the total content ratio of these elements is e.
  • Br is, for example, 0 ⁇ e1 ⁇ 0.55, or may be 0.20 ⁇ e1 ⁇ 0.40, or 0.30 ⁇ e1 ⁇ 0.34.
  • e1 is, for example, greater than 0, may be 0.20 or more, or may be 0.30 or more, or may be 0.55 or less, 0.40 or less, or 0.34 or less.
  • I for example, 0 ⁇ e2 ⁇ 0.55, 0.10 ⁇ e2 ⁇ 0.40, or 0.19 ⁇ e2 ⁇ 0.23 may be satisfied.
  • e2 is, for example, greater than 0, 0.10 or more, 0.19 or more, 0.55 or less, 0.40 or less, or 0.23 or less.
  • One embodiment of the combination of the above e1 and e2 with the content ratios of other constituent elements a, b, c, and d is the same as the combination of a, b, c, d, and e described above, but with e replaced by e1 and e2. That is, for example, the following conditions are satisfied: 3.00 ⁇ a ⁇ 3.60, 0.07 ⁇ b ⁇ 0.35, 3.40 ⁇ c ⁇ 3.80, 0.09 ⁇ d ⁇ 0.47, 0.30 ⁇ e1 ⁇ 0.34, and 0.19 ⁇ e2 ⁇ 0.23.
  • the sulfide solid electrolyte according to this embodiment may be in a crystalline phase or an amorphous phase, or may contain both a crystalline and an amorphous phase.
  • the above phase state is determined by the ratio of each raw material and nitride added, i.e., the composition of the sulfide solid electrolyte, the cooling rate, etc.
  • part or all of the amorphous phase may be converted to a crystalline phase.
  • the crystal structure of the crystalline phase is not particularly limited, but examples include argyrodite type, LPS type, and LGPS type. It may also be a Li-P-S-Ha type crystallized glass type.
  • the phase state and composition of the sulfide solid electrolyte can be identified by analyzing the elemental composition using various methods, such as crystal structure analysis by X-ray diffraction (XRD) measurement, ICP emission spectrometry measurement, atomic absorption spectrometry measurement, and ion chromatography measurement.
  • XRD X-ray diffraction
  • ICP emission spectrometry measurement atomic absorption spectrometry measurement
  • ion chromatography measurement ion chromatography measurement.
  • P, S, and M can be measured by ICP emission spectrometry, Li by atomic absorption spectrometry, and Ha by ion chromatography.
  • the N content can be determined by sealing the sample together with Cu in a Sn capsule under an Ar atmosphere and using an oxygen, nitrogen, and hydrogen analyzer (EMGA-930 manufactured by Horiba, Ltd.).
  • the sulfide solid electrolyte obtained by the manufacturing method according to this embodiment is used in lithium-ion secondary batteries.
  • sodium (Na) or potassium (K) may be used instead of lithium (Li).
  • Na or K can be identified by, for example, atomic absorption spectrometry.
  • the secondary particle diameter of the sulfide solid electrolyte according to this embodiment is preferably small from the viewpoint of obtaining good ionic conductivity when used in a secondary battery.
  • the secondary particle diameter is preferably 10 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 1 ⁇ m or less.
  • the lower limit of the secondary particle diameter is not particularly limited, but is usually 0.1 ⁇ m or more.
  • the secondary particle size can be measured using a Microtrac device.
  • the lithium ion conductivity of the sulfide solid electrolyte according to this embodiment at 25°C is preferably 0.1 x 10-3 S/cm or more, more preferably 1 x 10-3 S/cm or more, and even more preferably 2 x 10-3 S/cm or more, with the higher the better.
  • the lithium ion conductivity can be measured by an AC impedance method.
  • the value is measured using an AC impedance measuring device (for example, a potentiostat/galvanostat VSP manufactured by Bio-Logic Sciences Instruments) under the following conditions: measurement frequency: 100 Hz to 1 MHz, measurement voltage: 100 mV, and measurement temperature: 25°C.
  • an AC impedance measuring device for example, a potentiostat/galvanostat VSP manufactured by Bio-Logic Sciences Instruments
  • measurement frequency 100 Hz to 1 MHz
  • measurement voltage 100 mV
  • measurement temperature 25°C.
  • the sulfide solid electrolyte according to this embodiment is suitable for use in electrode mixtures and solid electrolyte layers used in secondary batteries, and is particularly suitable for all-solid-state secondary batteries, and more suitable for all-solid-state lithium-ion secondary batteries. That is, the electrode mixture is used in a secondary battery and contains the sulfide solid electrolyte and an active material.
  • the solid electrolyte layer is used in a secondary battery and contains the sulfide solid electrolyte.
  • the electrode mixture, solid electrolyte layer, and all-solid-state lithium-ion secondary battery may further contain other solid electrolytes in addition to the sulfide solid electrolyte according to this embodiment.
  • the active material contained in the electrode mixture can be a conventionally known material.
  • the positive electrode active material is not particularly limited as long as it can reversibly absorb and release alkali metal ions, desorb and insert (intercalate) alkali metal ions, or dope and dedope counter anions of the alkali metal ions.
  • the alkali metal ions are preferably lithium ions.
  • Specific examples of the positive electrode active material include lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, composite metal oxides, and polyanion olivine type positive electrodes.
  • the negative electrode active material is not particularly limited as long as it can reversibly absorb and release alkali metal ions, desorb and insert (intercalate) alkali metal ions, or dope and dedope counter anions of the alkali metal ions.
  • the alkali metal ions are preferably lithium ions.
  • Specific examples of the negative electrode active material include lithium metal, carbonaceous materials such as graphite, hard carbon, and soft carbon, metals capable of forming alloys with lithium such as aluminum, silicon, and tin, amorphous oxides such as silicon oxide and tin oxide, and lithium titanate.
  • the solid electrolyte layer may contain the sulfide solid electrolyte according to this embodiment, but may also contain other solid electrolytes and additives such as a binder.
  • a binder Any conventionally known binder can be used, such as butadiene rubber, acrylate butadiene rubber, styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, etc.
  • the content of the binder in the solid electrolyte layer may also be within a conventionally known range.
  • the all-solid-state secondary battery is not particularly limited as long as it includes a positive electrode and a negative electrode in addition to the sulfide solid electrolyte according to this embodiment.
  • the positive electrode and the negative electrode may be an electrode mixture containing the sulfide solid electrolyte according to this embodiment.
  • the positive electrode active material can be the same as the positive electrode active material described in the electrode mixture, and the positive electrode may further contain a positive electrode current collector, a binder, a conductive additive, etc.
  • the positive electrode current collector can be made of aluminum, an alloy thereof, a thin metal plate of stainless steel, etc.
  • the negative electrode active material can be the same as the negative electrode active material described in the electrode mixture, and the negative electrode may further contain a negative electrode current collector, binder, conductive additive, etc. as necessary.
  • the negative electrode current collector can be a thin metal plate such as copper or aluminum.
  • Example 1 Under a dry nitrogen gas atmosphere, each raw material and nitride were weighed and mixed in a mortar to obtain a raw material mixture. Specifically, the following molar ratios were used: 56.8 mol% lithium sulfide powder (manufactured by Sigma, purity 99.98%) as the raw material containing Li and S; 19.2 mol% diphosphorus pentasulfide powder (manufactured by Sigma, purity 99%) as the raw material containing P and S; 12.0 mol% lithium bromide powder (manufactured by Sigma, purity 99.995%) as the raw material containing Li and Br; 8.0 mol% lithium iodide powder (manufactured by Tokyo Chemical Industry Co., Ltd., purity 99.9%, low moisture grade) as the raw material containing Li and I; 4.0 mol% Si 3 N 4 (manufactured by Sigma, purity ⁇ 98.5%, specific surface area 35 m 2 /g) as the nitride represented by the formula M
  • the raw material mixture obtained above was placed in a heat-resistant container and melted at 750°C for 1 hour in an atmosphere of gas containing elemental sulfur, after which it was cooled to room temperature at a rate of 10,000°C/s to obtain a solid.
  • Example 2 A solid was obtained in the same manner as in Example 1, except that 1.0 mol % of Si 3 N 4 (manufactured by Sigma, purity ⁇ 99.9% trace metals basis, specific surface area 11 m 2 /g) was used as the nitride represented by the formula M ⁇ N ⁇ .
  • Example 3 The raw material mixture obtained in the same manner as in Example 1 was further mixed using a planetary ball mill (LP-M2, manufactured by Ito Seisakusho Co., Ltd.) to obtain a powdery solid.
  • a planetary ball mill L-M2, manufactured by Ito Seisakusho Co., Ltd.
  • Example 4 The raw material mixture obtained in the same manner as in Example 2 was further mixed using a planetary ball mill (LP-M2, manufactured by Ito Seisakusho Co., Ltd.) to obtain a powdery solid.
  • a planetary ball mill L-M2, manufactured by Ito Seisakusho Co., Ltd.
  • Example 5 The solid obtained in Example 1 was further subjected to post-heat treatment at 220° C. for 10 minutes in a dry nitrogen gas atmosphere to obtain a solid.
  • Example 6 The solid obtained in Example 2 was further subjected to post-heat treatment at 195° C. for 10 minutes in a dry nitrogen gas atmosphere to obtain a solid.
  • compositions of the solids in Examples 1 and 2 whose reactivity was rated "good” or “fair” were identified. Specifically, the composition of each solid was determined by ICP optical emission spectrometry for P, S, and Si, atomic absorption spectrometry for Li, ion chromatography for Ha, and measurement using an oxygen, nitrogen, and hydrogen analyzer for N. Note that the N content was determined by sealing the solid together with Cu in a Sn capsule under an Ar atmosphere and using an oxygen, nitrogen, and hydrogen analyzer (EMGA-930 manufactured by Horiba, Ltd.). The results are shown in the "Composition” column in Table 1. It was confirmed that the obtained solid had a homogeneous amorphous phase and functioned as a sulfide solid electrolyte. Note that in Examples 3 and 4, a sulfide solid electrolyte containing N as a constituent element was not obtained, and therefore the composition is indicated as "-”.
  • thermal measurements were also performed on 20 mg of the solids from Examples 5 and 6.
  • DSC measurements were performed using a differential scanning calorimeter (BRUKER AXS, DSC3300) at a temperature increase rate of 5°C/min from 100 to 300°C, and DSC curves were obtained.
  • the resulting DSC curves are shown in Figure 5, and in both Examples 5 and 6, an exothermic peak due to the precipitation of highly ionic conductive crystals was confirmed in the range of 180 to 220°C.
  • ⁇ Lithium ion conductivity> The solids (sulfide solid electrolytes) obtained in Examples 1, 2, 5, and 6 were pulverized in a mortar and passed through a 100 ⁇ m sieve to obtain powders with a D50 of approximately 10 to 20 ⁇ m, where D50 refers to the volume-based median diameter.
  • the lithium ion conductivity of the powder obtained above was measured as a sample using an AC impedance measuring device (potentiostat/galvanostat VSP, manufactured by Bio-Logic Sciences Instruments). The measurement conditions were as follows: measurement frequency: 100 Hz to 1 MHz, measurement voltage: 100 mV, and measurement temperature: 25°C. The results are shown in Table 1. Note that in Examples 3 and 4, no measurement was performed because no sulfide solid electrolyte containing N as a constituent element was obtained.
  • the manufacturing method according to the present embodiment melts the raw materials and nitrides by heat treatment, and then cools and solidifies them, so that even if Si 3 N 4 , which is a stable nitride, is used, a sulfide solid electrolyte containing N as a constituent element can be obtained.
  • the sulfide solid electrolyte according to this embodiment exhibits lithium ion conductivity equal to or higher than that of conventional ones, and also achieves good water resistance due to the inclusion of N as a constituent element.
  • the results of Examples 5 and 6 show that even after the post-heat treatment, a higher lithium ion conductivity could be achieved while maintaining good water resistance.

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Abstract

La présente invention concerne un procédé de production d'un électrolyte solide au sulfure, le procédé consistant, dans l'ordre, à : chauffer des produits de départ, qui contiennent respectivement du Li, du P et du S, et un nitrure qui est représenté par la formule MαNβ de façon à obtenir une masse fondue ; et refroidir la masse fondue de façon à précipiter un solide. L'élément représenté par M est au moins un élément qui est choisi dans le groupe constitué par des éléments métalliques ou éléments métalloïdes de groupe 2 à 14 dans le tableau périodique, et α et β dans la formule MαNβ correspondent respectivement aux rapports stoechiométriques de M et N dans le nitrure qui est représenté par la formule MαNβ.
PCT/JP2025/010117 2024-03-21 2025-03-17 Procédé de production d'électrolyte solide au sulfure, procédé de production de batterie rechargeable au lithium-ion et électrolyte solide au sulfure Pending WO2025197831A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06115911A (ja) * 1992-09-29 1994-04-26 Matsushita Electric Ind Co Ltd 硫化物系リチウムイオン導電性固体電解質の製造法
WO2020045634A1 (fr) * 2018-08-30 2020-03-05 株式会社Ｇｓユアサ Procédé de fabrication d'électrolyte solide de sulfure, électrolyte solide de sulfure, batterie entièrement solide et procédé de sélection de composé de matière première utilisé pour fabriquer un électrolyte solide de sulfure
WO2024018976A1 (fr) * 2022-07-19 2024-01-25 Ａｇｃ株式会社 Électrolyte solide au sulfure et son procédé de production
WO2024117146A1 (fr) * 2022-11-30 2024-06-06 株式会社Ｇｓユアサ Électrolyte solide, électrolyte solide pour électrode positive, composite, électrode positive pour élément de stockage d'énergie, et élément de stockage d'énergie

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06115911A (ja) * 1992-09-29 1994-04-26 Matsushita Electric Ind Co Ltd 硫化物系リチウムイオン導電性固体電解質の製造法
WO2020045634A1 (fr) * 2018-08-30 2020-03-05 株式会社Ｇｓユアサ Procédé de fabrication d'électrolyte solide de sulfure, électrolyte solide de sulfure, batterie entièrement solide et procédé de sélection de composé de matière première utilisé pour fabriquer un électrolyte solide de sulfure
WO2024018976A1 (fr) * 2022-07-19 2024-01-25 Ａｇｃ株式会社 Électrolyte solide au sulfure et son procédé de production
WO2024117146A1 (fr) * 2022-11-30 2024-06-06 株式会社Ｇｓユアサ Électrolyte solide, électrolyte solide pour électrode positive, composite, électrode positive pour élément de stockage d'énergie, et élément de stockage d'énergie

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