WO2021065228A1 - 硫化物系無機固体電解質材料用の硫化リン組成物 - Google Patents

硫化物系無機固体電解質材料用の硫化リン組成物 Download PDF

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WO2021065228A1
WO2021065228A1 PCT/JP2020/031132 JP2020031132W WO2021065228A1 WO 2021065228 A1 WO2021065228 A1 WO 2021065228A1 JP 2020031132 W JP2020031132 W JP 2020031132W WO 2021065228 A1 WO2021065228 A1 WO 2021065228A1
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solid electrolyte
sulfide
based inorganic
inorganic solid
composition
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French (fr)
Japanese (ja)
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樹史 吉田
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Furukawa Co Ltd
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Furukawa Co Ltd
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Priority to KR1020227011208A priority Critical patent/KR102702128B1/ko
Priority to JP2021550410A priority patent/JP7297911B2/ja
Priority to CN202080069933.XA priority patent/CN114467148B/zh
Priority to US17/765,987 priority patent/US12418045B2/en
Priority to EP20872728.9A priority patent/EP4039642B1/en
Publication of WO2021065228A1 publication Critical patent/WO2021065228A1/ja
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Priority to JP2023097583A priority patent/JP7605908B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • 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
    • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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 phosphorus sulfide composition for a sulfide-based inorganic solid electrolyte material.
  • Lithium-ion batteries are generally used as a power source for small portable devices such as mobile phones and laptop computers. Recently, in addition to small portable devices, lithium-ion batteries have begun to be used as power sources for electric vehicles and electric power storage.
  • lithium-ion batteries use an electrolytic solution containing a flammable organic solvent.
  • a lithium-ion battery in which the electrolyte is replaced with a solid electrolyte and the battery is completely solidified (hereinafter, also referred to as an all-solid-state lithium-ion battery) does not use a flammable organic solvent in the battery, and thus is a safety device. It is considered that the manufacturing cost and productivity are excellent because of the simplification of the battery.
  • solid electrolyte material used for such a solid electrolyte for example, a sulfide-based inorganic solid electrolyte material is known.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-27545
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-27545
  • has a peak at the position of 2 ⁇ 29.86 ° ⁇ 1.00 ° in X-ray diffraction measurement using CuK ⁇ ray, and Li 2y + 3 PS 4 (0).
  • a sulfide-based solid electrolyte material having a composition of .1 ⁇ y ⁇ 0.175) is described.
  • Patent Document 2 International Publication No. 2016/067631 describes a method for producing sulfide glass using phosphorus sulfide according to the following formula (1) as a raw material. 100 ⁇ A / B ⁇ 37 ... (1) (In the formula, A indicates the peak area of the peak appearing in the range of 57.2 ppm or more and 58.3 ppm or less and 63.0 ppm or more and 64.5 ppm or less in the 31 PNMR spectrum analysis, and B is measured. Shows the sum of the peak areas of all peaks.)
  • the sulfide-based inorganic solid electrolyte material was excellent in electrochemical stability and lithium ion conductivity, it was inferior in lithium ion conductivity to the electrolytic solution. From the above, the sulfide-based inorganic solid electrolyte material used for the lithium ion battery is required to further improve the lithium ion conductivity while having electrochemical stability.
  • the present invention has been made in view of the above circumstances, and provides a phosphorus sulfide composition capable of improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.
  • the present inventors have diligently studied to provide a sulfide-based inorganic solid electrolyte material having improved lithium ion conductivity.
  • the use of phosphorus sulfide composition content of a specific range of P 4 S 10 calculated from the solid 31 P-NMR spectrum obtained We have found that the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material can be improved, and have reached the present invention.
  • a phosphorus sulfide composition for sulfide-based inorganic solid electrolyte materials Including P 4 S 10 and P 4 S 9
  • Phosphorus sulfide composition content is 99 wt% or less than 70 wt% of the P 4 S 10 calculated from the solid 31 P-NMR spectrum is provided.
  • a raw material composition of a sulfide-based inorganic solid electrolyte material containing the above phosphorus sulfide composition and lithium sulfide is provided.
  • a method for producing a sulfide-based inorganic solid electrolyte material which comprises a step of mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material.
  • a sulfide-based inorganic solid electrolyte material obtained by using the above phosphorus sulfide composition as a raw material is provided.
  • a solid electrolyte containing the sulfide-based inorganic solid electrolyte material is provided.
  • a solid electrolyte membrane containing the above solid electrolyte as a main component is provided.
  • a lithium ion battery including a positive electrode including a positive electrode active material layer, an electrolyte layer, and a negative electrode including a negative electrode active material layer.
  • a lithium ion battery in which at least one of the positive electrode active material layer, the electrolyte layer, and the negative electrode active material layer contains the sulfide-based inorganic solid electrolyte material is provided.
  • a phosphorus sulfide composition capable of improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.
  • the phosphorus sulfide composition according to the present embodiment is a phosphorus sulfide composition for a sulfide-based inorganic solid electrolyte material (hereinafter, also referred to as a phosphorus sulfide composition), and includes P 4 S 10 and P 4 S 9 . , Calculated from the solid 31 P-NMR spectrum when the total content of P 4 S 10 , P 4 S 9 , P 4 S 7 and P 4 S 3 in the phosphorus sulfide composition is 100% by mass.
  • the content of P 4 S 10 is 70% by mass or more and 99% by mass or less, preferably 72% by mass or more, more preferably 75% by mass or more, further preferably 77% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content of P 4 S 10 calculated from the solid 31 P-NMR spectrum is not particularly limited, but may be 98% by mass or less, or 95% by mass or less.
  • the phosphorus sulfide composition according to the present embodiment can improve the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material when the content of P 4 S 10 is at least the above lower limit value. Is not necessarily clear about this reason, phosphorus sulfide compositions according to the present embodiment, since a relatively high content of P 4 S 10, phosphorus sulfide compounds having a boiling point below comparable P 4 S 10 (P It is considered that this is because the content of 4 S 9 , P 4 S 7 , P 4 S 3 etc.) or phosphorus sulfide polymer (insoluble sulfur) is reduced.
  • the phosphorus sulfide composition according to the present embodiment has a relatively small amount of the phosphorus sulfide compound or the phosphorus sulfide polymer having a relatively low boiling point, it can be obtained by using the phosphorus sulfide composition according to the present embodiment. It is considered that the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material can be improved.
  • the phosphorus sulfide composition in which the content of P 4 S 10 is within the above range is, for example, P 4 in the phosphorus sulfide composition by subjecting the raw material composition of phosphorus sulfide to vacuum heating.
  • the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is preferably 1% by mass or more and 30% by mass or less.
  • the upper limit of the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is preferably 28% by mass or less, more preferably 25% by mass or less, still more preferably 23% by mass or less, and in particular. It is preferably 20% by mass or less.
  • the lower limit of the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is not particularly limited, but may be 2% by mass or more, or 5% by mass or more.
  • the solid 31 P-NMR spectrum can be measured by, for example, the following method. First, filling the test sample into the sample tube for measurement of 3.2mm diameter in a glove box purged with N 2 gas, the magic angle to the external magnetic field (54.7 °) rotation in an inclined state (Magic Angle spining : MAS) and measure under the following conditions.
  • the integral value of the peaks derived from each component is proportional to the number of moles of phosphorus contained. Therefore, the content ratio can be calculated from the obtained integrated value and the molecular weight of each component.
  • the chemical shift of P 4 S 10 is 40 to 52 ppm
  • the chemical shift of P 4 S 9 is 52 to 70 ppm
  • the chemical shift of P 4 S 7 is 80 to 90 ppm, 90 to 100 ppm, 110 to 115 ppm, chemistry of P 4 S 3.
  • the shift is 80 to 90 ppm and 90 to 100 ppm.
  • the solid 31 P-NMR spectrum when the solid 31 P-NMR spectrum is measured, it is preferable that no peak is observed in the range of 80 ppm or more and 90 ppm or less. That is, it is preferable that the peaks of P 4 S 7 and P 4 S 3 are not observed.
  • it is possible to increase the ratio of P 4 S 10 in phosphorus sulfide composition it is possible to further improve the lithium ion conductive sulfide-based inorganic solid electrolyte material obtained.
  • the phosphorus sulfide composition according to this embodiment contains P 4 S 10 and P 4 S 9.
  • the total content of P 4 S 10 and P 4 S 9 in the phosphorus sulfide composition according to the present embodiment is 95 mass from the viewpoint that the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material can be further improved. % Or more is preferable, 97% by mass or more is more preferable, 98% by mass or more is further preferable, and 99% by mass or more is even more preferable.
  • the upper limit of the total content of P 4 S 10 and P 4 S 9 in the phosphorus sulfide composition according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.
  • examples of the components that may be contained in addition to P 4 S 10 and P 4 S 9 include P 4 S 7 and P 4 S 3.
  • Examples of the properties of the phosphorus sulfide composition according to the present embodiment include powder. Since the sulfide-based inorganic solid electrolyte material described later is generally produced by a dry method, if the phosphorus sulfide composition according to the present embodiment is in the form of powder, the sulfide-based inorganic solid electrolyte material can be produced. It will be easier.
  • the method for producing a phosphorus sulfide composition according to the present embodiment is different from the conventional method for producing a phosphorus sulfide composition. That is, the phosphorus sulfide composition in which the content of P 4 S 10 is within the above range is equivalent to P 4 S 10 in the phosphorus sulfide composition by, for example, vacuum heating the raw material composition of phosphorus sulfide.
  • the method for producing a phosphorus sulfide composition includes, for example, the following steps (X) and (Y).
  • a raw material composition of phosphorus sulfide is prepared. Is not particularly restricted but includes raw material composition of phosphorus sulfide used as the raw material, it may be used as it is diphosphorus pentasulfide, which is commercially available (P 4 S 10), the manufacturing method commonly known diphosphorus pentasulfide You may use the raw material composition of phosphorus sulfide obtained by using.
  • the raw material composition of phosphorus sulfide for example, in vacuum, a phosphorus sulfide compound having a boiling point equal to or lower than that of P 4 S 10 in the phosphorus sulfide composition (P 4 S 9 , P 4 S 7 , P 4 S) 3 etc.) and reduce the amount of phosphorus sulfide polymer.
  • vacuum heating is performed until the content of P 4 S 10 is within the above range.
  • the phosphorus sulfide composition according to the present embodiment can be obtained.
  • the raw material composition of phosphorus sulfide is, for example, vacuum-heated
  • the component that accumulates at the bottom of the container without evaporating is usually the phosphorus sulfide composition according to the present embodiment.
  • Conditions such as pressure, heating temperature, and treatment time when the raw material composition of phosphorus sulfide is vacuum-heated can be appropriately determined depending on the amount of the raw material composition of phosphorus sulfide to be treated.
  • the pressure in the vacuum heating device when the raw material composition of phosphorus sulfide is vacuum-heated is, for example, ⁇ 0.01 MPa or less, preferably ⁇ 0.07 MPa or less.
  • the heating temperature when the raw material composition of phosphorus sulfide is vacuum-heated is, for example, 220 ° C. or higher and 500 ° C. or lower, and preferably 250 ° C. or higher and 350 ° C. or lower.
  • the time for vacuum-heating the phosphorus sulfide raw material composition is, for example, 0.5 hours or more and 24 hours or less, preferably 1 hour or more and 5 hours or less.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained by using the phosphorus sulfide composition according to the present embodiment as a raw material.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment contains Li, P, and S as constituent elements from the viewpoint of further improving the electrochemical stability, the stability in moisture and air, and the handleability. Is preferable. Further, the sulfide-based inorganic solid electrolyte material according to the present embodiment is the sulfide from the viewpoint of further improving lithium ion conductivity, electrochemical stability, stability in water and air, handleability, and the like.
  • the molar ratio of the Li content to the P content in the based inorganic solid electrolyte material is preferably 1.0 or more and 5.0 or less, more preferably 2.0 or more and 4.0 or less.
  • the contents of Li, P and S in the sulfide-based inorganic solid electrolyte material according to the present embodiment can be determined by, for example, ICP emission spectroscopic analysis or X-ray analysis.
  • the degree is preferably 0.5 ⁇ 10 -3 S ⁇ cm -1 or more, more preferably 0.6 ⁇ 10 -3 S ⁇ cm -1 or more, still more preferably 0.8 ⁇ 10 -3 S ⁇ cm ⁇ . 1 or more, particularly preferably 1.0 ⁇ 10 -3 S ⁇ cm -1 or more.
  • the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material according to the present embodiment is at least the above lower limit value, a lithium ion battery having more excellent battery characteristics can be obtained. Further, when such a sulfide-based inorganic solid electrolyte material is used, a lithium ion battery having more excellent input / output characteristics can be obtained.
  • Examples of the shape of the sulfide-based inorganic solid electrolyte material according to the present embodiment include particulate matter.
  • the particulate sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited, but the average particle size d 50 in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 ⁇ m or more and 100 ⁇ m or less. , More preferably 3 ⁇ m or more and 80 ⁇ m or less, and further preferably 5 ⁇ m or more and 60 ⁇ m or less.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment preferably has excellent electrochemical stability.
  • the electrochemical stability means, for example, a property that is difficult to be redoxed in a wide voltage range. More specifically, in the sulfide-based inorganic solid electrolyte material according to the present embodiment, the sulfide-based inorganic solid electrolyte material measured under the conditions of a temperature of 25 ° C., a sweep voltage range of 0 to 5 V, and a voltage sweep rate of 5 mV / sec.
  • the maximum value of the oxidative decomposition current of the above is preferably 0.50 ⁇ A or less, more preferably 0.20 ⁇ A or less, further preferably 0.10 ⁇ A or less, and even more preferably 0.05 ⁇ A or less. It is preferably 0.03 ⁇ A or less, and particularly preferably 0.03 ⁇ A or less. It is preferable that the maximum value of the oxidative decomposition current of the sulfide-based inorganic solid electrolyte material is not more than the above upper limit value because the oxidative decomposition of the sulfide-based inorganic solid electrolyte material can be suppressed in the lithium ion battery.
  • the lower limit of the maximum value of the oxidative decomposition current of the sulfide-based inorganic solid electrolyte material is not particularly limited, but is, for example, 0.0001 ⁇ A or more.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment can be used in any application that requires lithium ion conductivity. Above all, the sulfide-based inorganic solid electrolyte material according to the present embodiment is preferably used for a lithium ion battery. More specifically, it is used for a positive electrode active material layer, a negative electrode active material layer, an electrolyte layer and the like in a lithium ion battery.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment is suitably used for the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte layer and the like constituting the all-solid-state lithium ion battery, and the all-solid-state lithium ion. It is particularly preferably used for the solid electrolyte layer constituting the battery.
  • An example of an all-solid-state lithium-ion battery to which the sulfide-based inorganic solid electrolyte material according to the present embodiment is applied includes a positive electrode, a solid electrolyte layer, and a negative electrode laminated in this order.
  • the method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment is, for example, mechanically using the raw material composition of the sulfide-based inorganic solid electrolyte material containing the phosphorus sulfide composition according to the present embodiment and lithium sulfide. Includes processing steps. More specifically, the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained, for example, by a production method including the following steps (A) and (B).
  • the method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment may further include the following steps (C) and (D), if necessary.
  • Step (C) Obtained by mechanically treating the raw material composition to vitrify the raw material phosphorus sulfide composition and lithium sulfide while chemically reacting to obtain a glassy sulfide-based inorganic solid electrolyte material. Step of heating at least a part of the sulfide-based inorganic solid electrolyte material in a glass state Step (D): Step of crushing, classifying, or granulating the obtained sulfide-based inorganic solid electrolyte material.
  • Step (A) of preparing a raw material composition of a sulfide-based inorganic solid electrolyte material First, a raw material composition of a sulfide-based inorganic solid electrolyte material containing the phosphorus sulfide composition according to the present embodiment, which is a raw material, and lithium nitride, and further containing lithium nitride, if necessary, is prepared. Here, the mixing ratio of each raw material in the raw material composition is adjusted so that the obtained sulfide-based inorganic solid electrolyte material has a desired composition ratio.
  • the method of mixing each raw material is not particularly limited as long as it is a mixing method capable of uniformly mixing each raw material, but for example, a ball mill, a bead mill, a vibration mill, a striking crusher, a mixer (pug mixer, ribbon mixer, tumbler mixer, drum). Mixing can be performed using a mixer, a V-type mixer, etc.), a kneader, a twin-screw kneader, an air flow crusher, a crusher, a rotary blade type crusher, or the like. Mixing conditions such as stirring speed, processing time, temperature, reaction pressure, and gravitational acceleration applied to the mixture when mixing each raw material can be appropriately determined depending on the processing amount of the mixture.
  • the lithium sulfide used as a raw material is not particularly limited, and commercially available lithium sulfide may be used, or for example, lithium sulfide obtained by reacting lithium hydroxide with hydrogen sulfide may be used. From the viewpoint of obtaining a high-purity sulfide-based inorganic solid electrolyte material and suppressing side reactions, it is preferable to use lithium sulfide having few impurities.
  • lithium sulfide also includes lithium polysulfide.
  • Lithium nitride may be used as a raw material.
  • nitrogen in lithium nitride is discharged into the system as N 2 , by using lithium nitride as the raw material inorganic compound, a sulfide-based inorganic solid containing Li, P, and S as constituent elements. It is possible to increase only the Li composition with respect to the electrolyte material.
  • the lithium nitride are commercially available (for example, Li 3 N, etc.) may be used, for example, metallic lithium (eg, Li foil) and a nitrogen gas Lithium nitride obtained by the above reaction may be used. From the viewpoint of obtaining a high-purity solid electrolyte material and suppressing side reactions, it is preferable to use lithium nitride having a small amount of impurities.
  • Step (B) for obtaining a glassy sulfide-based inorganic solid electrolyte material Subsequently, by mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material, the raw materials, the phosphorus sulfide composition and lithium sulfide, are vitrified while being chemically reacted, and the sulfide-based inorganic solid electrolyte in a glass state is vitrified. Get the material.
  • the mechanical treatment can be vitrified while chemically reacting by mechanically colliding two or more kinds of inorganic compounds, and examples thereof include mechanochemical treatment.
  • the mechanochemical treatment is a method of vitrifying the target composition while applying mechanical energy such as a shearing force or a collision force.
  • the mechanochemical treatment is preferably a dry mechanochemical treatment from the viewpoint of easily realizing an environment in which water and oxygen are removed at a high level.
  • each raw material can be mixed while being crushed into fine particles, so that the contact area of each raw material can be increased. As a result, the reaction of each raw material can be promoted, so that the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained even more efficiently.
  • the mechanochemical treatment is a method of vitrifying while applying mechanical energy such as shearing force, collision force or centrifugal force to the mixing target.
  • Devices that perform vitrification by mechanochemical treatment include crushers and dispersers such as ball mills, bead mills, vibration mills, turbo mills, mechanofusions, disc mills, and roll mills; rock drills and vibrations.
  • Rotation / impact crushing device consisting of a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by drills, impact drivers, etc .; high-pressure gliding rolls; roller-type vertical mills, ball-type vertical mills, etc. Vertical mills and the like can be mentioned.
  • ball mills and bead mills are preferable, and ball mills are particularly preferable, from the viewpoint of being able to efficiently generate extremely high impact energy.
  • a roll mill a rotary / impact crusher consisting of a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by a rock drill, a vibration drill, an impact driver, etc.
  • High-pressure gliding roll Vertical mills such as roller-type vertical mills and ball-type vertical mills are preferable.
  • the mixing conditions such as rotation speed, processing time, temperature, reaction pressure, and gravitational acceleration applied to the raw material inorganic composition when mechanically processing the raw material composition of the sulfide-based inorganic solid electrolyte material are the types of the raw material inorganic composition. It can be appropriately determined depending on the amount of processing and the amount of processing. In general, the faster the rotation speed, the faster the glass formation rate, and the longer the processing time, the higher the conversion rate to glass. Normally, when X-ray diffraction analysis using CuK ⁇ beam as a radiation source is performed, if the diffraction peak derived from the raw material disappears or decreases, the raw material composition of the sulfide-based inorganic solid electrolyte material is vitrified, which is desired. It can be determined that a sulfide-based inorganic solid electrolyte material has been obtained.
  • the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material by the AC impedance method under the measurement conditions of 27.0 ° C., an applied voltage of 10 mV, and a measurement frequency range of 0.1 Hz to 7 MHz is preferable.
  • a glass-ceramic state also referred to as crystallized glass.
  • the sulfide-based inorganic solid electrolyte material according to the present embodiment is preferably in a glass-ceramic state (crystallized glass state) from the viewpoint of excellent lithium ion conductivity.
  • the temperature at which the glassy sulfide-based inorganic solid electrolyte material is heated is preferably in the range of 220 ° C. or higher and 500 ° C. or lower, and more preferably in the range of 250 ° C. or higher and 350 ° C. or lower.
  • the time for heating the sulfide-based inorganic solid electrolyte material in the glass state is not particularly limited as long as the desired sulfide-based inorganic solid electrolyte material in the glass ceramic state can be obtained, but is not particularly limited, for example, 0.5. It is in the range of time or more and 24 hours or less, preferably 1 hour or more and 3 hours or less.
  • the heating method is not particularly limited, and examples thereof include a method using a firing furnace. The conditions such as temperature and time for heating can be appropriately adjusted in order to optimize the characteristics of the sulfide-based inorganic solid electrolyte material according to the present embodiment.
  • the heating of the sulfide-based inorganic solid electrolyte material in the glass state is preferably performed in an inert gas atmosphere, for example.
  • an inert gas atmosphere for example.
  • the inert gas when heating the glassy sulfide-based inorganic solid electrolyte material include argon gas, helium gas, nitrogen gas and the like. The higher the purity of these inert gases is, the more preferable it is to prevent impurities from being mixed into the product, and the dew point is preferably ⁇ 30 ° C. or lower, preferably ⁇ 70 ° C., in order to avoid contact with moisture.
  • the temperature is more preferably ° C. or lower, and particularly preferably ⁇ 80 ° C. or lower.
  • the method of introducing the inert gas into the mixed system is not particularly limited as long as the inside of the mixed system is filled with the inert gas atmosphere, but the method of purging the inert gas and the method of continuously introducing a certain amount of the inert gas are continued. The method and the like can be mentioned.
  • Step of crushing, classifying, or granulating (D) In the method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment, a step of pulverizing, classifying, or granulating the obtained sulfide-based inorganic solid electrolyte material may be further performed, if necessary.
  • a sulfide-based inorganic solid electrolyte material having a desired particle size can be obtained by making the particles finer by pulverization and then adjusting the particle size by a classification operation or a granulation operation.
  • the crushing method is not particularly limited, and known crushing methods such as a mixer, airflow crushing, mortar, rotary mill, and coffee mill can be used.
  • the classification method is not particularly limited, and a known method such as a sieve can be used. These pulverizations or classifications are preferably carried out in an inert gas atmosphere or a vacuum atmosphere from the viewpoint of preventing contact with moisture in the air.
  • the method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment is not limited to the above method, and by appropriately adjusting various conditions, the sulfide-based inorganic solid electrolyte material according to the present embodiment is used. A solid electrolyte material can be obtained.
  • the solid electrolyte according to the present embodiment includes the sulfide-based inorganic solid electrolyte material according to the present embodiment.
  • the solid electrolyte according to the present embodiment is not particularly limited, but as a component other than the sulfide-based inorganic solid electrolyte material according to the present embodiment, for example, as long as the object of the present invention is not impaired, the above-described embodiment It may contain a different kind of solid electrolyte material from the sulfide-based inorganic solid electrolyte material according to the above.
  • the solid electrolyte according to the present embodiment may contain a different type of solid electrolyte material from the sulfide-based inorganic solid electrolyte material according to the above-described embodiment.
  • the type of solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited as long as it has ionic conductivity and insulating properties, but is generally used for lithium ion batteries. Can be used.
  • an inorganic solid electrolyte material such as a sulfide-based inorganic solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment, an oxide-based inorganic solid electrolyte material, and other lithium-based inorganic solid electrolyte materials;
  • organic solid electrolyte materials such as polymer electrolytes.
  • Examples of the sulfide-based inorganic solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment described above include Li 2 SP 4 S 10 material, Li 2 S-Si S 2 material, and Li 2 S.
  • the Li 2 SP 4 S 10 material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition in a wide voltage range.
  • the Li 2 SP 4 S 10 material is a solid obtained by chemically reacting an inorganic composition containing at least Li 2 S (lithium sulfide) and P 4 S 10 with each other by mechanical treatment. Means electrolyte material.
  • lithium sulfide also includes lithium polysulfide.
  • oxide-based inorganic solid electrolyte material examples include NASICON type materials such as LiTi 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and (La 0.5 + x Li 0.5).
  • NASICON type materials such as LiTi 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and (La 0.5 + x Li 0.5).
  • Perovskite type such as TiO 3 , Li 2 O-P 2 O 5 material, Li 2 O-P 2 O 5 -Li 3 N material and the like can be mentioned.
  • examples of other lithium-based inorganic solid electrolyte materials include LiPON, LiNbO 3 , LiTaO 3 , Li 3 PO 4 , LiPO 4-x N x (x is 0 ⁇ x ⁇ 1), LiN, LiI, and LISION. Be done. Further, glass ceramic
  • organic solid electrolyte material for example, a polymer electrolyte such as a dry polymer electrolyte or a gel electrolyte can be used.
  • polymer electrolyte those generally used for lithium ion batteries can be used.
  • the solid electrolyte membrane according to the present embodiment contains a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the above-described embodiment as a main component.
  • the solid electrolyte membrane according to the present embodiment is used, for example, in the solid electrolyte layer constituting the all-solid-state lithium ion battery.
  • An example of an all-solid-state lithium-ion battery to which the solid electrolyte membrane according to the present embodiment is applied includes a battery in which a positive electrode, a solid electrolyte layer, and a negative electrode are laminated in this order.
  • the solid electrolyte layer is composed of the solid electrolyte membrane.
  • the average thickness of the solid electrolyte membrane according to the present embodiment is preferably 5 ⁇ m or more and 500 ⁇ m or less, more preferably 10 ⁇ m or more and 200 ⁇ m or less, and further preferably 20 ⁇ m or more and 100 ⁇ m or less.
  • the average thickness of the solid electrolyte membrane is at least the above lower limit value, the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane can be further suppressed.
  • the average thickness of the solid electrolyte membrane is not more than the upper limit value, the impedance of the solid electrolyte membrane can be further lowered. As a result, the battery characteristics of the obtained all-solid-state lithium-ion battery can be further improved.
  • the solid electrolyte membrane according to the present embodiment is preferably a pressure-molded particulate solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the above-described embodiment. That is, it is preferable to pressurize the particulate solid electrolyte to form a solid electrolyte membrane having a certain strength due to the anchor effect between the solid electrolyte materials.
  • the pressure molded product By forming the pressure molded product, the solid electrolytes are bonded to each other, and the strength of the obtained solid electrolyte membrane is further increased. As a result, the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane can be further suppressed.
  • the content of the sulfide-based inorganic solid electrolyte material according to the present embodiment described above in the solid electrolyte membrane according to the present embodiment is preferably 50% by mass or more, more preferably, when the entire solid electrolyte membrane is 100% by mass. It is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the contact property between the solid electrolytes is improved, and the interfacial contact resistance of the solid electrolyte membrane can be reduced.
  • the lithium ion conductivity of the solid electrolyte membrane can be further improved.
  • the upper limit of the content of the sulfide-based inorganic solid electrolyte material according to the above-described embodiment in the solid electrolyte membrane according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.
  • the planar shape of the solid electrolyte membrane is not particularly limited and can be appropriately selected according to the shape of the electrode or the current collector, but can be, for example, a rectangle.
  • the solid electrolyte film according to the present embodiment may contain a binder resin, but the content of the binder resin is preferably less than 0.5% by mass when the whole solid electrolyte film is 100% by mass. , More preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less. Further, it is even more preferable that the solid electrolyte membrane according to the present embodiment is substantially free of the binder resin, and most preferably no binder resin is contained. As a result, the contact property between the solid electrolytes is improved, and the interfacial contact resistance of the solid electrolyte membrane can be reduced. As a result, the lithium ion conductivity of the solid electrolyte membrane can be further improved.
  • substantially free of binder resin means that the binder resin may be contained to the extent that the effect of the present embodiment is not impaired.
  • the binder resin refers to a binder generally used in lithium ion batteries for binding inorganic solid electrolyte materials, for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, and polytetrafluoro. Examples thereof include ethylene, polyvinylidene fluoride, styrene-butadiene rubber, and polyimide.
  • the solid electrolyte membrane according to the present embodiment is obtained by, for example, depositing a particulate solid electrolyte on the surface of the cavity of the mold or on the surface of the base material in a film shape, and then pressurizing the solid electrolyte deposited in the film shape.
  • the method of pressurizing the solid electrolyte is not particularly limited. For example, when the particulate solid electrolyte is deposited on the surface of the cavity of the die, it is pressed by the die and the stamp, and the particulate solid electrolyte is applied to the surface of the base material. When deposited on top, a press with a die and a stamp, a roll press, a flat plate press, or the like can be used.
  • the pressure for pressurizing the solid electrolyte is, for example, 10 MPa or more and 500 MPa or less.
  • the inorganic solid electrolyte deposited in the form of a film may be pressurized and heated.
  • the solid electrolytes are fused and bonded to each other, and the strength of the obtained solid electrolyte membrane is further increased.
  • the temperature at which the solid electrolyte is heated is, for example, 40 ° C. or higher and 500 ° C. or lower.
  • FIG. 1 is a cross-sectional view showing an example of the structure of the lithium ion battery 100 according to the embodiment of the present invention.
  • the lithium ion battery 100 according to the present embodiment includes, for example, a positive electrode 110 including a positive electrode active material layer 101, an electrolyte layer 120, and a negative electrode 130 including a negative electrode active material layer 103. Then, at least one of the positive electrode active material layer 101, the negative electrode active material layer 103, and the electrolyte layer 120 contains the sulfide-based inorganic solid electrolyte material according to the present embodiment.
  • the positive electrode active material layer 101, the negative electrode active material layer 103, and the electrolyte layer 120 contain the sulfide-based inorganic solid electrolyte material according to the present embodiment.
  • the layer containing the positive electrode active material is referred to as the positive electrode active material layer 101.
  • the positive electrode 110 may or may not include the current collector 105 in addition to the positive electrode active material layer 101, if necessary.
  • the layer containing the negative electrode active material is referred to as the negative electrode active material layer 103.
  • the negative electrode 130 may or may not include the current collector 105 in addition to the negative electrode active material layer 103, if necessary.
  • the shape of the lithium ion battery 100 according to the present embodiment is not particularly limited, and examples thereof include a cylindrical type, a coin type, a square type, a film type, and any other shape.
  • the lithium ion battery 100 is manufactured according to a generally known method.
  • a positive electrode 110, an electrolyte layer 120, and a negative electrode 130 are stacked to form a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape, and if necessary, a non-aqueous electrolyte solution is sealed therein. It is made.
  • the positive electrode 110 is not particularly limited, and those generally used for lithium ion batteries can be used.
  • the positive electrode 110 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a positive electrode active material layer 101 containing a positive electrode active material on the surface of a current collector 105 such as an aluminum foil.
  • the thickness and density of the positive electrode active material layer 101 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
  • the positive electrode active material layer 101 contains a positive electrode active material.
  • Lithium-manganese-nickel oxide LiNi 1/3 Mn 1/3 Co 1/3 O 2
  • olivine-type lithium phosphorus oxide LiFePO 4
  • other compound oxides molecule; Li 2 S, CuS, Li -CuS compounds, TiS 2, FeS, MoS 2 , Li-MoS compounds, Li-TiS compounds, Li-V-S compounds, Li-FeS compound Sulfide-based positive electrode active materials such as, acetylene black impregnated with sulfur, porous carbon impregnated with sulfur, materials using sulfur as an active material such as a mixed powder of sulfur and carbon; and the like can be used. These positive electrode active materials may be used alone or in combination of two or more.
  • a sulfide-based positive electrode active material is preferable from the viewpoint of having a higher discharge capacity density and being superior in cycle characteristics, and Li-Mo-S compound, Li-Ti-S compound, and Li-VS. More preferably, one or more selected from the compounds.
  • the Li-Mo-S compound contains Li, Mo, and S as constituent elements, and the inorganic compositions containing molybdenum sulfide and lithium sulfide, which are usually raw materials, are chemically treated with each other by mechanical treatment. It can be obtained by reacting.
  • the Li—Ti—S compound contains Li, Ti, and S as constituent elements, and an inorganic composition containing titanium sulfide and lithium sulfide, which are usually raw materials, is chemically reacted with each other by mechanical treatment. It can be obtained by letting it.
  • the Li-VS compound contains Li, V, and S as constituent elements, and an inorganic composition containing vanadium sulfide and lithium sulfide, which are usually raw materials, is chemically reacted with each other by mechanical treatment. Can be obtained by
  • the positive electrode active material layer 101 is not particularly limited, but may contain one or more materials selected from, for example, a binder resin, a thickener, a conductive auxiliary agent, a solid electrolyte material, and the like as components other than the positive electrode active material. .. Hereinafter, each material will be described.
  • the positive electrode active material layer 101 may contain a binder resin having a role of binding the positive electrode active materials to each other and the positive electrode active material to the current collector 105.
  • the binder resin according to the present embodiment is not particularly limited as long as it is a normal binder resin that can be used in a lithium ion battery, and for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride, styrene, and the like. Examples thereof include butadiene rubber and polyimide. These binders may be used alone or in combination of two or more.
  • the positive electrode active material layer 101 may contain a thickener from the viewpoint of ensuring the fluidity of the slurry suitable for coating.
  • the thickener is not particularly limited as long as it is a normal thickener that can be used in a lithium ion battery, and for example, cellulosic polymers such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, and ammonium salts and alkali metal salts thereof. Examples thereof include water-soluble polymers such as polycarboxylic acid, polyethylene oxide, polyvinylpyrrolidone, polyacrylate, and polyvinyl alcohol. These thickeners may be used alone or in combination of two or more.
  • the positive electrode active material layer 101 may contain a conductive auxiliary agent from the viewpoint of improving the conductivity of the positive electrode 110.
  • the conductive auxiliary agent is not particularly limited as long as it is an ordinary conductive auxiliary agent that can be used in a lithium ion battery, and examples thereof include carbon black such as acetylene black and kechen black, and carbon materials such as vapor phase carbon fiber. ..
  • the positive electrode according to the present embodiment may contain a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment described above, and may be of a different type from the sulfide-based inorganic solid electrolyte material according to the present embodiment. It may contain a solid electrolyte containing a solid electrolyte material.
  • the type of solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited as long as it has ionic conductivity and insulating properties, but is generally used for lithium ion batteries. Can be used.
  • inorganic solid electrolyte materials such as sulfide-based inorganic solid electrolyte materials, oxide-based inorganic solid electrolyte materials, and other lithium-based inorganic solid electrolyte materials; and organic solid electrolyte materials such as polymer electrolytes can be mentioned. More specifically, the inorganic solid electrolyte material mentioned in the description of the solid electrolyte according to the present embodiment can be used.
  • the blending ratio of various materials in the positive electrode active material layer 101 is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.
  • the negative electrode 130 is not particularly limited, and those generally used for lithium ion batteries can be used.
  • the negative electrode 130 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a negative electrode active material layer 103 containing a negative electrode active material on the surface of a current collector 105 such as copper.
  • the thickness and density of the negative electrode active material layer 103 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
  • the negative electrode active material layer 103 contains a negative electrode active material.
  • the negative electrode active material is not particularly limited as long as it is a normal negative electrode active material that can be used for the negative electrode of a lithium ion battery, and for example, natural graphite, artificial graphite, resin charcoal, carbon fiber, activated charcoal, hard carbon, and soft carbon.
  • Carbon materials such as lithium, lithium alloy, tin, tin alloy, silicon, silicon alloy, gallium, gallium alloy, indium, indium alloy, aluminum, aluminum alloy, etc.
  • Conductive polymer Lithium-titanium composite oxide (for example, Li 4 Ti 5 O 12 ) and the like. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode active material layer 103 is not particularly limited, but may contain one or more materials selected from, for example, a binder resin, a thickener, a conductive auxiliary agent, a solid electrolyte material, and the like as components other than the negative electrode active material. .. These materials are not particularly limited, and examples thereof include the same materials as those used for the positive electrode 110 described above.
  • the blending ratio of various materials in the negative electrode active material layer 103 is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.
  • the electrolyte layer 120 is a layer formed between the positive electrode active material layer 101 and the negative electrode active material layer 103.
  • Examples of the electrolyte layer 120 include a separator impregnated with a non-aqueous electrolyte solution and a solid electrolyte layer containing a solid electrolyte.
  • the separator according to the present embodiment is not particularly limited as long as it has a function of electrically insulating the positive electrode 110 and the negative electrode 130 and transmitting lithium ions, but for example, a porous membrane can be used.
  • a microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, polyester and the like.
  • a porous polyolefin film is preferable, and specific examples thereof include a porous polyethylene film and a porous polypropylene film.
  • the non-aqueous electrolyte solution is a solution in which an electrolyte is dissolved in a solvent.
  • Any known lithium salt can be used as the electrolyte, and it may be selected according to the type of active material.
  • the solvent for dissolving the electrolyte is not particularly limited as long as it is usually used as a liquid for dissolving the electrolyte, and ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • DMC dimethyl carbonate
  • Sulfolans such as 3-methyl-2-oxazolidinone
  • sultons such as 1,3-propanesulton, 1,4-butanesulton, naphthalusulton; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the solid electrolyte layer according to the present embodiment is a layer formed between the positive electrode active material layer 101 and the negative electrode active material layer 103, and is a layer formed of a solid electrolyte containing a solid electrolyte material.
  • the solid electrolyte contained in the solid electrolyte layer is not particularly limited as long as it has lithium ion conductivity, but in the present embodiment, the solid containing the sulfide-based inorganic solid electrolyte material according to the present embodiment. It is preferably an electrolyte.
  • the content of the solid electrolyte in the solid electrolyte layer according to the present embodiment is not particularly limited as long as the desired insulating property can be obtained, but is, for example, in the range of 10% by volume or more and 100% by volume or less. Above all, it is preferably in the range of 50% by volume or more and 100% by volume or less. In particular, in the present embodiment, it is preferable that the solid electrolyte layer is composed only of the solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment.
  • the solid electrolyte layer according to the present embodiment may contain a binder resin.
  • a binder resin By containing the binder resin, a flexible solid electrolyte layer can be obtained.
  • the binder resin include fluorine-containing binders such as polytetrafluoroethylene and polyvinylidene fluoride.
  • the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m or more and 1000 ⁇ m or less, and more preferably in the range of 0.1 ⁇ m or more and 300 ⁇ m or less.
  • the content ratio was calculated from the obtained integral value and the molecular weight of each component.
  • P 4 S 10 chemical shifts are 40 ⁇ 52ppm
  • P 4 chemical shifts of S 9 is 52 ⁇ 70 ppm
  • the chemical shifts are 80 ⁇ 90 ppm of P 4 S 7, 90 ⁇ 100ppm , 110 ⁇ 115ppm
  • chemical P 4 S 3 The shift is 80 to 90 ppm and 90 to 100 ppm.
  • the lithium ion conductivity of the sulfide-based inorganic solid electrolyte materials obtained in Examples and Comparative Examples was measured by the AC impedance method.
  • the lithium ion conductivity was measured using a potentiostat / galvanostat SP-300 manufactured by Biologic.
  • the size of the sample was 9.5 mm in diameter and 1.2 to 2.0 mm in thickness, and the measurement conditions were an applied voltage of 10 mV, a measurement temperature of 27.0 ° C., a measurement frequency range of 0.1 Hz to 7 MHz, and an electrode of Li foil. ..
  • a sulfide-based inorganic solid electrolyte material was produced by the following procedure.
  • the raw material Li 2 S (Furukawa Co., purity 99.9%) was used and Li 3 N (Furukawa Co., Ltd.), phosphorus sulfide obtained in Examples and Comparative Examples are as phosphosulfurized Each composition was used.
  • a rotary blade type crusher and an alumina pot are placed in the glove box, and then high-purity dry argon gas (H) obtained through a gas purifier is placed in the glove box. Injection of 2 O ⁇ 1 ppm, O 2 ⁇ 1 ppm) and vacuum degassing were performed three times.
  • Li 2 S powder Li 2 S powder
  • phosphorus sulfide composition Li 3 N powder
  • the raw material inorganic composition and 500 g of ZrO 2 balls having a diameter of 10 mm were put into an alumina pot (internal volume 400 mL) in the glove box, and the pot was sealed.
  • the alumina pot was taken out from the glove box, the alumina pot was attached to a ball mill machine installed in an atmosphere of dry dry air introduced through a membrane air dryer, and the mechanochemical treatment was performed at 120 rpm for 500 hours to prepare the raw material.
  • the inorganic composition was vitrified. After every 48 hours of mixing, the powder on the inner wall of the pot was scraped off in the glove box, sealed, and milling was continued in a dry air atmosphere.
  • Example 2 As the raw material composition 2 for phosphorus sulfide, diphosphorus pentasulfide (product name: Normal S) manufactured by Perimeter Solutions was used. Next, the raw material composition 2 of phosphorus sulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Co., Ltd.). Then, it was vacuum-heated at 300 ° C. for 2 hours under a reduced pressure of ⁇ 0.094 MPa. Next, the components accumulated at the bottom of the quartz container were collected to obtain phosphorus sulfide composition 2. Each evaluation was performed on the obtained phosphorus sulfide composition 2. The results obtained are shown in Table 1.
  • Example 3 As the raw material composition 3 of phosphorus sulfide, diphosphorus pentasulfide (product name: Special S) manufactured by Perimeter Solutions Co., Ltd. was used. Next, the raw material composition of phosphorus sulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Co., Ltd.). Then, it was vacuum-heated at 300 ° C. for 2 hours under a reduced pressure of ⁇ 0.094 MPa. Next, the components accumulated at the bottom of the quartz container were collected to obtain a phosphorus sulfide composition 3. Each evaluation was performed on the obtained phosphorus sulfide composition 3. The results obtained are shown in Table 1.
  • the sulfide-based inorganic solid electrolyte material obtained by using the phosphorus sulfide composition of Examples as a raw material has more lithium ions than the sulfide-based inorganic solid electrolyte material obtained by using the phosphorus sulfide composition of Comparative Example as a raw material. It had excellent conductivity.

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JP2024070547A (ja) * 2022-11-11 2024-05-23 古河機械金属株式会社 硫化リン組成物の製造方法、硫化物系無機固体電解質材料の製造方法および硫化リン組成物の評価方法
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