WO2024018976A1 - 硫化物固体電解質及びその製造方法 - Google Patents

硫化物固体電解質及びその製造方法 Download PDF

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WO2024018976A1
WO2024018976A1 PCT/JP2023/025802 JP2023025802W WO2024018976A1 WO 2024018976 A1 WO2024018976 A1 WO 2024018976A1 JP 2023025802 W JP2023025802 W JP 2023025802W WO 2024018976 A1 WO2024018976 A1 WO 2024018976A1
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Prior art keywords
solid electrolyte
sulfide solid
sulfide
raw material
content
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 藤井
佑輝 福冨
哲人 遊佐
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AGC Inc
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Asahi Glass Co Ltd
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Priority to EP23842899.9A priority Critical patent/EP4559880A1/en
Priority to CN202380053707.6A priority patent/CN119546561A/zh
Priority to JP2024535052A priority patent/JPWO2024018976A1/ja
Priority to KR1020257001091A priority patent/KR20250039977A/ko
Publication of WO2024018976A1 publication Critical patent/WO2024018976A1/ja
Priority to US19/013,035 priority patent/US20250149628A1/en
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    • 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
    • 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
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • 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
    • H01M10/052—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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
    • H01M2300/008—Halides
    • 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 and a method for producing the same.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers.
  • liquid electrolytes have been used in lithium ion secondary batteries, but there are concerns about leakage and ignition, and it has been necessary to increase the size of the case for safety design. Additionally, improvements were desired in terms of short battery life and narrow operating temperature range.
  • Solid electrolytes are broadly classified into sulfide solid electrolytes and oxide solid electrolytes.
  • the sulfide ions that make up the sulfide solid electrolyte have a higher polarizability than the oxide ions that make up the oxide solid electrolyte, and exhibit high lithium ion conductivity.
  • Known examples of sulfide solid electrolytes include LGPS type crystals such as Li 10 GeP 2 S 12 , argyrodite type crystals such as Li 6 PS 5 Cl, and LPS crystallized glass such as Li 7 P 3 S 11 crystallized glass. It is being
  • Patent Document 1 discloses a Li-P-S solid electrolyte having a crystal ratio of 60 mol% to 100 mol% and having a unique peak in a solid-state 31 PNMR spectrum.
  • Patent Document 2 discloses a Li-P-S-Ha-based solid electrolyte having a crystal ratio of 60 mol% to 100 mol% and having a unique peak in a solid-state 31 PNMR spectrum.
  • Ha means a halogen element.
  • a solid electrolyte in which crystals are precipitated at a high volume fraction has poor contact between the electrolytes and between the electrolyte and the active material.
  • the heat treatment conditions for crystallization are severe, and slight differences in treatment can result in differences in state, resulting in large variations in quality as a solid electrolyte.
  • a solid electrolyte containing a glass phase has good contact between electrolytes and between an electrolyte and an active material. Further, even when a solid electrolyte containing a glass phase is pulverized and used in powder form, the decrease in conductivity due to pulverization is extremely small. Furthermore, by melting raw materials to produce a solid electrolyte containing a glass phase, the composition has good homogeneity and can be molded into any shape. On the other hand, conventionally known Li-P-S-based sulfide glasses have low lithium ion conductivity.
  • the present invention aims to provide a sulfide solid electrolyte containing a sulfide glass phase that has high lithium ion conductivity, and a method for producing the same.
  • a sulfide solid electrolyte containing a sulfide glass phase has a specific composition containing Ha in addition to Li, P, and S, and has a P S ratio of 7 units to P 2 S units.
  • the inventors have discovered that the above problem can be solved by mainly including four units, and have completed the present invention.
  • a manufacturing method in which raw materials are melted and rapidly cooled as a method for obtaining a homogeneous sulfide solid electrolyte with high lithium ion conductivity.
  • a sulfide solid electrolyte containing a sulfide glass phase including 4 PS units and 7 P 2 S units, where the peak intensity I (PS4) of the 4 PS units and the 7 P 2 S units in a Raman spectrum
  • the ratio of peak intensities I (P2S7) satisfies the relationship 0.05 ⁇ I (P2S7) /I (PS4) ⁇ 1.00, contains Li, P, S and Ha as constituent elements, and the Ha is A sulfide solid electrolyte, which is a halogen element, and the contents of the constituent elements are Li: 30 to 50%, P: 5 to 15%, and S: 30 to 60% in at%.
  • the Ha contains at least one selected from the group consisting of F, Cl, Br, and I, and the content of the constituent elements is expressed in at%, Li: 30 to 50%, P: 5 to 12 %, S: 30 to 50%, and Ha: 2 to 10%.
  • It further contains 6 P 2 S units, and the ratio of the peak intensity I (P2S6) of the 6 P 2 S units and the peak intensity I (P2S7) of the 7 P 2 S units in the Raman spectrum is 0.5 ⁇
  • the content ratio in at% of Li and P satisfies the relationship of 2.5 ⁇ (Li/P) ⁇ 7, described in [1] or [2] above.
  • sulfide solid electrolyte [5] The sulfide solid electrolyte according to [1] or [2], which has a peak in a wave number range of 150 to 180 cm -1 in a Raman spectrum, and the full width at half maximum of the peak is 20 cm -1 or more. [6] The sulfide solid electrolyte according to [1] or [2], wherein the content of the sulfide glass phase is 50% by weight or more.
  • the sulfide solid electrolyte according to the present invention high lithium ion conductivity can be achieved even though it contains a sulfide glass phase. Therefore, it is very useful as a solid electrolyte for lithium ion secondary batteries, and is expected to improve the battery characteristics of lithium ion secondary batteries.
  • FIG. 1 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte according to this embodiment.
  • FIG. 2 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte according to this embodiment.
  • FIG. 3 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte according to this embodiment.
  • FIG. 4 is a Raman spectrum of the sulfide solid electrolyte of Example 1.
  • FIG. 5 shows a Raman spectrum of the sulfide solid electrolyte of Example 1 and a baseline-corrected corrected spectrum.
  • FIG. 1 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte according to this embodiment.
  • FIG. 2 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte according to this embodiment.
  • FIG. 3 is a flow diagram showing a method for manufacturing a sulfide solid electrolyte
  • FIG. 6 shows a calculated spectrum of the Raman spectrum of the sulfide solid electrolyte of Example 1, including a baseline corrected spectrum, three spectra peak-separated from the corrected spectrum, and the sum of the three spectra.
  • FIG. 7 shows a baseline-corrected Raman spectrum of the sulfide solid electrolyte of Example 2, three spectra whose peaks were separated from the corrected spectrum, and a calculated spectrum obtained by adding the three spectra.
  • FIG. 8 shows a baseline-corrected Raman spectrum of the sulfide solid electrolyte of Example 3, three spectra whose peaks were separated from the corrected spectrum, and a calculated spectrum obtained by adding the three spectra.
  • the sulfide solid electrolyte (hereinafter sometimes simply referred to as "solid electrolyte") according to the present embodiment includes a sulfide glass phase.
  • the sulfide solid electrolyte contains 4 PS units and 7 P 2 S units, and the ratio of the peak intensity I of PS 4 units (PS4) to the peak intensity I of P 2 S 7 units (P2S7) in the Raman spectrum is 0.05 ⁇ The relationship ⁇ I (P2S7) /I (PS4) ⁇ 1.00 is satisfied.
  • the sulfide solid electrolyte contains Li, P, S, and Ha as constituent elements, and Ha is a halogen element. The contents of Li, P, and S in at% are 30 to 50% for Li, 5 to 15% for P, and 30 to 60% for S.
  • the PS 4 unit is a PS 4 tetrahedral unit having a Q0 structure represented by PS 4 3- .
  • the PS 4 unit has a peak at a wave number of 415 to 425 cm ⁇ 1 in the Raman spectrum.
  • the P 2 S 7 unit is a dimer unit in which two PS 4 tetrahedra are connected, and has a Q1 structure represented by P 2 S 7 4- .
  • the P 2 S 7 unit has a peak at a wave number of 402 to 412 cm ⁇ 1 in the Raman spectrum.
  • the sulfide solid electrolyte forms a conduction path for lithium ions by including PS 4 units, and can widen the range of vitrification by including P 2 S 7 units.
  • the inventors' studies have shown that in a specific composition containing Ha in addition to Li, P, and S, a solid electrolyte containing sulfide glass can be produced by mainly containing 4 units of PS to 7 units of P 2 S. It has been found that high lithium ion conductivity can be achieved even with high lithium ion conductivity.
  • Mainly containing 4 PS units to 7 P 2 S units means that the ratio of the peak intensity I of PS 4 units (PS4) to the peak intensity I of P 2 S 7 units (P2S7) in the Raman spectrum is 0.05 ⁇ This means that the relationship ⁇ I (P2S7) /I (PS4) ⁇ 1.00 is satisfied.
  • the sulfide glass phase contained in the solid electrolyte according to the present embodiment contains Ha in addition to Li, P, and S
  • the sulfide glass phase mainly contains 4 units of PS to 7 units of P 2 S.
  • the solid electrolyte may consist only of a sulfide glass phase, or may include a crystalline phase in addition to the sulfide glass phase.
  • the solid electrolyte includes a crystalline phase, the P 2 S 7 units or PS 4 units that constitute the glass phase cannot be distinguished from the P 2 S 7 units or PS 4 units that constitute the crystalline phase.
  • the solid electrolyte has a specific composition containing Ha in addition to Li, P, and S, and mainly contains 4 units of PS to 7 units of P 2 S
  • the sulfide glass phase also has a similar composition, and It can be considered that it mainly contains 4 units of PS compared to 7 units of P 2 S.
  • the ratio represented by ⁇ I (P2S7) /I (PS4) ⁇ is more than 0.05, it is easy to obtain the vitrification effect by P 2 S 7 units, and it is easy to obtain a sulfide glass phase. That is, since a sulfide glass phase can be obtained at an appropriate quenching rate, it is preferable that large-scale equipment for quenching is not required. Further, when mass producing the solid electrolyte according to this embodiment by the melt quenching method described later, the obtained sulfide glass phase may contain 7 P 2 S units.
  • the ratio represented by ⁇ I (P2S7) /I (PS4) ⁇ is less than 1.00, a lithium ion conduction path is well formed by the PS 4 unit, achieving high lithium ion conductivity. can.
  • the above ratio can be achieved, for example, when obtaining a sulfide solid electrolyte by melting a raw material mixture while suppressing volatilization of raw materials including P, and rapidly cooling at a faster cooling rate than conventionally.
  • the ratio represented by ⁇ I (P2S7) /I (PS4) ⁇ may be more than 0.05 and less than 1.00, but preferably 0.1 to 0.9, more preferably 0.12 to 0.7. preferable.
  • the lower limit of the above ratio is more than 0.05, preferably 0.1 or more, and more preferably 0.12 or more.
  • the upper limit of the ratio is less than 1.00, preferably 0.9 or less, and more preferably 0.7 or less.
  • the method of determining the peak intensities I (PS4) and I (P2S7) in the Raman spectra of PS 4 units and P 2 S 7 units is as follows. First, the sulfide solid electrolyte is ground in a mortar and passed through a 100 ⁇ m sieve to form a solid electrolyte powder with an average particle size D50 of about 20 ⁇ m.
  • the average particle diameter D50 is 50% by volume of the particles, which is determined from the volume-based particle size distribution chart obtained by measuring the particle size distribution using a particle size distribution analyzer using a laser diffraction method. is the median diameter, meaning the particle diameter below that value.
  • the obtained solid electrolyte powder is made into a pellet-like green compact, and Raman spectra are measured at arbitrary 10 points in an environment without exposure to the atmosphere. Measurement conditions were: excitation wavelength: 532 nm, power during sample irradiation: 5 mW, objective lens: 10x, numerical aperture: 0.25, confocal pinhole: 200 ⁇ m, grating: 1200 gr/mm, measurement time: 3 seconds x 10 times. , Spot diameter: 3 ⁇ m.
  • a baseline for peak separation is drawn in the region of 330 cm -1 to 460 cm -1 .
  • the full width at half maximum is 15 cm -1 for a peak with a peak top at a wave number of 415 to 425 cm -1 , 15 cm -1 for a peak with a peak top at a wave number of 402 to 412 cm -1 , and a peak at a wave number of 383 to 393 cm -1
  • the peaks having the top are fixed at 22 cm ⁇ 1 and peak separation is performed. After that, optimization is performed using the least squares method so that the difference between the spectrum obtained by subtracting the baseline and the calculated spectrum obtained by adding the separated peaks is minimized. Note that although the value of the full width at half maximum is fixed at the above-mentioned value in the current measurement system, it may be changed depending on the spectrum for analysis.
  • a peak having a peak top at a wave number of 415 to 425 cm -1 is defined as a peak of 4 units of PS, and a peak having a peak top at a wave number of 402 to 412 cm -1 is defined as a peak of 7 units of P 2 S.
  • the peak intensity of each peak is the peak top intensity, that is, the highest intensity of each peak.
  • the sulfide solid electrolyte according to this embodiment may further include 6 P 2 S units.
  • the P 2 S 6 unit is a unit having a structure in which S is deleted, represented by P 2 S 6 4- .
  • the P 2 S 6 unit has a peak at a wave number of 383 to 393 cm ⁇ 1 in the Raman spectrum.
  • the ratio of the peak intensity I (P2S6) of P 2 S 6 units and the peak intensity I ( P2S7) of P 2 S 7 units in the Raman spectrum is ⁇ I (P2S7) / I (P2S6) ⁇ is preferably more than 0.5 and less than 10, more preferably 1.0 to 9.0, and even more preferably 1.5 to 8.0.
  • the P 2 S 6 unit is a unit that lowers lithium ion conductivity, the above ratio is preferably more than 0.5, more preferably 1.0 or more, and even more preferably 1.5 or more.
  • the above ratio is preferably less than 10, more preferably 9.0 or less, and even more preferably 8.0 or less.
  • the above ratio can be achieved, for example, when obtaining a sulfide solid electrolyte by melting a raw material mixture while suppressing volatilization of raw materials including P, and rapidly cooling at a faster cooling rate than conventionally.
  • the sulfide solid electrolyte according to the present embodiment preferably has a peak in the wave number range of 150 to 180 cm ⁇ 1 in the Raman spectrum, and the full width at half maximum of this peak is more preferably 20 cm ⁇ 1 or more.
  • the details of this peak are not clear, but as shown in the examples below, a solid electrolyte that has a peak with a full width at half maximum of 20 cm -1 or more in the wave number region of 150 to 180 cm -1 is a lithium ion High conductivity results have been obtained.
  • a sulfide solid electrolyte with a high proportion of sulfide glass phase exhibits a strong broad peak.
  • the full width at half maximum is more preferably 22 cm -1 or more, more preferably 25 cm -1 or more.
  • the upper limit of the full width at half maximum is not particularly limited as long as it can be recognized as a peak, but is, for example, 50 cm -1 or less.
  • the full width at half maximum in a Raman spectrum is an index representing the extent of peak spread, and is the width between wave numbers that indicates half the intensity of the peak top intensity.
  • Elements constituting the sulfide solid electrolyte according to this embodiment include Li, P, S, and Ha.
  • Ha is a halogen element, and may contain only one type or two or more types. Specifically, the content of the constituent elements expressed in at% satisfies Li: 30 to 50%, P: 5 to 15%, and S: 30 to 60%, Li: 30 to 50%, P: It is preferable to satisfy 5 to 12%, S: 30 to 50%, and Ha: 2 to 10%.
  • Li 30 to 50%
  • P 5 to 15%
  • S 30 to 60%
  • Li 30 to 50%
  • P It is preferable to satisfy 5 to 12%
  • Ha 2 to 10%.
  • P is an element that forms a glass network, and the PS bond has high resistance to both oxidation and reduction among sulfides. Therefore, it has a wide potential window as a solid electrolyte and has excellent electrochemical stability.
  • the content of P expressed as at%, is 5 to 15%, preferably 6 to 13%, and more preferably 7 to 12%. From the viewpoint of expanding the vitrification range, the P content is 5% or more, preferably 6% or more, and more preferably 7% or more. Further, from the viewpoint of increasing lithium ion conductivity, the content of P is 15% or less, preferably 13% or less, and more preferably 12% or less.
  • Li is an element responsible for ionic conduction as a solid electrolyte.
  • the Li content expressed as at%, is 30 to 50%, preferably 35 to 45%, and more preferably 37 to 43%. From the viewpoint of increasing lithium ion conductivity, the Li content is 30% or more, preferably 35% or more, and more preferably 37% or more. Moreover, from the viewpoint of expanding the vitrification range, the Li content is 50% or less, preferably 45% or less, and more preferably 43% or less.
  • S is an element that forms a PS bond with P, and is an essential element for forming a glass phase.
  • the content of S is 30 to 60% in at%, preferably 33 to 50%, and more preferably 35 to 47%. From the viewpoint of expanding the vitrification range, the S content is 30% or more, preferably 33% or more, and more preferably 35% or more. Further, from the viewpoint of increasing lithium ion conductivity, the content of S is 60% or less, preferably 50% or less, and more preferably 47% or less.
  • Ha is an element necessary to form sulfide glass with high lithium ion conductivity. It is preferable that Ha includes at least one selected from the group consisting of F, Cl, Br and I, and more preferably at least one selected from the group consisting of Cl, Br and I.
  • the total content of Ha is preferably 2 to 10% in at%, more preferably 3 to 9%, and even more preferably 3.5 to 8%. From the viewpoint of obtaining high lithium ion conductivity, the total content of Ha is preferably 2% or more, more preferably 3% or more, and even more preferably 3.5% or more. Further, the total content of Ha is preferably 10% or less, more preferably 9% or less, and even more preferably 8% or less from the viewpoint of preventing precipitation of lithium halide crystals.
  • the content ratio (Li/P) expressed in at% of Li and P is preferably 2.5 to 7, more preferably 3.0 to 6.5, and 3.2 to 6. 2 is more preferred. From the viewpoint of relatively increasing PS 4 units and obtaining high lithium ion conductivity, the ratio is preferably 2.5 or more, more preferably 3.0 or more, and even more preferably 3.2 or more. Moreover, from the viewpoint of widening the vitrification range, the above ratio is preferably 7 or less, more preferably 6.5 or less, and even more preferably 6.2 or less.
  • the sulfide solid electrolyte according to this embodiment may contain other elements than the above Li, P, S, and Ha as constituent elements.
  • other elements examples include Si, B, Ge, Al, O, Na, K, Mg, Ca, Sr, Ba, Y, Zr, Cr, Zn, Ga, Sn, and Sb.
  • oxides such as SiO 2 , B 2 O 3 , P 2 O 5 , Al 2 O 3 , etc., it is preferable not to include such oxides since they become crystal nuclei. .
  • the total content of oxides is preferably 1 mol% or less, more preferably 0.1 mol% or less, even more preferably 0.05 mol% or less, expressed as mol% based on oxides, and does not contain, that is, 0. It may be mol%.
  • oxides there are also oxides that become glass network formers, such as SiO 2 , B 2 O 3 , P 2 O 5 , Al 2 O 3 and the like.
  • oxides that become glass network formers of the glass are included, their total content is preferably 3 to 20 mol%, more preferably 5 to 18 mol%, expressed as mol% based on oxides.
  • 7 to 16 mol% is more preferable.
  • the above-mentioned total content is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 7 mol% or more, from the viewpoint of promoting vitrification tendency. Moreover, from the viewpoint of realizing high lithium ion conductivity, the above-mentioned total content is preferably 20 mol% or less, more preferably 18 mol% or less, and even more preferably 16 mol% or less.
  • the content of Si is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5% in at%.
  • the content of Si may be included from the viewpoint of increasing the viscosity of the melt and promoting vitrification, but from the viewpoint of electrochemical stability, the content of Si should be 15% or less. It is preferably 10% or less, more preferably 5% or less.
  • the total content of oxides should be 1 mol% or less, or The content of Si expressed in at% is adjusted as appropriate so that the total content of oxides that become the glass network former is 3 to 20 mol%.
  • the content is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5% in at%.
  • the content of B may be included from the viewpoint of increasing the viscosity of the melt and promoting vitrification, but from the viewpoint of lithium ion conductivity, the content of B should be 15% or less. It is preferably 10% or less, more preferably 5% or less.
  • the total content of oxides should be 1 mol% or less, Alternatively, the content in at% of B is appropriately adjusted so that the total content of oxides that become the glass network former is 3 to 20 mol%.
  • the sulfide solid electrolyte When the sulfide solid electrolyte contains P as a constituent element, it basically exists in the form of a PS bond, but it may partially contain a PO bond. Although the effect of PO as a crystal nucleus is not well understood, it can serve as a network former for glass.
  • the content of P in terms of at% is 5 to 15% as described above, but a part of it may form a PO bond.
  • the proportion of P forming the P--O bond relative to the total P content is preferably 0 to 5% or 15 to 50%, more preferably more than 0% and 4% or less, or 15 to 40%, and 0.01 -2% or 15-30% is more preferred.
  • the content is preferably 0 to 5% within the industrially feasible range. From the same point of view, more than 0% is more preferable, and even more preferably 0.01% or more. Further, from the viewpoint of avoiding formation of crystal nuclei, the content is more preferably 4% or less, and even more preferably 2% or less. From the viewpoint of forming a network former and promoting vitrification, the proportion of P is preferably 15% or more. Further, from the viewpoint of lithium ion conductivity, the proportion of P is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less. Note that the ratio of P forming a PO bond to the total P content is determined by 31 P-NMR.
  • the content is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5% in at%.
  • the content of Al may be included from the viewpoint of increasing the viscosity of the melt and promoting vitrification, but from the viewpoint of lithium ion conductivity, the content of Al should be 15% or less. It is preferably 10% or less, more preferably 5% or less.
  • the total content of oxides should be 1 mol% or less, Alternatively, the content of Al expressed in at% is adjusted as appropriate so that the total content of oxides that become the glass network former is 3 to 20 mol%.
  • the O content is such that the total content of oxides is 1 mol% or less, or an oxide that becomes a glass network former.
  • the O content is preferably such that the total content of O is 3 to 20 mol%. Therefore, the content of O in at% is preferably 1% or less, and 0.5% or less, from the viewpoint of suppressing the formation of crystals with oxide as the core, although it varies depending on the types of other constituent elements. is more preferable, and even more preferably 0.1% or less.
  • the content of O is preferably as low as possible, and may be omitted, that is, 0%.
  • the content of O in at% is preferably 3 to 15%, more preferably 4 to 10% when it plays a role as a network former for glass, although it varies depending on the types of other constituent elements. , 5 to 8% is more preferable.
  • the content of O is preferably 3% or more, more preferably 4% or more, and even more preferably 5% or more.
  • the O content is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less.
  • the content of Zr is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5% in at%.
  • the content of Zr may be included from the viewpoint of increasing the viscosity of the melt and promoting vitrification, but from the viewpoint of lithium ion conductivity, the content of Zr should be 15% or less. It is preferably 10% or less, more preferably 5% or less.
  • Zr does not become a glass network former, when it has a Zr--O bond or is included as an oxide of ZrO 2 , it has the effect of increasing the viscosity of the melt and promoting vitrification.
  • the content of Zr expressed in at% is adjusted as appropriate so that the total content of oxides is 3 to 20 mol%.
  • the content of Zr expressed in at% is appropriately adjusted so that the total content of oxides is 1 mol% or less so as not to form crystal nuclei.
  • the other elements mentioned above, such as Sn and Sb, are similar to Zr, and their total content is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5% in at%.
  • other elements such as Sn and Sb may be included from the viewpoint of increasing the viscosity of the melt and promoting vitrification, but from the viewpoint of lithium ion conductivity, the above total content is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less.
  • other elements have a bond with O or are included as oxides, they have the effect of increasing the viscosity of the melt and promoting vitrification.
  • the total content is preferably 3% or more, more preferably 5% or more, even more preferably 8% or more, and the total content of oxides is 3 to 20 mol%.
  • the total content of other elements expressed in at% is adjusted as appropriate so that: Alternatively, as described above, in order to prevent the oxide from becoming a crystal nucleus, it is not necessary to substantially contain other elements, for example, 1 at % or less.
  • the sulfide glass phase contains Li, P, S, and Ha as constituent elements within a specific range, and mainly contains 4 units of PS to 7 units of P 2 S.
  • the content of the sulfide glass phase in the solid electrolyte is preferably 50% by weight or more, more preferably 70% by weight or more, from the viewpoints of contact between the electrolytes, contact between the electrolyte and the active material, composition homogeneity, etc. It is more preferably 80% by weight or more, and may be 100% by weight, that is, it may consist only of the sulfide glass phase.
  • a crystalline phase may be included, and in that case, the content of the sulfide glass phase is preferably 99% by weight or less, and 95% by weight or less. is more preferable, and even more preferably 90% by weight or less.
  • One embodiment of the content of the sulfide glass phase is 50 to 100% by weight, one embodiment is 70 to 99% by weight, and one embodiment is 80 to 95% by weight.
  • the content of the sulfide glass phase was determined by powdering the obtained electrolyte, performing powder X-ray diffraction (XRD) measurement together with crystalline powder serving as an internal standard, and performing Rietveld analysis. Desired.
  • the sulfide solid electrolyte according to this embodiment is suitable as an electrolyte for a lithium ion secondary battery. Furthermore, the sulfide solid electrolyte according to this embodiment has a wide potential window and is difficult to oxidize and decompose even on the high potential side. Therefore, it is also preferable to use a positive electrode with an operating potential of about 4V, called a 4V class positive electrode, or a positive electrode with an operating potential of about 5V, called a 5V class positive electrode.
  • the lithium ion conductivity of the sulfide solid electrolyte according to this embodiment is preferably over 1.0 ⁇ 10 ⁇ 4 S/cm, and 3.0 ⁇ It is more preferably 10 ⁇ 4 S/cm or more, and even more preferably 5.0 ⁇ 10 ⁇ 4 S/cm or more.
  • the lithium ion conductivity in this specification is a value measured by the following method. First, the sulfide solid electrolyte is ground in a mortar and passed through a 100 ⁇ m sieve to form a solid electrolyte powder with an average particle size D50 of about 20 ⁇ m. The obtained solid electrolyte powder is pressed into a powder compact at a pressure of 380 kN and used as a measurement sample. Using an AC impedance measurement device, measure the AC impedance of the measurement sample at a measurement frequency of 100 Hz to 1 MHz, a measurement voltage of 100 mV, and a measurement temperature of 25°C. Let it be ionic conductivity.
  • the sulfide solid electrolyte When used in a lithium ion secondary battery, it forms a solid electrolyte layer together with other components such as a binder as necessary.
  • a binder As the binder and other components, conventionally known materials can be used.
  • the content of the solid electrolyte in the entire solid electrolyte layer is preferably 80% by mass or more, more preferably 90% by mass or more.
  • the solid electrolyte may be mixed with a positive electrode active material or a negative electrode active material and used as a positive electrode layer or a negative electrode layer.
  • Conventionally known materials can be used as the positive electrode active material or negative electrode active material, current collector, binder, conductive aid, etc. used in the positive electrode layer or negative electrode layer.
  • a lithium ion secondary battery using a solid electrolyte includes the solid electrolyte layer, a positive electrode layer, and a negative electrode layer.
  • Conventionally known materials can also be used for the outer casing of the lithium ion secondary battery.
  • Conventionally known shapes of lithium ion secondary batteries can be used, such as coin shapes, sheet shapes (film shapes), folded shapes, rolled bottomed cylindrical shapes, button shapes, etc., depending on the application. You can select as appropriate.
  • the method for producing the sulfide solid electrolyte according to the present embodiment is not particularly limited as long as the solid electrolyte described in ⁇ Sulfide Solid Electrolyte> above can be obtained.
  • the sulfide solid electrolyte containing a sulfide glass phase it was difficult to realize a configuration mainly containing PS 4 units compared to P 2 S 7 units; was the main one.
  • production method i includes the following steps 1 to 3 in order.
  • Step 1 A step of mixing raw materials containing lithium element, sulfur element, and phosphorus element to obtain a raw material mixture.
  • Step 2 A step of heating and melting the raw material mixture in a gas atmosphere containing elemental sulfur to obtain a melt.
  • Step 3 A step of rapidly cooling the melt to obtain a solid.
  • the content ratio of lithium element and phosphorus element in the raw material mixture obtained in step 1 in at% is set to Li/P ⁇ 2.5. Further, the cooling rate of the rapid cooling in step 3 is 500° C./second or more.
  • step 1 is a step of mixing raw materials as step S1
  • step 2 is a step of heating and melting the raw material mixture obtained in step 1 as step S2.
  • step 3 is a step in which the melt obtained in step 2 is rapidly cooled as step S3.
  • step 1 it is preferable that a raw material containing a halogen element is further included. That is, step 1 in manufacturing method i is preferably the following step 1'.
  • Step 1' A step of mixing raw materials containing a lithium element, a sulfur element, a phosphorus element, and a halogen element to obtain a raw material mixture.
  • One embodiment of the above manufacturing method i includes manufacturing method a, which includes the following steps a1-1, a1-2, a2, and a3 in this order.
  • Step a1-1 A step of mixing raw materials containing lithium element, sulfur element, and phosphorus element to obtain a raw material mixture.
  • Step a1-2 A step of heating the raw material mixture to obtain an intermediate.
  • Step a2 A step of heating and melting the intermediate in a gas atmosphere containing elemental sulfur to obtain a melt.
  • Step a3 A step of rapidly cooling the melt to obtain a solid.
  • the raw materials are mixed so that the ratio of the contents of lithium element and phosphorus element expressed in at% in the raw material mixture obtained in step a1-1 becomes Li/P ⁇ 2.5.
  • the cooling rate of the rapid cooling in step a3 is 500° C./second or more.
  • a raw material containing a halogen element is further mixed to obtain the raw material mixture, or in step a2, the raw material containing a halogen element is added to the intermediate. After mixing, the above-mentioned melt is obtained by heating and melting.
  • Step b1-1 A step of mixing raw materials containing lithium element, sulfur element, and phosphorus element to obtain a raw material mixture.
  • Step b1-2 A step of sealing the raw material mixture in an airtight container.
  • Step b2 A step of heating the sealed container and heating and melting the raw material mixture to obtain a melt.
  • Step b3 A step in which the melt is rapidly cooled at the same time as it is removed from the closed container to obtain a solid.
  • the raw materials are mixed so that the content ratio of lithium element and phosphorus element in at% in the raw material mixture obtained in step b1-1 becomes Li/P ⁇ 2.5. Further, the cooling rate of the rapid cooling in step b3 is 500° C./second or more.
  • a raw material containing a halogen element is further mixed to obtain the raw material mixture.
  • step a1-1 in manufacturing method a is a step in which raw materials are mixed as step S11a. Specifically, raw materials containing a lithium element, a sulfur element, and a phosphorus element are mixed to obtain a raw material mixture. Moreover, in addition to the above, it is also preferable to mix a raw material containing a halogen element to obtain a raw material mixture.
  • the raw material containing a halogen element may be contained in the intermediate as it is without reacting when the intermediate is obtained by the heat treatment in the subsequent step a1-2. Therefore, in the manufacturing method according to the present embodiment, after the raw material mixture containing no raw material containing a halogen element is subjected to heat treatment in the subsequent step a1-2 to obtain an intermediate, the raw material containing a halogen element is converted into an intermediate.
  • a melt may be obtained by mixing and heating and melting in step a2.
  • compounds containing Ha can be used in appropriate combinations as desired.
  • the above compound may be a compound containing two or more selected from the group consisting of Li, S, P, and Ha.
  • diphosphorus pentasulfide (P 2 S 5 ) and the like can be mentioned as a compound that functions as both an S-containing compound and a P-containing compound.
  • a lithium halide can be mentioned as a compound that serves both as a compound containing Li and a compound containing Ha.
  • raw materials containing the Li element include lithium sulfide (Li 2 S), lithium carbonate (Li 2 CO 3 ), lithium sulfate (Li 2 SO 4 ), and lithium oxide (Li 2 O), and lithium compounds such as lithium hydroxide (LiOH).
  • lithium sulfide is preferable from the viewpoint of ease of synthesis of the intermediate described later and ease of handling.
  • lithium compounds other than lithium sulfide, metallic lithium, etc. are preferable.
  • lithium carbonate Li 2 CO 3
  • lithium sulfate Li 2 SO 4
  • lithium oxide Li 2 O
  • lithium hydroxide LiOH
  • Raw materials containing the S element include elemental sulfur, as well as compounds containing S, such as phosphorus sulfide and phosphorus such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ). Examples include other sulfur compounds and compounds containing sulfur.
  • Compounds containing sulfur include iron sulfides such as H 2 S, CS 2 , FeS, Fe 2 S 3 , FeS 2 , Fe 1-x S, bismuth sulfide (Bi 2 S 3 ), CuS, Cu 2 S, Cu Examples include copper sulfide such as 1-xS .
  • the raw material containing the S element is preferably phosphorus sulfide, from the viewpoint of ease of reaction when synthesizing the intermediate described later and preventing the inclusion of elements other than those constituting the target sulfide solid electrolyte. More preferred is diphosphorus (P 2 S 5 ). These may be used alone or in combination of two or more. Note that phosphorus sulfide is considered to be a compound that serves as both an S-containing substance and a P-containing substance.
  • raw materials containing P element include P-containing compounds such as phosphorus sulfide such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ), lithium thiophosphate (Li Examples include phosphorus compounds such as 3 PS 4-x O x ).
  • the raw material containing the P element is preferably phosphorus sulfide, from the viewpoint of ease of reaction when synthesizing the intermediate described later and preventing the inclusion of elements other than those constituting the target sulfide solid electrolyte. More preferred is diphosphorus (P 2 S 5 ). These may be used alone or in combination of two or more.
  • the raw material containing the P element contains an oxide
  • examples thereof include P 2 O 5 , Li 3 PO 4 , Li 4 P 2 O 7 and the like.
  • P 2 O 5 is preferred from the viewpoint of ease of production.
  • These compounds may be used alone or in combination of two or more.
  • Examples of compounds containing Ha which are raw materials containing the Ha element, include lithium halides such as lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), and lithium iodide (LiI); Examples include phosphorus, phosphoryl halide, sulfur halide, sodium halide, boron halide, and the like. From the viewpoint of preventing the inclusion of elements other than those constituting the target sulfide solid electrolyte, the raw material containing the Ha element is preferably lithium halide, and more preferably LiCl, LiBr, and LiI. These compounds may be used alone or in combination of two or more.
  • lithium halide is also a compound containing Li.
  • the raw material contains lithium halide, part or all of Li in the raw material may be derived from lithium halide.
  • the molar equivalent of Ha to P in the raw material is preferably 0.1 to 4 molar equivalents, more preferably 0.2 to 3 molar equivalents.
  • the molar equivalent of Ha is preferably 0.1 molar equivalent or more, and more preferably 0.2 molar equivalent or more.
  • the molar equivalent of Ha is preferably 4 molar equivalents or less, more preferably 3 molar equivalents or less.
  • raw materials containing the other elements are also mixed to obtain a raw material mixture.
  • raw materials containing these other elements may be mixed together to obtain a raw material mixture at the time of mixing the raw materials in step a1-1, as well as raw materials containing the Ha element, and in step a2, intermediates may be mixed together.
  • a melt may be obtained by mixing with the intermediate and melting it together with the intermediate.
  • the raw materials containing the other elements mentioned above will be explained.
  • Examples of the raw material containing the Si element include SiO 2 and SiS 2 . Among them, SiO 2 is more preferable from the viewpoint of lithium ion conductivity and water resistance. These compounds may be used alone or in combination of two or more.
  • Examples of the raw material containing element B include B 2 O 3 and B 2 S 3 .
  • B 2 O 3 is more preferable from the viewpoint of water resistance of the glass.
  • These compounds may be used alone or in combination of two or more.
  • Examples of the raw material containing the Al element include Al 2 S 3 , Al 2 O 3 , and AlCl 3 .
  • Al 2 S 3 and AlCl 3 are preferred, and Al 2 S 3 is more preferred.
  • These compounds may be used alone or in combination of two or more.
  • Examples of the raw material containing the O element include oxides of each of the above elements.
  • oxides of elements that serve as network formers for glass are preferable, and for example, SiO 2 , B 2 O 3 , P 2 O 5 , and Al 2 O 3 are preferable, and SiO 2 is more preferable.
  • These compounds may be used alone or in combination of two or more.
  • the raw materials can be mixed, for example, by mixing in a mortar, mixing using a media such as a planetary ball mill, media-less mixing such as a pin mill, a powder stirrer, or air flow mixing.
  • the raw materials may be made amorphous by mixing before heating.
  • the mixing ratio of the raw materials is adjusted as appropriate depending on the composition of the intended sulfide solid electrolyte and intermediate. Therefore, the mixing ratio of the raw materials is not particularly limited, but for example, Li/P, which is the at ratio of Li to P in the raw materials, is 2.5 or more, preferably 2.5 to 7, and 3.0 to 6. 5 is more preferable, and 3.2 to 6.2 is even more preferable.
  • Li/P is 2.5 or more from the viewpoint of accurately synthesizing the target intermediate and from the viewpoint of relatively increasing the PS 4 unit in the obtained sulfide solid electrolyte and obtaining high lithium ion conductivity. and is preferably 3.0 or more, more preferably 3.2 or more.
  • the above ratio is preferably 7 or less, more preferably 6.5 or less, and even more preferably 6.2 or less.
  • An example of a preferable combination of the above compounds is a combination of Li 2 S and P 2 S 5 .
  • Li 2 S and P 2 S 5 When combining Li 2 S and P 2 S 5 , by setting the molar ratio Li/P of Li and P within the above range, the boiling point of P 2 S 5 is lower than the melting point of Li 2 S. It also has the effect of making it easier to suppress volatilization of sulfur and phosphorus components during heat treatment.
  • the content of each element in at% is Li: 30 to 50%, P: 5 to 15%, and S: 30 to 60%. It is preferable to mix the raw materials so that Li: 30 to 50%, P: 5 to 12%, S: 30 to 50%, and Ha: 2 to 10%. preferable.
  • the particle size (D50) of the raw material is too large, it may affect the homogeneity of the sulfide solid electrolyte, and from this point of view as well, it is preferable that the particle size (D50) be small to some extent.
  • this manufacturing method since this manufacturing method has excellent composition controllability, for example, even if a raw material with a particle size that would reduce homogeneity in conventional manufacturing methods is used, this manufacturing method can produce a more homogeneous sulfide solid electrolyte. obtain.
  • the particle size (D50) of the raw material is preferably 1 mm or less, more preferably 500 ⁇ m or less, even more preferably 250 ⁇ m or less, even more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the particle size of the raw material is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and even more preferably 250 ⁇ m or more.
  • the particle size (D50) of the raw material is preferably 0.1 ⁇ m to 1 mm, more preferably 1 to 500 ⁇ m, even more preferably 5 to 250 ⁇ m, even more preferably 5 to 100 ⁇ m, and particularly preferably 5 to 50 ⁇ m. Further, from the viewpoint of manufacturing cost, the particle size (D50) of the raw material is preferably 10 ⁇ m to 1 mm, more preferably 100 ⁇ m to 1 mm, and even more preferably 250 to 500 ⁇ m.
  • the raw material may be a mixture of multiple compounds as described above.
  • the raw material may be in the form of a mixture of a plurality of substances having different particle sizes.
  • the particle size of each substance is preferably within the above range.
  • the particle size (D50) of the raw material is the median diameter ( D50).
  • step a1-2 is a step in which the raw material mixture obtained in step a1-1 is subjected to heat treatment as step S11b to obtain an intermediate.
  • Heat-resistant containers include, but are not particularly limited to, heat-resistant containers made of carbon, heat-resistant containers containing oxides such as quartz, quartz glass, borosilicate glass, aluminosilicate glass, alumina, zirconia, and mullite, silicon nitride, Examples include heat-resistant containers containing nitrides such as boron nitride, heat-resistant containers containing carbides such as silicon carbide, and the like. Further, these heat-resistant containers may have a bulk formed of the above-mentioned materials, or may have a layer formed of carbon, oxide, nitride, carbide, or the like.
  • the temperature at which the raw material mixture is heated is preferably 250 to 500°C, more preferably 255 to 450°C, even more preferably 260 to 400°C.
  • the temperature at which the raw material mixture is heated is preferably 250°C or higher, more preferably 255°C or higher, and even more preferably 260°C or higher.
  • the temperature at which the raw material mixture is heated is 500 ° C. The temperature is preferably below, more preferably 450°C or less, and even more preferably 400°C or less.
  • the temperature range during holding is preferably within a certain temperature range, for example, preferably within ⁇ 15°C of the reference temperature, more preferably within ⁇ 10°C.
  • the holding time in the heat treatment is preferably 1 to 600 minutes, more preferably 5 to 600 minutes, even more preferably 10 to 500 minutes, even more preferably 15 to 500 minutes, and particularly preferably 20 to 500 minutes.
  • the holding time is preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, even more preferably 15 minutes or more, Particularly preferred is 20 minutes or more.
  • the holding time is preferably 600 minutes or less, more preferably 500 minutes or less.
  • the above-mentioned holding time may be further shortened in some cases, such as when the raw material is subjected to a predetermined treatment.
  • Such treatments include, for example, reducing the particle size of the raw materials, removing or modifying the oxide layer on the surface of the particles contained in the raw materials as much as possible by etching, making the particles porous, and mixing the raw materials. Examples include adjusting conditions and improving the homogeneity of raw materials. These can enhance the reactivity between particles contained in the raw material.
  • the holding time is preferably 1 second to 10 minutes, more preferably 10 seconds to 10 minutes, even more preferably 20 seconds to 5 minutes.
  • the lower limit of the holding time is preferably 1 second or more, more preferably 10 seconds or more, and even more preferably 20 seconds or more, from the viewpoint of sufficiently advancing the reaction and obtaining the desired intermediate.
  • the holding time is preferably 10 minutes or less, more preferably 5 minutes or less.
  • the pressure during the heat treatment is not particularly limited, but, for example, normal pressure to slight pressure is preferable, and normal pressure is more preferable.
  • the heat treatment for synthesizing the intermediate is preferably performed under an inert gas atmosphere in order to prevent side reactions between the raw material mixture and water vapor, oxygen, and the like.
  • Specific examples include N 2 gas, argon gas, and helium gas.
  • the dew point during the heat treatment is preferably -20°C or lower, and the lower limit is not particularly limited, but is usually about -80°C.
  • the oxygen concentration is preferably 1000 ppm or less.
  • intermediates with different compositions can be obtained depending on the purpose by adjusting the compounds contained in the raw material mixture and their mixing ratio, as well as controlling the conditions during heat treatment.
  • the obtained intermediate may be directly used in the heat-melting step in the heating furnace used for intermediate synthesis without being removed from the heat-resistant container, or may be taken out and temporarily stored after cooling to room temperature. It is also possible to use a combination of a plurality of intermediates of different compositions that have been taken out and stored in the heat-melting process.
  • composition of the intermediate obtained in this step examples include compounds containing Li, P and S, such as Li 4 P 2 S 6 and Li 3 PS 4 .
  • the intermediate preferably contains at least one of Li 4 P 2 S 6 and Li 3 PS 4 .
  • Li 4 P 2 S 6 and Li 3 PS 4 are thermodynamically stable, they are preferable from the viewpoint of stability during temporary storage of the intermediate.
  • the reaction that occurs in the synthesis of the intermediate depends on the composition of the target sulfide solid electrolyte, but typically Li 2 S and P 2 S 5 contained in the raw materials react from about 250 ° C.
  • This reaction is characterized by the formation of at least one of Li 4 P 2 S 6 and Li 3 PS 4 .
  • Li 2 S and P 2 S 5 may be started from a raw material containing Li or a raw material containing P at a stage before obtaining each. In order to essentially speed up this reaction, it is preferable to increase the reactivity between the particles contained in the raw materials, as described above.
  • the particle size of Li 2 S with which P 2 S 5 first reacts tends to affect the synthesis reaction of the intermediate.
  • step a1-2 of obtaining an intermediate volatilization of the sulfur component and phosphorus component in the raw material can be suppressed compared to the case where the target sulfide solid electrolyte is directly obtained from the raw material. Therefore, compounds containing Li, P, and S, such as Li 4 P 2 S 6 and Li 3 PS 4 with clear composition information, can be synthesized as intermediates. Since these intermediates are thermodynamically stable, they can be taken out by lowering the temperature to room temperature after the heat treatment during intermediate synthesis. It is also possible to perform a compositional analysis on the intermediate thus extracted, so that the amount of sulfur introduced in the heat-melting process can be determined.
  • step a2 is a step in which the intermediate obtained in step a1-2 is heated and melted as step S12 in a gas atmosphere containing elemental sulfur to obtain a melt.
  • the intermediate to be heated and melted may be an intermediate composition in which multiple types of intermediates are mixed, if necessary.
  • a raw material containing the above elements may be added and then heated and melted.
  • step 2 of manufacturing method i the raw material mixture is heated and melted.
  • this production method a is employed in production method i, not the raw material mixture but the intermediate obtained by heat treatment of the raw material mixture becomes the target of heating and melting.
  • an intermediate composition in which a plurality of types of intermediates are mixed together, or an intermediate composition in which a raw material containing another element is added to the intermediate may be subjected to heating and melting.
  • Heat-resistant containers include, but are not particularly limited to, heat-resistant containers made of carbon, heat-resistant containers containing oxides such as quartz, quartz glass, borosilicate glass, aluminosilicate glass, alumina, zirconia, and mullite, silicon nitride, Examples include heat-resistant containers containing nitrides such as boron nitride, heat-resistant containers containing carbides such as silicon carbide, and the like. Further, these heat-resistant containers may have a bulk formed of the above-mentioned materials, or may have a layer formed of carbon, oxide, nitride, carbide, or the like.
  • the heating and melting is performed in a gas atmosphere containing elemental sulfur.
  • the gas containing elemental sulfur is, for example, a compound containing elemental sulfur or a gas containing elemental sulfur, such as sulfur gas, hydrogen sulfide gas, or carbon disulfide gas.
  • the gas containing sulfur element may be composed only of gaseous compounds containing sulfur element such as sulfur gas, hydrogen sulfide gas, carbon disulfide gas, etc., or it may be used as a carrier gas to transport the sulfur component from the viewpoint of cost reduction. In view of this, it is also preferable to include an inert gas such as N 2 gas, argon gas, helium gas, etc. Further, the gas containing elemental sulfur may contain impurities derived from the sulfur source, etc., as long as the effects of the present manufacturing method are not impaired.
  • the content of sulfur gas ( S It is more preferably 99% by volume, and even more preferably 0.2 to 98% by volume.
  • the content of sulfur gas is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, and 0.01% by volume or more. More preferably 2% by volume or more.
  • the content of sulfur gas is 100% by volume or less, but from the viewpoint of cost reduction and the use of an inert gas as a carrier gas, it is preferably 99% by volume or less, and more preferably 98% by volume or less.
  • Gas containing elemental sulfur is obtained by heating a sulfur source. Therefore, the sulfur source is not particularly limited as long as it is elemental sulfur or a sulfur compound that can be heated to produce a gas containing elemental sulfur; for example, elemental sulfur, hydrogen sulfide, organic sulfur compounds such as carbon disulfide, FeS, Fe2S , etc. 3 , iron sulfides such as FeS 2 and Fe 1-x S, bismuth sulfide (Bi 2 S 3 ), copper sulfides such as CuS, Cu 2 S, and Cu 1-x S, and polysulfides such as lithium polysulfide and sodium polysulfide. Examples include sulfide, polysulfide, and rubber treated with sulfur vulcanization.
  • these sulfur sources are heated in a separately provided sulfur source heating section to generate gas containing sulfur elements, which is then transported to a heating and melting furnace using an inert gas such as N2 gas, argon gas, or helium gas as a carrier gas.
  • an inert gas such as N2 gas, argon gas, or helium gas as a carrier gas.
  • a gas atmosphere containing elemental sulfur can be obtained.
  • the temperature at which the sulfur source is heated may be appropriately selected depending on the type of sulfur source used.
  • the heating temperature is preferably 250°C or higher, and preferably 750°C or lower.
  • solid sulfur sources such as elemental sulfur, H 2 S, Bi 2 S 3 , iron sulfide, copper sulfide, CS 2 , etc. are placed in a fine state such as powder in a heating melting furnace using a carrier gas.
  • a gas atmosphere containing sulfur element may be obtained by air flow conveyance.
  • a specific method for heating and melting the intermediate can be a conventionally known method.
  • a part that heats a sulfur source to generate a gas containing sulfur element and a part that supplies gas containing sulfur element from there.
  • a part for heating and melting the intermediate may be provided separately.
  • Sulfur components such as P 2 S 5 volatilized during the synthesis reaction of the intermediate may be recovered and used as a sulfur source in this step a2.
  • the reaction time for sulfur introduction can be shortened compared to the reaction in a solid phase state. Furthermore, since it is in a liquid phase state, it is easy to introduce sulfur homogeneously into the entire melt, and the composition of the obtained sulfide solid electrolyte is likely to be homogeneous. Note that the viscosity of the intermediate melt decreases due to the fluidization of the solid, and it is in a highly uniform state. As a result, the melt of the intermediate has high solubility and diffusivity for gases containing elemental sulfur. Therefore, the effect of shortening the reaction time and homogenizing the composition by reacting in a liquid phase state becomes more excellent. Further, it is more preferable to carry out heating and melting while stirring the melt or the gas containing the sulfur element, since the above-mentioned effects can be more easily obtained.
  • the heating and melting temperature is preferably 600 to 950°C, more preferably 630 to 900°C, even more preferably 650 to 850°C.
  • the heating melting temperature is preferably 600°C or higher, more preferably 630°C or higher, and even more preferably 650°C or higher.
  • the temperature of heating and melting is preferably 950°C or lower, more preferably 900°C or lower, and even more preferably 850°C or lower.
  • the heating and melting time is preferably 0.1 to 10 hours, more preferably 0.5 to 9.5 hours, even more preferably 0.7 to 9 hours, and particularly preferably 1 to 9 hours.
  • the heating and melting time is preferably 0.1 hour or more, more preferably 0.5 hour or more, even more preferably 0.7 hour or more, and even more preferably 1 hour or more. preferable.
  • the heating melting time is preferably 10 hours or less, more preferably 9.5 hours or less, and even more preferably 9 hours or less.
  • Heating and melting may be performed as a continuous process.
  • a continuous process is one in which the molten liquid is continuously allowed to flow down from a heat-resistant container.
  • What is input may be an intermediate or a raw material mixture.
  • the input may be continuous or intermittent.
  • the melt When heating and melting is carried out as a continuous process, the melt may be kept in a molten state for a long time under appropriate conditions that take into consideration the progress of the sulfur introduction reaction and the deterioration of components in the melt. good.
  • the long time may be, for example, about 24 hours.
  • the pressure during heating and melting is not particularly limited, but, for example, normal pressure to slight pressure is preferable, and normal pressure is more preferable. Further, it is preferable that the sulfur partial pressure is 10 ⁇ 3 to 100 atm. By setting such a sulfur partial pressure, sulfur can be efficiently introduced at low cost without complicating the device, and it is easy to obtain the desired sulfide solid electrolyte.
  • the dew point is preferably ⁇ 20° C. or lower.
  • the lower limit is not particularly limited, but is usually about -80°C.
  • the oxygen concentration is preferably 1000 ppm or less.
  • step a3 is a step in which the melt obtained in step a2 is rapidly cooled at a cooling rate of 500° C./second or more as step S13 to obtain a solid.
  • the melt obtained by heating and melting is rapidly cooled at a cooling rate of 500° C./second or more.
  • the resulting solid containing a sulfide glass phase has very high compositional homogeneity, and variations in quality can be suppressed very well. Further, it is possible to realize a configuration that mainly includes 4 PS units compared to 7 P 2 S units, and high lithium ion conductivity can be achieved.
  • the cooling rate may be 500°C/second or more, preferably 500 to 1,000,000°C/second, more preferably 700 to 100,000°C/second, and even more preferably 1,000 to 10,000°C/second.
  • the cooling rate is 500°C/second or more, preferably 700°C/second or more, and 1000°C/second or more. is more preferable.
  • the cooling rate of twin rollers which is generally said to have the fastest quenching rate
  • the cooling rate is preferably 1,000,000°C/second or less, and from the perspective of actual production, the cooling rate is more preferably 100,000°C/second or less.
  • 10,000° C./second or less is more preferable.
  • the atmosphere during quenching is preferably a low moisture content, inert atmosphere, as in the case of melting.
  • the crystallinity of a sulfide solid electrolyte containing a sulfide glass phase can be determined by the method of adding a compound that becomes a crystal nucleus to the raw material, the method of adding a compound that becomes a crystal nucleus to a melt, or the method described above. It can also be adjusted by the cooling rate.
  • the solid obtained in step a3 may be used as a sulfide solid electrolyte as it is, or may be used as a sulfide solid electrolyte after being pulverized, dried, etc., depending on the purpose.
  • step b1-1 in manufacturing method b is a step in which raw materials are mixed as step S21a.
  • the method is the same as step a1-1 in the above-described manufacturing method a, except that a raw material mixture containing a halogen element is also essential to obtain a raw material mixture, and the preferred embodiments are also the same. Note that if halogen is not required as a constituent element of the obtained sulfide solid electrolyte, mixing of raw materials containing a halogen element is not essential.
  • step b1-2 the raw material mixture obtained in step b1-1 is sealed in a closed container as step S21b.
  • the airtight container is not particularly limited as long as it is a heat-resistant container that can be sealed, but it may be a heat-resistant container made of carbon, or one containing an oxide such as quartz, quartz glass, borosilicate glass, aluminosilicate glass, alumina, zirconia, or mullite.
  • Examples include heat-resistant containers, heat-resistant containers containing nitrides such as silicon nitride and boron nitride, and heat-resistant containers containing carbides such as silicon carbide.
  • these heat-resistant containers may have a bulk formed of the above-mentioned materials, or may have a layer formed of carbon, oxide, nitride, carbide, or the like.
  • a vacuum atmosphere is preferable from the viewpoint of not increasing the internal pressure, but a trace amount of an inert gas such as nitrogen or argon may be mixed.
  • the pressure inside the closed container is not particularly limited as long as it is 1 to 2 atmospheres or less at the melting temperature, but vacuum is preferable from the viewpoint of not increasing the internal pressure.
  • the dew point inside the closed container is preferably ⁇ 20° C. or lower from the viewpoint of preventing side reactions with water vapor, oxygen, and the like.
  • the lower limit is not particularly limited, but is usually about -80°C.
  • the oxygen concentration is preferably 1000 ppm or less.
  • step b2 is a step in which the closed container in which the raw material mixture was sealed in step b1-2 is heated, and the raw material mixture is heated and melted in step S22 to obtain a melt.
  • the heating and melting temperature is preferably 600 to 950°C, more preferably 630 to 900°C, even more preferably 650 to 850°C.
  • the heating melting temperature is preferably 600°C or higher, more preferably 630°C or higher, and 650°C or higher. is even more preferable.
  • the temperature of heating and melting is preferably 950°C or lower, more preferably 900°C or lower, and even more preferably 850°C or lower.
  • the heating and melting time is preferably 0.1 to 10 hours, more preferably 0.5 to 9.5 hours, even more preferably 0.7 to 9 hours, and particularly preferably 1 to 9 hours.
  • the heating and melting time is preferably 0.1 hour or more, more preferably 0.5 hour or more, even more preferably 0.7 hour or more, and even more preferably 1 hour or more. preferable.
  • the heating melting time is preferably 10 hours or less, more preferably 9.5 hours or less, and even more preferably 9 hours or less.
  • this step b2 corresponds to heating and melting in a gas atmosphere containing sulfur element in step 2 of manufacturing method i.
  • step b3 is a step in which the melt obtained in step b2 is rapidly cooled at a cooling rate of 500° C./second or higher to obtain a solid.
  • the process is the same as step a3 in the manufacturing method a described above, except that the tip of the closed container is destroyed and simultaneously subjected to quenching using a quench roll or the like, and the preferred embodiments are also the same.
  • a sulfide solid electrolyte containing a sulfide glass phase including 4 units of PS and 7 units of P 2 S,
  • the ratio of the peak intensity I (PS4) of the PS 4 unit to the peak intensity I (P2S7) of the P 2 S 7 unit in the Raman spectrum is 0.05 ⁇ I (P2S7) /I (PS4) ⁇ 1.00 satisfies the relationship of Contains Li, P, S and Ha as constituent elements,
  • the Ha is a halogen element,
  • the content of the constituent elements is expressed in at%, Li: 30-50%
  • a sulfide solid electrolyte with P: 5 to 15% and S: 30 to 60% is expressed in at%, Li: 30-50%,
  • the Ha includes at least one selected from the group consisting of F, Cl, Br and I, The content of the constituent elements is expressed in at%, Li: 30-50%, P: 5-12%, The sulfide solid electrolyte according to [1] above, wherein S: 30 to 50% and Ha: 2 to 10%. [3] Further including 6 units of P 2 S, The ratio of the peak intensity I (P2S6) of the P 2 S 6 units and the peak intensity I (P2S7) of the P 2 S 7 units in the Raman spectrum is 0.5 ⁇ I (P2S7) /I (P2S6) ⁇ 10 The sulfide solid electrolyte according to [1] or [2] above, which satisfies the following relationship.
  • Example 1 and Examples 4 to 10 are examples, and Example 2 and Example 3 are comparative examples.
  • Example 1 Under a dry nitrogen atmosphere, lithium sulfide powder (manufactured by Sigma, purity 99.98%) and diphosphorus pentasulfide powder (manufactured by Sigma, purity 99%) were prepared to have the compositions (mol%) listed in Table 1. , and lithium bromide powder (manufactured by Sigma, purity 99.995%), and mixed in the same atmosphere with a mixer (manufactured by WARING, X-TREME (MX1100XTM)) in High mode for 1 minute. A mixture was obtained (step b1-1). The obtained raw material mixture was placed in a carbon-coated quartz tube and sealed in a vacuum atmosphere (step b1-2). The mixture was heated as it was at 750° C.
  • step b2 While in the molten state, the tip of the carbon-coated quartz tube was broken and cooled at 5000° C./sec using a quench roll to obtain a sulfide solid electrolyte (step b3).
  • step b2 no gas containing sulfur element is introduced from the outside.
  • the above step b2 corresponds to heating and melting in a gas atmosphere containing elemental sulfur.
  • composition (mol %) in Table 1 means that no additives are added except for inevitable impurities contained in the raw materials.
  • the composition of the obtained sulfide solid electrolyte was determined by composition analysis, and it was confirmed that it roughly matched the value of "composition (mol %)" in Table 1, which is the charging ratio. Note that “approximately matched” means that the difference from the charged composition ratio was within ⁇ 5%. Therefore, the “composition (at%)" in Table 1 is calculated from the “composition (mol%)” in Table 1, which is the charging ratio, but the content of the constituent elements of the obtained sulfide solid electrolyte ( at%). The same applies to Examples 2 to 10.
  • Example 3 Under a dry nitrogen atmosphere, lithium sulfide powder (manufactured by Sigma, purity 99.98%) and diphosphorus pentasulfide powder (manufactured by Sigma, purity 99%) were prepared to have the compositions (mol%) listed in Table 1. , and lithium bromide powder (manufactured by Sigma, purity 99.995%) were weighed and subjected to mechanical milling at 400 rpm for 20 hours in the same atmosphere using a planetary ball mill using ZrO 2 balls with a diameter of 4 mm to obtain sulfide. A solid electrolyte was obtained. Note that unlike Examples 1 and 2, Example 3 did not obtain a solid by cooling, so the cooling rate in Table 1 is indicated as "-".
  • Example 4 to Example 10 As a raw material, lithium bromide powder (manufactured by Sigma, purity 99.995%) or lithium bromide powder (manufactured by Sigma, purity 99.995) was used so as to have the composition (mol%) shown in Table 1. %), lithium chloride powder (manufactured by Sigma, purity 99.99%), lithium iodide powder (manufactured by Sigma, purity 99.99%), SiO 2 (manufactured by As One, quartz test tube SJT series) A sulfide solid electrolyte was obtained in the same manner as in Example 1, except that the sulfide solid electrolyte was appropriately used.
  • the sulfide solid electrolyte was ground in a mortar and passed through a 100 ⁇ m sieve to obtain a solid electrolyte powder with an average particle size D50 of about 20 ⁇ m.
  • the obtained solid electrolyte powder was formed into pellets with a diameter of 1 cm, and Raman spectra were measured at arbitrary 10 points in an environment without exposure to the atmosphere (equipment name: LabRAM HR Evolution manufactured by Horiba, Ltd.).
  • Measurement conditions were: excitation wavelength: 532 nm, power during sample irradiation: 5 mW, objective lens: 10x, numerical aperture: 0.25, confocal pinhole: 200 ⁇ m, grating: 1200 gr/mm, measurement time: 3 seconds x 10 times. , spot diameter: 3 ⁇ m.
  • the spectrum obtained in Example 1 is shown in FIG. 4, and as shown in FIG. 5, a corrected spectrum was obtained by performing baseline correction on the Raman spectrum.
  • peak separation was performed on the corrected spectrum using a function that is a mixture of a Gauss function and a Lorentz function.
  • a mixed function is a Gaussian function and a Lorentzian function.
  • f(x) (1-M) (Gaussian function) + (M) (Lorentz function)
  • the value of M representing the mixing ratio of functions (% Lorentz function) was set to 0.25.
  • a peak with a peak top at a wave number of 415 to 425 cm -1 is defined as a peak of PS 4 units
  • a peak having a peak top at a wave number of 402 to 412 cm -1 is defined as a peak of P 2 S 7 units
  • the peak having a peak top at -1 was defined as the P 2 S 6 unit peak.
  • a baseline was drawn in the region of 330 cm -1 to 460 cm -1 .
  • the full width at half maximum is 15 cm -1 for a peak with a peak top at a wave number of 415 to 425 cm -1 , 15 cm -1 for a peak with a peak top at a wave number of 402 to 412 cm -1 , and the peak top is at a wave number of 383 to 393 cm -1.
  • Peak separation was performed by fixing the peak having 22 cm ⁇ 1 at 22 cm ⁇ 1 . Optimization was performed using the least squares method so that the difference between the spectrum from which the baseline was subtracted and the calculated spectrum obtained by adding the separated peaks was minimized.
  • Example 1 the Raman spectrum is shown in FIG. 4, the Raman spectrum and the corrected spectrum after baseline correction are shown in FIG. 5, and the corrected spectrum and three peak-separated spectra are shown in FIG. 6, respectively.
  • FIG. 6 also shows a calculated spectrum obtained by adding together the three separated peaks, and it was verified that the peak separation was properly performed based on the similarity between the corrected spectrum and the calculated spectrum.
  • FIG. 7 shows the corrected spectrum of Example 2, the three peak-separated spectra, and the calculated spectrum obtained by adding the three peak-separated peaks
  • FIG. 8 shows the corrected spectrum of Example 3, the three peak-separated spectra, and A calculated spectrum obtained by adding together three peaks separated from each other is shown, respectively.
  • the sulfide solid electrolyte according to the present embodiment includes a sulfide glass phase and can achieve high lithium ion conductivity. This was achieved due to the high homogeneity of the glass obtained through the molten state, and also because it mainly contains 4 units of PS compared to 7 units of P 2 S.
  • the sulfide solid electrolyte according to Example 2 had low lithium ion conductivity even though the sulfide glass phase was more than 90% by weight. This is considered to be due to the higher proportion of P 2 S 7 units in Example 2 than in the sulfide solid electrolytes of Examples 1 and 4 to 10.
  • a sulfide solid electrolyte was produced using the same method as Example 2 so as to have the composition of Example 1. As a result, it was confirmed that a crystal peak was observed in the XRD measurement, and the lithium ion conductivity was also confirmed to be as low as 0.06 mS/cm, indicating that sulfide containing the desired sulfide glass phase A solid electrolyte could not be obtained.

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JP2012094482A (ja) * 2010-10-01 2012-05-17 Idemitsu Kosan Co Ltd 硫化物固体電解質、硫化物固体電解質シート及び全固体リチウム電池
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WO2022102535A1 (ja) * 2020-11-11 2022-05-19 Ａｇｃ株式会社 硫化物系固体電解質、固体電解質層及びリチウムイオン二次電池
JP2022114970A (ja) 2021-01-27 2022-08-08 株式会社バンダイ 玩具部品、及び人形玩具

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JP2012094482A (ja) * 2010-10-01 2012-05-17 Idemitsu Kosan Co Ltd 硫化物固体電解質、硫化物固体電解質シート及び全固体リチウム電池
JP2014093262A (ja) 2012-11-06 2014-05-19 Idemitsu Kosan Co Ltd 固体電解質
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