WO2024014382A1 - Électrolyte solide à base de sulfure et procédé pour sa production, mélange d'électrode, couche d'électrolyte solide, et batterie secondaire au lithium-ion entièrement solide - Google Patents

Électrolyte solide à base de sulfure et procédé pour sa production, mélange d'électrode, couche d'électrolyte solide, et batterie secondaire au lithium-ion entièrement solide Download PDF

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WO2024014382A1
WO2024014382A1 PCT/JP2023/025046 JP2023025046W WO2024014382A1 WO 2024014382 A1 WO2024014382 A1 WO 2024014382A1 JP 2023025046 W JP2023025046 W JP 2023025046W WO 2024014382 A1 WO2024014382 A1 WO 2024014382A1
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solid electrolyte
sulfide
tetrahedron
based solid
tetrahedrons
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Japanese (ja)
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槙子 稲葉
真弓 福峯
公章 赤塚
直樹 藤井
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • 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
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a sulfide-based solid electrolyte and a method for producing the same.
  • the present invention also relates to an electrode mixture, a fixed electrolyte layer, and an all-solid lithium ion secondary battery containing the sulfide-based solid electrolyte.
  • 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-based solid electrolytes and oxide-based solid electrolytes.
  • the sulfide ions constituting the sulfide-based solid electrolyte have a higher polarizability than the oxide ions constituting the oxide-based solid electrolyte, and exhibit high ionic conductivity.
  • Examples of sulfide-based 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. are known.
  • Patent Document 1 is cited as an example in which an argyrodite-type sulfide-based solid electrolyte is disclosed.
  • Non-Patent Document 1 discloses that in an argyrodite-type sulfide-based solid electrolyte, water resistance can be improved by substituting a part of the P element constituting the PS 4 tetrahedron with the Sn element.
  • Non-Patent Document 1 the P element in the argyrodite crystal structure is actually substituted, and the halogen elements are only Br and I.
  • the present invention relates to the following [1] to [17].
  • [1] Has a crystal structure having a plurality of tetrahedra T 1 and a plurality of tetrahedra T 2 , Each of the tetrahedrons T 1 has a P element as the center, and vertices are composed of a total of 4 elements among 1 to 4 S elements and 0 to 3 X elements, Each of the tetrahedrons T 2 has a Li element as the center, and vertices are composed of a total of 4 elements among 1 to 4 S elements and 0 to 3 X elements, Each of the tetrahedrons T 1 shares all vertices with the different tetrahedrons T 2 , The tetrahedron T 2 that shares a vertex with the tetrahedron T 1 shares a face or an edge with at least one adjacent tetrahedron T 2 ,
  • the X element is at least one element selected from the group consisting of O element
  • the sharing of a face or edge with the two adjacent tetrahedrons T 2 includes sharing an edge with one tetrahedron T 2 and sharing a face with the other tetrahedron T 2 ,
  • the two vertices included in the edge shared by the tetrahedron T2 are a vertex a and a vertex b
  • a method for producing a sulfide solid electrolyte comprising: Mixing raw materials containing Li element, P element, S element, and Z element and heating and melting in a heat-resistant container; then crystallizing by rapid cooling, The method for producing a sulfide-based solid electrolyte, wherein the Z element is at least one element selected from the group consisting of Si, Al, Sn, Ge, Zn, Sb, In, and Cu.
  • the raw material further contains X element, The X element is at least one element selected from the group consisting of O element and Ha element, and the Ha element is at least one element selected from the group consisting of F, Cl, Br, and I.
  • a novel sulfide-based solid electrolyte with improved water resistance can be obtained. Therefore, when an electrode mixture or solid electrolyte layer containing such a sulfide-based solid electrolyte is used in a lithium ion secondary battery, it is particularly advantageous in terms of cost because it can be manufactured even in a low dew point environment. Similarly, since it has excellent water resistance, an all-solid-state lithium ion secondary battery can be obtained at low cost and in a low dew point environment.
  • FIG. 1 is an explanatory diagram showing one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing the relationship between the tetrahedron T 1 and the tetrahedron T 2 in one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 3 is an explanatory diagram showing the relationship between the tetrahedron T 1 and the tetrahedron T 2 in one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 1 is an explanatory diagram showing one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing the relationship between the tetrahedron T 1 and the tetrahedron T 2 in one aspect of the crystal structure of the sulfide-based solid electrolyte according to the
  • FIG. 4 is an explanatory diagram showing the positional relationship of the tetrahedron T2 in one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 5 is an explanatory diagram showing the relationship between the tetrahedron T 1 and the tetrahedron T 2 in one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment.
  • FIG. 6 is a flow diagram showing a method for manufacturing a sulfide-based solid electrolyte according to this embodiment.
  • FIG. 7 is an XRD pattern of the sulfide-based solid electrolyte of Example 1.
  • FIG. 8 is an XRD pattern of the sulfide-based solid electrolyte of Example 2.
  • FIG. 9 is an XRD pattern of the sulfide-based solid electrolyte of Example 3.
  • FIG. 10 is an XRD pattern of the sulfide-based solid electrolyte of Example 4.
  • FIG. 11 is an XRD pattern of the sulfide-based solid electrolyte of Example 5.
  • FIG. 12 is an XRD pattern of the sulfide-based solid electrolyte of Example 6.
  • FIG. 13 is an XRD pattern of the sulfide-based solid electrolyte of Example 7.
  • FIG. 14 is an XRD pattern of the sulfide-based solid electrolyte of Example 8.
  • FIG. 15 is an XRD pattern of the sulfide-based solid electrolyte of Example 9.
  • the sulfide-based solid electrolyte (hereinafter sometimes simply referred to as "solid electrolyte") according to the present embodiment has a plurality of tetrahedra T1 and a plurality of tetrahedra T2 , and each of the above-mentioned tetrahedra T 1 and each of the above-mentioned tetrahedrons T 2 have a crystal structure in which they share a vertex.
  • Each of the above-mentioned tetrahedrons T 1 is a tetrahedron whose vertices are composed of a total of four elements among 1 to 4 S elements and 0 to 3 X elements, with the P element at the center.
  • each of the above-mentioned tetrahedrons T 2 is a tetrahedron whose vertices are composed of a total of four elements out of 1 to 4 S elements and 0 to 3 X elements, with the Li element at the center.
  • the X element is at least one element selected from the group consisting of O element and Ha element
  • the Ha element is at least one element selected from the group consisting of F, Cl, Br, and I.
  • Each tetrahedron T 1 shares all vertices with a different tetrahedron T 2 , and each tetrahedron T 2 that shares a vertex with the tetrahedron T 1 has at least one adjacent tetrahedron. Shares a face or edge with T2 .
  • the Li element is replaced with the Z element.
  • the Z element is at least one element selected from the group consisting of Si, Al, Sn, Ge, Zn, Sb, In, and Cu.
  • Tetrahedron T 1 has vertices composed of a total of 4 elements out of 1 to 4 S elements and 0 to 3 X elements, with P element as the center, but this is P (S + X) 4 tetrahedrons. It means a body.
  • the X element is at least one element selected from the group consisting of O element and Ha element
  • the Ha element is one element selected from the group consisting of F, Cl, Br, and I.
  • the combination of the S element and the X element constituting the P(S+X) 4 tetrahedron may be one type, or a plurality of types may be mixed.
  • the tetrahedron T 1 is preferably a PS 4 tetrahedron.
  • the central P element may be substituted with another element.
  • the central P element may be substituted with Si element.
  • the ratio of P element to Si element substitution is preferably 0.01 to 50%, more preferably 0.1 to 40%. That is, the above-mentioned substitution ratio is preferably 0.01% or more, more preferably 0.1% or more.
  • the above ratio is preferably 50% or less, more preferably 40% or less.
  • the substitution ratio may be 0%, that is, the Si element may not be substituted.
  • examples of elements other than the Si element that can be substituted for the P element include Al, Sn, Ge, Cu, In, Sb, B, and As. These elements may be substituted, whether intentionally or not, if they are included in the raw materials used in manufacturing the solid electrolyte or if they are mixed in during the manufacturing process.
  • the proportion of the element substituted from the P element is preferably 50% or less in total, including the substitution with the Si element.
  • the substitution ratio of elements constituting the crystal structure is determined by performing X-ray diffraction (XRD) measurement and performing Rietveld analysis from the obtained XRD pattern.
  • some of the plurality of tetrahedra T 1 contain an X element as an element constituting a vertex.
  • all of the tetrahedron T 1 may be composed of tetrahedra other than the PS 4 tetrahedron, that is, PS 3 X tetrahedron, PS 2 and a PS 3 X tetrahedron, a PS 2 X 2 tetrahedron, and a PSX 3 tetrahedron.
  • PS tetrahedrons are included.
  • the above-mentioned X element is preferably O element from the viewpoint of improving water resistance.
  • the ratio of the X element to the sum of the S element and the 0.01 to 25% is preferable, and 0.1 to 20% is more preferable. More specifically, the above ratio is preferably 0.01% or more, more preferably 0.1% or more. On the other hand, from the viewpoint of maintaining high lithium ion conductivity, the above ratio is preferably 25% or less, more preferably 20% or less.
  • all of the tetrahedrons T 1 may be PS 4 tetrahedrons, that is, the above ratio may be 0%.
  • a part of the S element and the X element constituting the vertices of the tetrahedron T1 may be substituted with other elements or groups.
  • elements or groups that can be substituted include Se, Te, BH 4 , CN, and the like. These elements or groups may be substituted, whether intentionally or not, if they are included in the raw materials used in producing the solid electrolyte or if they are mixed in during the production process.
  • the proportion of elements and groups other than the S element is preferably 50% or less of the total including the above-mentioned X element.
  • water resistance in this specification means hydrolysis resistance. Water resistance can be quantitatively evaluated from the amount of H 2 S generated when the solid electrolyte is exposed to a specific atmosphere with controlled humidity.
  • Tetrahedron T 2 has vertices composed of a total of 4 elements among 1 to 4 S elements and 0 to 3 X elements, with Li element as the center, but this is Li (S + It means a body.
  • the X element is at least one element selected from the group consisting of O element and Ha element
  • the Ha element is one element selected from the group consisting of F, Cl, Br, and I.
  • a LiS tetrahedron may be formed with four S elements for the Li element, one S element, an O element, a total of three Ha elements, two S elements and an O element for the Li element.
  • a tetrahedron may be formed with a total of two elements, Ha elements, or three S elements and one O element or one Ha element.
  • the combination of the S element and the X element constituting the Li(S+X) 4 tetrahedron may be one type or a plurality of types may be mixed.
  • the tetrahedron T 2 preferably contains one or more Ha elements among the X elements, in addition to the S element, as the elements forming the vertices.
  • the Ha element may be any element selected from the group consisting of F, Cl, Br, and I, preferably containing at least one of the Cl element and the Br element, and preferably containing both the Cl element and the Br element.
  • the tetrahedron T 2 contains an O element as the X element forming the apex.
  • the Li element is replaced with the Z element.
  • the Z element is at least one element selected from the group consisting of Si, Al, Sn, Ge, Sb, Zn, In, and Cu. Water resistance is significantly improved by replacing the Li element with the Z element in a part of the tetrahedron T2 .
  • the proportion of the tetrahedron T 2 in which the Li element is substituted with the Z element is preferably 0.01 to 50%, more preferably 0.1 to 45%, and 1 to 40% based on the total amount of the tetrahedron T 2 . More preferred. More specifically, from the viewpoint of improving water resistance, the above ratio is preferably 0.01% or more, more preferably 0.1% or more, and even more preferably 1% or more. On the other hand, since the lithium ion conductivity tends to decrease due to the above substitution, the Li element is substituted with the Z element in a part of the tetrahedron T2 .
  • the proportion of the tetrahedron T2 in which the Li element is substituted with the Z element is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less with respect to the total amount of the tetrahedron T2 . .
  • the Z element substituted from the Li element may be at least one element selected from the group consisting of Si, Al, Sn, Ge, Sb, Zn, In, and Cu, but from the viewpoint of electronegativity and ionic radius. Therefore, the Z element is preferably Sn, Sb, Ge, or In, more preferably Sn, Sb, or In, and still more preferably Sn.
  • the Z element may be substituted with two or more elements.
  • the substitution of the Li element with other elements other than the Z element is not excluded in any way.
  • elements other than the Z element that can be substituted for the Li element include Na, Mg, and the like. These elements may be substituted, whether intentionally or not, if they are included in the raw materials used in manufacturing the solid electrolyte or if they are mixed in during the manufacturing process.
  • the proportion of the element substituted from the Li element is preferably 50% or less in total, including the substitution with the Z element.
  • Each tetrahedron T 1 has a crystal structure in which all vertices share a vertex with a different tetrahedron T 2 . That is, each tetrahedron T 1 shares an S element or an X element constituting the vertex with at least one tetrahedron T 2 at each vertex, and a total of four or more tetrahedrons T 2 .
  • FIG. 1 shows one aspect of the crystal structure of the sulfide-based solid electrolyte according to the present embodiment. In FIG . There are free vertices. However, the free vertex actually also shares a vertex with another tetrahedron T2 , not shown.
  • Tetrahedron T 1 preferably shares vertices with 6 tetrahedrons T 2 per vertex, as shown in FIG. More preferably, it shares vertices with 24 different tetrahedra T2 .
  • Figure 2 for understanding the crystal structure, one vertex of tetrahedron T 1 and six tetrahedrons T 2 that share it are shown, but the other three vertices of tetrahedron T 1 Similarly, each of the vertices is shared with six tetrahedra T2 .
  • each tetrahedron T 1 and each tetrahedron T 2 is preferably an S element, and when they share an X element, an O element is preferred, and an S element is more preferred.
  • Tetrahedron T 2 that shares a vertex with tetrahedron T 1 shares a face or edge with at least one adjacent tetrahedron T 2 shares a face or edge with at least one adjacent tetrahedron T 2 , as shown in FIG.
  • FIG. 3 is an example in which two tetrahedrons T2 share a surface. As shown in FIG. 3 , the tetrahedron T 2 that shares a vertex with the tetrahedron T 1 and the tetrahedron T 2 that shares a face with it share the same vertex of the tetrahedron T 1 . is preferred.
  • the tetrahedron T 2 that shares a vertex with the tetrahedron T 1 and the tetrahedron T 2 that shares an edge with the tetrahedron T 1 may share the same vertex of the tetrahedron T 1 .
  • a tetrahedron T 1 shares a vertex with 6 tetrahedra T 2 per vertex, then the 6 tetrahedra T 2 have two adjacent tetrahedra T 2 that share the same vertex. shares a face or edge with the tetrahedron T2 .
  • FIG. 4 shows only the tetrahedron T 2 out of one aspect of the crystal structure of the sulfide - based solid electrolyte according to the present embodiment. It is preferable to share an edge with one tetrahedron T 2 and a surface with the other tetrahedron T 2 .
  • the two vertices included in the edge shared by the tetrahedron T 2 are apex a and the vertex b
  • the three vertices included in the face shared by the tetrahedron T 2 are the vertex a or the vertex b.
  • the remaining two vertices of the tetrahedron T2 are the remaining two vertices of the tetrahedron T2 .
  • tetrahedron T 2 -1 is composed of apex a1, vertex b1, vertex c1, and vertex d1
  • tetrahedron T 2 -2 is composed of vertex a1, vertex b2, vertex c1, and vertex d1.
  • d1 and the tetrahedron T 2 -3 is composed of apex a1, vertex b2, vertex c2, and vertex d2 (not shown).
  • the tetrahedron T 2 -1 and the tetrahedron T 2 -2 share a surface, and this surface is composed of a vertex a1, a vertex c1, and a vertex d1.
  • the tetrahedron T 2 -2 and the tetrahedron T 2 -3 share an edge, and this edge is composed of a vertex a1 and a vertex b2.
  • tetrahedron T 1 shares vertices with tetrahedron T 2 with 6 vertices per vertex, as shown in FIG. It is preferable that the tetrahedron T 1 shares a vertex with a total of two different tetrahedrons T 1 .
  • FIG. 5 is an example in which two tetrahedrons T2 share a surface and also share vertices with the same two tetrahedrons T1 .
  • an argyrodite type may be mentioned.
  • the argyrodite type is represented by the compositional formula Li 7-x BCh 6-x X x .
  • x is an arbitrary number
  • B is a group 15 element such as P or As
  • Ch is a group 16 element such as sulfur or selenium
  • X is a group 17 element such as chlorine or bromine.
  • Li sites exist in the voids of the BCh 4 -tetrahedral skeleton.
  • the tetrahedron centered on the Li element shares vertices with the BCh 4 -tetrahedron.
  • the peak position in the XRD pattern may vary depending on the type of element to be substituted and the position of the site. Therefore, unlike conventional argyrodite-type sulfide solid electrolytes, it is difficult to uniquely determine that the electrolyte is of the argyrodite type based on the peak position.
  • the tetrahedron T1 has a P element or a Si element substituted from the P element in the central 4b site, and an S element or an S element in the four 16e sites. It is preferable that an O element substituted with .
  • the central 48h site contains Li element or Z element substituted from Li element
  • the two 16e sites contain S element or O element
  • the 4a site and 4c site contain preferably contains S element or Ha element.
  • the above 4a site and 4c site correspond to the above vertex a and vertex b that share an edge.
  • the crystal structure of the solid electrolyte according to this embodiment is an argyrodite type
  • its composition is represented by (Li+Z) a (P+Si) 1 (S+O) b Ha c
  • the ratio of each element is 3 ⁇ a ⁇ 6.
  • 3 ⁇ b ⁇ 5 and 0 ⁇ c ⁇ 2, and 1 ⁇ c ⁇ 2 is more preferable.
  • Z in the composition is the Z element
  • Ha is the Ha element.
  • the ratio expressed as (Z/Li) preferably satisfies the relationship 0 ⁇ (Z/Li) ⁇ 0.1, and 0.001 ⁇ (Z/Li). It is more preferable to satisfy the relationship: Li) ⁇ 0.05, and even more preferably to satisfy the relationship: 0.005 ⁇ (Z/Li) ⁇ 0.03. More specifically, the ratio is more than 0, preferably 0.001 or more, more preferably 0.005 or more from the viewpoint of improving water resistance. Further, from the viewpoint of maintaining high lithium ion conductivity, the ratio represented by (Z/Li) is preferably less than 0.1, more preferably 0.05 or less, and even more preferably 0.03 or less. In addition, when the solid electrolyte contains two or more types of elements as Z elements, the above-mentioned Z means the total of these Z elements.
  • the ratio expressed as (Si/P) preferably satisfies the relationship 0 ⁇ (Si/P) ⁇ 1.0, and 0.0001 ⁇ (Si/P). It is more preferable to satisfy the relationship P) ⁇ 0.5, and even more preferable to satisfy the relationship 0.001 ⁇ (Si/P) ⁇ 0.4. It is also more preferable to satisfy the relationship 0 ⁇ (Si/P) ⁇ 0.4. More specifically, the ratio is 0 or more, preferably 0.0001 or more, and more preferably 0.001 or more from the viewpoint of improving lithium ion conductivity. Further, from the viewpoint of suppressing a decrease in lithium ion conductivity, the ratio represented by (Si/P) is preferably less than 1.0, more preferably 0.5 or less, further preferably 0.4 or less, and 0. Particularly preferred is less than 4.
  • both the ratio represented by (Z/Li) and the ratio represented by (Si/P) satisfy the above range.
  • the lattice constant becomes smaller as the proportion of tetrahedrons T 2 in which the Li element is replaced by the Z element increases.
  • the a-axis lattice constant is preferably 0.001 ⁇ or more smaller than the lattice constant of the unsubstituted product from the viewpoint of improving water resistance. , more preferably 0.002 ⁇ or more, and even more preferably 0.003 ⁇ or more.
  • the reason why the lattice constant decreases due to the substitution with the Z element is considered as follows.
  • the ionic radius of Li + which has a coordination number of 4, is 73 pm, while, for example, taking Sn as a Z element, the ionic radius of Sn 4+ , which has a coordination number of 4, is 69 pm, and Li + smaller than the ionic radius of Therefore, when a portion of the Li element is replaced, the lattice constant becomes smaller.
  • the above ionic radius indicates the crystal radius, and R. D. Shannon, Acta Crystallogr. , A32, 751 (1976).
  • crystal structure is an argyrodite type
  • cubic crystals such as F-43m are preferred, but hexagonal crystals such as rhombohedral crystals, tetragonal crystals, and rectangular crystals are also possible.
  • the a-axis lattice constant can be changed by increasing or decreasing the proportion of tetrahedron T2 substituted from Li element to Z element, but it can also be changed depending on the type of elements that make up the crystal structure. can. For example, by selecting Ha element, preferably at least one of Cl element and Br element as the element constituting the tetrahedron T2 , the lattice constant can be set within the above range. Note that the crystal system and a-axis lattice constant of the solid electrolyte are determined by Rietveld analysis of the XRD pattern of the solid electrolyte.
  • the secondary particle size of the solid electrolyte is preferably small from the viewpoint of obtaining good lithium ion conductivity when used in a lithium ion secondary battery, specifically, preferably 10 ⁇ m or less, more preferably 3 ⁇ m or less, More preferably, the thickness is 1 ⁇ m or less.
  • the lower limit of the secondary particle size is not particularly limited, but is usually 0.1 ⁇ m or more. Secondary particle size can be measured using a Microtrack device.
  • Water resistance means resistance to hydrolysis, and can be quantitatively evaluated from the amount of hydrogen sulfide (H 2 S) generated when the solid electrolyte is exposed to a specific atmosphere with controlled humidity. Under the same measurement conditions, the H 2 S generation amount of the standard solid electrolyte and the target solid electrolyte was measured, and the water resistance was determined based on the amount of H 2 S generated compared to the standard solid electrolyte. can be judged. The amount of H 2 S generated can be measured by the hydrogen sulfide concentration.
  • the H 2 S generation amount of the solid electrolyte is preferably 90% or less, more preferably 60% or less, and 50% or less of the H 2 S generation amount of the solid electrolyte as a reference. It is more preferable, and the smaller the value, the more preferable.
  • the substitution of the Li element with the Z element there is a limit to the substitution of the Li element with the Z element, and there is also a limit to the reduction in the amount of H 2 S generated.
  • the lithium ion conductivity of the sulfide solid electrolyte at 25° C. is preferably 1.0 ⁇ 10 ⁇ 4 S/cm or more, more preferably 1.0 ⁇ 10 ⁇ 3 S/cm or more, and 3.0 ⁇ 10 ⁇ 3 S/cm or more is more preferable, and the higher the value, the more preferable.
  • the solid electrolyte according to this embodiment is suitably used for an electrode mixture and a solid electrolyte layer used in a lithium ion secondary battery, and is particularly suitable for an all-solid lithium ion secondary battery. That is, the electrode mixture according to the present embodiment is used for a lithium ion secondary battery and includes the solid electrolyte and active material. Further, the solid electrolyte layer according to this embodiment is used in a lithium ion secondary battery and includes the solid electrolyte described above. Moreover, the all-solid-state lithium ion secondary battery according to this embodiment includes the solid electrolyte described above.
  • the electrode mixture, solid electrolyte layer, and all-solid lithium ion secondary battery may further contain other solid electrolytes.
  • Other solid electrolytes are not particularly limited, and include, for example, conventionally known solid electrolytes having an argyrodite crystal structure, Li 3 PS 4 , Li 4 P 2 S 6 , Li 2 S, LiHa, and the like.
  • the active material contained in the electrode mixture conventionally known materials can be used.
  • the positive electrode active material is not particularly limited as long as it can reversibly intercalate and deintercalate lithium ions, deintercalate and intercalate lithium ions, or dope and dedope counter anions of the lithium ions.
  • Specific examples include lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium nickel manganate, composite metal oxides, polyanion olivine type positive electrodes, and the like.
  • the negative electrode active material is also not particularly limited as long as it can reversibly insert and release lithium ions, desorb and insert (intercalate) lithium ions, or dope and dedope counter anions of the lithium ions.
  • carbon-based materials such as lithium metal, graphite, hard carbon, and soft carbon, metals that can form alloys with lithium such as aluminum, silicon, and tin, and amorphous materials such as silicon oxide and tin oxide.
  • metals that can form alloys with lithium such as aluminum, silicon, and tin
  • amorphous materials such as silicon oxide and tin oxide. Examples include oxides, lithium titanate, and the like.
  • the solid electrolyte layer only needs to contain the solid electrolyte according to the present embodiment, but may further contain additives such as a binder.
  • binders can be used, and examples thereof include butadiene rubber, acrylate butadiene rubber, styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, and the like.
  • the binder content in the solid electrolyte layer may also be within a conventionally known range.
  • the all-solid-state lithium ion secondary battery is not particularly limited as long as it includes a positive electrode and a negative electrode in addition to the solid electrolyte according to the present embodiment.
  • the positive electrode and the negative electrode may be an electrode mixture containing the solid electrolyte according to the present embodiment.
  • the active material of the positive electrode can be the same as the positive electrode active material described in the electrode mixture, and the positive electrode may further contain a positive electrode current collector, a binder, a conductive aid, etc. as necessary.
  • As the positive electrode current collector aluminum, an alloy thereof, a thin metal plate such as stainless steel, etc. can be used.
  • the same negative electrode active material as described in the electrode mixture can be used as the negative electrode active material, and the negative electrode may further contain a negative electrode current collector, a binder, a conductive aid, etc. as necessary.
  • a thin metal plate made of copper, aluminum, or the like can be used as the negative electrode current collector.
  • step S1 includes a step of mixing raw materials containing Li element, P element, S element, and Z element and heating and melting the mixture in a heat-resistant container;
  • the manufacturing method includes a step of crystallizing by rapid cooling as step S2. By the rapid cooling in this step, a crystal structure is obtained in which the Li element is substituted with the Z element in some of the plurality of tetrahedra T2 .
  • the Z element is at least one element selected from the group consisting of Si, Al, Sn, Ge, Zn, Sb, In, and Cu. Furthermore, after step S2, it is preferable to further include a step of performing heat treatment at 200 to 600° C. for 0.1 to 10 hours as step S3.
  • Step S1 which is a step of mixing and heating and melting raw materials containing Li element, P element, S element, and Z element, if it is desired to obtain a sulfide-based solid electrolyte containing X element, the raw material is further mixed with X It is preferable that the element is included.
  • the X element is at least one element selected from the group consisting of O element and Ha element
  • the Ha element is at least one element selected from the group consisting of F, Cl, Br, and I. .
  • the raw materials containing Li element, P element, S element, Z element, and X element conventionally known materials can be used to obtain an argyrodite crystal containing Li element, P element, S element, and X element.
  • a simple Li or a compound containing Li, a simple P or a compound containing P, a simple S or a compound containing S can be used in appropriate combinations.
  • the X element is the Ha element
  • a compound containing Ha may be further used in combination
  • the X element is the O element
  • an oxide may be used as the compound.
  • the above compound may be a compound containing two or more of Li, P, S, and Ha.
  • a compound that functions as both an S-containing compound and a P-containing compound includes diphosphorus pentasulfide (P 2 S 5 ).
  • a lithium halide can be mentioned as a compound that serves both as a compound containing Li and a compound containing Ha.
  • Examples of compounds containing Li include lithium sulfide (Li 2 S), lithium carbonate (Li 2 CO 3 ), lithium sulfate (Li 2 SO 4 ), lithium oxide (Li 2 O), and lithium hydroxide (LiOH).
  • Examples include lithium compounds such as From the viewpoint of ease of handling, lithium sulfide is preferred.
  • lithium sulfide is expensive, from the viewpoint of reducing manufacturing costs, lithium compounds other than lithium sulfide, metallic lithium, etc. are preferable.
  • one or more selected from the group consisting of metallic lithium, lithium carbonate (Li 2 CO 3 ), lithium sulfate (Li 2 SO 4 ), lithium oxide (Li 2 O), and lithium hydroxide (LiOH) is preferable. . These may be used alone or in combination of two or more.
  • Examples of compounds containing S include phosphorus sulfide such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ), other sulfur compounds containing phosphorus, elemental sulfur, and sulfur. Examples include compounds. Compounds containing sulfur include H 2 S, CS 2 , iron sulfide (FeS, Fe 2 S 3 , FeS 2 , Fe 1-x S, etc.), bismuth sulfide (Bi 2 S 3 ), copper sulfide (CuS, Cu 2 S, Cu 1-x S, etc.).
  • phosphorus sulfide such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 )
  • other sulfur compounds containing phosphorus, elemental sulfur, and sulfur examples include compounds.
  • Compounds containing sulfur include H 2 S, CS 2 , iron sulfide (FeS, Fe 2 S 3
  • phosphorus sulfide is preferred, and diphosphorus pentasulfide (P 2 S 5 ) is more preferred, from the viewpoint of preventing the inclusion of elements other than those constituting the target sulfide-based solid electrolyte. These may be used alone or in combination of two or more. Note that phosphorus sulfide is a compound that serves as both an S-containing compound and a P-containing compound.
  • Examples of compounds containing P include phosphorus sulfides such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ), and phosphorus compounds such as sodium phosphate (Na 3 PO 4 ). It will be done. Among these, phosphorus sulfide is preferred, and diphosphorus pentasulfide (P 2 S 5 ) is more preferred, from the viewpoint of preventing the inclusion of elements other than those constituting the target sulfide-based solid electrolyte. These may be used alone or in combination of two or more.
  • Examples of compounds containing Ha include lithium halides such as lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), and lithium iodide (LiI), phosphorus halides, phosphoryl halides, and halogens.
  • lithium halides such as lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), and lithium iodide (LiI), phosphorus halides, phosphoryl halides, and halogens.
  • sulfur halides sodium halides, and boron halides.
  • lithium halides are preferred, and LiCl, LiBr, and LiI are more preferred, from the viewpoint of preventing the inclusion of elements other than those constituting the target sulfide-based solid electrolyte.
  • These compounds may be used alone or in combination of two or more.
  • Examples of raw materials containing the Si element among the Z elements 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 raw materials containing the Al element include Al 2 S 3 , Al 2 O 3 , and AlCl 3 . Among these, from the viewpoint of lithium ion conductivity and water resistance, 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 raw materials containing the Sn element among the Z elements include SnS, SnS 2 , SnO, SnO 2 , and SnCl 2 . Among these, from the viewpoint of lithium ion conductivity and water resistance, SnS 2 and SnCl 2 are preferred, and SnS 2 is more preferred. These compounds may be used alone or in combination of two or more.
  • examples of raw materials containing the Ge element include GeO 2 , GeS, GeS 2 , and GeCl 2 . Among them, from the viewpoint of lithium ion conductivity and water resistance, GeS 2 and GeCl 2 are preferable, and GeS 2 is more preferable. These compounds may be used alone or in combination of two or more.
  • examples of raw materials containing the Zn element include ZnO, ZnS, and ZnCl 2 .
  • ZnS and ZnCl2 are preferred, and ZnS is more preferred, 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 raw materials containing the Sb element among the Z elements include Sb 2 O 3 , Sb 2 S 3 , and SbCl 3 .
  • Sb 2 S 3 and SbCl 3 are preferred, and Sb 2 S 3 is more preferred.
  • These compounds may be used alone or in combination of two or more.
  • examples of raw materials containing the In element include In 2 O 3 , In 2 S 3 , and InCl 3 . Among them, from the viewpoint of lithium ion conductivity and water resistance, In 2 S 3 and InCl 3 are preferred, and In 2 S 3 is more preferred. These compounds may be used alone or in combination of two or more.
  • Examples of raw materials containing the Cu element among the Z elements include Cu 2 O, CuO, Cu 2 S, CuS, and CuCl 2 . Among these, from the viewpoint of lithium ion conductivity and water resistance, CuS and CuCl 2 are preferred, and CuS is more preferred. 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 specific method of heating and melting the mixture of raw materials is not particularly limited, and the raw materials are placed in a heat-resistant container and heated in a heating furnace.
  • the mixture of raw materials may be sealed in a heat-resistant container, or the mixture may be melted in an atmosphere containing elemental sulfur.
  • the atmosphere containing elemental sulfur include sulfur gas, hydrogen sulfide gas, and sulfur dioxide gas.
  • Heat-resistant containers include 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, boron nitride, etc.
  • a heat-resistant container containing a nitride, a heat-resistant container containing a carbide such as silicon carbide, or the like may be used.
  • these heat-resistant containers may be made of the above-mentioned materials in bulk, or they may be made of a layer of carbon, oxide, nitride, carbide, etc., such as a carbon-coated quartz tube. It may be.
  • the heating temperature when heating and melting the mixture of raw materials is preferably 600 to 1000°C, more preferably 630 to 950°C, even more preferably 650 to 900°C. More specifically, from the viewpoint of increasing the fluidity of the melt, the heating temperature is preferably 600°C or higher, more preferably 630°C or higher, and even more preferably 650°C or higher. From the viewpoint of suppressing deterioration and decomposition, the heating temperature is preferably 1000°C or less, more preferably 950°C or less, and even more preferably 900°C or less.
  • 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 9.5 hours, and even more preferably 1 to 9 hours. More specifically, from the viewpoint of advancing the reaction, the time is preferably 0.1 hour or more, more preferably 0.5 hour or more, even more preferably 0.7 hour or more, even more preferably 1 hour or more, and the melt From the viewpoint of suppressing deterioration and decomposition of the components therein due to heating, the heat-melting time is preferably 10 hours or less, more preferably 9.5 hours or less, and even more preferably 9 hours or less.
  • step S2 the mixture of raw materials heated and melted in step S1 is rapidly cooled to perform crystallization.
  • a solid electrolyte is obtained in which each of the tetrahedra T 1 and each of the tetrahedra T 2 share vertices, and in which the Li element is replaced with the Z element in some of the plurality of tetrahedra T 2 .
  • the tetrahedron T 1 , the tetrahedron T 2 , and the Z element are all as described above.
  • the rapid cooling may be performed at a cooling rate of 1° C./second or more, preferably 10° C./second or more, and more preferably 100° C./second or more.
  • the upper limit value of the cooling rate is not particularly limited, but if the cooling rate of twin rollers, which is generally said to have the fastest quenching rate, is taken into account, the upper limit value is 1,000,000° C./second or less.
  • stabilization treatment may be performed by further performing heat treatment in step S3.
  • Heat treatment increases crystallinity.
  • the sealed state is maintained as it is and subjected to step S2, the sealed state is maintained in step S2 and the subsequent step S3.
  • the duration of the heat treatment is preferably 0.1 to 10 hours, more preferably 0.2 to 5 hours. More specifically, from the viewpoint of more reliably performing crystal precipitation, the heat treatment time is preferably 0.1 hour or more, more preferably 0.2 hours or more, and from the viewpoint of suppressing thermal deterioration due to heating, the heat treatment time is preferably 10 hours or less. More preferably 5 hours or less. Further, from the viewpoint of preventing the lithium ion conductivity from decreasing too much due to excessive crystallization, the heat treatment time is preferably 0.1 to 3 hours, and the upper limit is more preferably 2 hours or less.
  • the temperature of the heat treatment is preferably higher than the glass transition temperature and lower than the thermal decomposition temperature, for example, more preferably 200 to 600°C, and even more preferably 250 to 575°C. More specifically, the temperature is preferably at least the glass transition temperature of the solid electrolyte, for example, preferably at least 200°C, more preferably at least 250°C.
  • the heat treatment temperature is preferably at most the thermal decomposition temperature, for example, preferably at most 600°C, and more preferably at most 575°C.
  • the heat treatment temperature is preferably higher than the glass transition temperature and lower than 550°C, and more preferably the upper limit is 530°C or lower.
  • the obtained solid electrolyte is used as an electrode mixture or solid electrolyte layer for lithium ion secondary batteries, or an all-solid lithium ion secondary battery, it is subjected to conventionally known processes together with other components as necessary. Served.
  • the sharing of a face or edge with the two adjacent tetrahedrons T 2 includes sharing an edge with one tetrahedron T 2 and sharing a face with the other tetrahedron T 2 ,
  • the two vertices included in the edge shared by the tetrahedron T2 are a vertex a and a vertex b
  • the composition constituting the crystal structure is (Li+Z) a (P+Si) 1 (S+O) b Ha c (3 ⁇ a ⁇ 6, 3 ⁇ b ⁇ 5 and 0 ⁇ c ⁇ 2), Z in the composition is the Z element, Ha in the composition is the Ha element, The ratio of Li and Z constituting the composition satisfies the relationship 0 ⁇ (Z/Li) ⁇ 0.1, and The sulfide-based solid electrolyte according to [5] above, wherein the ratio of P and Si constituting the composition satisfies the relationship 0 ⁇ (Si/P) ⁇ 0.4.
  • a solid electrolyte layer used in a lithium ion secondary battery comprising the sulfide solid electrolyte according to any one of [1] to [11] above.
  • An all-solid lithium ion secondary battery comprising the sulfide-based solid electrolyte according to any one of [1] to [11] above.
  • Example 1 Example 4, and Example 7 are comparative examples
  • Example 2 Example 3, Example 5, Example 6, Example 8, and Example 9 are examples.
  • Hydrolysis resistance was evaluated by exposing the sulfide-based solid electrolyte to a humidified N 2 atmosphere with a dew point of -20°C and detecting the total amount of hydrogen sulfide generated. Specifically, 10 mg of each sample was weighed, placed in a sample tube, and humidified N 2 gas was passed through it. The total amount of hydrogen sulfide generated was calculated by monitoring the concentration of hydrogen sulfide in the gas generated by the flow of humidity-adjusted N 2 gas until the generation of hydrogen sulfide stopped. As the detection tube, a hydrogen sulfide concentration meter (Model 3000RS, manufactured by Techne Keizoku Co., Ltd.) was used.
  • Lithium ion conductivity A sulfide-based solid electrolyte was used as a measurement sample as a compact at a pressure of 380 kPa, and was measured using an AC impedance measurement device (potentiostat/galvanostat VSP, manufactured by Bio-Logic Sciences Instruments) to determine the lithium ion conductivity. Ta.
  • the measurement conditions were: measurement frequency: 100 Hz to 1 MHz, measurement voltage: 100 mV, and measurement temperature: 25°C. The results are shown in " ⁇ Li + (mS/cm)" in Table 1.
  • Example 1 Under a dry nitrogen atmosphere, lithium sulfide powder (manufactured by Sigma, purity 99.98%) and diphosphorus pentasulfide powder were mixed to have a composition ratio of Li 5.3 P 0.95 S 4.225 Cl 1.6 . (manufactured by Sigma, purity 99%), lithium chloride powder (manufactured by Sigma, purity 99.99%), and SiO 2 powder (manufactured by Sigma, purity greater than 99%) were weighed and mixed in a mortar. The obtained mixture was placed in a carbon-coated quartz tube, sealed in a vacuum state, and then heated and melted at 750° C. for 1 hour.
  • the lattice constant of the a-axis is shown in "Lattice constant ( ⁇ )" in Table 1.
  • the composition constituting the crystal structure of the obtained solid electrolyte is expressed as (Li+Z) a (P+Si) 1 (S+O) b Ha c )
  • the ratio of Li element to Z element and the ratio of P element to Si element are , shown in “Z/Li” and "Si/P” in Table 1, respectively.
  • Example 2 to Example 9 Lithium sulfide powder (manufactured by Sigma, purity 99.98%), diphosphorus pentasulfide powder (manufactured by Sigma, purity 99%) so that each composition ratio described in "Composition (preparation ratio)" in Table 1 is achieved. , lithium chloride powder (manufactured by Sigma, purity 99.99%), SiO 2 powder (manufactured by Sigma, purity over 99%), SnS 2 (manufactured by Kojundo Kagaku Kenkyusho, Ltd., which is a raw material for Sn as necessary) A sulfide-based solid electrolyte and A solid was obtained.
  • the solid electrolytes of Examples 2 and 3 were argyrodites in which a plurality of PS 4 -tetrahedrons and a plurality of Li(S+Cl) 4 -tetrahedrons shared vertices, respectively.
  • the crystal structure was found to be cubic. It was also found that in some of the plurality of tetrahedra T2 , the Li element was substituted with the Sn element, and in some of the plurality of tetrahedra T1 , the P element was substituted with the Si element.
  • the solid electrolytes of Examples 4 and 7 have an argyrodite-type crystal structure in which a plurality of PS 4 -tetrahedrons and a plurality of Li(S+Cl+Br) 4 -tetrahedrons share vertices, and the crystal structure is cubic. I understand.
  • the solid electrolytes of Examples 5, 6, 8, and 9 have an argyrodite-type crystal structure in which a plurality of PS 4 -tetrahedrons and a plurality of Li(S+Cl+Br) 4 -tetrahedrons share vertices, respectively. was found to be a cubic crystal. It was also found that in some of the plurality of tetrahedra T2 , the Li element was substituted with the Sn element, and in some of the plurality of tetrahedra T1 , the P element was substituted with the Si element.
  • composition constituting the crystal structure, the a-axis lattice constant, the ratio of Li element to Z element, and the ratio of P element to Si element are as shown in Table 1, respectively. Further, the XRD patterns of the solid electrolytes of Examples 1 to 9 are shown in FIGS. 7 to 15, respectively.

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Abstract

La présente invention concerne un électrolyte solide à base de sulfure qui a une structure cristalline spécifique qui comprend une pluralité de tétraèdres T1 et une pluralité de tétraèdres T 2, dans lequel les tétraèdres T1 ont un atome de P au centre, et les tétraèdres T2 ont un atome de Li au centre ; un total de quatre atomes parmi un à quatre atomes S et de zéro à trois atomes X sont au niveau des sommets ; et dans certains de la pluralité de tétraèdres T2, l'atome de Li est substitué par un atome de Z (Si, Al, Sn, Ge, Zn, Sb, in, Cu).
PCT/JP2023/025046 2022-07-11 2023-07-05 Électrolyte solide à base de sulfure et procédé pour sa production, mélange d'électrode, couche d'électrolyte solide, et batterie secondaire au lithium-ion entièrement solide WO2024014382A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013118723A1 (fr) * 2012-02-06 2013-08-15 国立大学法人東京工業大学 Matériau d'électrolyte solide au sulfure, batterie, et procédé de fabrication de matériau d'électrolyte solide au sulfure
WO2017002971A1 (fr) * 2015-07-02 2017-01-05 国立大学法人東京工業大学 Matériau d'électrolyte solide à base de sulfure, batterie, et procédé de production d'un matériau d'électrolyte solide à base de sulfure
WO2018173939A1 (fr) * 2017-03-22 2018-09-27 三菱瓦斯化学株式会社 Procédé de fabrication d'électrolyte solide à base de lgps
WO2022009934A1 (fr) * 2020-07-07 2022-01-13 Ａｇｃ株式会社 Électrolyte solide à base de sulfure utilisé pour une batterie secondaire au lithium-ion et sa méthode de production, couche d'électrolyte solide et batterie secondaire au lithium-ion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013118723A1 (fr) * 2012-02-06 2013-08-15 国立大学法人東京工業大学 Matériau d'électrolyte solide au sulfure, batterie, et procédé de fabrication de matériau d'électrolyte solide au sulfure
WO2017002971A1 (fr) * 2015-07-02 2017-01-05 国立大学法人東京工業大学 Matériau d'électrolyte solide à base de sulfure, batterie, et procédé de production d'un matériau d'électrolyte solide à base de sulfure
WO2018173939A1 (fr) * 2017-03-22 2018-09-27 三菱瓦斯化学株式会社 Procédé de fabrication d'électrolyte solide à base de lgps
WO2022009934A1 (fr) * 2020-07-07 2022-01-13 Ａｇｃ株式会社 Électrolyte solide à base de sulfure utilisé pour une batterie secondaire au lithium-ion et sa méthode de production, couche d'électrolyte solide et batterie secondaire au lithium-ion

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