WO2010038313A1 - 全固体型リチウム電池の製造方法 - Google Patents
全固体型リチウム電池の製造方法 Download PDFInfo
- Publication number
- WO2010038313A1 WO2010038313A1 PCT/JP2008/068071 JP2008068071W WO2010038313A1 WO 2010038313 A1 WO2010038313 A1 WO 2010038313A1 JP 2008068071 W JP2008068071 W JP 2008068071W WO 2010038313 A1 WO2010038313 A1 WO 2010038313A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- sulfide
- dew point
- lithium battery
- atmosphere
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- 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
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to a method for manufacturing an all-solid-state lithium battery capable of easily performing dew point management in a battery assembly process.
- the lithium battery currently on the market uses an organic electrolyte that uses a flammable organic solvent as a solvent. Improvement is required.
- an all-solid-state lithium battery in which the liquid electrolyte is changed to a solid electrolyte to make the battery all solid does not use a flammable organic solvent in the battery, so that the safety device can be simplified, and the manufacturing cost and It has the advantage of excellent productivity.
- sulfide solid electrolytes are known as solid electrolytes used in such all solid-state lithium batteries.
- Patent Document 1 discloses a method for synthesizing a sulfide solid electrolyte that is heated and melted in an inert gas flow having a water content of 100 ppm or less.
- Non-Patent Document 1 discloses a crystal structure of Li 7 P 3 S 11 , specifically, a P 2 S 7 unit (unit represented by structural formula B described later) containing bridging sulfur, A crystal structure is disclosed in which PS 4 units (units represented by structural formula C described later) having no bridging sulfur are arranged at a ratio of 1: 1.
- Li 7 P 3 S 11 is on a molar basis
- the present invention has been made in view of the above problems, and a main object of the present invention is to provide a method for producing an all-solid-state lithium battery capable of easily performing dew point management in a battery assembly process.
- Li 2 S, P 2 S 5 and P 2 O 5 are converted into (Li 2 S) / (P 2 S 5 ) on a molar basis. + P 2 O 5 ) ⁇ 3
- the sulfide solid electrolyte using a raw material composition obtained by adding so as to satisfy the relationship of 3 has a low lithium ion conductivity even in an atmosphere with a high dew point temperature. I found.
- the present invention has been made based on such knowledge.
- Li 2 S, P 2 S 5 and P 2 O 5 are made to satisfy the relationship of (Li 2 S) / (P 2 S 5 + P 2 O 5 ) ⁇ 3 on a molar basis.
- a preparation step of preparing a raw material composition a synthesis step of synthesizing a sulfide solid electrolyte from the raw material composition by vitrification means, and a dew point temperature of ⁇ 60 ° C. or higher using the sulfide solid electrolyte.
- a battery assembly process for assembling an all-solid-state lithium battery in an atmosphere.
- a sulfide solid electrolyte having a P 2 S 6 O unit is synthesized by using a raw material composition to which P 2 O 5 is further added in addition to Li 2 S and P 2 S 5.
- P 2 S 6 O unit is more stable to moisture than the P 2 S 7 unit, the lithium ion conductivity of the sulfide solid electrolyte is reduced even in an atmosphere with a high dew point temperature. Can be suppressed. Therefore, the dew point management can be facilitated.
- the battery assembly step is preferably performed in an atmosphere having a dew point temperature of ⁇ 30 ° C. or lower. This is because a decrease in lithium ion conductivity due to moisture can be sufficiently suppressed.
- the sulfide solid electrolyte is preferably used as a solid electrolyte membrane disposed between a positive electrode active material layer and a negative electrode active material layer. This is because an all solid-state lithium battery having excellent lithium ion conductivity can be obtained.
- the vitrification means is preferably mechanical milling. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- the material composition is, on a molar basis, preferably satisfy the relation (P 2 O 5) / ( Li 2 S + P 2 S 5 + P 2 O 5) ⁇ 10. This is because the stability to moisture can be improved while maintaining high lithium ion conductivity.
- the dew point can be easily managed in the battery assembly process.
- Method for manufacturing an all-solid-state lithium battery of the present invention Li 2 S, P 2 S 5 and P 2 O 5, on a molar basis, (Li 2 S) / ( P 2 S 5 + P 2 O 5) ⁇ 3
- the dew point temperature, the preparation step of preparing the raw material composition, the synthesis step of synthesizing the sulfide solid electrolyte from the raw material composition by vitrification means Has a battery assembly step of assembling an all-solid-state lithium battery in an atmosphere of ⁇ 60 ° C. or higher.
- FIG. 1 is an explanatory diagram for explaining an example of the manufacturing method of the manufacturing method of the all-solid-state lithium battery of the present invention.
- Li 2 S, P 2 S 5 and P 2 O 5 are first prepared as starting materials. Further, this starting material is added at a predetermined ratio to prepare a raw material composition (preparation step).
- a sulfide solid electrolyte made of sulfide glass is synthesized from the raw material composition by vitrification means (for example, mechanical milling) (synthesis step).
- sulfide glass may be fired to form sulfide glass ceramic, and the sulfide glass ceramic may be used as a sulfide solid electrolyte.
- an all solid-state lithium battery is assembled in an atmosphere of a predetermined dew point temperature (battery assembly process).
- a sulfide solid electrolyte having units represented by the following structural formulas A to C can be obtained by the above synthesis step.
- a P 2 S 6 O unit represented by Structural Formula A (sometimes simply referred to as “P 2 S 6 O unit”) and a P 2 S 7 unit represented by Structural Formula B ( it may be simply referred to as “P 2 S 7 unit”. and)
- PS 4 units represented by the structural formula C (simply referred to as "PS 4 unit”.)
- the sulfide solid electrolyte usually has Li ions as a counter for each unit.
- a sulfide solid electrolyte having a P 2 S 6 O unit is synthesized by using a raw material composition to which P 2 O 5 is further added in addition to Li 2 S and P 2 S 5.
- P 2 S 6 O unit is more stable to moisture than the P 2 S 7 unit, the lithium ion conductivity of the sulfide solid electrolyte is reduced even in an atmosphere with a high dew point temperature. Can be suppressed. Therefore, the dew point management can be facilitated.
- the battery can be assembled in an atmosphere having a high dew point temperature, the cost for maintaining the dew point temperature can be reduced. In particular, when a battery assembly process is performed, a large work space is usually required. Therefore, it is important to facilitate dew point management and to reduce the cost for maintaining the dew point temperature.
- Non-Patent Document 1 In the above-mentioned Non-Patent Document 1 and Non-Patent Document 2, there is no description or suggestion about the stability of the sulfide solid electrolyte with respect to moisture. Hereafter, the manufacturing method of the all-solid-state lithium battery of this invention is demonstrated for every process.
- Preparation Step The preparation step in the present invention satisfies the relationship of (Li 2 S) / (P 2 S 5 + P 2 O 5 ) ⁇ 3 on a molar basis with Li 2 S, P 2 S 5 and P 2 O 5. It is the process of adding so that a raw material composition may be prepared.
- Li 2 S, P 2 S 5 and P 2 O 5 are used as starting materials for the sulfide solid electrolyte.
- Li 2 S, P 2 S 5 and P 2 O 5 each preferably have few impurities. This is because side reactions can be suppressed.
- Examples of the method for synthesizing Li 2 S used in the present invention include the method described in JP-A-7-330312.
- Li 2 S is preferably purified using the method described in WO2005 / 040039.
- P 2 S 5 and P 2 O 5 used in the present invention may be used those commercially available.
- Li 2 S, P 2 S 5 and P 2 O 5 are added on a molar basis so as to satisfy the relationship of (Li 2 S) / (P 2 S 5 + P 2 O 5 ) ⁇ 3.
- the raw material composition preferably satisfies the relationship 1 ⁇ (Li 2 S) / (P 2 S 5 + P 2 O 5 ) ⁇ 3 on a molar basis, and 1.5 ⁇ (Li 2 S) / (P 2 S 5 + P 2 O 5 ) ⁇ 3 is more preferable.
- the addition amount of P 2 O 5 with respect to the sum of the addition amounts of Li 2 S, P 2 S 5 and P 2 O 5 is (Li 2 S) / (Li 2 S + P 2 S 5 + P 2 O 5 ).
- the raw material composition preferably satisfies the relationship of (P 2 O 5 ) / (Li 2 S + P 2 S 5 + P 2 O 5 ) ⁇ 10 on a molar basis, and (P 2 O 5 ) / More preferably, the relationship (Li 2 S + P 2 S 5 + P 2 O 5 ) ⁇ 8 is satisfied, and the relationship (P 2 O 5 ) / (Li 2 S + P 2 S 5 + P 2 O 5 ) ⁇ 6 is satisfied.
- the raw material composition preferably satisfies the relationship of 0.5 ⁇ (P 2 O 5 ) / (Li 2 S + P 2 S 5 + P 2 O 5 ) on a molar basis, and 1.0 ⁇ (P 2 O 5 ) / (Li 2 S + P 2 S 5 + P 2 O 5 ) is more preferable, and the relationship of 1.5 ⁇ (P 2 O 5 ) / (Li 2 S + P 2 S 5 + P 2 O 5 ) is satisfied. It is more preferable to satisfy. This is because if the addition ratio of P 2 O 5 is too small, stability against moisture may not be improved.
- x is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
- x is preferably 0.5 or more, more preferably 1 or more, and further preferably 1.5 or more.
- the ratio of Li 2 S, P 2 S 5 and P 2 O 5 in the raw material composition is not particularly limited as long as the above relationship is satisfied.
- the content of Li 2 S contained in the raw material composition is preferably in the range of 68 mol% to 74 mol%, for example.
- the content of P 2 S 5 contained in the raw material composition is preferably in the range of 16 mol% to 31.5 mol%, for example.
- the content of P 2 O 5 contained in the raw material composition is, for example, preferably 0.5 mol% or more, more preferably 1 mol% or more, and further preferably 1.5 mol% or more.
- the content of P 2 O 5 is preferably 10 mol% or less, more preferably 8 mol% or less, and still more preferably 6 mol% or less.
- Li 2 S may be one containing only P 2 S 5 and P 2 O 5, Li 2 S , in addition to P 2 S 5 and P 2 O 5, it added It may contain an agent.
- An example of the additive includes at least one sulfide selected from the group consisting of Al 2 S 3 , B 2 S 3, GeS 2 and SiS 2 . By adding such a sulfide, a more stable sulfide glass can be obtained.
- Another example of the additive is at least one lithium orthooxoate selected from the group consisting of Li 3 PO 4 , Li 4 SiO 4 , Li 4 GeO 4 , Li 3 BO 3 and Li 3 AlO 3. Can be mentioned.
- the raw material composition in the present invention may contain both the sulfide and the lithium orthooxo acid. Moreover, it is preferable to set the addition amount of an additive suitably according to a use.
- the synthesis step in the present invention is a step of synthesizing a sulfide solid electrolyte from the raw material composition by vitrification means.
- a sulfide solid electrolyte made of sulfide glass is obtained by vitrification means.
- sulfide glass may be fired to form sulfide glass ceramic, and the sulfide glass ceramic may be used as a sulfide solid electrolyte.
- the vitrification means in the present invention is not particularly limited as long as it is a means capable of synthesizing a sulfide glass from a raw material composition, and examples thereof include mechanical milling and a melt quenching method. Milling is preferred. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- the present invention it is preferable to synthesize sulfide glass from the raw material composition in an inert gas atmosphere. This is because moisture, oxygen and the like easily react with the starting material.
- the inert gas include argon and nitrogen.
- the mechanical milling is not particularly limited as long as mechanical energy can be imparted to the raw material composition, and examples thereof include a ball mill, a turbo mill, a mechano-fusion, a disk mill, and the like. And a planetary ball mill is particularly preferable. This is because it is general-purpose and the sulfide glass can be obtained efficiently.
- the various conditions of the mechanical milling are preferably set to such an extent that a desired sulfide glass can be obtained, and are preferably selected as appropriate according to the type of mechanical milling.
- a sulfide glass is synthesized by a planetary ball mill, usually, the raw material composition and grinding balls are added to the pot, and the treatment is performed at a predetermined number of revolutions and time.
- the higher the number of rotations the faster the generation rate of sulfide glass, and the longer the treatment time, the higher the conversion rate of the raw material to sulfide glass.
- the rotation speed when performing the planetary ball mill is preferably in the range of 200 rpm to 500 rpm, and more preferably in the range of 300 rpm to 400 rpm.
- the processing time when performing the planetary ball mill is preferably in the range of 0.5 to 100 hours, and more preferably in the range of 10 to 40 hours.
- sulfide glass may be fired to obtain sulfide glass ceramic, and the sulfide glass ceramic may be used as a sulfide solid electrolyte.
- the temperature of the firing treatment is not particularly limited as long as the desired sulfide glass ceramic can be obtained. For example, it is in the range of 150 ° C. to 360 ° C., and in particular in the range of 200 ° C. to 350 ° C. It is preferable that If the firing temperature is too low, the glass transition temperature of the sulfide glass may not be reached and crystallization may not proceed. If the firing temperature is too high, the desired crystal structure may not be formed. Because. Further, the firing time is preferably in the range of 1 minute to 2 hours, and more preferably in the range of 10 minutes to 1 hour.
- the firing of sulfide glass in an inert gas atmosphere is preferable to perform the firing of sulfide glass in an inert gas atmosphere.
- the inert gas include argon and nitrogen.
- a general baking furnace and the like can be exemplified as a device for performing the baking treatment.
- the battery assembling step in the present invention is a step of assembling an all-solid-state lithium battery using the sulfide solid electrolyte in an atmosphere having a dew point temperature of ⁇ 60 ° C. or higher.
- the atmosphere in the battery assembly process has a dew point temperature of preferably ⁇ 55 ° C. or higher, more preferably ⁇ 50 ° C. or higher. This is because, even in an atmosphere with a high dew point temperature, a decrease in lithium ion conductivity due to moisture can be sufficiently suppressed.
- the atmosphere in the battery assembly process has a dew point temperature of preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower, still more preferably ⁇ 35 ° C. or lower, and ⁇ 40 ° C. or lower. It is particularly preferred. This is because a decrease in lithium ion conductivity due to moisture can be sufficiently suppressed.
- the dew point temperature can be determined by a dew point meter (for example, an optional dew point meter of a vacuum glove box (MDB-2B) manufactured by Miwa Seisakusho Co., Ltd.).
- the moisture concentration of the atmosphere in the battery assembly process is preferably a concentration range corresponding to the above dew point temperature range.
- the upper limit of the dew point temperature of the atmosphere in the battery assembly process may be determined by a 10-hour storage test described in the examples described later. Preliminary tests were performed at various dew point temperatures, and a dew point temperature at which the lithium ion conductivity after the 10-hour storage test was 1 ⁇ 10 ⁇ 3 (S ⁇ cm ⁇ 1 ) was obtained, and this dew point temperature was determined as an atmosphere in the battery assembly process. It may be the upper limit of the dew point temperature.
- the atmosphere in the battery assembly process is usually an inert gas atmosphere.
- the inert gas used include argon and nitrogen.
- an all solid-state lithium battery is assembled using a sulfide solid electrolyte.
- the sulfide solid electrolyte may be used as a solid electrolyte film disposed between the positive electrode active material layer and the negative electrode active material layer, and used as a solid electrolyte material added to the positive electrode active material layer and / or the negative electrode active material layer. Also good.
- the power generation element is usually formed using a positive electrode current collector, a positive electrode active material layer, a negative electrode current collector, and a negative electrode active material layer.
- the method for forming the power generation element is the same as the general method and is not particularly limited.
- the negative electrode current collector / negative electrode active material layer / solid electrolyte membrane / positive electrode active material layer / positive electrode current collector In order to obtain the configuration, a method of sequentially performing compression molding can be exemplified.
- the power generation element may be formed by forming the negative electrode active material layer, the solid electrolyte membrane, and the positive electrode active material layer into pellets and compressing them.
- FIG. 2 is a schematic cross-sectional view showing an example of a power generation element of an all solid-state lithium battery obtained by the present invention.
- a power generation element 10 shown in FIG. 2 includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte film 3 using a sulfide solid electrolyte, a positive electrode active material layer 4, and a positive electrode current collector 5.
- the solid electrolyte membrane is preferably formed using the above-mentioned sulfide solid electrolyte.
- the thickness of the solid electrolyte membrane is, for example, in the range of 0.1 ⁇ m to 1000 ⁇ m, and preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
- the positive electrode active material layer used in the present invention has at least a positive electrode active material.
- the positive electrode active material include LiCoO 2 , LiMnO 2 , Li 2 NiMn 3 O 8 , LiVO 2 , LiCrO 2 , LiFePO 4 , LiCoPO 4 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2, and the like. Can be mentioned.
- the positive electrode active material layer may contain a conductive material in order to improve conductivity. Examples of the conductive material include acetylene black and carbon fiber.
- the positive electrode active material layer may contain a solid electrolyte in order to improve lithium ion conductivity.
- the thickness of the positive electrode active material layer is, for example, in the range of 1 ⁇ m to 100 ⁇ m.
- the positive electrode current collector used in the present invention is not particularly limited as long as it has a function of collecting current of the positive electrode active material layer.
- Examples of the material for the positive electrode current collector include SUS.
- Examples of the shape of the positive electrode current collector include a foil shape and a mesh shape.
- the negative electrode active material layer used in the present invention has at least a negative electrode active material.
- the negative electrode active material include a metal active material and a carbon active material.
- the metal active material include In, Al, Si, Sn, and alloys thereof.
- examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon.
- the negative electrode active material layer may contain the above-described conductive material, solid electrolyte, and the like.
- the negative electrode active material layer used in the present invention may be a metal film of a metal active material, or may be a compression-molded powder of a negative electrode active material.
- the thickness of the negative electrode active material layer is, for example, in the range of 1 ⁇ m to 100 ⁇ m.
- the negative electrode current collector used in the present invention is not particularly limited as long as it has a function of collecting current of the negative electrode active material layer.
- Examples of the material for the negative electrode current collector include SUS.
- Examples of the shape of the negative electrode current collector include a foil shape and a mesh shape.
- an all-solid-state lithium battery is usually assembled by storing the above-described power generation element in a battery case.
- the material and shape of the battery case is the same as that of a general all solid-state lithium battery.
- the above power generation element may be formed in a hollow portion of the insulating ring.
- the all solid-state lithium battery obtained by the present invention may be a primary battery or a secondary battery.
- a vehicle-mounted battery can be exemplified.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
- a pot made of zirconia was attached to a planetary ball mill and mechanical milling was performed at a rotational speed of 370 rpm for 20 hours to obtain powdered sulfide glass.
- XRD X-ray diffraction
- peaks of Li 2 S is disappeared, it was confirmed that vitrification is in progress.
- the obtained sulfide glass was baked under conditions of 280 ° C. for 1 hour while flowing Ar gas to obtain a sulfide solid electrolyte made of sulfide glass ceramics.
- Example 1-1 A test was performed in which the sulfide solid electrolyte obtained in Synthesis Example 1 was stored for 10 hours in a glove box in an Ar atmosphere having a dew point temperature of ⁇ 20 ° C.
- Example 1-2 A test was conducted in which the sulfide solid electrolyte obtained in Synthesis Example 1 was stored for 10 hours in a glove box in an Ar atmosphere having a dew point temperature of ⁇ 30 ° C.
- Example 1-3 A test was conducted in which the sulfide solid electrolyte obtained in Synthesis Example 1 was stored for 10 hours in a glove box in an Ar atmosphere having a dew point temperature of ⁇ 40 ° C.
- Example 1-4 A test was performed in which the sulfide solid electrolyte obtained in Synthesis Example 1 was stored for 10 hours in a glove box in an Ar atmosphere having a dew point temperature of ⁇ 60 ° C.
- Example 1-1 the lithium ion conductivity could be kept high as compared with Comparative Example 1-3. This is also considered to be due to the influence of the P 2 S 6 O unit.
- Example 2 An evaluation cell was produced using the sulfide solid electrolyte obtained in Example 1-3.
- the evaluation cell was produced in a glove box in an Ar atmosphere with a dew point temperature of ⁇ 40 ° C., as in the synthesis of the sulfide solid electrolyte.
- a negative electrode active material graphite
- a press machine to form a negative electrode active material layer.
- the sulfide solid electrolyte obtained in Example 1-2 was added to the surface of the negative electrode active material layer and pressed to form a solid electrolyte membrane.
- a positive electrode active material LiCoO 2
- SiCoO 2 a positive electrode active material
- SUS electrical power collector
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
Description
2 … 負極活物質層
3 … 固体電解質膜
4 … 正極活物質層
5 … 正極集電体
10 … 全固体型リチウム電池の発電要素
以下、本発明の全固体型リチウム電池の製造方法について、工程ごとに説明する。
本発明における調製工程は、Li2S、P2S5およびP2O5を、モル基準で、(Li2S)/(P2S5+P2O5)<3の関係を満たすように添加し、原料組成物を調製する工程である。
次に、本発明における合成工程について説明する。本発明における合成工程は、ガラス化手段により、前記原料組成物から硫化物固体電解質を合成する工程である。通常は、ガラス化手段により、硫化物ガラスからなる硫化物固体電解質が得られる。なお、本発明においては、硫化物ガラスを焼成して硫化物ガラスセラミックスとし、その硫化物ガラスセラミックスを硫化物固体電解質として用いても良い。
次に、本発明における電池組立工程について説明する。本発明における電池組立工程は、上記硫化物固体電解質を用い、露点温度が-60℃以上の雰囲気中で、全固体型リチウム電池を組立てる工程である。
[合成例1]
出発原料として、硫化リチウム結晶(Li2S)、五硫化二リン(P2S5)および五酸化二リン(P2O5)を用意した。これらの粉末をアルゴン雰囲気のグローブボックス内で、Li2S:P2S5:P2O5=70:26:4(モル基準)の割合で秤量し、ジルコニア製ポットに投入した。さらに、φ=15mmのジルコニア製粉砕用ボール6個を、容積45ccのジルコニア製ポットに投入し、完全密封した。次に、ジルコニア製ポットを遊星型ボールミル機に取り付け、370rpmの回転速度で20時間メカニカルミリングを行い、粉末状の硫化物ガラスを得た。なお、得られた硫化物ガラスをX線回折(XRD)法で測定した結果、Li2Sのピークは消失しており、ガラス化が進行していることが確認できた。次に、得られた硫化物ガラスを、Arガスをフローしながら、280℃、1時間の条件で焼成処理し、硫化物ガラスセラミックスからなる硫化物固体電解質を得た。
Li2S:P2S5:P2O5=70:28:2(モル基準)としたこと以外は、合成例1と同様にして、硫化物系固体電解質材料を得た。なお、合成途中で得られた硫化物ガラスをX線回折(XRD)法で測定した結果、Li2Sのピークは消失しており、ガラス化が進行していることが確認できた。
Li2S:P2S5:P2O5=70:24:6(モル基準)としたこと以外は、合成例1と同様にして、硫化物系固体電解質材料を得た。なお、合成途中で得られた硫化物ガラスをX線回折(XRD)法で測定した結果、Li2Sのピークは消失しており、ガラス化が進行していることが確認できた。
Li2S:P2S5:P2O5=70:20:10(モル基準)としたこと以外は、合成例1と同様にして、硫化物系固体電解質材料を得た。なお、合成途中で得られた硫化物ガラスをX線回折(XRD)法で測定した結果、Li2Sのピークは消失しており、ガラス化が進行していることが確認できた。
P2O5を用いず、Li2S:P2S5=70:30(モル基準)としたこと以外は、合成例1と同様にして、硫化物固体電解質を得た。
合成例1で得られた硫化物固体電解質を、露点温度が-20℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
合成例1で得られた硫化物固体電解質を、露点温度が-30℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
合成例1で得られた硫化物固体電解質を、露点温度が-40℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
合成例1で得られた硫化物固体電解質を、露点温度が-60℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
合成例1で得られた硫化物固体電解質を、露点温度が-70℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
合成例1で得られた硫化物固体電解質を、露点温度が-80℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-20℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-30℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-40℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-60℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-70℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
比較合成例で得られた硫化物固体電解質を、露点温度が-80℃であるAr雰囲気のグローブボックス内で10時間保存する試験を行った。
実施例1-1~実施例1-4および比較例1-1~比較例1-8で得られた硫化物固体電解質のリチウムイオン伝導度を評価した。まず試験終了後に、そのグローブボックス内で、硫化物固体電解質を5.1mg秤量した。次に、その硫化物固体電解質を、5.1t/cm2の圧力で圧縮成形することで、φ10mmのペレットを得た。次に、このペレットを用いて、交流インピーダンス法によりリチウムイオン伝導度を測定した。その測定条件を以下に示す。
(測定条件)
電極:SUS304
インピーダンス測定システム:ソーラートロン1260(ソーラートロン社製)
印加電圧:5mV
測定周波数:0.01MHz~10MHz
実施例1-3で得られた硫化物固体電解質を用いて、評価用セルを作製した。なお、評価用セルの作製は、硫化物固体電解質の合成と同様に、露点温度が-40℃のAr雰囲気のグローブボックス内で行った。まず、プレス機を用いて、負極活物質(グラファイト)をプレスし、負極活物質層を形成した。次に、負極活物質層の表面上に、実施例1-2で得られた硫化物固体電解質を添加し、プレスすることで、固体電解質膜を形成した。次に、固体電解質膜の表面上に、正極活物質(LiCoO2)を添加し、プレスすることで、正極活物質層を形成した。これにより、負極活物質層/固体電解質膜/正極活物質層の積層体を得た。さらに、この積層体の両面を、集電体(SUS)で挟持し、評価用セルを得た。
実施例2で得られた評価用セルを用いて、127mA/cm2の電流で、充電4.08Vの電圧規制、放電3Vの電圧規制の条件で、充放電試験を行った。その結果を図4に示す。図4に示されるように、評価用セルは充放電可能であり、二次電池として機能することが確認できた。
比較例1-7で得られた硫化物固体電解質を用いて、大気フローによるラマン分光スペクトルの変動を評価した。大気フローの条件は、温度24℃、湿度37%RH、流速1L/min.とした。また、0分、0.5分、1分、5.5分および15分のタイミングでラマン分光スペクトルを測定した。その結果を図5に示す。図5において、402cm-1のピークはP2S7ユニットのピークであり、417cm-1のピークはPS4ユニットのピークである。図5に示されるように、大気フローの時間が長くなると、P2S7ユニットのピーク(402cm-1)が、PS4ユニットのピーク(417cm-1)に比べて、急速に減少していることが確認できた。これは、P2S7ユニットが優先的に大気中の水分と反応し、硫化水素を発生させているためであると考えられる。さらに、P2S7ユニットの構造を考慮すると、架橋部分に位置する硫黄が大気中の水分と反応していることが示唆される。これに対して、本発明に用いられる硫化物固体電解質は、P2S7ユニットの架橋硫黄を酸素に置換したP2S6Oユニットを有するため、水分に対する安定性が向上すると考えられる。その結果、露点温度が高い雰囲気で電池の組立を行った場合であっても、リチウムイオン伝導度の低下を抑制できる。
Claims (6)
- Li2S、P2S5およびP2O5を、モル基準で、(Li2S)/(P2S5+P2O5)<3の関係を満たすように添加し、原料組成物を調製する調製工程と、
ガラス化手段により、前記原料組成物から硫化物固体電解質を合成する合成工程と、
前記硫化物固体電解質を用い、露点温度が-60℃以上の雰囲気中で、全固体型リチウム電池を組立てる電池組立工程と、
を有することを特徴とする全固体型リチウム電池の製造方法。 - 前記電池組立工程を、露点温度が-30℃以下の雰囲気中で行うことを特徴とする請求の範囲第1項に記載の全固体型リチウム電池の製造方法。
- 前記硫化物固体電解質を、正極活物質層および負極活物質層の間に配置される固体電解質膜として用いることを特徴とする請求の範囲第1項または第2項に記載の全固体型リチウム電池の製造方法。
- 前記ガラス化手段が、メカニカルミリングであることを特徴とする請求の範囲第1項から第3項までのいずれかに記載の全固体型リチウム電池の製造方法。
- 前記原料組成物が、モル基準で、(Li2S)/(P2S5+P2O5)=7/3の関係を満たすことを特徴とする請求の範囲第1項から第4項までのいずれかに記載の全固体型リチウム電池の製造方法。
- 前記原料組成物が、モル基準で、(P2O5)/(Li2S+P2S5+P2O5)≦10の関係を満たすことを特徴とする請求の範囲第1項から第5項までのいずれかに記載の全固体型リチウム電池の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/059,844 US8591603B2 (en) | 2008-10-03 | 2008-10-03 | Method for producing all solid lithium battery |
PCT/JP2008/068071 WO2010038313A1 (ja) | 2008-10-03 | 2008-10-03 | 全固体型リチウム電池の製造方法 |
CN200880131152.8A CN102160232B (zh) | 2008-10-03 | 2008-10-03 | 全固体型锂电池的制造方法 |
KR1020117005892A KR20110055635A (ko) | 2008-10-03 | 2008-10-03 | 전고체형 리튬 전지의 제조 방법 |
JP2010531699A JP5278437B2 (ja) | 2008-10-03 | 2008-10-03 | 全固体型リチウム電池の製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2008/068071 WO2010038313A1 (ja) | 2008-10-03 | 2008-10-03 | 全固体型リチウム電池の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010038313A1 true WO2010038313A1 (ja) | 2010-04-08 |
Family
ID=42073105
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/068071 WO2010038313A1 (ja) | 2008-10-03 | 2008-10-03 | 全固体型リチウム電池の製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8591603B2 (ja) |
JP (1) | JP5278437B2 (ja) |
KR (1) | KR20110055635A (ja) |
CN (1) | CN102160232B (ja) |
WO (1) | WO2010038313A1 (ja) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010199033A (ja) * | 2009-02-27 | 2010-09-09 | Osaka Prefecture Univ | 硫化物固体電解質材料 |
WO2011030696A1 (ja) * | 2009-09-09 | 2011-03-17 | 公立大学法人大阪府立大学 | 硫化物固体電解質 |
JP2011086556A (ja) * | 2009-10-16 | 2011-04-28 | Sumitomo Electric Ind Ltd | 硫化物固体電解質の製造方法、および複合体 |
WO2012026238A1 (en) * | 2010-08-26 | 2012-03-01 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
JP2012048971A (ja) * | 2010-08-26 | 2012-03-08 | Toyota Motor Corp | 硫化物固体電解質材料、正極体およびリチウム固体電池 |
CN102959646A (zh) * | 2010-06-29 | 2013-03-06 | 丰田自动车株式会社 | 硫化物固体电解质材料的制造方法、锂固体电池的制造方法 |
WO2013094757A1 (ja) * | 2011-12-22 | 2013-06-27 | 国立大学法人東京工業大学 | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
JP2014056818A (ja) * | 2013-08-16 | 2014-03-27 | Toyota Motor Corp | 硫化物固体電解質材料、正極体およびリチウム固体電池 |
JP2014091664A (ja) * | 2012-11-06 | 2014-05-19 | Idemitsu Kosan Co Ltd | 固体電解質ガラス粒子及びリチウムイオン電池 |
US8968939B2 (en) | 2009-05-01 | 2015-03-03 | Toyota Jidosha Kabushiki Kaisha | Solid electrolyte material, electrode element that includes solid electrolyte material, all-solid battery that includes solid electrolyte material, and manufacturing method for solid electrolyte material |
JPWO2013042371A1 (ja) * | 2011-09-22 | 2015-03-26 | 出光興産株式会社 | ガラス粒子 |
JP2015153466A (ja) * | 2014-02-10 | 2015-08-24 | 古河機械金属株式会社 | 固体電解質シートおよび全固体型リチウムイオン電池 |
US10008735B2 (en) | 2009-12-16 | 2018-06-26 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
JP2018129307A (ja) * | 2018-03-19 | 2018-08-16 | 古河機械金属株式会社 | 固体電解質シートおよび全固体型リチウムイオン電池 |
JP2019192490A (ja) * | 2018-04-25 | 2019-10-31 | 国立大学法人東京工業大学 | 硫化物固体電解質および全固体電池 |
JP2021510905A (ja) * | 2018-01-12 | 2021-04-30 | ユニバーシティー オブ ヒューストン システム | ナトリウム電池のための固体電解質 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014093263A (ja) * | 2012-11-06 | 2014-05-19 | Idemitsu Kosan Co Ltd | 固体電解質及びリチウム電池 |
KR101646416B1 (ko) * | 2014-12-18 | 2016-08-05 | 현대자동차주식회사 | 붕산염이 첨가된 전고체 이차전지용 황화물계 결정화 유리 및 이의 제조방법 |
KR101684130B1 (ko) * | 2015-06-16 | 2016-12-07 | 현대자동차주식회사 | 리튬 이온 전도성 황화물의 제조방법, 이에 의하여 제조된 리튬 이온 전도성 황화물, 및 이를 포함하는 고체전해질, 전고체 배터리 |
KR101930992B1 (ko) | 2016-02-15 | 2018-12-19 | 한양대학교 산학협력단 | 황화물계 고체 전해질의 제조방법, 이로부터 제조된 황화물계 고체 전해질 및 이를 포함하는 전고체 리튬 이차전지 |
KR102484902B1 (ko) | 2017-12-27 | 2023-01-04 | 현대자동차주식회사 | 전고체 전지 |
CN111029662A (zh) * | 2019-12-30 | 2020-04-17 | 江苏智泰新能源科技有限公司 | 一种硫化物电解质材料制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002109955A (ja) * | 2000-10-02 | 2002-04-12 | Osaka Prefecture | 硫化物系結晶化ガラス、固体型電解質及び全固体二次電池 |
WO2004106232A1 (ja) * | 2003-05-30 | 2004-12-09 | Nippon Chemical Industrial Co., Ltd. | 硫化リチウム粉体、その製造方法および無機固体電解質 |
JP2006151725A (ja) * | 2004-11-26 | 2006-06-15 | Nippon Chem Ind Co Ltd | 硫化リチウム粒子粉末、その製造方法および無機固体電解質 |
JP2007005279A (ja) * | 2004-12-13 | 2007-01-11 | Matsushita Electric Ind Co Ltd | 活物質層と固体電解質層とを含む積層体およびこれを用いた全固体リチウム二次電池 |
JP2007227362A (ja) * | 2006-01-27 | 2007-09-06 | Matsushita Electric Ind Co Ltd | 固体電池の製造方法 |
JP2007273214A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2008287970A (ja) * | 2007-05-16 | 2008-11-27 | Toyota Motor Corp | 全固体リチウム二次電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3125507B2 (ja) | 1993-03-26 | 2001-01-22 | 松下電器産業株式会社 | 硫化物系リチウムイオン導電性固体電解質及びその合成法 |
CA2305837C (en) * | 1999-04-14 | 2011-05-31 | Sony Corporation | Material for negative electrode and nonaqueous-electrolyte battery incorporating the same |
CN100495801C (zh) * | 2004-12-13 | 2009-06-03 | 松下电器产业株式会社 | 包含活性材料层和固体电解质层的叠层体及使用这种叠层体的全固态锂二次电池 |
US20070259271A1 (en) | 2004-12-13 | 2007-11-08 | Tetsuo Nanno | Laminate Including Active Material Layer and Solid Electrolyte Layer, and All Solid Lithium Secondary Battery Using the Same |
US20070175020A1 (en) * | 2006-01-27 | 2007-08-02 | Matsushita Electric Industrial Co., Ltd. | Method for producing solid state battery |
-
2008
- 2008-10-03 US US13/059,844 patent/US8591603B2/en active Active
- 2008-10-03 KR KR1020117005892A patent/KR20110055635A/ko not_active Application Discontinuation
- 2008-10-03 JP JP2010531699A patent/JP5278437B2/ja active Active
- 2008-10-03 CN CN200880131152.8A patent/CN102160232B/zh active Active
- 2008-10-03 WO PCT/JP2008/068071 patent/WO2010038313A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002109955A (ja) * | 2000-10-02 | 2002-04-12 | Osaka Prefecture | 硫化物系結晶化ガラス、固体型電解質及び全固体二次電池 |
WO2004106232A1 (ja) * | 2003-05-30 | 2004-12-09 | Nippon Chemical Industrial Co., Ltd. | 硫化リチウム粉体、その製造方法および無機固体電解質 |
JP2006151725A (ja) * | 2004-11-26 | 2006-06-15 | Nippon Chem Ind Co Ltd | 硫化リチウム粒子粉末、その製造方法および無機固体電解質 |
JP2007005279A (ja) * | 2004-12-13 | 2007-01-11 | Matsushita Electric Ind Co Ltd | 活物質層と固体電解質層とを含む積層体およびこれを用いた全固体リチウム二次電池 |
JP2007227362A (ja) * | 2006-01-27 | 2007-09-06 | Matsushita Electric Ind Co Ltd | 固体電池の製造方法 |
JP2007273214A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2008287970A (ja) * | 2007-05-16 | 2008-11-27 | Toyota Motor Corp | 全固体リチウム二次電池 |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010199033A (ja) * | 2009-02-27 | 2010-09-09 | Osaka Prefecture Univ | 硫化物固体電解質材料 |
US9064615B2 (en) | 2009-02-27 | 2015-06-23 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material |
US8968939B2 (en) | 2009-05-01 | 2015-03-03 | Toyota Jidosha Kabushiki Kaisha | Solid electrolyte material, electrode element that includes solid electrolyte material, all-solid battery that includes solid electrolyte material, and manufacturing method for solid electrolyte material |
WO2011030696A1 (ja) * | 2009-09-09 | 2011-03-17 | 公立大学法人大阪府立大学 | 硫化物固体電解質 |
JP2011057500A (ja) * | 2009-09-09 | 2011-03-24 | Osaka Prefecture Univ | 硫化物固体電解質 |
US9537174B2 (en) | 2009-09-09 | 2017-01-03 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte |
CN102574728A (zh) * | 2009-09-09 | 2012-07-11 | 丰田自动车株式会社 | 硫化物固体电解质 |
JP2011086556A (ja) * | 2009-10-16 | 2011-04-28 | Sumitomo Electric Ind Ltd | 硫化物固体電解質の製造方法、および複合体 |
US10008735B2 (en) | 2009-12-16 | 2018-06-26 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
US10707518B2 (en) | 2009-12-16 | 2020-07-07 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
CN102959646B (zh) * | 2010-06-29 | 2016-02-24 | 丰田自动车株式会社 | 硫化物固体电解质材料的制造方法、锂固体电池的制造方法 |
CN102959646A (zh) * | 2010-06-29 | 2013-03-06 | 丰田自动车株式会社 | 硫化物固体电解质材料的制造方法、锂固体电池的制造方法 |
US10193185B2 (en) | 2010-08-26 | 2019-01-29 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
WO2012026238A1 (en) * | 2010-08-26 | 2012-03-01 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
KR101484424B1 (ko) * | 2010-08-26 | 2015-01-19 | 도요타 지도샤(주) | 황화물 고체 전해질 재료, 정극체 및 리튬 고상 전지 |
US9680179B2 (en) | 2010-08-26 | 2017-06-13 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, cathode body and lithium solid state battery |
EP2609652A2 (en) | 2010-08-26 | 2013-07-03 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, cathode body and lithium solid state battery |
JP2012048971A (ja) * | 2010-08-26 | 2012-03-08 | Toyota Motor Corp | 硫化物固体電解質材料、正極体およびリチウム固体電池 |
US9356315B2 (en) | 2010-08-26 | 2016-05-31 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
EP2988360A1 (en) * | 2010-08-26 | 2016-02-24 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material material and lithium solid state battery |
JPWO2013042371A1 (ja) * | 2011-09-22 | 2015-03-26 | 出光興産株式会社 | ガラス粒子 |
WO2013094757A1 (ja) * | 2011-12-22 | 2013-06-27 | 国立大学法人東京工業大学 | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
US9263763B2 (en) | 2011-12-22 | 2016-02-16 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material |
JP2013149599A (ja) * | 2011-12-22 | 2013-08-01 | Tokyo Institute Of Technology | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
JP2014091664A (ja) * | 2012-11-06 | 2014-05-19 | Idemitsu Kosan Co Ltd | 固体電解質ガラス粒子及びリチウムイオン電池 |
JP2014056818A (ja) * | 2013-08-16 | 2014-03-27 | Toyota Motor Corp | 硫化物固体電解質材料、正極体およびリチウム固体電池 |
JP2015153466A (ja) * | 2014-02-10 | 2015-08-24 | 古河機械金属株式会社 | 固体電解質シートおよび全固体型リチウムイオン電池 |
JP2021510905A (ja) * | 2018-01-12 | 2021-04-30 | ユニバーシティー オブ ヒューストン システム | ナトリウム電池のための固体電解質 |
JP7301272B2 (ja) | 2018-01-12 | 2023-07-03 | ユニバーシティー オブ ヒューストン システム | ナトリウム電池のための固体電解質 |
JP2018129307A (ja) * | 2018-03-19 | 2018-08-16 | 古河機械金属株式会社 | 固体電解質シートおよび全固体型リチウムイオン電池 |
JP2019192490A (ja) * | 2018-04-25 | 2019-10-31 | 国立大学法人東京工業大学 | 硫化物固体電解質および全固体電池 |
CN112020787A (zh) * | 2018-04-25 | 2020-12-01 | 国立大学法人东京工业大学 | 硫化物固体电解质和全固体电池 |
WO2019207956A1 (ja) * | 2018-04-25 | 2019-10-31 | 国立大学法人東京工業大学 | 硫化物固体電解質および全固体電池 |
JP7332275B2 (ja) | 2018-04-25 | 2023-08-23 | 国立大学法人東京工業大学 | 硫化物固体電解質および全固体電池 |
Also Published As
Publication number | Publication date |
---|---|
CN102160232A (zh) | 2011-08-17 |
JPWO2010038313A1 (ja) | 2012-02-23 |
CN102160232B (zh) | 2014-07-02 |
US8591603B2 (en) | 2013-11-26 |
KR20110055635A (ko) | 2011-05-25 |
JP5278437B2 (ja) | 2013-09-04 |
US20110167625A1 (en) | 2011-07-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5278437B2 (ja) | 全固体型リチウム電池の製造方法 | |
CN110498611B (zh) | 硫化物系固体电解质、该硫化物系固体电解质的制造方法和全固体电池的制造方法 | |
JP5158008B2 (ja) | 全固体電池 | |
JP5358522B2 (ja) | 固体電解質材料およびリチウム電池 | |
US20180269521A1 (en) | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery | |
JP5521899B2 (ja) | 硫化物固体電解質材料およびリチウム固体電池 | |
JP5594364B2 (ja) | 硫化物固体電解質材料の製造方法、リチウム固体電池の製造方法 | |
US9172112B2 (en) | Sulfide solid electrolyte glass, lithium solid state battery and producing method of sulfide solid electrolyte glass | |
JP5660210B2 (ja) | 固体電解質材料、固体電池、固体電解質材料の製造方法 | |
JP5368711B2 (ja) | 全固体リチウム二次電池用の固体電解質膜、正極膜、又は負極膜、及びそれらの製造方法並びに全固体リチウム二次電池 | |
JP4989183B2 (ja) | 極材及びそれを用いた固体二次電池 | |
JP5552974B2 (ja) | 硫化物固体電解質材料、硫化物固体電解質材料の製造方法およびリチウム固体電池 | |
JP5458740B2 (ja) | 硫化物固体電解質材料 | |
JP5110093B2 (ja) | 硫化物固体電解質材料 | |
KR20160048894A (ko) | 전고체 전지 및 전극 활물질의 제조 방법 | |
KR20160048892A (ko) | 전고체 전지 | |
JP5472237B2 (ja) | 電池用活物質、電池用活物質の製造方法、および電池 | |
JP2008103204A (ja) | 正極活物質及びそれを用いた二次電池 | |
JP2011159534A (ja) | リチウム電池 | |
JP5001621B2 (ja) | 固体電解質及びそれを用いた固体二次電池 | |
US9640835B2 (en) | Ion conducting glass-ceramics, method for manufacturing same and all-solid-state secondary battery including same | |
JP2019053850A (ja) | 硫化物固体電解質 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880131152.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08877168 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2010531699 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13059844 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20117005892 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 08877168 Country of ref document: EP Kind code of ref document: A1 |