WO2020203367A1 - Method for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery, sheet for all-solid-state secondary battery, and all-solid-state secondary battery - Google Patents
Method for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery, sheet for all-solid-state secondary battery, and all-solid-state secondary battery Download PDFInfo
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- WO2020203367A1 WO2020203367A1 PCT/JP2020/012416 JP2020012416W WO2020203367A1 WO 2020203367 A1 WO2020203367 A1 WO 2020203367A1 JP 2020012416 W JP2020012416 W JP 2020012416W WO 2020203367 A1 WO2020203367 A1 WO 2020203367A1
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- 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
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- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
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- 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
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- 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
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- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- 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
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- 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
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- 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
Definitions
- the present invention relates to a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery.
- the negative electrode, the electrolyte, and the positive electrode are all made of solid, and it is expected that the problems of safety and reliability, which are problems of the battery using the organic electrolytic solution, can be greatly improved. It is also said that it will be possible to extend the service life. Further, the all-solid-state secondary battery can have a structure in which electrodes and electrolytes are directly arranged side by side and arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.
- any of the constituent layers (solid electrolyte layer, negative electrode active material layer, and positive electrode active material layer) is formed of an inorganic solid electrolyte and a binder (binding agent) composed of a specific polymer. It has been proposed to use a layer containing and.
- Patent Document 1 describes an inorganic solid electrolyte (A) having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and urethane in the main chain.
- a polymer (B) having at least one of a bond, a urea bond, an amide bond, an imide bond and an ester bond and having a graft structure is contained, and an active material (D) is added as required.
- the solid electrolyte-containing sheet to be contained is described.
- the constituent layer formed of solid particles does not have an interfacial contact state between the solid particles. It is sufficient and the interfacial resistance tends to be high. Further, if the binding property between the solid particles by the binder is weak, poor contact between the solid particles occurs. Moreover, the active material expands and contracts due to charging and discharging, which causes poor contact between the active material layer and the solid electrolyte layer. Further, if the binding property between the solid particles and the current collector is weak, poor contact between the active material layer and the current collector is also caused. When these poor contacts occur, the resistance of the all-solid-state secondary battery increases (battery performance deteriorates).
- the solid electrolyte-containing sheet described in Patent Document 1 has high binding properties between solid particles and excellent ionic conductivity, and this sheet can impart excellent characteristics to an all-solid secondary battery.
- This sheet can impart excellent characteristics to an all-solid secondary battery.
- the cycle characteristics and rate characteristics are also increasing as the battery performance required for all-solid-state secondary batteries. Therefore, there is a demand for the development of an all-solid-state secondary battery that exhibits more excellent battery performance by further enhancing the binding property between solid particles.
- the present invention is a method for producing a sheet for an all-solid-state secondary battery, which can be used as a constituent layer of an all-solid-state secondary battery to enhance the binding property between solid particles and impart excellent battery performance to the all-solid-state secondary battery.
- An object of the present invention is to provide a method for manufacturing an all-solid-state secondary battery using this manufacturing method.
- Another object of the present invention is to provide an all-solid-state secondary battery that exhibits excellent battery performance.
- the present inventors have specified a mixture containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less and a particulate organic component in a specific mass ratio at a specific temperature and a specific value. It has been found that a sheet for an all-solid secondary battery having excellent binding properties between solid particles can be produced by heating and pressurizing under the pressure conditions of. Further, they have found that by using this sheet for an all-solid-state secondary battery as a constituent layer of an all-solid-state secondary battery, excellent battery performance can be imparted to the all-solid-state secondary battery. The present invention has been further studied based on these findings and has been completed.
- a method for producing a sheet for an all-solid secondary battery containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less and a particulate organic component It contains a particulate organic component and a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less, and the content of the particulate organic component is the sum of the sulfide-based inorganic solid electrolyte and the particulate organic component.
- a mixture having a content of 15% by mass or less has an elasticity of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component.
- a method for producing a sheet for an all-solid secondary battery which comprises pressurizing at a pressure higher than 1/10. ⁇ 2> The method for producing an all-solid-state secondary battery sheet according to ⁇ 1>, wherein the elastic modulus is 150 MPa or more.
- ⁇ 4> The sheet for an all-solid secondary battery according to any one of ⁇ 1> to ⁇ 3>, which comprises a step of adjusting the sulfide-based inorganic solid electrolyte constituting the mixture to a volume average particle diameter of 1.0 ⁇ m or less.
- ⁇ 5> The method for producing a sheet for an all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 4>, wherein the mixture contains an active material.
- ⁇ 6> The method for manufacturing an all-solid-state secondary battery sheet according to ⁇ 5>, wherein the active material is a negative electrode active material.
- ⁇ 7> The method for producing an all-solid-state secondary battery sheet according to ⁇ 6>, wherein the negative electrode active material contains a silicon element or a tin element.
- ⁇ 8> The method for manufacturing an all-solid-state secondary battery sheet according to any one of ⁇ 1> to ⁇ 7>, wherein the glass transition temperature is 30 ° C. or higher.
- ⁇ 9> The method for producing a sheet for an all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 8>, wherein the pressurization of the mixture is performed at a temperature higher than the glass transition temperature by 50 ° C. or more.
- the all-solid-state secondary battery sheet obtained by the method for producing an all-solid-state secondary battery sheet according to any one of ⁇ 1> to ⁇ 10> is used as the positive electrode active material layer, the solid electrolyte layer, and the negative electrode.
- a method for manufacturing an all-solid-state secondary battery which comprises a step of incorporating as at least one layer of an active material layer.
- An all-solid-state secondary battery in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the sheet for an all-solid secondary battery according to ⁇ 12>.
- the method for producing an all-solid-state secondary battery sheet of the present invention can produce an all-solid-state secondary battery sheet having excellent binding properties.
- the method for producing an all-solid-state secondary battery of the present invention can produce an all-solid-state secondary battery exhibiting excellent battery performance. Further, the sheet for an all-solid-state secondary battery of the present invention exhibits strong binding properties of solid particles, and the all-solid-state secondary battery of the present invention exhibits excellent battery performance.
- FIG. 1 is a vertical sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention.
- FIG. 2 is a vertical cross-sectional view schematically showing an all-solid-state secondary battery (coin battery) produced in the examples.
- the method for producing an all-solid secondary battery sheet of the present invention is a method for producing an all-solid secondary battery sheet containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less and a particulate organic component. It contains a particulate organic component and a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less, and the content of the particulate organic component is that of the sulfide-based inorganic solid electrolyte and the particulate organic component.
- the elasticity of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C.
- the method for producing a sheet for an all-solid-state secondary battery of the present invention preferably has the following steps.
- step (2) The particulate organic component and the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less obtained in the above step, and the content of the particulate organic component is the sulfide-based inorganic solid electrolyte and the particulate organic component. Step of mixing so as to be 15% by mass or less in the total content of
- Pressurizing step (hereinafter, also referred to as step (3)) :. Obtained by the step of mixing at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component at a pressure higher than 1/10 of the elastic modulus of the particulate organic component.
- step (3) Obtained by the step of mixing at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component at a pressure higher than 1/10 of the elastic modulus of the particulate organic component.
- the above step (1) is not essential, and the volume average particle size of the sulfide-based inorganic solid electrolyte used in the above step (2) exceeds 1.0 ⁇ m.
- the method for producing an all-solid-state secondary battery sheet of the present invention performs step (1). This step is usually carried out before the step of mixing, but may be carried out in the above-mentioned mixing step (the volume average particle size of the sulfide-based inorganic solid electrolyte may be adjusted by mixing in the mixing step).
- SEa is the volume average particle size of the sulfide-based inorganic solid electrolyte
- Ba is the volume average particle size of the particulate organic component.
- an all-solid secondary battery sheet having an electrode active material layer (positive electrode active material layer or negative electrode active material layer) may be referred to as an electrode sheet (positive electrode sheet or negative electrode sheet).
- a sheet for an all-solid secondary battery having a solid electrolyte layer may be referred to as a sheet for a solid electrolyte layer.
- the sheet for an all-solid secondary battery having an electrode active material layer and a solid electrolyte layer shall be an electrode sheet.
- the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
- a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
- the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iV) a hydride-based solid electrolyte.
- a sulfide-based inorganic solid electrolyte used in step (1) will be described.
- sulfide-based inorganic solid electrolyte ii) oxide-based inorganic solid electrolyte, (iii) halide-based inorganic solid electrolyte, and (iV)
- a hydride-based solid electrolyte may be used.
- the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
- the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain elements.
- composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
- the sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
- Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
- Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2 ).
- the ratio of Li 2 S and P 2 S 5 is, Li 2 S: at a molar ratio of P 2 S 5, preferably 60: 40 ⁇ It is 90:10, more preferably 68:32 to 78:22.
- the lithium ion conductivity can be made high.
- the lithium ion conductivity can be preferably 1 ⁇ 10 -4 S / cm or more, and more preferably 1 ⁇ 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
- Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5- P 2 O 5 , Li 2 S-P 2 S 5- SiS 2 , Li 2 S-P 2 S 5- SiS 2- LiCl, Li 2 S-P 2 S 5- SnS, Li 2 S-P 2 S 5- Al 2 S 3 , Li 2 S-GeS 2 , Li 2 S-GeS 2 , Li 2 S-Ge
- the mixing ratio of each raw material does not matter.
- an amorphization method can be mentioned.
- the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
- the oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
- the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5 S / cm or more. It is particularly preferable that it is / cm or more.
- the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
- Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
- LLT Li xb Layb Zr zb M bb mb Onb
- M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
- Xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. Satisfies.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
- Xc is 0 ⁇ xc ⁇ 5 , Yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, nc satisfies 0 ⁇ nc ⁇ 6); Li xd (Al, Ga) yd (Ti, Ge) zd Si.
- Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3 , zf satisfies 1 ⁇ zf ⁇ 10);.
- Li xg S yg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, zg satisfies 1 ⁇ zg ⁇ 10.
- Halide-based inorganic solid electrolyte contains halogen atoms, has the conductivity of ions of metals belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. Insulating compounds are preferred.
- the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
- the hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a property is preferable.
- the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
- the sulfide-based inorganic solid electrolyte may be a mixture of one type or two or more types.
- the mass (mg) (grain amount) of the sulfide-based inorganic solid electrolyte per unit area (cm 2 ) of the solid electrolyte layer sheet is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the amount of the sulfide-based inorganic solid electrolyte is preferably in the above range as the total amount of the active material and the sulfide-based inorganic solid electrolyte.
- the content of the sulfide-based inorganic solid electrolyte in the sheet for the solid electrolyte layer is preferably 50% by mass or more, preferably 70% by mass or more, based on 100% by mass of the solid content, in terms of reduction of interfacial resistance and binding property. It is more preferably% or more, and particularly preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
- the content of the sulfide-based inorganic solid electrolyte in the electrode active material layer is preferably such that the total content of the active material and the sulfide-based inorganic solid electrolyte is in the above range.
- the solid content (solid component) is a mixture containing the particulate organic component in an amount of 15% by mass or less based on the total content of the sulfide-based inorganic solid electrolyte and the particulate organic component.
- mixture used in the present invention refers to a component that does not volatilize or evaporate and disappear when dried at 170 ° C. for 6 hours under a pressure of 1 mmHg and a nitrogen atmosphere. Typically, it refers to a component other than the dispersion medium described later.
- the particulate organic component (preferably a binder) is not particularly limited, but a particulate polymer having a glass transition temperature is preferable.
- a particulate polymer having a glass transition temperature is preferable.
- the particulate polymer constituting the particulate organic component a polymer having at least one of a urethane bond, a urea bond, an amide bond, and an imide bond, or a (meth) acrylic polymer is preferable.
- a polymer having a urethane bond and a (meth) acrylic polymer are more preferable from the viewpoint of adhesion to a sulfide-based inorganic solid electrolyte.
- polyurethane, polyurea, polyamide, polyimide or (meth) acrylic polymer is preferable, polyurethane or acrylic polymer is more preferable, and polyurethane is further preferable.
- the particulate organic component may be flat, amorphous or the like, but is preferably spherical or granular.
- the urethane value of the polyurethane is not particularly limited, but is preferably 1.5 mmol / g or more, and more preferably 2.0 mmol / g or more.
- the upper limit of the urethane value is preferably 5 mmol / g or less.
- the urethane value can be determined by the method described in the section of Examples described later.
- the mass average molecular weight of the particulate polymer is not particularly limited. For example, 10,000 or more is preferable, 20,000 or more is more preferable, and 30,000 or more is further preferable.
- the upper limit is preferably 2,000,000 or less, more preferably 1,500,000 or less, further preferably 1,000,000 or less, and particularly preferably 200,000 or less.
- the mass average molecular weight is measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
- GPC gel permeation chromatography
- the value measured by the method of the following condition 1 or condition 2 (priority) is basically used.
- an appropriate eluent may be appropriately selected and used depending on the type of polymer (specific polymer, etc.) to be measured.
- the glass transition temperature of the particulate polymer is not particularly limited, but is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, in order to maintain the particle shape and not cover the entire surface of the solid particles. It is preferably 40 ° C. or higher, and more preferably 40 ° C. or higher.
- the glass transition temperature is a value measured by the method described in Examples described later.
- the glass transition temperature used as the reference for the heating temperature in step (3) is the highest glass transition temperature when the particulate polymer has a plurality of glass transition temperatures.
- the decomposition temperature of the particulate polymer is not particularly limited, but is preferably 150 ° C. or higher, more preferably 180 ° C.
- the upper limit is preferably 500 ° C. or lower, more preferably 480 ° C. or lower, and even more preferably 450 ° C. or lower.
- the decomposition temperature is a value measured by the method described in Examples described later.
- the elastic modulus of the particulate polymer is not particularly limited, but is preferably 150 MPa or more, more preferably 180 MPa or more, and even more preferably 200 MPa or more.
- the upper limit of the elastic modulus of the particulate polymer is not particularly limited, but is preferably 2000 MPa or less, and more preferably 1800 MPa or less.
- the elastic modulus is a value measured by the method described in Examples described later.
- the volume average particle size of the particulate polymer in the constituent layers of the all-solid secondary battery is measured in advance by, for example, disassembling the battery and peeling off the constituent layer containing the particulate polymer, and then measuring the constituent layers. It can be measured by excluding the measured value of the volume average particle diameter of the particles other than the particulate polymer.
- the volume average particle size of the particulate polymer shall be a value obtained by the measuring method described in the section of Examples described later. It is preferable that the volume average particle size Ba of the particulate polymer and the volume average particle size SEa of the sulfide-based inorganic solid electrolyte satisfy (adjust) the relationship defined by the following formula (I).
- the resistance increase can be suppressed by binding the sulfide-based inorganic solid electrolytes without inhibiting the ionic conduction between the sulfide-based inorganic solid electrolytes, and further. It is considered that characteristics such as handleability as an electrode and low resistance following expansion and contraction during electrode operation are exhibited.
- the volume average particle diameter Ba and the volume average particle diameter SEa preferably satisfy the relationship specified by the following formula (IA), and more preferably satisfy the relationship specified by the following formula (IB). ..
- the active material When the all-solid-state secondary battery sheet obtained by the method for producing an all-solid-state secondary battery sheet of the present invention is used as the electrode active material layer, the active material is used in the above step (2).
- the active material include (i) positive electrode active material and (ii) negative electrode active material, which will be described below.
- the positive electrode active material is preferably one capable of reversibly inserting and releasing lithium ions.
- the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an element that can be composited with Li such as sulfur, or the like.
- the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed.
- the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
- transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
- transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
- LiCoO 2 lithium cobalt oxide
- LiNi 2 O 2 lithium nickel oxide
- LiNi 0.85 Co 0.10 Al 0. 05 O 2 Lithium Nickel Cobalt Aluminate [NCA]
- LiNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium Nickel Manganese Cobalt Oxide [NMC]
- LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
- (MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 can be mentioned.
- Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4.
- Examples thereof include cobalt phosphates of the above, and monoclinic panacicon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
- (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Fluorophosphate cobalts such as.
- Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
- a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
- a normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size.
- a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used.
- wet pulverization in which an organic solvent such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size.
- the classification is not particularly limited, and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can be used.
- the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
- the positive electrode active material may be a mixture of one type or two or more types.
- the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and more preferably 40 to 93% by mass in terms of solid content of 100% by mass. , 50 to 90% by mass is more preferable, and 60 to 80% by mass is further preferable.
- the negative electrode active material is preferably one capable of reversibly inserting and releasing lithium ions.
- the material is not particularly limited as long as it has the above characteristics, and examples thereof include a carbonaceous material, a metal oxide, a metal composite oxide, a lithium simple substance, a lithium alloy, and a negative electrode active material capable of forming an alloy with lithium. .. Among them, a carbonaceous material, a metal composite oxide or a simple substance of lithium is preferably used from the viewpoint of reliability.
- the carbonaceous material used as the negative electrode active material is a material substantially composed of carbon.
- carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin.
- Examples thereof include carbonic materials obtained by firing a resin.
- various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers and activated carbon fibers.
- carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the size of crystallites described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473.
- the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
- As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
- the metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of a metal element oxide (metal oxide) and a metal element.
- metal oxide metal oxide
- examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides).
- metal composite oxides oxides or composite oxides of metal elements and semi-metal elements
- oxides of semi-metal elements semi-metal elements
- amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the Periodic Table, are also preferable.
- the semi-metallic element means an element exhibiting properties intermediate between the metallic element and the non-semi-metallic element, and usually contains 6 elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Astatine.
- amorphous means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2 ⁇ value, and a crystalline diffraction line is used. You may have.
- the strongest intensity of the crystalline diffraction lines found at the 2 ⁇ value of 40 ° to 70 ° is 100 times or less the diffraction line intensity at the apex of the broad scattering band seen at the 2 ⁇ value of 20 ° to 40 °. It is preferable that it is 5 times or less, and it is particularly preferable that it does not have a crystalline diffraction line.
- the amorphous oxide of the semi-metal element or the chalcogenide is more preferable, and the elements of the groups 13 (IIIB) to 15 (VB) of the periodic table (for example).
- Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more (composite) oxides, or chalcogenides are particularly preferred.
- preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2.
- Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include a carbonaceous material capable of occluding and / or releasing lithium ions or lithium metal, lithium alone, and lithium.
- a negative electrode active material that can be alloyed with an alloy or lithium is preferably used.
- the oxide of a metal or a metalloid element contains at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
- the lithium-containing metal composite oxide include lithium oxide and the metal (composite) oxide or a composite oxide of the chalcogenide, more specifically, Li 2 SnO 2.
- the negative electrode active material for example, a metal oxide, contains a titanium element (titanium oxide).
- Li 4 Ti 5 O 12 lithium titanate [LTO]
- Li 4 Ti 5 O 12 has excellent rapid charge / discharge characteristics due to small volume fluctuations during storage and release of lithium ions, and electrode deterioration is suppressed and lithium ion secondary It is preferable in that the life of the battery can be improved.
- the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of the secondary battery, and examples thereof include a lithium aluminum alloy.
- the negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery.
- Such an active material has a large expansion and contraction due to charge and discharge, and the binding property of solid particles is lowered as described above, but in the present invention, a high binding property can be achieved by the step (3).
- Examples of such an active material include a negative electrode active material (alloy) having a silicon element or a tin element, and each metal such as Al and In, and a negative negative active material (silicon element) having a silicon element that enables a higher battery capacity.
- a silicon element-containing active material having a silicon element content of 50 mol% or more of all the constituent elements is more preferable.
- a negative electrode containing these negative electrode active materials Si negative electrode containing a silicon element-containing active material, Sn negative electrode containing an active material containing a tin element, etc.
- a carbon negative electrode graphite, acetylene black, etc.
- silicon element-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,).
- LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi 2 / Si), as well as other silicon and tin elements such as SnSiO 3 , SnSiS 3 Examples include active materials containing.
- SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since Si is generated by the operation of an all-solid-state secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
- the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and the active material containing the silicon element and the tin element.
- a composite oxide with lithium oxide for example, Li 2 SnO 2 can also be mentioned.
- the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment as the negative electrode active material.
- a silicon element-containing active material or a negative electrode active material having a tin element is preferable, and it is more preferable to contain silicon (Si) or a silicon-containing alloy.
- the chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measuring method and the mass difference of the powder before and after firing as a simple method.
- ICP inductively coupled plasma
- the shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles.
- the volume average particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
- the volume average particle size of the negative electrode active material particles can be measured in the same manner as the average particle size of the positive electrode active material. In order to obtain a predetermined particle size, a normal crusher or classifier is used as in the case of the positive electrode active material.
- the negative electrode active material may be a mixture of one type or two or more types.
- the mass (mg) (weight) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the content of the negative electrode active material in the negative electrode active material layer is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 80% by mass in terms of solid content of 100% by mass. It is more preferably%, more preferably 40 to 75% by mass, and further preferably 40 to 65% by mass.
- the negative electrode active material layer when the negative electrode active material layer is formed by charging the secondary battery, instead of the above-mentioned negative electrode active material, the periodic table group 1 or 1 generated in the all-solid secondary battery Ions of metals belonging to Group 2 can be used.
- the negative electrode active material layer can be formed by combining these ions with electrons and precipitating them as a metal.
- Li 4 Ti 5 O 12 Li 2 Ti 2 O 5 , LiTaO 3 , LiNbO 3 , LiAlO 2 , Li 2 ZrO 3 , Li 2 WO 4 , Li 2 TiO 3 , Li 2 B 4 O 7 , Li 3 PO 4 , Li 2 MoO 4 , Li 3 BO 3 , LiBO 2 , Li 2 CO 3 , Li 2 SiO 3 , SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , B 2 O 3, and the like.
- the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
- the surface of the positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
- the conductive auxiliary agent one kind may be mixed, or two or more kinds may be mixed.
- the shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
- the content of the conductive auxiliary agent in the electrode active material layer is not particularly limited, and is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, based on 100% by mass of the solid content. It is more preferably 1 to 10% by mass.
- a lithium salt (supporting electrolyte)
- a lithium salt (supporting electrolyte)
- the lithium salt the lithium salt usually used for this kind of product is preferable, and there is no particular limitation.
- the lithium salt described in paragraphs 882 to 985 of JP2015-088486 is preferable.
- the content of the lithium salt is preferably 0.1 part by mass or more, preferably 5 parts by mass or more, based on 100 parts by mass of the sulfide-based inorganic solid electrolyte. Is more preferable.
- the upper limit is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.
- a dispersion medium (dispersion medium) may be used, as long as each of the above components is dispersed or dissolved, and a particulate organic component and solid particles are preferably dispersed.
- the dispersion medium include various organic solvents. Examples of the organic solvent include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds and the like.
- ether compound examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, and dipropylene glycol.
- alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, and dipropylene glycol.
- amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide and acetamide. , N-Methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
- Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
- Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone.
- Examples of the aromatic compound include aromatic hydrocarbon compounds such as benzene, toluene and xylene.
- Examples of the aliphatic compound include aliphatic hydrocarbon compounds such as hexane, heptane, octane, and decane.
- Examples of the nitrile compound include acetonitrile, propyronitrile, isobutyronitrile and the like.
- ester compound examples include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, butyl pentanate and the like.
- non-aqueous dispersion medium examples include the above aromatic compounds and aliphatic compounds.
- ether compounds, ketone compounds, aromatic compounds, aliphatic compounds and ester compounds are preferable, and ketone compounds are more preferable.
- the dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher.
- the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
- the dispersion medium may be a mixture of one type or two or more types.
- a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less can be obtained.
- the sulfide-based inorganic solid electrolyte is added, for example, a solvent in which the sulfide-based solid electrolyte does not deteriorate (a dispersion medium that does not easily react with the sulfide-based solid electrolyte), and the diameter, rotation speed, and time of the pulverized media are further adjusted.
- Sulfide-based inorganic solid electrolyte used may be using those available, for example, it may be synthesized from the above lithium sulfide (Li 2 S) and phosphorus ingredients sulfide.
- the volume average particle size of the sulfide-based inorganic solid electrolyte can be measured by the method described in the section of Examples described later.
- the volume average particle diameter of the sulfide-based inorganic solid electrolyte used in the step (2) (adjusted in the step (1)) is preferably 0.8 ⁇ m or less in order to reduce the voids between the particles and reduce the resistance.
- the above-mentioned particulate organic component and the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less obtained in the above step are used as the above-mentioned particulate organic component.
- the step of mixing is performed so that the content is 15% by mass or less, preferably 10% by mass or less, based on the total content of the sulfide-based inorganic solid electrolyte and the particulate organic component.
- a sulfide-based inorganic solid electrolyte and a particulate organic component are usually mixed at the above mixing ratio to prepare a mixture.
- the lower limit of the mixing ratio is not particularly limited as long as it exceeds 0% by mass, and can be, for example, 0.1% by mass or more, preferably 0.5% by mass or more.
- step (2) the sulfide-based inorganic solid electrolyte, particulate organic components, and optionally the active material, dispersion medium, lithium salt, and any other components are mixed, for example, in various commonly used mixers. Therefore, a mixture (preferably a composition, more preferably a slurry containing a dispersion medium) can be obtained.
- the active material to be mixed is appropriately selected according to the form of the sheet, but the negative electrode active material is preferably an active material containing a silicon element or a tin element in terms of battery capacity.
- the mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially.
- the mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.
- the mixing amount of the active material is not particularly limited, but is preferably set within the same range as the content in the active material layer described above.
- the mixing amount of the lithium salt is not particularly limited, but is preferably set within the same range as the content in the all-solid-state secondary battery sheet described above.
- the mixing amount of the dispersion medium is not particularly limited, but it is preferably set within the same range as the content in the above-mentioned mixture. The mixing amount of other components is appropriately determined.
- the method for producing a sheet for an all-solid secondary battery of the present invention has an elastic modulus of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component.
- the step of pressurizing the mixture at a pressure higher than 1/10 of the rate is performed.
- the method of pressurizing at the above heating temperature is not particularly limited, and examples thereof include a method using a hot press, a hot plate, and the like.
- the pressurization time can be, for example, 3 to 30 minutes.
- the mixture used in the present invention contains a dispersion medium
- the above mixture slurry or the like
- the dispersion medium was dried to obtain a solid state (applied dry layer). Then, pressurize in the above temperature range.
- the method of applying the mixture is not particularly limited and can be appropriately selected.
- coating preferably wet coating
- spray coating spin coating coating
- dip coating dip coating
- slit coating stripe coating
- bar coating coating can be mentioned.
- the drying temperature of the dispersion medium is not particularly limited.
- the lower limit is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher.
- the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
- the dispersion medium is not completely removed in the drying step after applying the slurry. Specifically, it is preferable to heat the obtained mixture so that the dispersion medium is not completely removed, and pressurize the obtained coating dry layer.
- the residual amount of the dispersion medium in the coating dry layer at this time is not particularly limited, but is preferably 10 to 2000 ppm, more preferably 10 to 1500 ppm, and even more preferably 10 to 1000 ppm. It is more preferably about 500 ppm, and particularly preferably 10 to 200 ppm.
- the coating dry layer Pressurize the coating dry layer with the dispersion medium remaining as described above.
- a sheet having a coating dry layer and a base material or a current collector is used on a hot plate and a press machine
- the above sheet is placed on the hot plate so that the base material or the current collector is in contact with the hot plate, and the hot plate is used.
- the dispersion medium may be dried above to form a coating dry layer, which may be pressed by a press machine.
- the heating time can be, for example, 1 to 30 minutes
- the pressurization time can be, for example, 1 to 30 minutes. It is preferable that the press presser is pressurized in advance at the same temperature as the heating temperature of the hot plate.
- an all-solid-state secondary battery sheet of the present invention it is an all-solid-state secondary battery sheet having excellent binding properties, and exhibits excellent battery characteristics when used as a constituent layer of an all-solid-state secondary battery.
- An all-solid-state secondary battery can be realized. The reason is not clear, but it is presumed as follows.
- the mixture used in the present invention contains the particulate organic component in an amount of 15% by mass or less based on the total content of the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less and the particulate organic component.
- the dispersion medium moderately softens the particulate organic components and improves the contact between the sulfide-based inorganic solid electrolytes, thereby suppressing aggregation of the solid particles. It is thought that it can be done. Further, using this mixture, the above-mentioned pressurizing step suppresses the decomposition of the particulate organic component, and imparts flexibility to the particulate organic component to enhance the binding property between solid particles. Is thought to be possible.
- Short circuits can be suppressed by enhancing the binding properties between solid particles containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less, and voids formed during expansion and contraction of the active material can be suppressed. It is considered that the cycle characteristics and rate characteristics of the all-solid secondary battery can be improved because the production can be suppressed.
- the method for manufacturing an all-solid-state secondary battery of the present invention is usual except that a sheet for an all-solid-state secondary battery obtained by the method for manufacturing a sheet for an all-solid-state secondary battery of the present invention is incorporated as at least one constituent layer. Can be manufactured by law. As a result, an all-solid-state secondary battery showing excellent battery performance can be manufactured. The details will be described below.
- a normal solid electrolyte composition containing a positive electrode active material is applied as a positive electrode material (composition for a positive electrode layer) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and a positive electrode is formed. Make a sheet.
- the solid electrolyte layer sheet (solid electrolyte layer) obtained by the method for producing an all-solid secondary battery sheet of the present invention is superposed on the positive electrode active material layer.
- a normal solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (composition for the negative electrode layer) on the solid electrolyte layer to form a negative electrode active material layer.
- an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery. Further, by reversing the forming method of each layer, a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is superposed to manufacture an all-solid secondary battery. You can also do it.
- a positive electrode sheet having a positive electrode active material layer on a current collector a solid electrolyte layer sheet having a solid electrolyte layer on a base material, and a current collector.
- a negative electrode sheet having a negative electrode active material layer on the body is produced.
- a solid electrolyte layer sheet is layered on the active material layer of either the positive electrode sheet or the negative electrode sheet so that the active material layer and the solid electrolyte layer are in contact with each other.
- the other of the positive electrode sheet and the negative electrode sheet is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
- an all-solid-state secondary battery can be manufactured.
- the following method can be mentioned. That is, according to the method for producing an all-solid-state secondary battery sheet of the present invention, a positive electrode sheet having a positive electrode active material layer on a current collector, a solid electrolyte layer sheet having a solid electrolyte layer on a base material, and a current collector. A negative electrode sheet having a negative electrode active material layer on the body is produced. Further, the positive electrode sheet and the negative electrode sheet are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, an all-solid-state secondary battery can be manufactured.
- the pressurize the all-solid-state secondary battery after manufacturing the all-solid-state secondary battery. It is also preferable to pressurize the layers in a laminated state.
- Examples of the pressurizing method include a hydraulic cylinder press machine and the like.
- the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
- the atmosphere during pressurization is not particularly limited, and may be any of air, dry air (dew point ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas) and the like.
- the pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more).
- an all-solid-state secondary battery restraint screw tightening pressure, etc.
- the press pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
- the press pressure can be changed according to the area or film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
- the pressed surface may be smooth or roughened.
- the all-solid-state secondary battery sheet produced by the method for producing an all-solid-state secondary battery sheet of the present invention has a layer obtained by pressure-molding the mixture used in the present invention.
- the layer of this sheet contains a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 ⁇ m or less and a particulate organic component, contains an active material depending on the form of the sheet, and appropriately conducts assistance. It may contain an agent and other components.
- the details of the existence state of the sulfide-based inorganic solid electrolyte and the particulate organic component in this layer are not clear, but the state of being bound as described above can be mentioned.
- the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
- the sheet for the solid electrolyte layer of the present invention may be a sheet having a solid electrolyte layer, and even a sheet in which the solid electrolyte layer is formed on the base material does not have a base material and is formed from the solid electrolyte layer. It may be a sheet that is present.
- the sheet for the solid electrolyte layer may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
- Examples of the sheet for the solid electrolyte layer of the present invention include a sheet having a solid electrolyte layer and a protective layer in this order on a base material.
- the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-shaped body) such as an organic material and an inorganic material.
- a material described in the current collector described later a sheet body (plate-shaped body) such as an organic material and an inorganic material.
- the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
- the inorganic material include glass, ceramic and the like.
- composition and layer thickness of the solid electrolyte layer of the sheet for the all-solid-state secondary battery are the same as the composition and layer thickness of the solid electrolyte layer described in the all-solid-state secondary battery of the present invention.
- the electrode sheet of the present invention may be an electrode sheet having an active material layer, and even a sheet in which the active material layer is formed on a base material (current collector) does not have a base material and is formed from the active material layer. It may be a formed sheet.
- This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included.
- the electrode sheet of the present invention may have the other layers described above.
- the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
- the all-solid-state secondary battery sheet of the present invention at least one of the solid electrolyte layer and the active material layer is produced by the method for producing the all-solid-state secondary battery sheet of the present invention, and the solid particles in this layer are firmly bonded to each other. It is tied up. Further, in the electrode sheet, the active material layer produced by the method for producing an all-solid-state secondary battery sheet of the present invention is firmly bonded to the current collector. In the present invention, an increase in interfacial resistance between solid particles can be effectively suppressed. Therefore, the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet capable of forming a constituent layer of an all-solid-state secondary battery. When an all-solid-state secondary battery is manufactured using the sheet for an all-solid-state secondary battery of the present invention, excellent battery performance is exhibited.
- the all-solid secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer.
- the positive electrode active material layer is preferably formed on the positive electrode current collector to form the positive electrode.
- the negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode. At least one of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is produced by the method for producing an all-solid-state secondary battery sheet of the present invention, and all the layers are for the all-solid-state secondary battery of the present invention.
- the active material layer or the solid electrolyte layer is not produced by the method for producing a sheet for an all-solid secondary battery of the present invention, a normal active material layer or a solid electrolyte layer can be used.
- the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
- the thickness of each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, respectively, in consideration of the dimensions of a general all-solid-state secondary battery.
- the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m.
- the positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
- the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing.
- the housing may be made of metal or resin (plastic). When a metallic material is used, for example, one made of aluminum alloy or stainless steel can be mentioned. It is preferable that the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
- FIG. 1 is a schematic cross-sectional view showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
- the all-solid-state secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. ..
- Each layer is in contact with each other and has an adjacent structure.
- the lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating portion 6.
- a light bulb is used as a model for the operating portion 6, and the light bulb is turned on by electric discharge.
- the all-solid-state secondary battery having the layer structure shown in FIG. 1 When the all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032 type coin case, the all-solid-state secondary battery is referred to as an all-solid-state secondary battery laminate, and the all-solid-state secondary battery laminate is referred to as an all-solid-state secondary battery laminate.
- a battery manufactured by putting it in a 2032 type coin case is sometimes called an all-solid-state secondary battery.
- the all-solid-state secondary battery 10 In the all-solid-state secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are manufactured by the method for producing a sheet for an all-solid-state secondary battery of the present invention.
- the all-solid-state secondary battery 10 exhibits excellent battery performance.
- the sulfide-based inorganic solid electrolyte and the particulate organic component contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same type or different from each other.
- either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. Further, either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
- the negative electrode active material layer can be a lithium metal layer.
- the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like.
- the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
- the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
- either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
- a current collector As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
- As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel.
- aluminum, copper, copper alloy and stainless steel are more preferable.
- the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
- the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
- a functional layer, a member, or the like is appropriately interposed or arranged between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may. Further, each layer may be composed of a single layer or a plurality of layers.
- the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use.
- the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
- the all-solid-state secondary battery of the present invention can be applied to various applications.
- the application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc.
- Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
- the SEa was measured as follows.
- the LPS was diluted with heptane in a 20 mL sample bottle to prepare a 1 mass% dispersion.
- the diluted dispersed sample was irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it was used for the test.
- data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell.
- the volume average particle size was obtained.
- JIS Z 8828 2013 "Particle size analysis-Dynamic light scattering method" as necessary. Five samples were prepared for each level and the average value was adopted.
- acrylic latex 1 was obtained.
- the decomposition temperature of the acrylic polymer in the acrylic latex 1 was 192 ° C.
- the mass average molecular weight of the acrylic polymer in the acrylic latex 1 was 65,000, and the volume average particle diameter was 120 nm.
- urethane latex 1 Preparation of urethane latex 1
- 2,4-pentanediol and 1.86 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Corporation) were added to a 200 mL three-necked flask and dissolved in 80 g of THF (tetrahydrofuran).
- 4.2 g of diphenylmethane diisocyanate was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it.
- 290 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours to obtain a viscous polymer solution.
- the mass average molecular weight of polyurethane in urethane latex 1 was 35,000, and the volume average particle diameter was 80 nm.
- the urethane valence of polyurethane in urethane latex 1 was 4.39 mmol / g.
- the urethane valence was calculated as follows.
- Urethane value Urethane bond amount (mmol) of 1 mol of particulate organic component / mass (g) of 1 mol of organic component
- the urethane bond amount (mmol) of 1 mol of the particulate organic component was measured by 1 1 H-NMR.
- urethane latex 2 (Preparation of urethane latex 2) 0.74 g of 2,4-pentanediol and 13.86 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Corporation) were added to a 200 mL three-necked flask and dissolved in 80 g of THF (tetrahydrofuran). 4.2 g of diphenylmethane diisocyanate was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it. To the obtained solution, 290 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours to obtain a viscous polymer solution.
- Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours to obtain a viscous polymer solution.
- the mass average molecular weight of the polyurethane in the urethane latex 2 was 45,000, and the volume average particle diameter was 30 nm.
- the urethane valence of the polyurethane in the urethane latex 2 was 1.8 mmol / g.
- Urethane latex 3 (solid content 10% by mass) was obtained in the same manner as urethane latex 2 except that dicyclohexylmethane diisocyanate (manufactured by Tokyo Kasei Co., Ltd.) was used instead of diphenylmethane diisocyanate.
- the decomposition temperature of the polyurethane in the urethane latex 3 was 220 ° C.
- the mass average molecular weight of the polyurethane in the urethane latex 3 was 42,000, and the volume average particle diameter was 70 nm.
- the urethane valence of the polyurethane in the urethane latex 3 was 1.7 mmol / g.
- the Tg (° C.), decomposition temperature (° C.), elastic modulus (MPa) and volume average particle size ( ⁇ m) of the synthesized particulate polymer were measured as follows.
- the glass transition point was measured under the following conditions using a differential scanning calorimeter (DSC7000 manufactured by SII Technology Co., Ltd.) using the dried samples of acrylic latex 1 and urethane latex 1 to 3.
- DSC7000 differential scanning calorimeter manufactured by SII Technology Co., Ltd.
- As a dry sample 10 g of the synthesized latex solution was placed on an aluminum pan, heated at 120 ° C. for 2 hours, the solvent was distilled off, and the sample was dried in a vacuum state for 6 hours. The measurement was carried out twice with the same sample, and the result of the second measurement was adopted.
- Atmosphere in the measurement room Nitrogen (60 mL / min) ⁇ Temperature rise rate: 3 ° C / min ⁇ Measurement start temperature: -100 ° C ⁇ Measurement end temperature: 200 ° C ⁇ Sample pan: Aluminum pan ⁇ Mass of measurement sample: 5 mg -Calculation of Tg: Tg was calculated by rounding off the decimal point of the intermediate temperature between the descending start point and the descending end point of the DSC chart.
- the acrylic latex 1 and urethane latex 1 to 3 were vacuum dried at a temperature of 120 ° C. for 2 hours to obtain a particulate polymer.
- the particulate polymer was subjected to thermogravimetric differential thermal simultaneous measurement (Tg-DTA) under a nitrogen atmosphere. The mass at the start of measurement of the particulate polymer was taken as 100%, and the temperature at which the mass decreased by 10% (became 90%) was taken as the decomposition temperature.
- a differential scanning calorimeter (DSC7000, manufactured by SII Technology Co., Ltd.) was used for the simultaneous measurement of thermal mass and differential heat.
- the tensile modulus was measured at 25 ° C. according to JIS K 7127 (1999).
- the above-prepared dispersion of particulate organic components was cast on a Teflon (registered trademark) film to prepare a single film of a particulate polymer having a film thickness of 100 ⁇ m. This single film was cut into 1 cm ⁇ 2 cm, and a tensile test (elongation between chucks) was performed at 30 mm / min to determine the tensile elastic modulus.
- a solid electrolyte composition was prepared as follows in a dry room having a dew point of ⁇ 60 ° C., and a sheet S-1 for a solid electrolyte layer was prepared using this solid electrolyte composition.
- 180 zirconia beads having a diameter of 5 mm are put into a 45 mL container made of zirconia (manufactured by Fritsch), and the LPS having a volume average particle diameter of 0.8 ⁇ m synthesized above is 4.6 g and the acrylic latex 1 solid content is 0.4 g.
- this container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and stirred at a temperature of 25 ° C. and a rotation speed of 350 rpm for 2 hours. Before and after this step, LPS maintained the volume average particle size.
- the slurry of the solid electrolyte composition thus obtained is applied onto an aluminum foil having a thickness of 20 ⁇ m by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 150 ⁇ m after drying. Then, it was dried at 100 ° C. for 1 hour to form a coating dry layer.
- a 500 mg sample was cut out from the coated dry layer, extracted with toluene, and the amount of diisobutyl ketone contained was measured by gas chromatography and found to contain 100 ppm on a mass basis.
- a 15 mm square sample was cut out from the coating dry layer so as to remove the cut-out portion of the sample, and this sample was pressurized under the following condition 1 to prepare a sheet S-1 for a solid electrolyte layer.
- the composition and pressurization conditions were changed to the compositions and conditions shown in Table 1 below, but in the same manner as in the solid electrolyte layer sheet S-1, Table 1 below.
- a sheet for a solid electrolyte layer other than the sheet for a solid electrolyte layer S-1 shown in the above was produced.
- the solid electrolyte layer sheet in which condition 1 was adopted as the pressurization condition was produced in a dry room (dew point -60 ° C.).
- the solid electrolyte layer sheet in which condition 2 was adopted as the pressurization condition was produced in a glove box (Ar atmosphere, dew point -60 ° C.). The same applies to the production of the positive electrode sheet and the negative electrode sheet described later.
- the content of the dispersion medium of the coating dry layer contained in the sheet produced under Condition 2 is the content after being placed on the hot plate of Condition 2 and before being pressurized.
- the content of the particulate organic component is the content of the solid content.
- a positive electrode composition was prepared as follows in a dry room having a dew point of ⁇ 60 ° C., and a positive electrode sheet SS-1 was prepared using this positive electrode composition.
- 180 zirconia beads with a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), and 7.8 g of LPS synthesized above, an amount of acrylic latex 1 solid content of 0.3 g, and 10 g of diisobutyl ketone were put into the container. did.
- This container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and stirring was continued for 6 hours at a temperature of 25 ° C.
- the positive electrode sheets other than the positive electrode sheet SS-1 shown in Table 1 below were produced except that the composition and the pressurizing conditions were changed to the compositions and conditions shown in Table 1 below. did.
- NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2
- the content of the dispersion medium of the coating dry layer contained in the sheet produced under Condition 2 is the content after being placed on the hot plate of Condition 2 and before being pressurized.
- the content of the particulate organic component is the content of the solid content.
- a composition for a negative electrode was prepared as follows in a dry room having a dew point of ⁇ 60 ° C., and a negative electrode sheet FS-1 was prepared using this composition for a negative electrode.
- 180 zirconia beads with a diameter of 5 mm were placed in a 45 mL container made of zirconia (manufactured by Fritsch), and 8.6 g of LPS synthesized above, an amount of acrylic latex 1 solid content of 0.4 g, and 10 g of diisobutyl ketone were added. I put it in.
- This container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and the mixture was stirred at a temperature of 25 ° C. and a rotation speed of 350 rpm for 6 hours. Further, 10.0 g of Si powder (Silicon Powder volume average particle diameter 1 to 5 ⁇ m manufactured by Alfa Aesar) and 1.0 g of acetylene black were charged into the container, and further 5 g of diisobutyl ketone was charged.
- This container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch) and stirred at a temperature of 25 ° C. and a rotation speed of 100 rpm for 5 minutes to obtain a composition for a negative electrode.
- the slurry of the negative electrode composition thus obtained is placed on a 20 ⁇ m stainless steel foil with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) and the mass of the negative electrode composition after drying is 1 cm 2.
- an applicator trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.
- Around 3.3 mg was applied and dried at 100 ° C. for 1 hour to form a coating dry layer.
- a 500 mg sample was cut out from the coated dry layer, extracted with toluene, and the amount of diisobutyl ketone contained was measured by gas chromatography and found to contain 80 ppm.
- a 15 mm square sample was cut out from the coating dry layer so as to remove the cut-out portion of the sample, and this sample was pressurized for 5 minutes under the above condition 1 to prepare a negative electrode sheet FS-1.
- Negative electrode sheets FS-2 to FS-13 are the same as the negative electrode sheet FS-1, except that the composition and pressurization conditions are changed to the compositions and conditions shown in Table 1 below in the production of the negative electrode sheet FS-1. And HFS-1 to HFS-5 were prepared.
- the content of the dispersion medium of the coating dry layer contained in the sheet produced under Condition 2 is the content after being placed on the hot plate of Condition 2 and before being pressurized.
- FS-8 was carried out under vacuum, and the others were heated at atmospheric pressure.
- FS-9 was carried out by changing the pressurizing time of condition 1 from 5 minutes to 2 hours.
- the content of the particulate organic component is the content of the solid content.
- a laminate for an all-solid-state battery was prepared by pressurizing with.
- the all-solid-state secondary battery 13 shown in FIG. 2 was manufactured using this laminate for the all-solid-state secondary battery.
- the laminate 12 for an all-solid-state secondary battery was cut out into a disk shape having a diameter of 10 mm.
- An all-solid-state secondary battery laminate with a diameter of 10 mm is placed in a stainless steel 2032 type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2), and the 2032 type coin case 11 is crimped (restraint pressure: 0). .1 MPa) to produce an all-solid-state secondary battery 13.
- Discharge capacity retention rate (%) (Discharge capacity in the 20th cycle / Discharge capacity in the 1st cycle) x 100
- Discharge capacity retention rate 70% or more and 99% or less
- B Discharge capacity retention rate 60% or more and less than 70%
- C Discharge capacity retention rate 50% or more and less than 60%
- D Discharge capacity retention rate 35% or more and less than 50%
- Discharge capacity retention rate (%) (Discharge capacity in the second cycle / Discharge capacity in the first cycle) x 100
- the all-solid-state secondary battery having no sheet obtained by the method for producing a sheet for an all-solid-state secondary battery of the present invention failed in both battery characteristics and binding properties.
- the all-solid-state secondary battery having at least one layer of the sheet obtained by the method for producing a sheet for an all-solid-state secondary battery of the present invention was acceptable in terms of battery characteristics and binding properties.
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Abstract
Description
ところが、近年、電気自動車の高性能化、実用化等の研究開発が急速に進行し、全固体二次電池に求められる電池性能としてサイクル特性及びレート特性等も高くなっている。そのため、固体粒子間の結着性を更に高める等により、より優れた電池性能を発揮する全固体二次電池の開発が求められている。 The solid electrolyte-containing sheet described in
However, in recent years, research and development for improving the performance and practical application of electric vehicles have progressed rapidly, and the cycle characteristics and rate characteristics are also increasing as the battery performance required for all-solid-state secondary batteries. Therefore, there is a demand for the development of an all-solid-state secondary battery that exhibits more excellent battery performance by further enhancing the binding property between solid particles.
<1>
体積平均粒子径1.0μm以下の硫化物系無機固体電解質及び粒子状有機成分を含有する全固体二次電池用シートの製造方法であって、
粒子状有機成分及び体積平均粒子径1.0μm以下の硫化物系無機固体電解質を含有し、上記粒子状有機成分の含有量が、上記硫化物系無機固体電解質及び上記粒子状有機成分の合計の含有量中、15質量%以下である混合物を、上記粒子状有機成分のガラス転移温度より20℃以上高く、この粒子状有機成分の分解温度未満の温度において、この粒子状有機成分の弾性率の1/10より高い圧力で、加圧すること
を含む、全固体二次電池用シートの製造方法。
<2>
上記弾性率が150MPa以上である、<1>に記載の全固体二次電池用シートの製造方法。
<3>
上記硫化物系無機固体電解質及び上記粒子状有機成分が、体積平均粒子径について下記式(I)で規定する関係を満たす、<1>又は<2>に記載の全固体二次電池用シートの製造方法。
Ba<SEa<20Ba 式(I)
式中、SEaは上記硫化物系無機固体電解質の体積平均粒子径であり、Baは上記粒子状有機成分の体積平均粒子径である。
<4>
上記混合物を構成する硫化物系無機固体電解質を1.0μm以下の体積平均粒子径に調整する工程を含む、<1>~<3>のいずれか1つに記載の全固体二次電池用シートの製造方法。
<5>
上記混合物が活物質を含有する、<1>~<4>のいずれか1つに記載の全固体二次電池用シートの製造方法。
<6>
上記活物質が負極活物質である、<5>に記載の全固体二次電池用シートの製造方法。
<7>
上記負極活物質がケイ素元素又はスズ元素を含む、<6>に記載の全固体二次電池用シートの製造方法。
<8>
上記ガラス転移温度が30℃以上である、<1>~<7>のいずれか1つに記載の全固体二次電池用シートの製造方法。
<9>
上記混合物の加圧を上記ガラス転移温度より50℃以上高い温度で行う、<1>~<8>のいずれか1つに記載の全固体二次電池用シートの製造方法。
<10>
上記混合物が分散媒を含有し、上記製造方法は、上記加圧の前に上記混合物を、分散媒を完全に除去させずに加熱する工程を含む、<1>~<9>のいずれか1つに記載の全固体二次電池用シートの製造方法。
<11>
正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池の製造方法であって、
<1>~<10>のいずれか1つに記載の全固体二次電池用シートの製造方法により得た全固体二次電池用シートを、上記正極活物質層、上記固体電解質層及び上記負極活物質層のうちの少なくとも1層として組込む工程を含む、全固体二次電池の製造方法。
<12>
<1>~<10>いずれか1つに記載の全固体二次電池用シートの製造方法により得た全固体二次電池用シート。
<13>
正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池であって、
上記正極活物質層、上記固体電解質層及び上記負極活物質層の少なくとも1つの層が、<12>に記載の全固体二次電池用シートで構成した層である全固体二次電池。 That is, the above problem was solved by the following means.
<1>
A method for producing a sheet for an all-solid secondary battery containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less and a particulate organic component.
It contains a particulate organic component and a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less, and the content of the particulate organic component is the sum of the sulfide-based inorganic solid electrolyte and the particulate organic component. A mixture having a content of 15% by mass or less has an elasticity of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component. A method for producing a sheet for an all-solid secondary battery, which comprises pressurizing at a pressure higher than 1/10.
<2>
The method for producing an all-solid-state secondary battery sheet according to <1>, wherein the elastic modulus is 150 MPa or more.
<3>
The sheet for an all-solid secondary battery according to <1> or <2>, wherein the sulfide-based inorganic solid electrolyte and the particulate organic component satisfy the relationship defined by the following formula (I) with respect to the volume average particle diameter. Production method.
Ba <SEa <20Ba formula (I)
In the formula, SEa is the volume average particle size of the sulfide-based inorganic solid electrolyte, and Ba is the volume average particle size of the particulate organic component.
<4>
The sheet for an all-solid secondary battery according to any one of <1> to <3>, which comprises a step of adjusting the sulfide-based inorganic solid electrolyte constituting the mixture to a volume average particle diameter of 1.0 μm or less. Manufacturing method.
<5>
The method for producing a sheet for an all-solid-state secondary battery according to any one of <1> to <4>, wherein the mixture contains an active material.
<6>
The method for manufacturing an all-solid-state secondary battery sheet according to <5>, wherein the active material is a negative electrode active material.
<7>
The method for producing an all-solid-state secondary battery sheet according to <6>, wherein the negative electrode active material contains a silicon element or a tin element.
<8>
The method for manufacturing an all-solid-state secondary battery sheet according to any one of <1> to <7>, wherein the glass transition temperature is 30 ° C. or higher.
<9>
The method for producing a sheet for an all-solid-state secondary battery according to any one of <1> to <8>, wherein the pressurization of the mixture is performed at a temperature higher than the glass transition temperature by 50 ° C. or more.
<10>
Any one of <1> to <9>, wherein the mixture contains a dispersion medium, and the production method comprises a step of heating the mixture before the pressurization without completely removing the dispersion medium. The method for manufacturing a sheet for an all-solid-state secondary battery according to the above.
<11>
A method for manufacturing an all-solid-state secondary battery, which comprises a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
The all-solid-state secondary battery sheet obtained by the method for producing an all-solid-state secondary battery sheet according to any one of <1> to <10> is used as the positive electrode active material layer, the solid electrolyte layer, and the negative electrode. A method for manufacturing an all-solid-state secondary battery, which comprises a step of incorporating as at least one layer of an active material layer.
<12>
An all-solid-state secondary battery sheet obtained by the method for manufacturing an all-solid-state secondary battery sheet according to any one of <1> to <10>.
<13>
An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
An all-solid-state secondary battery in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the sheet for an all-solid secondary battery according to <12>.
硫化物系無機固体電解質の体積平均粒子径を1.0μm以下に調整する工程 Particle size adjustment step (hereinafter, also referred to as step (1)):
Step of adjusting the volume average particle size of the sulfide-based inorganic solid electrolyte to 1.0 μm or less
粒子状有機成分及び上記工程で得た体積平均粒子径1.0μm以下の硫化物系無機固体電解質を、上記粒子状有機成分の含有量が、上記硫化物系無機固体電解質及び上記粒子状有機成分の合計の含有量中、15質量%以下になるように混合する工程 Mixing step (step of preparing a mixture, hereinafter also referred to as step (2)):
The particulate organic component and the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less obtained in the above step, and the content of the particulate organic component is the sulfide-based inorganic solid electrolyte and the particulate organic component. Step of mixing so as to be 15% by mass or less in the total content of
上記粒子状有機成分のガラス転移温度より20℃以上高く、上記粒子状有機成分の分解温度未満の温度において、上記粒子状有機成分の弾性率の1/10より高い圧力で、混合する工程により得られた混合物を加圧する工程 Pressurizing step: (hereinafter, also referred to as step (3)) :.
Obtained by the step of mixing at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component at a pressure higher than 1/10 of the elastic modulus of the particulate organic component. The process of pressurizing the mixture
式中、SEaは硫化物系無機固体電解質の体積平均粒子径であり、Baは粒子状有機成分の体積平均粒子径である。 Ba <SEa <20Ba formula (I)
In the formula, SEa is the volume average particle size of the sulfide-based inorganic solid electrolyte, and Ba is the volume average particle size of the particulate organic component.
以下、本発明の全固体二次電池用シートの製造方法に用いる成分及び用いうる成分について説明する。 <Raw materials>
Hereinafter, the components used in the method for producing a sheet for an all-solid-state secondary battery of the present invention and the components that can be used will be described.
本発明において、無機固体電解質とは、無機の固体電解質のことであり、固体電解質とは、その内部においてイオンを移動させることができる固体状の電解質のことである。主たるイオン伝導性材料として有機物を含むものではないことから、有機固体電解質(ポリエチレンオキシド(PEO)などに代表される高分子電解質、リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)などに代表される有機電解質塩)とは明確に区別される。また、無機固体電解質は定常状態では固体であるため、通常カチオン及びアニオンに解離又は遊離していない。この点で、電解液、又は、ポリマー中でカチオン及びアニオンに解離若しくは遊離している無機電解質塩(LiPF6、LiBF4、リチウムビス(フルオロスルホニル)イミド(LiFSI)、LiClなど)とも明確に区別される。無機固体電解質は周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有するものであれば、特に限定されず、電子伝導性を有しないものが一般的である。本発明の全固体二次電池がリチウムイオン電池の場合、無機固体電解質は、リチウムイオンのイオン伝導性を有することが好ましい。
上記無機固体電解質は、全固体二次電池に通常使用される固体電解質材料を適宜選定して用いることができる。無機固体電解質は(i)硫化物系無機固体電解質、(ii)酸化物系無機固体電解質、(iii)ハロゲン化物系無機固体電解質、及び、(iV)水素化物系固体電解質が挙げられる。 (Sulfide-based inorganic solid electrolyte)
In the present invention, the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polymer electrolyte represented by polyethylene oxide (PEO), organic represented by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from electrolyte salts). Further, since the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from inorganic electrolyte salts (LiPF 6 , LiBF 4 , Lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in the electrolyte or polymer. Will be done. The inorganic solid electrolyte is not particularly limited as long as it has the ionic conductivity of a metal belonging to
As the inorganic solid electrolyte, a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used. Examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iV) a hydride-based solid electrolyte.
硫化物系無機固体電解質は、硫黄原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものが好ましい。硫化物系無機固体電解質は、元素として少なくともLi、S及びPを含有し、リチウムイオン伝導性を有しているものが好ましいが、目的又は場合に応じて、Li、S及びP以外の他の元素を含んでもよい。 (I) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to
La1Mb1Pc1Sd1Ae1 (1)
式中、LはLi、Na及びKから選択される元素を示し、Liが好ましい。Mは、B、Zn、Sn、Si、Cu、Ga、Sb、Al及びGeから選択される元素を示す。Aは、I、Br、Cl及びFから選択される元素を示す。a1~e1は各元素の組成比を示し、a1:b1:c1:d1:e1は1~12:0~5:1:2~12:0~10を満たす。a1は1~9が好ましく、1.5~7.5がより好ましい。b1は0~3が好ましく、0~1がより好ましい。d1は2.5~10が好ましく、3.0~8.5がより好ましい。e1は0~5が好ましく、0~3がより好ましい。 Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (1).
L a1 M b1 P c1 S d1 A e1 (1)
In the formula, L represents an element selected from Li, Na and K, with Li being preferred. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. A represents an element selected from I, Br, Cl and F. a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10. a1 is preferably 1 to 9, more preferably 1.5 to 7.5. b1 is preferably 0 to 3, more preferably 0 to 1. The d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5. e1 is preferably 0 to 5, more preferably 0 to 3.
硫化物系無機固体電解質は、例えば硫化リチウム(Li2S)、硫化リン(例えば五硫化二燐(P2S5))、単体燐、単体硫黄、硫化ナトリウム、硫化水素、ハロゲン化リチウム(例えばLiI、LiBr、LiCl)及び上記Mで表される元素の硫化物(例えばSiS2、SnS、GeS2)の中の少なくとも2つ以上の原料の反応により製造することができる。 The sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized. For example, Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2 ).
酸化物系無機固体電解質は、酸素原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものが好ましい。
酸化物系無機固体電解質は、イオン伝導度として、1×10-6S/cm以上であることが好ましく、5×10-6S/cm以上であることがより好ましく、1×10-5S/cm以上であることが特に好ましい。上限は特に制限されないが、1×10-1S/cm以下であることが実際的である。 (Ii) Oxide-based Inorganic Solid Electrolyte The oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to
The oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 × 10 -6 S / cm or more, more preferably 5 × 10 -6 S / cm or more, and 1 × 10 -5 S / cm or more. It is particularly preferable that it is / cm or more. The upper limit is not particularly limited, but it is practical that it is 1 × 10 -1 S / cm or less.
またLi、P及びOを含むリン化合物も望ましい。例えばリン酸リチウム(Li3PO4); リン酸リチウムの酸素原子の一部を窒素で置換したLiPON; LiPOD1(D1は、好ましくは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt及びAuから選ばれる1種以上の元素である。)等が挙げられる。
更に、LiA1ON(A1は、Si、B、Ge、Al、C及びGaから選ばれる1種以上の元素である。)等も好ましく用いることができる。 As a specific compound example, for example, Li xa La ya TiO 3 [xa satisfies 0.3 ≦ xa ≦ 0.7, and ya satisfies 0.3 ≦ ya ≦ 0.7. (LLT); Li xb Layb Zr zb M bb mb Onb (M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn. Xb satisfies 5 ≦ xb ≦ 10, yb satisfies 1 ≦ yb ≦ 4, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, and nb satisfies 5 ≦ nb ≦ 20. Satisfies.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn. Xc is 0 <xc ≦ 5 , Yc satisfies 0 <yc ≦ 1, zc satisfies 0 <zc ≦ 1, nc satisfies 0 <nc ≦ 6); Li xd (Al, Ga) yd (Ti, Ge) zd Si. ad P md O nd (xd satisfies 1 ≦ xd ≦ 3, yd satisfies 0 ≦ yd ≦ 1, zd satisfies 0 ≦ zd ≦ 2, ad satisfies 0 ≦ ad ≦ 1, md is 1 ≦ met md ≦ 7, nd satisfies 3 ≦ nd ≦ 13);. Li (3-2xe) M ee xe D ee O (xe represents a number of 0 to 0.1, M ee divalent .D ee representing the metal atom represents a combination of halogen atom or two or more halogen atoms);. Li xf Si yf O zf (xf satisfies 1 ≦ xf ≦ 5, yf satisfies 0 <yf ≦ 3 , zf satisfies 1 ≦ zf ≦ 10);. Li xg S yg O zg (xg satisfies 1 ≦ xg ≦ 3, yg satisfies 0 <yg ≦ 2, zg satisfies 1 ≦ zg ≦ 10. ); Li 3 BO 3 ; Li 3 BO 3- Li 2 SO 4 ; Li 2 O-B 2 O 3- P 2 O 5 ; Li 2 O-SiO 2 ; Li 6 BaLa 2 Ta 2 O 12 ; Li 3 PO (4-3 / 2w) N w (w is w <1); Li 3.5 Zn 0.25 GeO 4 having a LISION (Lithium super ionic controller) type crystal structure; La 0.55 having a perovskite type crystal structure Li 0.35 TiO 3 ; LiTi 2 P 3 O 12 having a NASICON (Naturium super ionic controller) type crystal structure; Li 1 + xh + yh (Al, Ga) xh (Ti, Ge) 2-xh Sihy 3-yh O 12 (xh satisfies 0 ≦ xh ≦ 1, yh satisfies 0 ≦ yh ≦ 1. ); Examples thereof include Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li 3 PO 4 ); LiPON in which a part of the oxygen atom of lithium phosphate is replaced with nitrogen; LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni). , Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and one or more elements selected from Au) and the like.
Further, LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.
ハロゲン化物系無機固体電解質は、ハロゲン原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有し、かつ、電子絶縁性を有する化合物が好ましい。
ハロゲン化物系無機固体電解質としては、特に制限されないが、例えば、LiCl、LiBr、LiI、ADVANCED MATERIALS,2018,30,1803075に記載のLi3YBr6、Li3YCl6等の化合物が挙げられる。中でも、Li3YBr6、Li3YCl6を好ましい。 (Iii) Halide-based inorganic solid electrolyte The halide-based inorganic solid electrolyte contains halogen atoms, has the conductivity of ions of metals belonging to
The halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
水素化物系無機固体電解質は、水素原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有する化合物が好ましい。
水素化物系無機固体電解質としては、特に制限されないが、例えば、LiBH4、Li4(BH4)3I、3LiBH4-LiCl等が挙げられる。 (IV) Hydride-based Inorganic Solid Electrolyte The hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to
The hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
固体電解質層用シートの単位面積(cm2)当たりの硫化物系無機固体電解質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。
一方、電極シートの電極活物質層では、硫化物系無機固体電解質の目付量は、活物質と硫化物系無機固体電解質との合計量が上記範囲であることが好ましい。 In the step (1), the sulfide-based inorganic solid electrolyte may be a mixture of one type or two or more types.
The mass (mg) (grain amount) of the sulfide-based inorganic solid electrolyte per unit area (cm 2 ) of the solid electrolyte layer sheet is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
On the other hand, in the electrode active material layer of the electrode sheet, the amount of the sulfide-based inorganic solid electrolyte is preferably in the above range as the total amount of the active material and the sulfide-based inorganic solid electrolyte.
一方、電極シートでは、電極活物質層中の硫化物系無機固体電解質の含有量は、活物質と硫化物系無機固体電解質との合計含有量が上記範囲であることが好ましい。
本明細書において、固形分(固形成分)とは、上記粒子状有機成分を、上記硫化物系無機固体電解質及び上記粒子状有機成分の合計の含有量中、15質量%以下で含有する混合物(以下、「本発明に用いられる混合物」とも称する。)を、1mmHgの気圧下、窒素雰囲気下170℃で6時間乾燥処理したときに、揮発又は蒸発して消失しない成分をいう。典型的には、後述の分散媒以外の成分を指す。 The content of the sulfide-based inorganic solid electrolyte in the sheet for the solid electrolyte layer is preferably 50% by mass or more, preferably 70% by mass or more, based on 100% by mass of the solid content, in terms of reduction of interfacial resistance and binding property. It is more preferably% or more, and particularly preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
On the other hand, in the electrode sheet, the content of the sulfide-based inorganic solid electrolyte in the electrode active material layer is preferably such that the total content of the active material and the sulfide-based inorganic solid electrolyte is in the above range.
In the present specification, the solid content (solid component) is a mixture containing the particulate organic component in an amount of 15% by mass or less based on the total content of the sulfide-based inorganic solid electrolyte and the particulate organic component. Hereinafter, also referred to as "mixture used in the present invention") refers to a component that does not volatilize or evaporate and disappear when dried at 170 ° C. for 6 hours under a pressure of 1 mmHg and a nitrogen atmosphere. Typically, it refers to a component other than the dispersion medium described later.
粒子状有機成分(好ましくはバインダー)は、特に制限されないが、ガラス転移温度を有する粒子状ポリマーが好ましい。以下、工程(2)で用いられる粒子状ポリマーについて記載する。 (Particulate organic component)
The particulate organic component (preferably a binder) is not particularly limited, but a particulate polymer having a glass transition temperature is preferable. Hereinafter, the particulate polymer used in the step (2) will be described.
本発明では粒子状ポリマーとして、ポリウレタン、ポリウレア、ポリアミド、ポリイミド又は(メタ)アクリルポリマーが好ましく、ポリウレタン又はアクリルポリマーがより好ましく、ポリウレタンが更に好ましい。
粒子状有機成分は、偏平状、無定形等であってもよいが、球状若しくは顆粒状が好ましい。 As the particulate polymer constituting the particulate organic component, a polymer having at least one of a urethane bond, a urea bond, an amide bond, and an imide bond, or a (meth) acrylic polymer is preferable. Among them, a polymer having a urethane bond and a (meth) acrylic polymer are more preferable from the viewpoint of adhesion to a sulfide-based inorganic solid electrolyte.
In the present invention, as the particulate polymer, polyurethane, polyurea, polyamide, polyimide or (meth) acrylic polymer is preferable, polyurethane or acrylic polymer is more preferable, and polyurethane is further preferable.
The particulate organic component may be flat, amorphous or the like, but is preferably spherical or granular.
ウレタン価は後記実施例の項に記載の方法により決定することができる。 The urethane value of the polyurethane is not particularly limited, but is preferably 1.5 mmol / g or more, and more preferably 2.0 mmol / g or more. On the other hand, from the viewpoint of imparting particulate formation stability, the upper limit of the urethane value is preferably 5 mmol / g or less.
The urethane value can be determined by the method described in the section of Examples described later.
本発明において、質量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)による標準ポリスチレン換算の質量平均分子量を計測する。測定法としては、基本として下記条件1又は条件2(優先)の方法により測定した値とする。ただし、測定する重合体(特定のポリマー等)の種類によっては適宜適切な溶離液を選定して用いればよい。
(条件1)
カラム:TOSOH TSKgel Super AWM-Hを2本つなげる。
キャリア:10mMLiBr/N-メチルピロリドン
測定温度:40℃
キャリア流量:1.0ml/min
試料濃度:0.1質量%
検出器:RI(屈折率)検出器
(条件2)
カラム:TOSOH TSKgel Super HZM-H、TOSOH TSKgel Super HZ4000、TOSOH TSKgel Super HZ2000をつないだカラムを用いる。
キャリア:テトラヒドロフラン
測定温度:40℃
キャリア流量:1.0ml/min
試料濃度:0.1質量%
検出器:RI(屈折率)検出器 -Measurement of molecular weight-
In the present invention, the mass average molecular weight is measured by gel permeation chromatography (GPC) in terms of standard polystyrene. As the measurement method, the value measured by the method of the
(Condition 1)
Column: Connect two TOSOH TSKgel Super AWM-H.
Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (condition 2)
Column: A column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are connected is used.
Carrier: tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector
粒子状ポリマーの分解温度は、特に制限されないが、加熱プロセスとのバランスの点で、150℃以上が好ましく、180℃以上がより好ましく、190℃以上が更に好ましい。上限は、500℃以下であることが好ましく、480℃以下であることがより好ましく、450℃以下であることが更に好ましい。分解温度は、後述する実施例で説明する方法で測定した値とする。
粒子状ポリマーの弾性率は、特に制限されないが、150MPa以上であることが好ましく、180MPa以上であることがより好ましく、200MPa以上であることが更に好ましい。粒子状ポリマーの弾性率の上限は特に制限されないが、2000MPa以下であることが好ましく、1800MPa以下であることがより好ましい。弾性率は、後述する実施例で説明する方法で測定した値とする。 The glass transition temperature of the particulate polymer is not particularly limited, but is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, in order to maintain the particle shape and not cover the entire surface of the solid particles. It is preferably 40 ° C. or higher, and more preferably 40 ° C. or higher. The glass transition temperature is a value measured by the method described in Examples described later. In the present invention, the glass transition temperature used as the reference for the heating temperature in step (3) is the highest glass transition temperature when the particulate polymer has a plurality of glass transition temperatures.
The decomposition temperature of the particulate polymer is not particularly limited, but is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 190 ° C. or higher in terms of balance with the heating process. The upper limit is preferably 500 ° C. or lower, more preferably 480 ° C. or lower, and even more preferably 450 ° C. or lower. The decomposition temperature is a value measured by the method described in Examples described later.
The elastic modulus of the particulate polymer is not particularly limited, but is preferably 150 MPa or more, more preferably 180 MPa or more, and even more preferably 200 MPa or more. The upper limit of the elastic modulus of the particulate polymer is not particularly limited, but is preferably 2000 MPa or less, and more preferably 1800 MPa or less. The elastic modulus is a value measured by the method described in Examples described later.
粒子状ポリマーの体積平均粒子径は、例えば、粒子状ポリマーの分散液を調製する際に用いる分散媒の種類、粒子状ポリマー中の構成成分の含有量等により、調整できる。
全固体二次電池の構成層における粒子状ポリマーの体積平均粒子径は、例えば、電池を分解して粒子状ポリマーを含有する構成層を剥がした後、その構成層について測定を行い、予め測定していた粒子状ポリマー以外の粒子の体積平均粒子径の測定値を排除することにより、測定することができる。
粒子状ポリマーの体積平均粒子径は、後記実施例の項で記載の測定方法で得られる値とする。
粒子状ポリマーの体積平均粒子径Baと、硫化物系無機固体電解質の体積平均粒子径SEaとは、下記式(I)で規定する関係を満たすこと(調整されること)が好ましい。
下記体積平均粒子径の関係を満たすことにより、硫化物系無機固体電解質間のイオン伝導を阻害せずに、硫化物系無機固体電解質間を結着することで、抵抗上昇を抑制し、さらに、電極としての取り扱い性、電極稼働時の膨張収縮に追随し低抵抗である等の特性が発現すると考えられる。
上記効果の点で、体積平均粒子径Baと体積平均粒子径SEaとは、下記式(IA)で規定する関係を満たすことが好ましく、下記式(IB)で規定する関係を満たすことがより好ましい。 The volume average particle size of the particulate polymer is not particularly limited, but is preferably 0.5 μm or less, more preferably 0.4 μm or less, and 0.2 μm or less from the viewpoint of binding without coating the sulfide-based solid electrolyte. More preferred. The lower limit of the volume average particle diameter is not particularly limited, but is actually 0.005 μm or more, preferably 0.01 μm or more, and more preferably 0.015 μm or more.
The volume average particle size of the particulate polymer can be adjusted, for example, by the type of dispersion medium used when preparing the dispersion liquid of the particulate polymer, the content of the constituent components in the particulate polymer, and the like.
The volume average particle size of the particulate polymer in the constituent layers of the all-solid secondary battery is measured in advance by, for example, disassembling the battery and peeling off the constituent layer containing the particulate polymer, and then measuring the constituent layers. It can be measured by excluding the measured value of the volume average particle diameter of the particles other than the particulate polymer.
The volume average particle size of the particulate polymer shall be a value obtained by the measuring method described in the section of Examples described later.
It is preferable that the volume average particle size Ba of the particulate polymer and the volume average particle size SEa of the sulfide-based inorganic solid electrolyte satisfy (adjust) the relationship defined by the following formula (I).
By satisfying the following volume average particle size relationship, the resistance increase can be suppressed by binding the sulfide-based inorganic solid electrolytes without inhibiting the ionic conduction between the sulfide-based inorganic solid electrolytes, and further. It is considered that characteristics such as handleability as an electrode and low resistance following expansion and contraction during electrode operation are exhibited.
In terms of the above effects, the volume average particle diameter Ba and the volume average particle diameter SEa preferably satisfy the relationship specified by the following formula (IA), and more preferably satisfy the relationship specified by the following formula (IB). ..
Ba<SEa≦15Ba 式(IA)
Ba<SEa≦10Ba 式(IB) Ba <SEa <20Ba formula (I)
Ba <SEa ≤ 15 Ba formula (IA)
Ba <SEa≤10Ba equation (IB)
本発明の全固体二次電池用シートの製造方法で得られた全固体二次電池用シートを電極活物質層として用いる場合、上記工程(2)で活物質を用いる。活物質としては、以下に説明するが、(i)正極活物質及び(ii)負極活物質が挙げられる。 (Active material)
When the all-solid-state secondary battery sheet obtained by the method for producing an all-solid-state secondary battery sheet of the present invention is used as the electrode active material layer, the active material is used in the above step (2). Examples of the active material include (i) positive electrode active material and (ii) negative electrode active material, which will be described below.
正極活物質は、可逆的にリチウムイオンを挿入及び放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく、遷移金属酸化物、又は、硫黄などのLiと複合化できる元素などでもよい。
中でも、正極活物質としては、遷移金属酸化物を用いることが好ましく、遷移金属元素Ma(Co、Ni、Fe、Mn、Cu及びVから選択される1種以上の元素)を有する遷移金属酸化物がより好ましい。また、この遷移金属酸化物に元素Mb(リチウム以外の金属周期律表の第1(Ia)族の元素、第2(IIa)族の元素、Al、Ga、In、Ge、Sn、Pb、Sb、Bi、Si、P及びBなどの元素)を混合してもよい。混合量としては、遷移金属元素Maの量(100mol%)に対して0~30mol%が好ましい。Li/Maのモル比が0.3~2.2になるように混合して合成されたものが、より好ましい。
遷移金属酸化物の具体例としては、(MA)層状岩塩型構造を有する遷移金属酸化物、(MB)スピネル型構造を有する遷移金属酸化物、(MC)リチウム含有遷移金属リン酸化合物、(MD)リチウム含有遷移金属ハロゲン化リン酸化合物及び(ME)リチウム含有遷移金属ケイ酸化合物等が挙げられる。 (I) Positive electrode active material The positive electrode active material is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an element that can be composited with Li such as sulfur, or the like.
Among them, as the positive electrode active material, a transition metal oxide having preferably used a transition metal oxide, a transition metal element M a (Co, Ni, Fe , Mn, 1 or more elements selected from Cu and V) the The thing is more preferable. Further, the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed. The mixing amount is preferably 0 ~ 30 mol% relative to the amount of the transition metal element M a (100mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
(MB)スピネル型構造を有する遷移金属酸化物の具体例として、LiMn2O4(LMO)、LiCoMnO4、Li2FeMn3O8、Li2CuMn3O8、Li2CrMn3O8及びLi2NiMn3O8が挙げられる。
(MC)リチウム含有遷移金属リン酸化合物としては、例えば、LiFePO4及びLi3Fe2(PO4)3等のオリビン型リン酸鉄塩、LiFeP2O7等のピロリン酸鉄類、LiCoPO4等のリン酸コバルト類並びにLi3V2(PO4)3(リン酸バナジウムリチウム)等の単斜晶ナシコン型リン酸バナジウム塩が挙げられる。
(MD)リチウム含有遷移金属ハロゲン化リン酸化合物としては、例えば、Li2FePO4F等のフッ化リン酸鉄塩、Li2MnPO4F等のフッ化リン酸マンガン塩及びLi2CoPO4F等のフッ化リン酸コバルト類が挙げられる。
(ME)リチウム含有遷移金属ケイ酸化合物としては、例えば、Li2FeSiO4、Li2MnSiO4、Li2CoSiO4等が挙げられる。
本発明では、(MA)層状岩塩型構造を有する遷移金属酸化物が好ましく、LCO又はNMCがより好ましい。 (MA) Specific examples of the transition metal oxide having a layered rock salt structure include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
(MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) ,
Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4. Examples thereof include cobalt phosphates of the above, and monoclinic panacicon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
(MD) as the lithium-containing transition metal halogenated phosphate compound, for example,
Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
In the present invention, a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
正極活物質の粒子径の測定は、以下の手順で行う。正極活物質粒子を、水(水に不安定な物質の場合はヘプタン)を用いて20mLサンプル瓶中で1質量%の分散液を希釈調製する。希釈後の分散試料は、1kHzの超音波を10分間照射し、その直後に試験に使用する。この分散液試料を用い、レーザ回折/散乱式粒度分布測定装置LA-920(商品名、HORIBA社製)を用いて、温度25℃で測定用石英セルを使用してデータ取り込みを50回行い、体積平均粒子径を得る。その他の詳細な条件等は必要によりJIS Z 8828:2013「粒子径解析-動的光散乱法」の記載を参照する。1水準につき5つの試料を作製しその平均値を採用する。 The shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles. The particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm.
The particle size of the positive electrode active material is measured by the following procedure. The positive electrode active material particles are prepared by diluting a 1% by mass dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance). The diluted dispersed sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test. Using this dispersion sample, data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell. Obtain the volume average particle size. For other detailed conditions, etc., refer to the description of JIS Z 8828: 2013 “Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
焼成法によって得られた正極活物質は、水、酸性水溶液、アルカリ性水溶液、有機溶剤にて洗浄した後使用してもよい。 A normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used. At the time of pulverization, wet pulverization in which an organic solvent such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size. The classification is not particularly limited, and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can be used.
The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
正極活物質層を形成する場合、正極活物質層の単位面積(cm2)当たりの正極活物質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。 The positive electrode active material may be a mixture of one type or two or more types.
When the positive electrode active material layer is formed, the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
負極活物質は、可逆的にリチウムイオンを挿入及び放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく、炭素質材料、金属酸化物、金属複合酸化物、リチウム単体、リチウム合金、リチウムと合金形成可能な負極活物質等が挙げられる。中でも、炭素質材料、金属複合酸化物又はリチウム単体が信頼性の点から好ましく用いられる。 (Ii) Negative electrode active material The negative electrode active material is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and examples thereof include a carbonaceous material, a metal oxide, a metal composite oxide, a lithium simple substance, a lithium alloy, and a negative electrode active material capable of forming an alloy with lithium. .. Among them, a carbonaceous material, a metal composite oxide or a simple substance of lithium is preferably used from the viewpoint of reliability.
これらの炭素質材料は、黒鉛化の程度により難黒鉛化炭素質材料(ハードカーボンともいう。)と黒鉛系炭素質材料に分けることもできる。また炭素質材料は、特開昭62-22066号公報、特開平2-6856号公報、同3-45473号公報に記載される面間隔又は密度、結晶子の大きさを有することが好ましい。炭素質材料は、単一の材料である必要はなく、特開平5-90844号公報記載の天然黒鉛と人造黒鉛の混合物、特開平6-4516号公報記載の被覆層を有する黒鉛等を用いることもできる。
炭素質材料としては、ハードカーボン又は黒鉛が好ましく用いられ、黒鉛がより好ましく用いられる。 The carbonaceous material used as the negative electrode active material is a material substantially composed of carbon. For example, various synthesis of petroleum pitch, carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin. Examples thereof include carbonic materials obtained by firing a resin. Furthermore, various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers and activated carbon fibers. Kind, mesophase microspheres, graphite whisker, flat graphite and the like can also be mentioned.
These carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the size of crystallites described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
As the carbonaceous material, hard carbon or graphite is preferably used, and graphite is more preferably used.
Sn、Si、Geを中心とする非晶質酸化物負極活物質に併せて用いることができる負極活物質としては、リチウムイオン又はリチウム金属を吸蔵及び/又は放出できる炭素質材料、リチウム単体、リチウム合金、リチウムと合金化可能な負極活物質が好適に挙げられる。 Among the compound group consisting of the amorphous oxide and the chalcogenide, the amorphous oxide of the semi-metal element or the chalcogenide is more preferable, and the elements of the groups 13 (IIIB) to 15 (VB) of the periodic table (for example). , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more (composite) oxides, or chalcogenides are particularly preferred. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2. O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , GeS, PbS, PbS 2 , Sb 2 S 3 or Sb 2 S 5 is preferably mentioned.
Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include a carbonaceous material capable of occluding and / or releasing lithium ions or lithium metal, lithium alone, and lithium. A negative electrode active material that can be alloyed with an alloy or lithium is preferably used.
負極活物質、例えば金属酸化物は、チタン元素を含有すること(チタン酸化物)も好ましく挙げられる。具体的には、Li4Ti5O12(チタン酸リチウム[LTO])がリチウムイオンの吸蔵放出時の体積変動が小さいことから急速充放電特性に優れ、電極の劣化が抑制されリチウムイオン二次電池の寿命向上が可能となる点で好ましい。 It is preferable that the oxide of a metal or a metalloid element, particularly a metal (composite) oxide and the chalcogenide, contains at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics. Examples of the lithium-containing metal composite oxide (lithium composite metal oxide) include lithium oxide and the metal (composite) oxide or a composite oxide of the chalcogenide, more specifically, Li 2 SnO 2. Can be mentioned.
It is also preferable that the negative electrode active material, for example, a metal oxide, contains a titanium element (titanium oxide). Specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) has excellent rapid charge / discharge characteristics due to small volume fluctuations during storage and release of lithium ions, and electrode deterioration is suppressed and lithium ion secondary It is preferable in that the life of the battery can be improved.
一般的に、これらの負極活物質を含有する負極(ケイ素元素含有活物質を含有するSi負極、スズ元素を有する活物質を含有するSn負極等)は、炭素負極(黒鉛及びアセチレンブラックなど)に比べて、より多くのLiイオンを吸蔵できる。すなわち、単位質量あたりのLiイオンの吸蔵量が増加する。そのため、電池容量を大きくすることができる。その結果、バッテリー駆動時間を長くすることができるという利点がある。
ケイ素元素含有活物質としては、例えば、Si、SiOx(0<x≦1)等のケイ素材料、更には、チタン、バナジウム、クロム、マンガン、ニッケル、銅、ランタン等を含むケイ素含有合金(例えば、LaSi2、VSi2、La-Si、Gd-Si、Ni-Si)、又は組織化した活物質(例えば、LaSi2/Si)、他にも、SnSiO3、SnSiS3等のケイ素元素及びスズ元素を含有する活物質等が挙げられる。なお、SiOxは、それ自体を負極活物質(半金属酸化物)として用いることができ、また、全固体二次電池の稼働によりSiを生成するため、リチウムと合金化可能な負極活物質(その前駆体物質)として用いることができる。
スズ元素を有する負極活物質としては、例えば、Sn、SnO、SnO2、SnS、SnS2、更には上記ケイ素元素及びスズ元素を含有する活物質等が挙げられる。また、酸化リチウムとの複合酸化物、例えば、Li2SnO2を挙げることもできる。 The negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery. Such an active material has a large expansion and contraction due to charge and discharge, and the binding property of solid particles is lowered as described above, but in the present invention, a high binding property can be achieved by the step (3). Examples of such an active material include a negative electrode active material (alloy) having a silicon element or a tin element, and each metal such as Al and In, and a negative negative active material (silicon element) having a silicon element that enables a higher battery capacity. (Containing active material) is preferable, and a silicon element-containing active material having a silicon element content of 50 mol% or more of all the constituent elements is more preferable.
Generally, a negative electrode containing these negative electrode active materials (Si negative electrode containing a silicon element-containing active material, Sn negative electrode containing an active material containing a tin element, etc.) is used as a carbon negative electrode (graphite, acetylene black, etc.). In comparison, more Li ions can be occluded. That is, the occlusal amount of Li ions per unit mass increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery drive time can be lengthened.
Examples of the silicon element-containing active material include silicon materials such as Si and SiOx (0 <x≤1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,). LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi 2 / Si), as well as other silicon and tin elements such as SnSiO 3 , SnSiS 3 Examples include active materials containing. In addition, SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since Si is generated by the operation of an all-solid-state secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
Examples of the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and the active material containing the silicon element and the tin element. Further, a composite oxide with lithium oxide, for example, Li 2 SnO 2 can also be mentioned.
負極活物質層の単位面積(cm2)当たりの負極活物質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。 The negative electrode active material may be a mixture of one type or two or more types.
The mass (mg) (weight) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
正極活物質及び負極活物質の表面は別の金属酸化物で表面被覆されていてもよい。表面被覆剤としてはTi、Nb、Ta、W、Zr、Al、Si又はLiを含有する金属酸化物等が挙げられる。具体的には、チタン酸スピネル、タンタル系酸化物、ニオブ系酸化物、ニオブ酸リチウム系化合物等が挙げられ、具体的には、Li4Ti5O12、Li2Ti2O5、LiTaO3、LiNbO3、LiAlO2、Li2ZrO3、Li2WO4、Li2TiO3、Li2B4O7、Li3PO4、Li2MoO4、Li3BO3、LiBO2、Li2CO3、Li2SiO3、SiO2、TiO2、ZrO2、Al2O3、B2O3等が挙げられる。
また、正極活物質又は負極活物質を含む電極表面は硫黄又はリンで表面処理されていてもよい。
更に、正極活物質又は負極活物質の粒子表面は、上記表面被覆の前後において活性光線又は活性気体(プラズマ等)により表面処理を施されていてもよい。 -Coating of active material-
The surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide. Examples of the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples include spinel titanate, tantalate oxide, niobate oxide, lithium niobate compound, and the like. Specifically, Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , LiTaO 3 , LiNbO 3 , LiAlO 2 , Li 2 ZrO 3 , Li 2 WO 4 , Li 2 TiO 3 , Li 2 B 4 O 7 , Li 3 PO 4 , Li 2 MoO 4 , Li 3 BO 3 , LiBO 2 , Li 2 CO 3 , Li 2 SiO 3 , SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , B 2 O 3, and the like.
Further, the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
Further, the surface of the positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
工程(2)で、導電助剤を用いてもよく、特に負極活物質としてのスズ元素含有活物質又はケイ素元素含有活物質は導電助剤と併用されることが好ましい。
導電助剤としては、特に制限はなく、一般的な導電助剤として知られているものを用いることができる。例えば、電子伝導性材料である、天然黒鉛、人造黒鉛などの黒鉛類、アセチレンブラック、ケッチェンブラック、ファーネスブラックなどのカーボンブラック類、ニードルコークスなどの無定形炭素、気相成長炭素繊維若しくはカーボンナノチューブなどの炭素繊維類、グラフェン若しくはフラーレンなどの炭素質材料であってもよいし、銅、ニッケルなどの金属粉、金属繊維でもよく、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリフェニレン誘導体などの導電性高分子を用いてもよい。
本発明において、活物質と導電助剤とを併用する場合、上記の導電助剤のうち、電池を充放電した際にLiの挿入と放出が起きず、活物質として機能しないものを導電助剤とする。したがって、導電助剤の中でも、電池を充放電した際に活物質層中において活物質として機能しうるものは、導電助剤ではなく活物質に分類する。電池を充放電した際に活物質として機能するか否かは、一義的ではなく、活物質との組み合わせにより決定される。 (Conductive aid)
In the step (2), a conductive auxiliary agent may be used, and it is particularly preferable that the tin element-containing active material or the silicon element-containing active material as the negative electrode active material is used in combination with the conductive auxiliary agent.
The conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used. For example, electron conductive materials such as natural graphite, artificial graphite and other graphite, acetylene black, ketjen black, furnace black and other carbon blacks, needle coke and other amorphous carbon, vapor-grown carbon fibers or carbon nanotubes. It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. May be used.
In the present invention, when the active material and the conductive auxiliary agent are used in combination, among the above-mentioned conductive auxiliary agents, the conductive auxiliary agent that does not insert and release Li when the battery is charged and discharged and does not function as the active material. And. Therefore, among the conductive auxiliary agents, those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials instead of conductive auxiliary agents. Whether or not the battery functions as an active material when it is charged and discharged is not unique and is determined by the combination with the active material.
導電助剤の形状は、特に制限されないが、粒子状が好ましい。
導電助剤の、電極活物質層中における含有量は特に制限されず、固形分100質量%において、0.1~15質量%であることが好ましく、0.5~12質量%がより好ましく、1~10質量%であることが更に好ましい。 As the conductive auxiliary agent, one kind may be mixed, or two or more kinds may be mixed.
The shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
The content of the conductive auxiliary agent in the electrode active material layer is not particularly limited, and is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, based on 100% by mass of the solid content. It is more preferably 1 to 10% by mass.
工程(2)では、リチウム塩(支持電解質)を用いてもよい。
リチウム塩としては、通常この種の製品に用いられるリチウム塩が好ましく、特に制限はなく、例えば、特開2015-088486号公報の段落0082~0085記載のリチウム塩が好ましい。
本発明の全固体二次電池用シートがリチウム塩を含む場合、リチウム塩の含有量は、硫化物系無機固体電解質100質量部に対して、0.1質量部以上が好ましく、5質量部以上がより好ましい。上限としては、50質量部以下が好ましく、20質量部以下がより好ましい。 (Lithium salt)
In step (2), a lithium salt (supporting electrolyte) may be used.
As the lithium salt, the lithium salt usually used for this kind of product is preferable, and there is no particular limitation. For example, the lithium salt described in paragraphs 882 to 985 of JP2015-088486 is preferable.
When the sheet for an all-solid secondary battery of the present invention contains a lithium salt, the content of the lithium salt is preferably 0.1 part by mass or more, preferably 5 parts by mass or more, based on 100 parts by mass of the sulfide-based inorganic solid electrolyte. Is more preferable. The upper limit is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.
工程(2)では分散媒(分散媒体)を用いてもよく、上記の各成分を分散又は溶解させるものであればよく、粒子状有機成分及び固体粒子を分散させるものが好ましい。分散媒としては、例えば、各種の有機溶媒が挙げられる。有機溶媒としては、アルコール化合物、エーテル化合物、アミド化合物、アミン化合物、ケトン化合物、芳香族化合物、脂肪族化合物、ニトリル化合物、エステル化合物等の各溶媒が挙げられる。 (Dispersion medium)
In the step (2), a dispersion medium (dispersion medium) may be used, as long as each of the above components is dispersed or dissolved, and a particulate organic component and solid particles are preferably dispersed. Examples of the dispersion medium include various organic solvents. Examples of the organic solvent include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds and the like.
アルコール化合物としては、例えば、メチルアルコール、エチルアルコール、1-プロピルアルコール、2-プロピルアルコール、2-ブタノール、エチレングリコール、プロピレングリコール、グリセリン、1,6-ヘキサンジオール、シクロヘキサンジオール、ソルビトール、キシリトール、2-メチル-2,4-ペンタンジオール、1,3-ブタンジオール、1,4-ブタンジオールが挙げられる。 Specific examples of each of the above solvents are shown below.
Examples of the alcohol compound include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol can be mentioned.
ケトン化合物としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジイソブチルケトンなどが挙げられる。
芳香族化合物としては、例えば、ベンゼン、トルエン、キシレンなどの芳香族炭化水素化合物が挙げられる。
脂肪族化合物としては、例えば、ヘキサン、ヘプタン、オクタン、デカンなどの脂肪族炭化水素化合物が挙げられる。
ニトリル化合物としては、例えば、アセトニトリル、プロピロニトリル、イソブチロニトリルなどが挙げられる。
エステル化合物としては、例えば、酢酸エチル、酢酸ブチル、酢酸プロピル、酪酸ブチル、ペンタン酸ブチルなどが挙げられる。
非水系分散媒としては、上記芳香族化合物、脂肪族化合物等が挙げられる。 Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone.
Examples of the aromatic compound include aromatic hydrocarbon compounds such as benzene, toluene and xylene.
Examples of the aliphatic compound include aliphatic hydrocarbon compounds such as hexane, heptane, octane, and decane.
Examples of the nitrile compound include acetonitrile, propyronitrile, isobutyronitrile and the like.
Examples of the ester compound include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, butyl pentanate and the like.
Examples of the non-aqueous dispersion medium include the above aromatic compounds and aliphatic compounds.
上記分散媒は、1種を混合しても、2種以上を混合してもよい。 The dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher. The upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
The dispersion medium may be a mixture of one type or two or more types.
工程(2)において、上記各成分以外の他の成分として、適宜に、消泡剤、レベリング剤、脱水剤、酸化防止剤等を用いることができる。イオン液体は、イオン伝導度をより向上させるため含有されるものであり、公知のものを特に制限されることなく用いることができる。また、上記粒子状ポリマー以外のポリマー、通常用いられる結着剤等を用いてもよい。 (Other additives)
In the step (2), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant and the like can be appropriately used as components other than the above-mentioned components. The ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation. Further, a polymer other than the above-mentioned particulate polymer, a commonly used binder or the like may be used.
以下、本発明の全固体二次電池用シートの好ましい製造方法に含まれる各工程について説明する。 [Manufacturing method of all-solid-state secondary battery sheet]
Hereinafter, each step included in the preferable manufacturing method of the sheet for an all-solid-state secondary battery of the present invention will be described.
この工程では、硫化物系無機固体電解質を例えば、メカニカルミリングの時間を調節することにより、体積平均粒子径1.0μm以下の硫化物系無機固体電解質を得ることができる。また、硫化物系無機固体電解質を、例えば、硫化物系固体電解質が劣化しない溶媒(硫化物系固体電解質と反応しにくい分散媒)を添加し、更に粉砕メディアの径及び回転数と時間を調整し、メカニカルミリングを行い、粉砕することによって体積平均粒子径を1.0μm以下にすることができる。用いる硫化物系無機固体電解質は、入手可能なものをもちいてもよく、例えば、上述した硫化リチウム(Li2S)及び硫化リン等の原料から合成してもよい。
硫化物系無機固体電解質の体積平均粒子径は後記実施例の項に記載の方法により測定することができる。
工程(2)に用いる(工程(1)で調整される)硫化物系無機固体電解質の体積平均粒子径は、粒子間の空隙を少なくして抵抗を低減するために、0.8μm以下が好ましく、0.7μm以下がより好ましい。体積平均粒子径の下限は、特に制限されないが、実際的には0.01μm以上であることが好ましく、0.02μm以上がより好ましく、0.05μm以上がより好ましく、0.1μm以上がより好ましく、0.3μm以上が更に好ましい。
硫化物系固体電解質の体積平均粒子径を1.0μmにすることで、固体電解質粒子間の空隙を少なくすることができる。全固体二次電池が、固体電解質粒子が密に充填された固体電解質層を具備することで、リチウムデンドライトによる短絡を生じにくくすることができる。一方、全固体二次電池が、固体電解質粒子が密に充填された電極活物質層を具備することで、イオン伝導性を向上させることができる。 <Process (1)>
In this step, for example, by adjusting the time of mechanical milling of the sulfide-based inorganic solid electrolyte, a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less can be obtained. Further, the sulfide-based inorganic solid electrolyte is added, for example, a solvent in which the sulfide-based solid electrolyte does not deteriorate (a dispersion medium that does not easily react with the sulfide-based solid electrolyte), and the diameter, rotation speed, and time of the pulverized media are further adjusted. Then, mechanical milling is performed and pulverized to reduce the volume average particle diameter to 1.0 μm or less. Sulfide-based inorganic solid electrolyte used may be using those available, for example, it may be synthesized from the above lithium sulfide (
The volume average particle size of the sulfide-based inorganic solid electrolyte can be measured by the method described in the section of Examples described later.
The volume average particle diameter of the sulfide-based inorganic solid electrolyte used in the step (2) (adjusted in the step (1)) is preferably 0.8 μm or less in order to reduce the voids between the particles and reduce the resistance. , 0.7 μm or less is more preferable. The lower limit of the volume average particle diameter is not particularly limited, but is actually preferably 0.01 μm or more, more preferably 0.02 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm or more. , 0.3 μm or more is more preferable.
By setting the volume average particle diameter of the sulfide-based solid electrolyte to 1.0 μm, the voids between the solid electrolyte particles can be reduced. Since the all-solid-state secondary battery includes a solid electrolyte layer densely packed with solid electrolyte particles, it is possible to prevent short circuits due to lithium dendrite from occurring. On the other hand, the all-solid-state secondary battery can improve the ionic conductivity by providing the electrode active material layer densely packed with solid electrolyte particles.
本発明の全固体二次電池用シートの製造方法では、上述した粒子状有機成分及び上記工程で得た体積平均粒子径1.0μm以下の硫化物系無機固体電解質を、上記粒子状有機成分の含有量が、上記硫化物系無機固体電解質及び上記粒子状有機成分の合計の含有量中、15質量%以下、好ましくは10質量%以下になるように混合する工程を行う。
この工程は、通常、上記混合比で、硫化物系無機固体電解質と粒子状有機成分とを混合して、混合物を調製する。
上記混合比の下限は、0質量%を越えている限り特に制限されず、例えば、0.1質量%以上とすることができ、0.5質量%以上が好ましい。 <Process (2)>
In the method for producing a sheet for an all-solid secondary battery of the present invention, the above-mentioned particulate organic component and the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less obtained in the above step are used as the above-mentioned particulate organic component. The step of mixing is performed so that the content is 15% by mass or less, preferably 10% by mass or less, based on the total content of the sulfide-based inorganic solid electrolyte and the particulate organic component.
In this step, a sulfide-based inorganic solid electrolyte and a particulate organic component are usually mixed at the above mixing ratio to prepare a mixture.
The lower limit of the mixing ratio is not particularly limited as long as it exceeds 0% by mass, and can be, for example, 0.1% by mass or more, preferably 0.5% by mass or more.
混合する活物質としては、シートの形態に応じて適宜に選択されるが、負極活物質は、電池容量の点で、ケイ素元素又はスズ元素を含む活物質が好ましい。
混合方法は特に制限されず、一括して混合してもよく、順次混合してもよい。混合する環境は特に制限されないが、乾燥空気下又は不活性ガス下等が挙げられる。
活物質の混合量は、特に制限されないが、上述の活物質層中における含有量と同じ範囲に設定されることが好ましい。リチウム塩の混合量は、特に制限されないが、上述の、全固体二次電池用シート中における含有量と同じ範囲に設定されることが好ましい。分散媒の混合量は特に制限されないが、上述の混合物中の含有量と同じ範囲に設定されることが好ましい。他の成分の混合量は適宜に決定される。 In step (2), the sulfide-based inorganic solid electrolyte, particulate organic components, and optionally the active material, dispersion medium, lithium salt, and any other components are mixed, for example, in various commonly used mixers. Therefore, a mixture (preferably a composition, more preferably a slurry containing a dispersion medium) can be obtained.
The active material to be mixed is appropriately selected according to the form of the sheet, but the negative electrode active material is preferably an active material containing a silicon element or a tin element in terms of battery capacity.
The mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially. The mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.
The mixing amount of the active material is not particularly limited, but is preferably set within the same range as the content in the active material layer described above. The mixing amount of the lithium salt is not particularly limited, but is preferably set within the same range as the content in the all-solid-state secondary battery sheet described above. The mixing amount of the dispersion medium is not particularly limited, but it is preferably set within the same range as the content in the above-mentioned mixture. The mixing amount of other components is appropriately determined.
本発明の全固体二次電池用シートの製造方法は、上記粒子状有機成分のガラス転移温度より20℃以上高く、上記粒子状有機成分の分解温度未満の温度において、上記粒子状有機成分の弾性率の1/10より高い圧力で、上記混合物を加圧する工程を行う。 <Process (3)>
The method for producing a sheet for an all-solid secondary battery of the present invention has an elastic modulus of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component. The step of pressurizing the mixture at a pressure higher than 1/10 of the rate is performed.
また、上記圧力は、上記粒子状有機成分の弾性率の1/7より高いことが好ましく、1/6より高いことがより好ましく、1/5より高いことがより好ましく、1/4より高いことがより好ましく、1/3より高いことが更に好ましい。一方、圧力の上限値は、特に制限されないが、通常、1500MPa以下に設定され、1200MPa以下が好ましく、1000MPa以下がより好ましい。
上記範囲の加熱温度で加圧することにより、粒子状有機成分が柔軟になり、硫化物系無機固体電解質との結着性が向上し、なおかつ、硫化物系無機固体電解質間のイオン伝導を阻害せずに、強固な固体電解質層又は電極活物質層を形成することができると考えられる。これにより、固体電解質層の抵抗の低減を実現でき、電極活物質層中、活物質の体積膨張による空隙生成を抑制することができ、電池性能を向上させることができると考えられる。 The heating temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and even more preferably 50 ° C. or higher than the glass transition temperature of the particulate organic component. On the other hand, the upper limit of the heating temperature may be lower than the decomposition temperature, but is preferably a
Further, the pressure is preferably higher than 1/7, more preferably higher than 1/6, more preferably higher than 1/5, and higher than 1/4 of the elastic modulus of the particulate organic component. Is more preferable, and higher than 1/3 is further preferable. On the other hand, the upper limit of the pressure is not particularly limited, but is usually set to 1500 MPa or less, preferably 1200 MPa or less, and more preferably 1000 MPa or less.
By pressurizing at a heating temperature in the above range, the particulate organic component becomes flexible, the binding property with the sulfide-based inorganic solid electrolyte is improved, and the ion conduction between the sulfide-based inorganic solid electrolytes is inhibited. It is considered that a strong solid electrolyte layer or electrode active material layer can be formed without. As a result, it is considered that the resistance of the solid electrolyte layer can be reduced, the formation of voids due to the volume expansion of the active material in the electrode active material layer can be suppressed, and the battery performance can be improved.
上記混合物が分散媒を含む場合、分散媒の乾燥温度は特に制限されない。下限は30℃以上が好ましく、60℃以上がより好ましく、80℃以上が更に好ましい。上限は、300℃以下が好ましく、250℃以下がより好ましく、200℃以下が更に好ましい。 The method of applying the mixture is not particularly limited and can be appropriately selected. For example, coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, bar coating coating can be mentioned.
When the mixture contains a dispersion medium, the drying temperature of the dispersion medium is not particularly limited. The lower limit is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher. The upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
このときの塗布乾燥層中の分散媒の残留量は、特に制限されないが、10~2000ppmであることが好ましく、10~1500ppmであることがより好ましく、10~1000ppmであることがより好ましく、10~500ppmであることが更に好ましく、10~200ppmであることが特に好ましい。分散媒を完全に除去しない状態で上記工程(3)を行うことにで、より固体粒子間の結着性を向上させることができる。 In the present invention, it is preferable that the dispersion medium is not completely removed in the drying step after applying the slurry. Specifically, it is preferable to heat the obtained mixture so that the dispersion medium is not completely removed, and pressurize the obtained coating dry layer.
The residual amount of the dispersion medium in the coating dry layer at this time is not particularly limited, but is preferably 10 to 2000 ppm, more preferably 10 to 1500 ppm, and even more preferably 10 to 1000 ppm. It is more preferably about 500 ppm, and particularly preferably 10 to 200 ppm. By performing the above step (3) in a state where the dispersion medium is not completely removed, the binding property between the solid particles can be further improved.
本発明に用いられる混合物が、粒子状有機成分を、体積平均粒子径1.0μm以下の硫化物系無機固体電解質及び粒子状有機成分の合計の含有量中、15質量%以下で含有することで、この混合物が分散媒を含む状態であっても、分散媒が適度に粒子状有機成分を軟化して、硫化物系無機固体電解質間の接触を良化するため、固体粒子同士の凝集を抑制することができると考えられる。さらに、この混合物を用いて、上述の加圧工程により、粒子状有機成分の分解を抑制し、また、粒子状有機成分に柔軟性を付与して、固体粒子間の結着性を高めたシートを得ることができると考えられる。体積平均粒子径を1.0μm以下の硫化物系無機固体電解質を含む固体粒子間の結着性を高めることにより、短絡を抑制することができ、また、活物質の膨張収縮時に生成する空隙の生成を抑制することができるため、全固体二次電池のサイクル特性及びレート特性を向上させることができると考えられる。 According to the method for producing an all-solid-state secondary battery sheet of the present invention, it is an all-solid-state secondary battery sheet having excellent binding properties, and exhibits excellent battery characteristics when used as a constituent layer of an all-solid-state secondary battery. An all-solid-state secondary battery can be realized. The reason is not clear, but it is presumed as follows.
The mixture used in the present invention contains the particulate organic component in an amount of 15% by mass or less based on the total content of the sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less and the particulate organic component. Even when this mixture contains a dispersion medium, the dispersion medium moderately softens the particulate organic components and improves the contact between the sulfide-based inorganic solid electrolytes, thereby suppressing aggregation of the solid particles. It is thought that it can be done. Further, using this mixture, the above-mentioned pressurizing step suppresses the decomposition of the particulate organic component, and imparts flexibility to the particulate organic component to enhance the binding property between solid particles. Is thought to be possible. Short circuits can be suppressed by enhancing the binding properties between solid particles containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less, and voids formed during expansion and contraction of the active material can be suppressed. It is considered that the cycle characteristics and rate characteristics of the all-solid secondary battery can be improved because the production can be suppressed.
本発明の全固体二次電池の製造方法は、構成層の少なくとも1層として本発明の全固体二次電池用シートの製造方法により得られる全固体二次電池用シートを組込むこと以外は、常法により製造できる。これにより、優れた電池性能を示す全固体二次電池を製造できる。以下、詳述する。 [Manufacturing method of all-solid-state secondary battery]
The method for manufacturing an all-solid-state secondary battery of the present invention is usual except that a sheet for an all-solid-state secondary battery obtained by the method for manufacturing a sheet for an all-solid-state secondary battery of the present invention is incorporated as at least one constituent layer. Can be manufactured by law. As a result, an all-solid-state secondary battery showing excellent battery performance can be manufactured. The details will be described below.
また、各層の形成方法を逆にして、負極集電体上に、負極活物質層、固体電解質層及び正極活物質層を形成し、正極集電体を重ねて、全固体二次電池を製造することもできる。 For example, a normal solid electrolyte composition containing a positive electrode active material is applied as a positive electrode material (composition for a positive electrode layer) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and a positive electrode is formed. Make a sheet. Next, the solid electrolyte layer sheet (solid electrolyte layer) obtained by the method for producing an all-solid secondary battery sheet of the present invention is superposed on the positive electrode active material layer. Further, a normal solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (composition for the negative electrode layer) on the solid electrolyte layer to form a negative electrode active material layer. By superimposing a negative electrode current collector (metal leaf) on the negative electrode active material layer, an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
Further, by reversing the forming method of each layer, a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is superposed to manufacture an all-solid secondary battery. You can also do it.
また別の方法として、次の方法が挙げられる。すなわち、本発明の全固体二次電池用シートの製造方法により、集電体上に正極活物質層を有する正極シート、基材上に固体電解質層を有する固体電解質層用シート、及び、集電体上に負極活物質層を有する負極シートを作製する。更に、正極シート及び負極シートで、基材から剥がした固体電解質層を挟むように積層する。このようにして、全固体二次電池を製造することができる。 As another method, the following method can be mentioned. That is, according to the method for producing an all-solid-state secondary battery sheet of the present invention, a positive electrode sheet having a positive electrode active material layer on a current collector, a solid electrolyte layer sheet having a solid electrolyte layer on a base material, and a current collector. A negative electrode sheet having a negative electrode active material layer on the body is produced. A solid electrolyte layer sheet is layered on the active material layer of either the positive electrode sheet or the negative electrode sheet so that the active material layer and the solid electrolyte layer are in contact with each other. After the base material is peeled off, the other of the positive electrode sheet and the negative electrode sheet is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this way, an all-solid-state secondary battery can be manufactured.
As another method, the following method can be mentioned. That is, according to the method for producing an all-solid-state secondary battery sheet of the present invention, a positive electrode sheet having a positive electrode active material layer on a current collector, a solid electrolyte layer sheet having a solid electrolyte layer on a base material, and a current collector. A negative electrode sheet having a negative electrode active material layer on the body is produced. Further, the positive electrode sheet and the negative electrode sheet are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, an all-solid-state secondary battery can be manufactured.
プレス時間は短時間(例えば数時間以内)で高い圧力をかけてもよいし、長時間(1日以上)かけて中程度の圧力をかけてもよい。全固体二次電池用シート以外、例えば全固体二次電池の場合には、中程度の圧力をかけ続けるために、全固体二次電池の拘束具(ネジ締め圧等)を用いることもできる。
プレス圧はシート面等の被圧部に対して均一であっても異なる圧であってもよい。
プレス圧は被圧部の面積又は膜厚に応じて変化させることができる。また同一部位を段階的に異なる圧力で変えることもできる。
プレス面は平滑であっても粗面化されていてもよい。 The atmosphere during pressurization is not particularly limited, and may be any of air, dry air (dew point −20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas) and the like.
The pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more). In the case of an all-solid-state secondary battery other than the all-solid-state secondary battery sheet, for example, in the case of an all-solid-state secondary battery, an all-solid-state secondary battery restraint (screw tightening pressure, etc.) can be used in order to continue applying a medium pressure.
The press pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
The press pressure can be changed according to the area or film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
The pressed surface may be smooth or roughened.
本発明の全固体二次電池用シートの製造方法で製造される全固体二次電池用シートは、本発明に用いられる混合物を加圧成形して得られる層を有している。このシートが有する層は、体積平均粒子径1.0μm以下の硫化物系無機固体電解質及び粒子状有機成分を含有しており、シートの形態に応じて活物質を含有し、適宜に、導電助剤、他の成分を含有していてもよい。この層において、硫化物系無機固体電解質と粒子状有機成分との存在状態については、その詳細は明らかではないが、上述のように結着している状態が挙げられる。
本発明の全固体二次電池用シートは、全固体二次電池の構成層を形成しうるシート状成形体であって、その用途に応じて種々の態様を含む。 [Sheet for all-solid-state secondary battery]
The all-solid-state secondary battery sheet produced by the method for producing an all-solid-state secondary battery sheet of the present invention has a layer obtained by pressure-molding the mixture used in the present invention. The layer of this sheet contains a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less and a particulate organic component, contains an active material depending on the form of the sheet, and appropriately conducts assistance. It may contain an agent and other components. The details of the existence state of the sulfide-based inorganic solid electrolyte and the particulate organic component in this layer are not clear, but the state of being bound as described above can be mentioned.
The sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
本発明の固体電解質層用シートとして、例えば、基材上に、固体電解質層と、保護層とをこの順で有するシートが挙げられる。
基材としては、固体電解質層を支持できるものであれば特に限定されず、後述する集電体で説明する材料、有機材料、無機材料等のシート体(板状体)等が挙げられる。有機材料としては、各種ポリマー等が挙げられ、具体的には、ポリエチレンテレフタレート、ポリプロピレン、ポリエチレン、セルロース等が挙げられる。無機材料としては、例えば、ガラス、セラミック等が挙げられる。 The sheet for the solid electrolyte layer of the present invention may be a sheet having a solid electrolyte layer, and even a sheet in which the solid electrolyte layer is formed on the base material does not have a base material and is formed from the solid electrolyte layer. It may be a sheet that is present. The sheet for the solid electrolyte layer may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
Examples of the sheet for the solid electrolyte layer of the present invention include a sheet having a solid electrolyte layer and a protective layer in this order on a base material.
The base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-shaped body) such as an organic material and an inorganic material. Examples of the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose. Examples of the inorganic material include glass, ceramic and the like.
本発明の全固体二次電池用シートを用いて全固体二次電池を製造すると、優れた電池性能を示す。 In the all-solid-state secondary battery sheet of the present invention, at least one of the solid electrolyte layer and the active material layer is produced by the method for producing the all-solid-state secondary battery sheet of the present invention, and the solid particles in this layer are firmly bonded to each other. It is tied up. Further, in the electrode sheet, the active material layer produced by the method for producing an all-solid-state secondary battery sheet of the present invention is firmly bonded to the current collector. In the present invention, an increase in interfacial resistance between solid particles can be effectively suppressed. Therefore, the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet capable of forming a constituent layer of an all-solid-state secondary battery.
When an all-solid-state secondary battery is manufactured using the sheet for an all-solid-state secondary battery of the present invention, excellent battery performance is exhibited.
本発明の全固体二次電池は、正極活物質層と、この正極活物質層に対向する負極活物質層と、正極活物質層及び負極活物質層の間に配置された固体電解質層とを有する。正極活物質層は、好ましくは正極集電体上に形成され、正極を構成する。負極活物質層は、好ましくは負極集電体上に形成され、負極を構成する。
負極活物質層、正極活物質層及び固体電解質層の少なくとも1つの層は、本発明の全固体二次電池用シートの製造方法で作製され、全ての層が本発明の全固体二次電池用シートの製造方法で作製されることがより好ましい。なお、活物質層又は固体電解質層が本発明の全固体二次電池用シートの製造方法で作製されない場合、通常の活物質層又は固体電解質層を用いることができる。
負極活物質層、固体電解質層及び正極活物質層の厚さは、それぞれ、特に制限されない。各層の厚さは、一般的な全固体二次電池の寸法を考慮すると、それぞれ、10~1,000μmが好ましく、20μm以上500μm未満がより好ましい。本発明の全固体二次電池においては、正極活物質層及び負極活物質層の少なくとも1層の厚さが、50μm以上500μm未満であることが更に好ましい。
正極活物質層及び負極活物質層は、それぞれ、固体電解質層とは反対側に集電体を備えていてもよい。 [All-solid-state secondary battery]
The all-solid secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer. Have. The positive electrode active material layer is preferably formed on the positive electrode current collector to form the positive electrode. The negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
At least one of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is produced by the method for producing an all-solid-state secondary battery sheet of the present invention, and all the layers are for the all-solid-state secondary battery of the present invention. It is more preferable that it is produced by the method for producing a sheet. When the active material layer or the solid electrolyte layer is not produced by the method for producing a sheet for an all-solid secondary battery of the present invention, a normal active material layer or a solid electrolyte layer can be used.
The thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited. The thickness of each layer is preferably 10 to 1,000 μm, more preferably 20 μm or more and less than 500 μm, respectively, in consideration of the dimensions of a general all-solid-state secondary battery. In the all-solid-state secondary battery of the present invention, the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 μm or more and less than 500 μm.
The positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
本発明の全固体二次電池は、用途によっては、上記構造のまま全固体二次電池として使用してもよいが、乾電池の形態とするためには更に適当な筐体に封入して用いることが好ましい。筐体は、金属性のものであっても、樹脂(プラスチック)製のものであってもよい。金属性のものを用いる場合には、例えば、アルミニウム合金又は、ステンレス鋼製のものを挙げることができる。金属性の筐体は、正極側の筐体と負極側の筐体に分けて、それぞれ正極集電体及び負極集電体と電気的に接続させることが好ましい。正極側の筐体と負極側の筐体とは、短絡防止用のガスケットを介して接合され、一体化されることが好ましい。 [Case]
Depending on the application, the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing. Is preferable. The housing may be made of metal or resin (plastic). When a metallic material is used, for example, one made of aluminum alloy or stainless steel can be mentioned. It is preferable that the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
全固体二次電池10においては、正極活物質層、固体電解質層及び負極活物質層のいずれも本発明の全固体二次電池用シートの製造方法で作製されている。この全固体二次電池10は優れた電池性能を示す。正極活物質層4、固体電解質層3及び負極活物質層2が含有する硫化物系無機固体電解質及び粒子状有機成分は、それぞれ、互いに同種であっても異種であってもよい。
本発明において、正極活物質層及び負極活物質層のいずれか、又は、両方を合わせて、単に、活物質層又は電極活物質層と称することがある。また、正極活物質及び負極活物質のいずれか、又は両方を合わせて、単に、活物質又は電極活物質と称することがある。 (Positive electrode active material layer, solid electrolyte layer, negative electrode active material layer)
In the all-solid-state
In the present invention, either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. Further, either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
本発明において、正極集電体及び負極集電体のいずれか、又は、両方を合わせて、単に、集電体と称することがある。
正極集電体を形成する材料としては、アルミニウム、アルミニウム合金、ステンレス鋼、ニッケル及びチタンなどの他に、アルミニウム又はステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたもの(薄膜を形成したもの)が好ましく、その中でも、アルミニウム及びアルミニウム合金がより好ましい。
負極集電体を形成する材料としては、アルミニウム、銅、銅合金、ステンレス鋼、ニッケル及びチタンなどの他に、アルミニウム、銅、銅合金又はステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたものが好ましく、アルミニウム、銅、銅合金及びステンレス鋼がより好ましい。 The positive electrode
In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
As a material for forming the negative electrode current collector, in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Preferably, aluminum, copper, copper alloy and stainless steel are more preferable.
集電体の厚みは、特に制限されないが、1~500μmが好ましい。また、集電体表面は、表面処理により凹凸を付けることも好ましい。 The shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
上記のようにして製造した全固体二次電池は、製造後又は使用前に初期化を行うことが好ましい。初期化は特に制限されず、例えば、プレス圧を高めた状態で初充放電を行い、その後、全固体二次電池の一般使用圧力になるまで圧力を開放することにより、行うことができる。 <Initialization of all-solid-state secondary battery>
The all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use. The initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
本発明の全固体二次電池は種々の用途に適用することができる。適用態様には特に制限はないが、例えば、電子機器に搭載する場合、ノートパソコン、ペン入力パソコン、モバイルパソコン、電子ブックプレーヤー、携帯電話、コードレスフォン子機、ページャー、ハンディーターミナル、携帯ファックス、携帯コピー、携帯プリンター、ヘッドフォンステレオ、ビデオムービー、液晶テレビ、ハンディークリーナー、ポータブルCD、ミニディスク、電気シェーバー、トランシーバー、電子手帳、電卓、メモリーカード、携帯テープレコーダー、ラジオ、バックアップ電源などが挙げられる。その他民生用として、自動車、電動車両、モーター、照明器具、玩具、ゲーム機器、ロードコンディショナー、時計、ストロボ、カメラ、医療機器(ペースメーカー、補聴器、肩もみ機など)などが挙げられる。更に、各種軍需用、宇宙用として用いることができる。また、太陽電池と組み合わせることもできる。 [Applications for all-solid-state secondary batteries]
The all-solid-state secondary battery of the present invention can be applied to various applications. The application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
硫化物系無機固体電解質として、T.Ohtomo,A.Hayashi,M.Tatsumisago,Y.Tsuchida,S.HamGa,K.Kawamoto,Journal of Power Sources,233,(2013),pp231-235およびA.Hayashi,S.Hama,H.Morimoto,M.Tatsumisago,T.Minami,Chem.Lett.,(2001),pp872-873の非特許文献を参考にして、Li-P-S系ガラスを合成した。
具体的には、アルゴン雰囲気下(露点-70℃)のグローブボックス内で、硫化リチウム(Li2S、Aldrich社製、純度>99.98%)2.42g及び五硫化二リン(P2S5、Aldrich社製、純度>99%)3.90gをそれぞれ秤量し、メノウ製乳鉢に投入し、メノウ製乳棒を用いて、5分間混合した。Li2S及びP2S5の混合比は、モル比でLi2S:P2S5=75:25とした。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを66g投入し、上記の硫化リチウムと五硫化二リンの混合物全量を投入し、アルゴン雰囲気下で容器を密閉した。遊星ボールミルP-7(商品名、フリッチュ社製)に容器をセットし、温度25℃で、回転数510rpmで20時間メカニカルミリングを行うことで、黄色粉体の硫化物系無機固体電解質(以下、「LPS」と記載する。)6.10gを得た。このLPSの体積平均粒子径(SEa)は、0.8μmであった。
後記表1~3に記載の、上記LPS以外のLPSは、上記と同様にして合成した。なお、SEaは、メカニカルミリングを行う時間を調節することにより調整した。 <Sulfide-based inorganic solid electrolyte synthesis>
As a sulfide-based inorganic solid electrolyte, T.I. Ohtomo, A. Hayashi, M. et al. Tassumisago, Y. et al. Tsuchida, S.A. HamGa, K.K. Kawamoto, Journal of Power Sources, 233, (2013), pp231-235 and A. et al. Hayashi, S.A. Hama, H.M. Morimoto, M.D. Tassumisago, T. et al. Minami, Chem. Lett. , (2001), pp872-873, Li-PS-based glass was synthesized with reference to non-patent documents.
Specifically, 2.42 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%) and diphosphorus pentasulfide (P 2 S) in a glove box under an argon atmosphere (dew point -70 ° C). 5. Aldrich, purity> 99%) 3.90 g was weighed, placed in an agate mortar, and mixed for 5 minutes using an agate mortar. The mixing ratio of Li 2 S and P 2 S 5 was Li 2 S: P 2 S 5 = 75: 25 in terms of molar ratio.
66 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), the entire amount of the above mixture of lithium sulfide and diphosphorus pentasulfide was put into the container, and the container was sealed under an argon atmosphere. By setting the container on the planetary ball mill P-7 (trade name, manufactured by Fritsch) and performing mechanical milling at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours, a sulfide-based inorganic solid electrolyte of yellow powder (hereinafter referred to as “2”) Described as "LPS") 6.10 g was obtained. The volume average particle diameter (SEa) of this LPS was 0.8 μm.
LPS other than the above LPS described in Tables 1 to 3 below were synthesized in the same manner as described above. SEa was adjusted by adjusting the time for performing mechanical milling.
上記SEaは以下のようにして測定した。
上記LPSを、ヘプタンを用いて20mLサンプル瓶中で希釈することにより、1質量%の分散液を調製した。希釈後の分散試料は、1kHzの超音波を10分間照射し、その直後に試験に使用した。この分散液試料を用い、レーザ回折/散乱式粒度分布測定装置LA-920(商品名、HORIBA社製)を用いて、温度25℃で測定用石英セルを使用してデータ取り込みを50回行い、体積平均粒子径を得た。その他の詳細な条件等は必要によりJIS Z 8828:2013「粒子径解析-動的光散乱法」の記載を参照した。1水準につき5つの試料を作製しその平均値を採用した。 (Measurement method of SEa)
The SEa was measured as follows.
The LPS was diluted with heptane in a 20 mL sample bottle to prepare a 1 mass% dispersion. The diluted dispersed sample was irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it was used for the test. Using this dispersion sample, data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell. The volume average particle size was obtained. For other detailed conditions, etc., refer to the description of JIS Z 8828: 2013 "Particle size analysis-Dynamic light scattering method" as necessary. Five samples were prepared for each level and the average value was adopted.
(アクリルラテックス1の調製)
還流冷却管、ガス導入コックを付した300mL三口フラスコにトルエン(富士フイルム和光純薬社製)を115g注ぎ、流速200mL/minにて窒素ガスを10分間導入した後に、95℃に昇温した。別容器にて調製した液(メタクリル酸エチル(富士フイルム和光純薬社製)を25.7g、メタクリル酸ドデシル(富士フイルム和光純薬社製)を51.8g、アクリル酸(富士フイルム和光純薬社製)を0.8g、V-601(商品名、油溶性アゾ重合開始剤、富士フイルム和光純薬社製)を1.5g混合した液)を2時間かけて滴下した。滴下完了後、V-601を0.8g添加した。その後95℃で1時間攪拌した後、グリシジルメタクリレート(東京化成工業社製)2.96g、トリエチルアミン(富士フイルム和光純薬社製)0.29g、2,2,6,6-テトラメチルピペリジン 1-オキシル(東京化成工業社製)0.01gを添加し、100℃で3時間攪拌した。室温まで冷却し、トルエン1Lで希釈後メタノールに再沈殿させた後、デカンテーションを行い80℃で乾燥することでマクロモノマーB-1を得た。
200mL3つ口フラスコに、マクロモノマーB-1溶液を13.7gとヘプタン20gを入れ、攪拌しながら80℃に昇温した(溶液A)。別途、50mLメスシリンダーに2-ヒドロキシエチルアクリレートを12.8g、こはく酸モノ(2-アクリロイルオキシエチル)を3.0g、V-601 0.61gを加えて攪拌し、均一に溶解させた(溶液B)。溶液Aに溶液Bを80℃で2時間かけて滴下し、その後さらに80℃で2時間、90℃で2時間攪拌して重合した後、室温まで冷却した。こうして、アクリルラテックス1を得た。アクリルラテックス1中のアクリルポリマーの分解温度は192℃であった。また、アクリルラテックス1中のアクリルポリマーの質量平均分子量は65,000、体積平均粒子径は120nmであった。 <Synthesis of particulate organic components (particulate polymers)>
(Preparation of acrylic latex 1)
115 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was poured into a 300 mL three-necked flask equipped with a reflux condenser and a gas introduction cock, nitrogen gas was introduced at a flow rate of 200 mL / min for 10 minutes, and then the temperature was raised to 95 ° C. Liquid prepared in a separate container (25.7 g of ethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 51.8 g of dodecyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) 0.8 g of (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.5 g of V-601 (trade name, oil-soluble azo polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added dropwise over 2 hours. After the dropping was completed, 0.8 g of V-601 was added. Then, after stirring at 95 ° C. for 1 hour, 2.96 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.29 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2,6,6-tetramethylpiperidin 1- 0.01 g of oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, diluted with 1 L of toluene, reprecipitated in methanol, decanted and dried at 80 ° C. to obtain macromonomer B-1.
13.7 g of macromonomer B-1 solution and 20 g of heptane were placed in a 200 mL three-necked flask, and the temperature was raised to 80 ° C. with stirring (solution A). Separately, 12.8 g of 2-hydroxyethyl acrylate, 3.0 g of monosuccinate (2-acryloyloxyethyl) and 0.61 g of V-601 were added to a 50 mL graduated cylinder and stirred to uniformly dissolve (solution). B). Solution B was added dropwise to solution A at 80 ° C. for 2 hours, and then the mixture was further stirred at 80 ° C. for 2 hours and 90 ° C. for 2 hours for polymerization, and then cooled to room temperature. In this way,
200mL3つ口フラスコに、2,4-ペンタンジオール 1.58gと、NISSO-PB GI-1000(商品名、日本曹達社製)1.86gとを加え、THF(テトラヒドロフラン)80gに溶解した。この溶液に、ジフェニルメタンジイソシアネート4.2gを加えて60℃で撹拌し、均一に溶解させた。得られた溶液に、ネオスタンU-600(商品名、日東化成社製)290mgを添加して60℃で6時間攪伴し、粘性ポリマー溶液を得た。このポリマー溶液にメタノール0.8gを加えてポリマー末端を封止して、重合反応を停止し、ポリマーの20質量%THF溶液(ポリマー溶液)を得た。
次に、上記で得られたポリマー溶液を350rpmで撹拌しながら、2,6-ジメチル-4-ヘプタノン110gを1時間かけて滴下し、ウレタンラテックス1の乳化液を得た。乳化液を40mPa、40℃で1時間減圧することで、THFを除去した。こうして、ウレタンラテックス1(固形分10質量%)を得た。ウレタンラテックス1中のポリウレタンの分解温度は230℃であった。ウレタンラテックス1中のポリウレタンの質量平均分子量は35,000、体積平均粒子径は80nmであった。
ウレタンラテックス1中のポリウレタンのウレタン価数は、4.39mmol/gであった。ウレタン価数は以下のようにして算出した。 (Preparation of urethane latex 1)
1.58 g of 2,4-pentanediol and 1.86 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Corporation) were added to a 200 mL three-necked flask and dissolved in 80 g of THF (tetrahydrofuran). 4.2 g of diphenylmethane diisocyanate was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it. To the obtained solution, 290 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours to obtain a viscous polymer solution. 0.8 g of methanol was added to this polymer solution to seal the polymer ends, and the polymerization reaction was stopped to obtain a 20 mass% THF solution (polymer solution) of the polymer.
Next, 110 g of 2,6-dimethyl-4-heptanone was added dropwise over 1 hour while stirring the polymer solution obtained above at 350 rpm to obtain an emulsion of
The urethane valence of polyurethane in
粒子状有機成分1molのウレタン結合量(mmol)は、1H-NMRにより測定した。 Urethane value = Urethane bond amount (mmol) of 1 mol of particulate organic component / mass (g) of 1 mol of organic component
The urethane bond amount (mmol) of 1 mol of the particulate organic component was measured by 1 1 H-NMR.
200mL3つ口フラスコに、2,4-ペンタンジオール 0.74gと、NISSO-PB GI-1000(商品名、日本曹達社製)13.86gとを加え、THF(テトラヒドロフラン)80gに溶解した。この溶液に、ジフェニルメタンジイソシアネート4.2gを加えて60℃で撹拌し、均一に溶解させた。得られた溶液に、ネオスタンU-600(商品名、日東化成社製)290mgを添加して60℃で6時間攪伴し、粘性ポリマー溶液を得た。このポリマー溶液にメタノール0.8gを加えてポリマー末端を封止して、重合反応を停止し、ポリマーの20質量%THF溶液(ポリマー溶液)を得た。
次に、上記で得られたポリマー溶液を350rpmで撹拌しながら、2,6-ジメチル-4-ヘプタノン110gを1時間かけて滴下し、ウレタンラテックス2の乳化液を得た。乳化液を40mPa、40℃で1時間減圧することで、THFを除去した。こうして、ウレタンラテックス2(固形分10質量%)を得た。ウレタンラテックス2中のポリウレタンの分解温度は230℃であった。ウレタンラテックス2中のポリウレタンの質量平均分子量は45,000、体積平均粒子径は30nmであった。ウレタンラテックス2中のポリウレタンのウレタン価数は、1.8mmol/gであった。 (Preparation of urethane latex 2)
0.74 g of 2,4-pentanediol and 13.86 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Corporation) were added to a 200 mL three-necked flask and dissolved in 80 g of THF (tetrahydrofuran). 4.2 g of diphenylmethane diisocyanate was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it. To the obtained solution, 290 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours to obtain a viscous polymer solution. 0.8 g of methanol was added to this polymer solution to seal the polymer ends, and the polymerization reaction was stopped to obtain a 20 mass% THF solution (polymer solution) of the polymer.
Next, 110 g of 2,6-dimethyl-4-heptanone was added dropwise over 1 hour while stirring the polymer solution obtained above at 350 rpm to obtain an emulsion of
ジフェニルメタンジイソシアネートの代わりにジシクロヘキシルメタンジイソシアネート(東京化成社製)を用いる以外はウレタンラテックス2と同様にしてウレタンラテックス3(固形分10質量%)を得た。ウレタンラテックス3中のポリウレタンの分解温度は220℃であった。ウレタンラテックス3中のポリウレタンの質量平均分子量は42,000、体積平均粒子径は70nmであった。ウレタンラテックス3中のポリウレタンのウレタン価数は、1.7mmol/gであった。 (Preparation of urethane latex 3)
Urethane latex 3 (
ガラス転移点は、上記アクリルラテックス1及びウレタンラテックス1~3の乾燥試料を用いて、示差走査熱量計(SIIテクノロジー社製、DSC7000)を用いて下記の条件で測定した。乾燥試料は、合成したラテックス液をアルミニウムパンの上に10g入れ、120℃で2時間加熱し、溶媒を留去後、真空状態で6時間乾燥した。測定は同一の試料で二回実施し、二回目の測定結果を採用した。
・測定室内の雰囲気:窒素(60mL/min)
・昇温速度:3℃/min
・測定開始温度:-100℃
・測定終了温度:200℃
・試料パン:アルミニウム製パン
・測定試料の質量:5mg
・Tgの算定:DSCチャートの下降開始点と下降終了点の中間温度の小数点以下を四捨五入することでTgを算定した。 (Measuring method of Tg (° C))
The glass transition point was measured under the following conditions using a differential scanning calorimeter (DSC7000 manufactured by SII Technology Co., Ltd.) using the dried samples of
・ Atmosphere in the measurement room: Nitrogen (60 mL / min)
・ Temperature rise rate: 3 ° C / min
・ Measurement start temperature: -100 ° C
・ Measurement end temperature: 200 ° C
・ Sample pan: Aluminum pan ・ Mass of measurement sample: 5 mg
-Calculation of Tg: Tg was calculated by rounding off the decimal point of the intermediate temperature between the descending start point and the descending end point of the DSC chart.
上記アクリルラテックス1及びウレタンラテックス1~3を、温度120℃で2時間真空乾燥させて粒子状ポリマーを得た。この粒子状ポリマーについて、窒素雰囲気下で熱質量示差熱同時測定(Tg-DTA)を行った。粒子状ポリマーの測定開始時の質量を100%として、質量が10%減少した(90%となった)温度を分解温度とした。
上記熱質量・示差熱同時測定には、示差走査熱量計(SIIテクノロジー社製、DSC7000)を用いた。 (Measurement of decomposition temperature of particulate polymer)
The
A differential scanning calorimeter (DSC7000, manufactured by SII Technology Co., Ltd.) was used for the simultaneous measurement of thermal mass and differential heat.
JIS K 7127(1999)に準拠して25℃で引張弾性率を測定した。
上記調製した粒子状有機成分の分散液をテフロン(登録商標)フィルム上にキャストして、100μm膜厚の粒子状ポリマーの単独膜を作製した。この単独膜を1cm×2cmに切り出し、30mm/minで引張試験(チャック間伸び)を行い、引張弾性率を決定した。 (Measuring method of elastic modulus (MPa))
The tensile modulus was measured at 25 ° C. according to JIS K 7127 (1999).
The above-prepared dispersion of particulate organic components was cast on a Teflon (registered trademark) film to prepare a single film of a particulate polymer having a film thickness of 100 μm. This single film was cut into 1 cm × 2 cm, and a tensile test (elongation between chucks) was performed at 30 mm / min to determine the tensile elastic modulus.
上記SEaの測定において、LPSの分散液に代えて上記調製した粒子状有機成分の分散液を用いたこと以外は、上記SEaの測定と同様にして、粒子状有機成分の体積平均粒子径Baを測定した。 (Measuring method of volume average particle diameter (μm))
In the measurement of SEa, the volume average particle diameter Ba of the particulate organic component was determined in the same manner as in the measurement of SEa, except that the dispersion of the particulate organic component prepared above was used instead of the dispersion of LPS. It was measured.
露点-60℃のドライルームにおいて、以下のようにして固体電解質組成物を調製し、この固体電解質組成物を用いて固体電解質層用シートS-1の作製を作製した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを180個投入し、上記で合成した体積平均粒子径0.8μmのLPS 4.6g、アクリルラテックス1 固形分が0.4gとなる量、及び、ジイソブチルケトン 12.0gを投入した後、この容器を遊星ボールミルP-7(商品名、フリッチュ社製)にセットし、温度25℃、回転数350rpmで2時間攪拌した。
なお、この工程の前後でLPSは体積平均粒子径を維持していた。 <Preparation of sheet S-1 for solid electrolyte layer>
A solid electrolyte composition was prepared as follows in a dry room having a dew point of −60 ° C., and a sheet S-1 for a solid electrolyte layer was prepared using this solid electrolyte composition.
180 zirconia beads having a diameter of 5 mm are put into a 45 mL container made of zirconia (manufactured by Fritsch), and the LPS having a volume average particle diameter of 0.8 μm synthesized above is 4.6 g and the
Before and after this step, LPS maintained the volume average particle size.
塗布乾燥層から500mgの試料を切り出し、トルエンで抽出し、含まれるジイソブチルケトンの量をガスクロマトグラフィで計量したところ、質量基準で100ppm含有していた。
試料を切り出した部分を除くようにして、上記塗布乾燥層から15mm四方の試料を切り出し、この試料を下記条件1で加圧し、固体電解質層用シートS-1を作製した。 The slurry of the solid electrolyte composition thus obtained is applied onto an aluminum foil having a thickness of 20 μm by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 150 μm after drying. Then, it was dried at 100 ° C. for 1 hour to form a coating dry layer.
A 500 mg sample was cut out from the coated dry layer, extracted with toluene, and the amount of diisobutyl ketone contained was measured by gas chromatography and found to contain 100 ppm on a mass basis.
A 15 mm square sample was cut out from the coating dry layer so as to remove the cut-out portion of the sample, and this sample was pressurized under the
熱プレス機(アズワン社製小型熱プレス機H300-15(商品名))を用いて下記表1に記載の加熱温度及び圧力で5分間加圧した。
-条件2-
ホットプレートを下記表1に記載の温度にして、15mm四方の試料を15分間乗せた後、この試料を、プレス機により下記表1に記載の圧力で5分間加圧した。 -Condition 1-
A heat press machine (small heat press machine H300-15 (trade name) manufactured by AS ONE Corporation) was used to pressurize for 5 minutes at the heating temperature and pressure shown in Table 1 below.
-Condition 2-
The hot plate was brought to the temperature shown in Table 1 below, and a 15 mm square sample was placed on the hot plate for 15 minutes, and then this sample was pressed by a press at the pressure shown in Table 1 below for 5 minutes.
なお、加圧の条件として条件1を採用した固体電解質層用シートの作製は、ドライルーム(露点-60℃)内で行った。一方、加圧の条件として条件2を採用した固体電解質層用シートの作製は、グローブボックス(Ar雰囲気化、露点-60℃)内で行った。
後述の正極シート及び負極シートの作製も同様である。 In the preparation of the solid electrolyte layer sheet S-1, the composition and pressurization conditions were changed to the compositions and conditions shown in Table 1 below, but in the same manner as in the solid electrolyte layer sheet S-1, Table 1 below. A sheet for a solid electrolyte layer other than the sheet for a solid electrolyte layer S-1 shown in the above was produced.
The solid electrolyte layer sheet in which
The same applies to the production of the positive electrode sheet and the negative electrode sheet described later.
条件2で作製したシートが有する塗布乾燥層の分散媒体の含有量は、条件2のホットプレートに乗せた後、加圧前の含有量である。
粒子状有機成分の含有量は固形分の含有量である。 [Note to table]
The content of the dispersion medium of the coating dry layer contained in the sheet produced under
The content of the particulate organic component is the content of the solid content.
露点-60℃のドライルームにおいて、以下のようにして正極用組成物を調製し、この正極用組成物を用いて正極シートSS-1を作製した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを180個投入し、上記で合成したLPS 7.8g、アクリルラテックス1 固形分が0.3gとなる量、及び、ジイソブチルケトン 10g投入した。この容器を遊星ボールミルP-7(商品名、フリッチュ社製)にセットし、温度25℃、回転数350rpmで6時間攪拌を続けた。このようにして、固体電解質組成物を調製した。
この固体電解質組成物9.1gに対し、NMC 3.5g、アセチレンブラック 0.15g、及び、ジイソブチルケトン 5gをジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを180個とあわせて投入し、この容器を遊星ボールミルP-7にセットし、温度25℃、回転数50rpmで5分間攪拌して正極用組成物を得た。 <Preparation of positive electrode sheet SS-1>
A positive electrode composition was prepared as follows in a dry room having a dew point of −60 ° C., and a positive electrode sheet SS-1 was prepared using this positive electrode composition.
180 zirconia beads with a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), and 7.8 g of LPS synthesized above, an amount of
For 9.1 g of this solid electrolyte composition, 3.5 g of NMC, 0.15 g of acetylene black, and 5 g of diisobutylketone are combined with 180 zirconia beads having a diameter of 5 mm in a 45 mL container (Fritsch) made of zirconia. The container was charged, set in a planetary ball mill P-7, and stirred at a temperature of 25 ° C. and a rotation speed of 50 rpm for 5 minutes to obtain a positive electrode composition.
塗布乾燥層から500mgの試料を切り出し、トルエンで抽出し、含まれるジイソブチルケトンの量をガスクロマトグラフィで計量したところ、質量基準で80ppm含有していた。
試料を切り出した部分を除くようにして、上記塗布乾燥層から15mm四方の試料を切り出し、この試料を、上記条件1で5分間加圧し、正極シートSS-1を作製した。 The slurry of the positive electrode composition thus obtained is placed on an aluminum foil having a thickness of 20 μm by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) and the mass of the positive electrode composition after drying is 1 cm. It was applied so as to be 20 mg per two and dried at 120 ° C. for 1 hour to form a coating dry layer.
A 500 mg sample was cut out from the coated dry layer, extracted with toluene, and the amount of diisobutyl ketone contained was measured by gas chromatography and found to contain 80 ppm on a mass basis.
A 15 mm square sample was cut out from the coating dry layer so as to remove the cut-out portion of the sample, and this sample was pressed for 5 minutes under the
NMC:LiNi1/3Co1/3Mn1/3O2
条件2で作製したシートが有する塗布乾燥層の分散媒体の含有量は、条件2のホットプレートに乗せた後、加圧前の含有量である。
粒子状有機成分の含有量は固形分の含有量である。 [Note to table]
NMC: LiNi 1/3 Co 1/3 Mn 1/3 O 2
The content of the dispersion medium of the coating dry layer contained in the sheet produced under
The content of the particulate organic component is the content of the solid content.
露点-60℃のドライルームにおいて、以下のようにして負極用組成物を調製し、この負極用組成物を用いて負極シートFS-1を作製した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを180個投入し、上記で合成したLPS 8.6g、アクリルラテックス1 固形分が0.4gとなる量、及び、ジイソブチルケトン 10gを投入した。この容器を遊星ボールミルP-7(商品名、フリッチュ社製)にセットし、温度25℃、回転数350rpmで6時間攪拌した。
更に、容器に、Si粉末(Alfa Aesar社製 Silicon Powder 体積平均粒子径1~5μm) 10.0g及びアセチレンブラック 1.0gを投入し、更にジイソブチルケトン 5gを投入した。この容器を遊星ボールミルP-7(商品名、フリッチュ社製)にセットし、温度25℃、回転数100rpmで5分間攪拌して負極用組成物を得た。
このようにして得た負極用組成物のスラリーを20μmのステンレス箔の上にアプリケーター(商品名:SA-201ベーカー式アプリケータ、テスター産業社製)により負極用組成物の乾燥後質量が1cm2辺り3.3mgになるように塗布し100℃で1時間乾燥して塗布乾燥層を形成した。
塗布乾燥層から500mgの試料を切り出し、トルエンで抽出し、含まれるジイソブチルケトンの量をガスクロマトグラフィで計量したところ、80ppm含有していた。
試料を切り出した部分を除くようにして、上記塗布乾燥層から15mm四方の試料を切り出し、この試料を、上記条件1で5分間加圧し、負極シートFS-1を作製した。 <Manufacturing of negative electrode sheet FS-1>
A composition for a negative electrode was prepared as follows in a dry room having a dew point of −60 ° C., and a negative electrode sheet FS-1 was prepared using this composition for a negative electrode.
180 zirconia beads with a diameter of 5 mm were placed in a 45 mL container made of zirconia (manufactured by Fritsch), and 8.6 g of LPS synthesized above, an amount of
Further, 10.0 g of Si powder (Silicon Powder volume
The slurry of the negative electrode composition thus obtained is placed on a 20 μm stainless steel foil with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) and the mass of the negative electrode composition after drying is 1 cm 2. Around 3.3 mg was applied and dried at 100 ° C. for 1 hour to form a coating dry layer.
A 500 mg sample was cut out from the coated dry layer, extracted with toluene, and the amount of diisobutyl ketone contained was measured by gas chromatography and found to contain 80 ppm.
A 15 mm square sample was cut out from the coating dry layer so as to remove the cut-out portion of the sample, and this sample was pressurized for 5 minutes under the
条件2で作製したシートが有する塗布乾燥層の分散媒体の含有量は、条件2のホットプレートに乗せた後、加圧前の含有量である。
FS-8は、真空下で行い、他は大気圧化で加熱した。
FS-9は、条件1の加圧時間を5分間から2時間に変更して行った。
粒子状有機成分の含有量は固形分の含有量である。 [Note to table]
The content of the dispersion medium of the coating dry layer contained in the sheet produced under
FS-8 was carried out under vacuum, and the others were heated at atmospheric pressure.
FS-9 was carried out by changing the pressurizing time of
The content of the particulate organic component is the content of the solid content.
以下のようにして、図1に示す層構成を有する全固体二次電池T1を作製した。
負極シートFS-1の負極活物質層上に、固体電解質層用シートS-3を、負極活物質層と固体電解質層とが接するようにして重ね、このようにして得た積層体を室温化100MPaでプレスした後、固体電解質層用シートS-3が有するアルミニウム箔を剥離した。この積層体に、固体電解質層と正極活物質層とが接するようにして、正極シートSS-3を有するシートを重ね、このようにして得た積層体を150MPa120℃で熱プレスした後、更に400MPaで5分加圧することで全固体電池用積層体を作製した。
この全固体二次電池用積層体を用いて図2に示す全固体二次電池13を作製した。
全固体二次電池用積層体12を直径10mmの円板状に切り出した。直径10mmの全固体二次電池積層体をスペーサーとワッシャー(図2において図示せず)を組み込んだ、ステンレス製の2032型コインケース11に入れ、2032型コインケース11をかしめる(拘束圧:0.1MPa)ことで、全固体二次電池13を作製した。 <Manufacturing of all-solid-state secondary battery T1>
An all-solid-state secondary battery T1 having the layer structure shown in FIG. 1 was produced as follows.
The solid electrolyte layer sheet S-3 was laminated on the negative electrode active material layer of the negative electrode sheet FS-1 so that the negative electrode active material layer and the solid electrolyte layer were in contact with each other, and the laminate thus obtained was brought to room temperature. After pressing at 100 MPa, the aluminum foil contained in the solid electrolyte layer sheet S-3 was peeled off. A sheet having the positive electrode sheet SS-3 is laminated on this laminate so that the solid electrolyte layer and the positive electrode active material layer are in contact with each other, and the laminate thus obtained is hot-pressed at 150 MPa 120 ° C. and then further 400 MPa. A laminate for an all-solid-state battery was prepared by pressurizing with.
The all-solid-state
The laminate 12 for an all-solid-state secondary battery was cut out into a disk shape having a diameter of 10 mm. An all-solid-state secondary battery laminate with a diameter of 10 mm is placed in a stainless steel 2032
上記で作製した、全固体二次電池を用い、30℃の環境下、充電電流値0.1mAおよび放電電流値0.1mAの条件で4.3V~3.0Vの充放電を1回繰り返した。
その後、サイクル試験として、25℃の環境下、充放電電流値0.6mAの条件で4.3V~3.0Vの充放電を繰り返す試験を実施した。
1サイクル目の放電容量と20サイクル目の放電容量とを測定し、下記評価基準に従って評価した。本試験において「C」以上が合格である。 -Cycle property test-
Using the all-solid-state secondary battery produced above, charging / discharging of 4.3V to 3.0V was repeated once under the conditions of a charging current value of 0.1 mA and a discharging current value of 0.1 mA in an environment of 30 ° C. ..
Then, as a cycle test, a test was carried out in which charging / discharging of 4.3V to 3.0V was repeated under the condition of a charging / discharging current value of 0.6 mA in an environment of 25 ° C.
The discharge capacity in the first cycle and the discharge capacity in the 20th cycle were measured and evaluated according to the following evaluation criteria. In this test, "C" or higher passes.
A 放電容量維持率:70%以上99%以下
B 放電容量維持率:60%以上70%未満
C 放電容量維持率:50%以上60%未満
D 放電容量維持率:35%以上50%未満
E 放電容量維持率:35%未満 -Evaluation criteria-
A Discharge capacity retention rate: 70% or more and 99% or less B Discharge capacity retention rate: 60% or more and less than 70% C Discharge capacity retention rate: 50% or more and less than 60% D Discharge capacity retention rate: 35% or more and less than 50% E Discharge Capacity retention rate: less than 35%
上記で作製した、全固体二次電池を用い、30℃の環境下、充電電流値0.1mAおよび放電電流値0.1mAの条件で4.3V~3.0Vの充放電を1回行った。
その後、レート特性試験として、25℃の環境下、充電電流値0.2mAの条件で4.3Vまで充電した後、放電電流値0.2mAで3.0Vまで放電を実施した(1サイクル目)。
次に、25℃の環境下、充電電流値0.2mAの条件で4.3Vまで充電した後、放電電流値1mAで3.0Vまで放電を実施した(2サイクル目)。 -Rate characteristic test-
Using the all-solid-state secondary battery produced above, charging / discharging of 4.3V to 3.0V was performed once under the conditions of a charging current value of 0.1 mA and a discharging current value of 0.1 mA in an environment of 30 ° C. ..
Then, as a rate characteristic test, the battery was charged to 4.3 V under the condition of a charging current value of 0.2 mA in an environment of 25 ° C., and then discharged to 3.0 V at a discharge current value of 0.2 mA (first cycle). ..
Next, in an environment of 25 ° C., the battery was charged to 4.3 V under the condition of a charging current value of 0.2 mA, and then discharged to 3.0 V at a discharge current value of 1 mA (second cycle).
A 55%以上99%
B 35%以上55%未満
C 25%以上35%未満
D 10%以上25%未満
E 10%未満 -Evaluation criteria-
A 55% or more 99%
B 35% or more and less than 55% C 25% or more and less than 35
直径10mmの円板状に切り出した上記全固体二次電池用積層体のステンレス箔を下にして机の上におき、縦1cm、横5cmテープ(商品名:NITTO TAPE P-222、日東電工社製)を全固体二次電池用積層体のアルミニウム箔上に貼り付けた。このテープをアルミニウム箔に対して90°の角度で引張速度30mm/minで剥離し(90°剥離試験)、全固体二次電池用積層体の箔と構成層間、又は、構成層間で剥離が生じた際のテープを引っ張る強度を下記評価基準にあてはめ評価した。
上記剥離が生ぜずテープだけが剥がれた場合、別の全固体二次電池用積層体を用いて再度評価を行った。
本試験において「D」以上が合格である。
-評価基準-
A 0.3N/cm以上
B 0.2N/cmを越え0.3N/cm未満
C 0.1N/cm以上0.2N/cm以下
D 0.01N/cm以上0.1N/cm未満
E テープを付着させただけで割れ又は欠け発生した。
F 試験前から割れ又は欠けが発生した。 -Cohesion test-
Place the above-mentioned all-solid-state secondary battery laminate stainless foil cut out into a disk shape with a diameter of 10 mm on a desk with the stainless foil facing down, and place it on a desk with a length of 1 cm and a width of 5 cm. Was affixed onto the aluminum foil of the all-solid-state secondary battery laminate. This tape is peeled off from the aluminum foil at a tensile speed of 30 mm / min at an angle of 90 ° (90 ° peeling test), and peeling occurs between the foil of the all-solid-state secondary battery laminate and the constituent layers or between the constituent layers. The tensile strength of the tape at that time was evaluated by applying it to the following evaluation criteria.
When the above peeling did not occur and only the tape was peeled off, another evaluation was performed using another all-solid-state secondary battery laminate.
In this test, "D" or higher is a pass.
-Evaluation criteria-
A 0.3N / cm or more B More than 0.2N / cm and less than 0.3N / cm C 0.1N / cm or more and 0.2N / cm or less D 0.01N / cm or more and less than 0.1N / cm E Tape Cracks or chips occurred just by adhering.
Cracks or chips occurred before the F test.
これに対して、本発明の全固体二次電池用シートの製造方法により得たシートを少なくとも1層有する全固体二次電池は、電池特性及び結着性がいずれも合格であった。 As is clear from Table 4, the all-solid-state secondary battery having no sheet obtained by the method for producing a sheet for an all-solid-state secondary battery of the present invention failed in both battery characteristics and binding properties.
On the other hand, the all-solid-state secondary battery having at least one layer of the sheet obtained by the method for producing a sheet for an all-solid-state secondary battery of the present invention was acceptable in terms of battery characteristics and binding properties.
2 負極活物質層
3 固体電解質層
4 正極活物質層
5 正極集電体
6 作動部位
10 全固体二次電池
11 2032型コインケース
12 全固体二次電池用積層体
13 全固体二次電池(コイン電池) 1 Negative electrode
Claims (13)
- 体積平均粒子径1.0μm以下の硫化物系無機固体電解質及び粒子状有機成分を含有する全固体二次電池用シートの製造方法であって、
粒子状有機成分及び体積平均粒子径1.0μm以下の硫化物系無機固体電解質を含有し、前記粒子状有機成分の含有量が、前記硫化物系無機固体電解質及び前記粒子状有機成分の合計の含有量中、15質量%以下である混合物を、前記粒子状有機成分のガラス転移温度より20℃以上高く、該粒子状有機成分の分解温度未満の温度において、該粒子状有機成分の弾性率の1/10より高い圧力で、加圧すること
を含む、全固体二次電池用シートの製造方法。 A method for producing a sheet for an all-solid secondary battery containing a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less and a particulate organic component.
It contains a particulate organic component and a sulfide-based inorganic solid electrolyte having a volume average particle diameter of 1.0 μm or less, and the content of the particulate organic component is the sum of the sulfide-based inorganic solid electrolyte and the particulate organic component. A mixture having a content of 15% by mass or less is the elastic coefficient of the particulate organic component at a temperature higher than the glass transition temperature of the particulate organic component by 20 ° C. or more and lower than the decomposition temperature of the particulate organic component. A method for producing a sheet for an all-solid secondary battery, which comprises pressurizing at a pressure higher than 1/10. - 前記弾性率が150MPa以上である、請求項1に記載の全固体二次電池用シートの製造方法。 The method for manufacturing an all-solid-state secondary battery sheet according to claim 1, wherein the elastic modulus is 150 MPa or more.
- 前記硫化物系無機固体電解質及び前記粒子状有機成分が、体積平均粒子径について下記式(I)で規定する関係を満たす、請求項1又は2に記載の全固体二次電池用シートの製造方法。
Ba<SEa<20Ba 式(I)
式中、SEaは前記硫化物系無機固体電解質の体積平均粒子径であり、Baは前記粒子状有機成分の体積平均粒子径である。 The method for producing an all-solid-state secondary battery sheet according to claim 1 or 2, wherein the sulfide-based inorganic solid electrolyte and the particulate organic component satisfy the relationship defined by the following formula (I) with respect to the volume average particle diameter. ..
Ba <SEa <20Ba formula (I)
In the formula, SEa is the volume average particle size of the sulfide-based inorganic solid electrolyte, and Ba is the volume average particle size of the particulate organic component. - 前記混合物を構成する硫化物系無機固体電解質を1.0μm以下の体積平均粒子径に調整する工程を含む、請求項1~3のいずれか1項に記載の全固体二次電池用シートの製造方法。 The production of a sheet for an all-solid secondary battery according to any one of claims 1 to 3, which comprises a step of adjusting the sulfide-based inorganic solid electrolyte constituting the mixture to a volume average particle diameter of 1.0 μm or less. Method.
- 前記混合物が活物質を含有する、請求項1~4のいずれか1項に記載の全固体二次電池用シートの製造方法。 The method for producing an all-solid-state secondary battery sheet according to any one of claims 1 to 4, wherein the mixture contains an active material.
- 前記活物質が負極活物質である、請求項5に記載の全固体二次電池用シートの製造方法。 The method for manufacturing an all-solid-state secondary battery sheet according to claim 5, wherein the active material is a negative electrode active material.
- 前記負極活物質がケイ素元素又はスズ元素を含む、請求項6に記載の全固体二次電池用シートの製造方法。 The method for producing an all-solid-state secondary battery sheet according to claim 6, wherein the negative electrode active material contains a silicon element or a tin element.
- 前記ガラス転移温度が30℃以上である、請求項1~7のいずれか1項に記載の全固体二次電池用シートの製造方法。 The method for manufacturing an all-solid-state secondary battery sheet according to any one of claims 1 to 7, wherein the glass transition temperature is 30 ° C. or higher.
- 前記混合物の加圧を前記ガラス転移温度より50℃以上高い温度で行う、請求項1~8のいずれか1項に記載の全固体二次電池用シートの製造方法。 The method for producing a sheet for an all-solid-state secondary battery according to any one of claims 1 to 8, wherein the pressurization of the mixture is performed at a temperature higher than the glass transition temperature by 50 ° C. or more.
- 前記混合物が分散媒を含有し、前記製造方法は、前記加圧の前に前記混合物を、分散媒を完全に除去させずに加熱する工程を含む、請求項1~9のいずれか1項に記載の全固体二次電池用シートの製造方法。 The production method comprises the step of heating the mixture without completely removing the dispersion medium before the pressurization, wherein the mixture contains a dispersion medium, according to any one of claims 1 to 9. The method for manufacturing a sheet for an all-solid-state secondary battery described.
- 正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池の製造方法であって、
請求項1~10のいずれか1項に記載の全固体二次電池用シートの製造方法により得た全固体二次電池用シートを、前記正極活物質層、前記固体電解質層及び前記負極活物質層のうちの少なくとも1層として組込む工程を含む、全固体二次電池の製造方法。 A method for manufacturing an all-solid-state secondary battery, which comprises a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
The all-solid-state secondary battery sheet obtained by the method for producing an all-solid-state secondary battery sheet according to any one of claims 1 to 10 is used as the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material. A method for manufacturing an all-solid-state secondary battery, which comprises a step of incorporating as at least one of the layers. - 請求項1~10いずれか1項に記載の全固体二次電池用シートの製造方法により得た全固体二次電池用シート。 An all-solid-state secondary battery sheet obtained by the method for manufacturing an all-solid-state secondary battery sheet according to any one of claims 1 to 10.
- 正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池であって、
前記正極活物質層、前記固体電解質層及び前記負極活物質層の少なくとも1つの層が、請求項12に記載の全固体二次電池用シートで構成した層である全固体二次電池。 An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
An all-solid-state secondary battery in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the sheet for an all-solid secondary battery according to claim 12.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2013125858A (en) * | 2011-12-14 | 2013-06-24 | Dexerials Corp | Connection method, connection structure, anisotropic conductive film and method for producing the anisotropic conductive film |
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