WO2021066101A1 - 負極用活物質層及びその製造方法、蓄電デバイス負極用電極合剤ペースト、蓄電デバイス用負極、ならびに蓄電デバイス - Google Patents
負極用活物質層及びその製造方法、蓄電デバイス負極用電極合剤ペースト、蓄電デバイス用負極、ならびに蓄電デバイス Download PDFInfo
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- H—ELECTRICITY
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- 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
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Definitions
- the present invention relates to an active material layer for a negative electrode and a method for manufacturing the same, an electrode mixture paste for a negative electrode of a power storage device, a negative electrode for a power storage device, and a power storage device.
- a power storage device is a device that can store electrical energy when needed and extract energy when needed.
- a typical storage device includes a secondary battery such as a lithium ion secondary battery, which is widely used as a drive power source for mobile information terminals.
- a secondary battery such as a lithium ion secondary battery
- development of higher capacity storage devices has been promoted in anticipation of development in industrial applications such as electric / hybrid vehicles and unmanned aerial vehicles.
- One of the attempts is to increase the charge / discharge capacity by using, for example, silicon or tin having a large amount of lithium occlusion per unit volume or an alloy containing these as the negative electrode active material of the power storage device. ..
- an active material having a large charge / discharge capacity such as silicon, tin, or an alloy containing these causes a very large volume change with charge / discharge.
- a general-purpose binder such as polyvinylidene fluoride or a rubber-based resin is used for the electrode containing such an active material, the active material layer is destroyed or the interface between the current collector and the active material layer is peeled off due to the volume change. There is a problem that the cycle characteristics of the power storage device are deteriorated.
- Non-Patent Document 1 a negative electrode focusing on the shape of the active material layer has also been studied.
- the negative electrode of Patent Document 6 can maintain the discharge capacity ratio of 0.9 in the cycle characteristics based on the second discharge / charge capacity when it is repeated 10 times.
- the porosity By simply specifying the porosity, the capacity is high enough to withstand practical use in industrial applications, and excellent cycle characteristics have not been achieved at the same time.
- Electrode mixture paste for negative electrode of power storage device negative electrode active material layer, negative electrode for power storage device. And to provide a power storage device.
- the present invention particularly relates to the following items.
- 1. Carbon particles, Negative electrode active material layer containing silicon as a component, silicon particles capable of occluding and releasing lithium ions, and a polyimide binder which is an organic polymer having an imide bond in the main chain and having a porosity of more than 40%. .. 2.
- Item 2. The negative electrode active material layer according to Item 1, wherein the silicon-based particles have an average particle size of less than 10 ⁇ m. 3.
- IIItem 2. The negative electrode active material layer according to Item 1 or 2, wherein the carbon particles are graphite particles. 4.
- the negative electrode active material layer according to any one of Items 1 to 4, wherein the precursor for forming the polyimide binder is a polyamic acid containing a repeating unit represented by the following chemical formula (I).
- A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, a tetravalent group obtained by removing a carboxyl group from an aliphatic tetracarboxylic acid, and a carboxyl group obtained by removing a carboxyl group from an alicyclic tetracarboxylic acid.
- B is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine. And one or more selected from the group consisting of divalent groups obtained by removing the amino group from the alicyclic diamine.
- the negative electrode active material layer which is one of the embodiments of the present invention, is a negative electrode active material containing carbon particles and silicon-based particles capable of occluding and releasing lithium ions, and a polyimide which is an organic polymer having an imide bond in the main chain. Contains a system binder.
- the negative electrode active material layer of the present invention is characterized by having a porosity of more than 40%.
- the polyimide-based binder contained in the negative electrode active material layer of the present invention is an organic polymer having an imide bond in the main chain.
- the polyimide-based binder is not particularly limited, and a known polyimide-based binder used for the electrode binder may be used. Specific examples thereof include organic polymers having an imide bond in the main chain such as polyimide, polyamide-imide, and polyesterimide.
- a substance for forming a "polyimide-based binder" in the negative electrode active material layer is called a "precursor", and a substance containing a "precursor", a solvent, and if necessary, other compounds is called “precursor”. It is called “precursor composition”.
- the precursor composition is sometimes called a "varnish”.
- the "precursor” is an organic polymer having an imide bond in the main chain, or a polymer or compound capable of forming an organic polymer having an imide bond in the main chain by heating or a chemical reaction.
- Examples of the "precursor” which is an organic polymer having an imide bond in the main chain include polyimide, polyamide-imide, polyesterimide, etc., and these are generally used in the form of a precursor composition (varnish) dissolved in a solvent. Will be done. These may be the same as the organic polymer which is a "polyimide-based binder", and may have a small imidization ratio or a small molecular weight.
- polyamic acid examples include polyamic acid and the like. These are also generally used in the form of a precursor composition (varnish) dissolved in a solvent.
- the polyamic acid may have a part of the amic acid moiety imidized.
- the organic polymer which is a "polyimide-based binder” does not have to be completely imidized.
- Such a polyimide-based binder or precursor may be used alone or in combination of two or more.
- the "precursor” or “precursor composition” may also be referred to as a "binder”, and in the following description, the "precursor” may also be referred to as a "polydeoxide-based binder”.
- the term is used whether it refers to a precursor or a polyimide binder in the negative electrode active material layer.
- a polyamic acid particularly a polyamic acid containing a repeating unit represented by the following chemical formula (I) is preferable.
- A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, a tetravalent group obtained by removing a carboxyl group from an aliphatic tetracarboxylic acid, and a carboxyl group obtained by removing a carboxyl group from an alicyclic tetracarboxylic acid.
- B is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- B is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- B is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- divalent groups obtained by removing the amino group from the alicyclic diamine is
- a polyimide containing a repeating unit represented by the following chemical formula (II) is preferable.
- X 1 is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, a tetravalent group obtained by removing a carboxyl group from an aliphatic tetracarboxylic acid, and a carboxyl group obtained by removing a carboxyl group from an alicyclic tetracarboxylic acid.
- Y 1 is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- Y 1 is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- Y 1 is a divalent group obtained by removing an amino group from an aromatic diamine, and a divalent group obtained by removing an amino group from an aliphatic diamine.
- Y 1 is a divalent group obtained by
- Precursors for forming such polyimide binder has the formula B structure or chemical formula of the tetracarboxylic acid component and the formula having X 1 structure
- a diamine component having one structure and other components as essential components can be prepared by a known method, if necessary.
- the tetracarboxylic acid component is not particularly limited, and can be appropriately selected in consideration of the porosity of the target negative electrode active material layer and the characteristics of the desired power storage device.
- Examples of the tetracarboxylic acid component include 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,2',.
- the diamine component is not particularly limited and can be appropriately selected in consideration of the porosity of the target negative electrode active material layer and the characteristics of the desired power storage device.
- Examples of the diamine component include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,4-toluenediamine, and 3,3'-dihydroxy-4,4.
- Aromatic diamines such as'-diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, 2,4-diaminotoluene, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,3,5,6-tetrafluoro-1,4-diaminobenzene, 2,4,5,6-tetrafluoro-1,3-diaminobenzene, 2,3,5,6-tetrafluoro-1,4 -Benzene (dimethaneamine), 2,2'-difluoro (1,1'-biphenyl) -4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, 2,2-bis (4-aminophenyl) hexa Fluoropropane, halogen-substituted diamines such as 4,4'-oxybis (2,3,5,6-tetraflu
- precursor products examples include UPIA (registered trademark) -AT, UPIA (registered trademark) -ST, UPIA (registered trademark) -NF, UPIA (registered trademark) of Ube Industries, Ltd. LB and the like can be mentioned.
- the molar ratio [tetracarboxylic acid component / diamine component] of the tetracarboxylic acid component and / or the diamine component constituting the polyamic acid and / or polyimide used in the present invention is approximately equimolar, specifically 0.95 to 1.05. It can be preferably set to be 0.97 to 1.03. By setting the molar ratio within this range, the molecular weight of the obtained polyimide is high, and it is often possible to secure toughness when used as a binder.
- the polyamic acid and / or polyimide used in the present invention has a logarithmic viscosity of 0.2 or more, preferably 0.4 or more, more preferably 0.6 or more, as measured at a temperature of 30 ° C.
- the weight average molecular weight determined by gel permeation chromatography is preferably 1,000 to 1,000,000, particularly preferably 5,000 to 500,000. Specifically, the weight average molecular weight is, for example, 1,000 or more, preferably 5,000 or more, more preferably 7,500 or more, still more preferably 9,000 or more, for example, 1,000,000 or less, preferably 1,000,000 or less.
- the polyamic acid and / or polyimide has a sufficiently high molecular weight that can exert its function even in a small amount.
- Examples of products (polyimide precursor composition; varnish) containing polyamic acid and / or polyimide having the above molecular weight include UPIA (registered trademark) -LB-1001 and UPIA (registered trademark) -LB of Ube Industries, Ltd. -2001 and the like can be mentioned.
- the polyamic acid can be easily prepared by reacting a tetracarboxylic acid component and a diamine component in a solvent according to a known method.
- the polyimide-based binder used in the present invention is polyimide
- the polyimide is preferably added with a tetracarboxylic acid component to a solution in which a diamine component is dissolved in a solvent at one time or in multiple steps, and heating, catalyst, or chemistry.
- a method of performing polymerization (imidization reaction) by adding an imidizing agent or the like is preferable.
- the amount of the polyimide binder blended is within a specific range of the porosity of the negative electrode active material layer.
- the amount may be any amount that does not hinder the formation, for example, 0.5% by mass to 30% by mass of the polyimide-based binder (precursor solid content) with respect to the total solid content of the electrode mixture paste for the negative electrode of the power storage device. It is by mass%, preferably 1% by mass or more and 25% by mass or less.
- the upper limit can be further preferably less than 20% by mass, further preferably less than 10% by mass, still more preferably less than 5% by mass.
- the present invention it is possible to sufficiently exert the binder function with a small amount of binder compounded (solid content), and as a result, the effects of the present application such as high discharge capacity and excellent cycle characteristics can be obtained. It is presumed that the use of a polyamic acid and / or polyimide having a high molecular weight is one of the reasons for the excellent effect in the present application.
- the solid content of the precursor means the mass when completely imidized.
- the negative electrode active material layer of the present invention contains carbon particles and silicon-based particles.
- the carbon particles in the present invention are not particularly limited as long as they are usually added to the negative electrode active material layer of a lithium ion battery or the like, and are, for example, graphite such as natural graphite and artificial graphite, and acetylene black and carbon black. And so on.
- graphite particles such as natural graphite and artificial graphite are preferable, and among them, artificial graphite can be preferably used.
- carbon particles may be used alone or in combination of two or more.
- the silicon-based particles in the present invention are particles that contain silicon as a component and can occlude and release lithium ions.
- Examples of the silicon-based particles include silicon, a silicon metal composite (including an alloy of silicon and another metal), silicon oxide, a silicon-silicon dioxide composite, and the like, and these can be used alone. Also, two or more types may be used.
- the shape of the negative electrode active material (including carbon particles and silicon-based particles; the same applies hereinafter) is not particularly limited, and may be any shape such as an indefinite shape, a spherical shape, and a fibrous shape.
- the average particle size of the negative electrode active material can be appropriately adjusted according to the type of particles used as the negative electrode active material.
- the average particle size is not particularly limited, and is preferably 0.1 ⁇ m to 20 ⁇ m, particularly preferably 1 ⁇ m to 15 ⁇ m, and further preferably 5 ⁇ m to 15 ⁇ m.
- the average particle size is not particularly limited, but is preferably less than 10 ⁇ m, and from the viewpoint of ensuring better cycle characteristics, particularly 5 ⁇ m or less, further 3 ⁇ m or less, particularly. It is preferably 1 ⁇ m or less.
- the average particle size is, for example, 0.01 ⁇ m or more.
- Each of the negative electrode active materials having such an average particle size may consist of one type, or may have an average particle size prepared by mixing two or more types.
- the average particle size is a value relating to the primary particles of the negative electrode active material, and means the average particle size of the carbon particle powder and the silicon-based particle powder, and is measured by, for example, a laser diffraction type particle size distribution measuring device. Can be done.
- the average particle size may be confirmed from a scanning electron microscope (SEM) image on the surface of the negative electrode after preparing the negative electrode using the negative electrode active material.
- SEM scanning electron microscope
- the particle size refers to the longest part (major axis) of the particles.
- the negative electrode active material can be used in an appropriate combination of the components, shapes and / or average particle diameters of the carbon particles according to the target charge / discharge capacity and other characteristics of the power storage device. Further, as the negative electrode active material, the components, shapes and / or average particle diameters of the silicon-based particles can be appropriately combined and used according to the target charge / discharge capacity and other characteristics of the power storage device.
- the mixing ratio of the carbon particles and the silicon-based particles in the negative electrode active material is not particularly limited as long as a specific porosity can be obtained when forming the negative electrode active material layer, and the discharge charge capacity or cycle is not particularly limited. It may be set appropriately in consideration of the characteristics of the power storage device such as the characteristics. For example, when the mass ratio of carbon particles: silicon particles is 97 to 70: 3 to 30, and further 95 to 80: 5 to 20, a synergistic effect may be exhibited, which is preferable. When two or more types of silicon-based particles are contained, the total amount thereof is defined as the blending amount of the silicon-based particles. Similarly, when two or more types of carbon particles are contained, the total amount thereof is taken as the blending amount of the carbon particles.
- the negative electrode active material of the present invention may contain other active materials other than carbon particles and silicon-based particles, if necessary.
- active materials known active materials other than carbon particles and silicon-based particles can be used, and examples thereof include metals such as tin, germanium, antimony silver, copper and nickel, and particles such as alloys thereof. be able to.
- the average particle size of these other active materials is not particularly limited, but is preferably 5 ⁇ m or less.
- the mixing ratio of the negative electrode active material (carbon particles and silicon-based particles) and other active materials is not particularly limited, and can be added as appropriate in consideration of charge / discharge capacity and other characteristics of the power storage device.
- the amount of the other active material added is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and the other active material is added. It is also preferable that it does not contain a substance.
- the content of the negative electrode active material in the negative electrode active material layer is not particularly limited as long as it functions as the negative electrode active material layer. Usually, it is 0.1 to 1000 times, preferably 1 to 1000 times, more preferably 5 to 1000 times, still more preferably 10 to 1000 times, based on the mass, the above-mentioned polyimide-based binder.
- the upper limit is preferably 500 times or less, more preferably 100 times or less, and further preferably 50 times or less. If the amount of the negative electrode active material is too large, the negative electrode active material is not sufficiently bound to the current collector and easily falls off. On the other hand, if the amount of the negative electrode active material is too small, the negative electrode active material layer formed on the current collector has many inactive portions, and the function as the negative electrode for the power storage device may be insufficient.
- the present invention is characterized in that the porosity of the negative electrode active material layer is larger than 40%. It is preferably 42% or more.
- the porosity is at least 70% or less, preferably 60% or less, and more preferably 50% or less.
- the porosity in the present invention refers to the apparent density of the negative electrode active material layer and the individual components constituting the negative electrode active material layer (for example, the negative electrode active material (silicon-based particles), the polyimide-based binder, and any material (others). It is a value calculated from the true density (specific gravity) and the blending amount of (active material, polymer binder, etc.)). Specifically, it can be calculated by the following formula 1.
- the negative electrode active material (true density DA1 (g / cm 3 )) is WA1 mass%
- the other active material (true density DA2 (g / cm 3 )) is WA2 mass%
- the polyimide binder (true density).
- other polymeric binder (true density D B2 (g / cm 3) ) of W B2 wt% apparent density of the negative electrode active material layer obtained by blending the N (g / The porosity (%) in the case of cm 3) is calculated from the following formula.
- a polymer-based binder other than the above-mentioned polyimide-based binder may be contained.
- a polymer-based binder is not particularly limited as long as it does not inhibit the functions of the polyimide-based binder and the negative electrode active material, and is an anionic type such as poly (meth) acrylic acid, polysulfonic acid, and salts thereof.
- Water-soluble cellulose derivatives such as polymers, carboxyalkyl celluloses and hydroxyalkyl celluloses, polyvinyl alcohols, polyalkylene glycols, polyvinylpyrrolidones, salts thereof, and water-soluble polymers such as alginates, acrylic resins, synthetic rubbers, polyamides and silicone-based resins. (Including silicone oil) and the like can be mentioned. Further, the present invention is not limited to these, and known electrode binders can also be used.
- the polymer binder other than the polyimide binder one kind or two or more kinds can be appropriately used according to the function to be given to the negative electrode active material layer, the power storage device and the like. Further, depending on the solvent to be used, a water-soluble polymer can be selected if it is an aqueous solvent system, or a polymer that is soluble in an organic solvent if it is an organic solvent system.
- the content of the polymer-based binder other than the polyimide-based binder (solid content of the precursor) can be appropriately set according to the intended purpose. For example, the amount of the other polymer-based binder is 0 to 1000 parts by mass (10 times the amount) with respect to 100 parts by mass of the polyimide-based binder (solid content of the precursor).
- the amount of the other polymer binder is 50 parts by mass or less, preferably 20 parts by mass or less, and it is also preferable that the polymer binder other than the polyimide binder is not contained at all (0 parts by mass). Further, in different embodiments, the amount of the other polymer-based binder is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, for example, with respect to 100 parts by mass of the polyimide-based binder (solid content of the precursor). It may be used in an amount of 300 parts by mass or less.
- the negative electrode active material layer of the present invention contains carbon particles, it is not necessary to add a conductive auxiliary agent separately from the carbon particles, but it may also contain a conductive auxiliary agent if necessary.
- a conductive auxiliary agent a conventionally known conductive auxiliary agent can be used, and one type or two or more types can be used depending on the characteristics of the target negative electrode active material layer and the power storage device. ..
- the conductive auxiliary agent is not particularly limited as long as it is a conventionally known conductive auxiliary agent, and for example, a metallic conductive auxiliary agent such as silver, copper, nickel, or an alloy thereof can be used.
- additives can be added to the negative electrode active material layer of the present invention, if necessary. As other additives, it can be used as long as the effects of the present invention are not impaired, and specifically, a catalyst (for example, an amine compound or an imidazole compound); a chemical imidizing agent (for example, an acid such as acetic anhydride).
- a catalyst for example, an amine compound or an imidazole compound
- a chemical imidizing agent for example, an acid such as acetic anhydride.
- Amine compounds such as anhydrides, pyridines and isoquinolins); Antioxidants (eg, phenol-based, phosphorus-based antioxidants); Light stabilizers (eg, hindered amine-based stabilizers); Antistatic agents (eg, surfactants, etc.) Carbon, metal oxides); plasticizers (eg ester-based plastics, epoxy or vegetable oils); oil-soluble solvents (eg 1-acetonafton, acetophenone, benzylacetone, methylacetophenone, dimethylacetophenone, propiophenone, valerophenone, anisole) , Methyl benzoate, benzyl benzoate); Defoamers (eg, zinc compounds, lead compounds, diphenylamines, etc., adipic acid, ethanolamine and monoethanolamine, ethylene glycol monoethyl ether, trimethylamine, nonylphenol, hexamethylenediamine, penta Erislithol, etc.,
- the thickness of the negative electrode active material layer of the present invention can be appropriately set according to the characteristics and shape of the target negative electrode and power storage device. For example, it can be about 1 ⁇ m to 300 ⁇ m, preferably 10 ⁇ m or more.
- the thickness of the negative electrode active material layer is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less.
- Electrode mixture paste for power storage device negative electrode is used for forming the above-mentioned negative electrode active material layer.
- the electrode mixture paste for the negative electrode of the power storage device contains a negative electrode active material, a polyimide-based binder, and other optional components. As each of these components, the same components as those disclosed in the above section of the negative electrode active material layer may be used. Further, the electrode mixture paste for the negative electrode of the power storage device of the present invention may contain various additives as needed.
- the electrode mixture paste for the negative electrode of the power storage device of the present invention may contain a solvent, if necessary.
- a solvent it can be appropriately selected depending on the target power storage device, electrode mixture paste and the like, and for example, an organic solvent, an aqueous solvent (water or a solvent containing water), or a mixture thereof can be used.
- a solvent used for preparing a polyimide-based binder polyamic acid, polyimide resin, etc.
- a solvent used for preparing a polyimide-based binder can be preferably used.
- the organic solvent is not particularly limited, but for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N.
- -Amid solvent such as vinyl-2-pyrrolidone, cyclic ester solvent such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethylene carbonate, propylene Carbonate solvent such as carbonate, glycol solvent such as triethylene glycol, phenol solvent such as phenol, o-cresol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1,3- Examples thereof include dimethyl-2-imidazolidinone, sulforane, dimethyl sulfoxide and the like.
- alcohol solvents such as methanol and ethanol
- ester solvents such as butyl acetate, ethyl acetate, isobutyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, butyl benzoate, ethyl benzoate, and methyl benzoate
- a general preparation method can be adopted.
- a polyimide binder is used with a negative electrode in an appropriate temperature range (preferably 10 ° C. to 60 ° C.).
- Examples include a method of mixing active materials.
- the method for producing the negative electrode active material layer which is one of the embodiments of the present invention, is not particularly limited as long as the target negative electrode active material layer can be produced.
- One example is a method of forming a negative electrode active material layer by casting or applying an electrode mixture paste for a negative electrode of a power storage device on a current collector and heat-treating it.
- the polyamic acid can be easily converted into polyimide by heat treatment or chemical treatment such as an imidizing agent.
- a method for producing the negative electrode active material layer will be described in detail with reference to this example.
- the current collector used in the present invention an electron conductor that does not cause a general chemical change can be used.
- the material forming these current collectors include aluminum, copper, copper alloy, iron, stainless steel, nickel, titanium, etc., and carbon on the surface of aluminum, copper, copper alloy, iron, and stainless steel. Those treated with nickel, titanium, silver or the like (thin films formed) can also be used. Among them, aluminum, copper, copper alloy, nickel-plated steel, stainless steel and the like can be preferably used.
- the current collector As the shape of the current collector, a foil-like (sheet-like) shape is usually used, but a net, a punched body, a porous body, a molded body of a fiber group, etc. may be appropriately used depending on the target power storage device. Can be used. Further, the current collector may have irregularities on the surface by surface treatment.
- the thickness of the current collector is not particularly limited, and can usually be 1 ⁇ m to 500 ⁇ m.
- metal foils such as copper foil, stainless steel foil, and nickel foil can be preferably used as the current collector, and among them, copper foil such as electrolytic copper foil and rolled copper foil can be preferably used. ..
- the thickness of these metal foils is not particularly limited, and is usually 5 to 50 ⁇ m, preferably 9 to 18 ⁇ m.
- the surface of the foil may be roughened or rust-proofed from the viewpoint of improving adhesiveness.
- a conductive adhesive layer may be laminated on the foil surface.
- the conductive adhesive layer can be formed by blending conductive particles such as graphite with an organic polymer compound.
- a method of applying the electrode mixture paste for the negative electrode of the power storage device on the current collector a method of continuously applying by roll-to-roll or a method of applying in sheets can be adopted.
- the coating device for example, a die coater, a multi-layer die coater, a gravure coater, a comma coater, a reverse roll coater, a doctor blade coater and the like can be used.
- the heat treatment removes the solvent contained in the electrode mixture paste for the negative electrode of the power storage device, melts or imidizes the polyimide binder, and integrates with other components (for example, the negative electrode active material) that form the negative electrode active material layer. It is preferable to carry out the operation under the condition that the current collector and the negative electrode active material layer can be adhered to each other. For example, it is preferable to perform the heat treatment at a temperature equal to or higher than the melting point of the polyimide binder to be used, and if necessary, under pressure. The heat treatment may be performed only once or may be performed a plurality of times.
- the heat treatment temperature is not particularly limited as long as it can produce a negative electrode active material layer, and the type of polyimide binder (precursor) contained in the electrode mixture paste for the negative electrode of the power storage device to be used, the type of solvent, etc. It can be set as appropriate according to.
- the heat treatment temperature is, for example, preferably 80 ° C. to 350 ° C., more preferably 100 ° C. to 300 ° C., and particularly preferably 120 ° C. to 250 ° C. If the heat treatment temperature is lower than 80 ° C, it may take a long time to remove the solvent, and it is not preferable because the melting is insufficient and the imidization reaction is slowed down. It is not preferable because the binder and / or the polymer-based binder is deteriorated. In the heat treatment, the temperature may be raised stepwise in multiple stages in order to prevent foaming and powdering.
- the heat treatment time is not particularly limited as long as it can produce a desired negative electrode active material layer, but can be set in the range of, for example, 3 minutes to 48 hours. Within the above range, the imidization reaction and the removal of the solvent can be sufficiently carried out, and it is preferable from the viewpoint of productivity. During this time, most of the solvent is removed, and the polyamic acid becomes substantially polyimide by the imidization reaction.
- a pressurizing step may be added. For example, it may be pressurized before the heat treatment, may be pressurized after the heat treatment, or may be pressurized at the same time as the heat treatment. When the heat treatment is performed a plurality of times, pressurization may be performed during the heat treatment.
- the specific pressurizing conditions and pressurizing means are not particularly limited, and examples thereof include a method of pressing with a linear pressure of 100 to 2000 kg / cm using a roll press machine.
- the porosity of the negative electrode active material layer should be appropriately adjusted according to the types and the like of the constituent components such as the polyimide binder and the negative electrode active material, and the necessary pressurizing conditions and the like of each constituent component should also be appropriately adjusted. The porosity is appropriately controlled so as to have a desired value in consideration of the type and the like.
- the porosity which is one of the constituent requirements of the present invention, cannot be unequivocally determined, but the porosity tends to decrease as the applied pressure is increased. Therefore, if the manufacturing conditions are adjusted using this tendency as an index. Good. It is also possible to make fine adjustments under detailed conditions such as heat shrinkage and crosslink density.
- the capacity retention rate calculated by (discharge capacity after cycle test) ⁇ is preferably more than 75%. It is more preferably 80% or more, further preferably 90% or more, and most preferably 95% or more. Further, when evaluated under the same conditions, the initial charge / discharge efficiency calculated by (initial discharge capacity) ⁇ (initial charge capacity) is preferably more than 75%, more preferably 80% or more, still more preferably 85%. That is all.
- Negative electrode for power storage device which is one of the embodiments of the present invention, has the above-mentioned negative electrode active material layer. More specifically, it has the negative electrode active material layer of the present invention on the current collector.
- a method for manufacturing a negative electrode for a power storage device as described above, a method of forming a negative electrode active material layer on a current collector may be adopted. Further, in the negative electrode for a power storage device, one or two or more types of various functional layers may be laminated on the negative electrode active material layer depending on the mode of the power storage device.
- the power storage device which is one of the embodiments of the present invention, includes the negative electrode for a power storage device having the above-mentioned negative electrode active material layer.
- the negative electrode for a power storage device of the present invention described above can be suitably used as a power storage device according to a known method.
- the obtained negative electrode and positive electrode for a power storage device are wound into a cylindrical shape while sandwiching a separator such as a porous polyolefin body, and the cylindrical electrode body is made flat by leaving it in a cylindrical shape or by crushing it.
- a power storage device can be preferably obtained.
- the positive electrode in the present invention has a layer containing at least a positive electrode active material formed on the current collector.
- a general positive electrode active material can be used. Examples thereof include lithium-containing composite metal oxides, olivine-type lithium salts, chalcogen compounds, and manganese dioxide.
- the lithium-containing composite metal oxide is a metal oxide containing lithium and a transition metal, or a metal oxide in which a part of the transition metal in the metal oxide is replaced by a dissimilar element.
- examples of the dissimilar elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, and Mn, Al, Co, and Ni.
- lithium-containing composite metal oxides are preferable.
- the lithium-containing composite metal oxide include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , Li x Co y M 1-y O z , and Li x.
- LiMPO 4 F Li 2 MPO 4 F
- M is Na, Mg, Sc, Y , Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, V and B.
- X 0 to 1.2
- y 0 to. 0.9
- z 2.0 to 2.3
- the x value indicating the molar ratio of lithium increases or decreases depending on charging and discharging.
- LiFePO 4 can be mentioned.
- Examples of the chalcogen compound include titanium disulfide and molybdenum disulfide.
- One type of positive electrode active material can be used alone, or two or more types can be used in combination.
- As the current collector used for the positive electrode a commonly used current collector can be used.
- the non-aqueous electrolytic solution is not particularly limited as long as it is usually used for a power storage device, and a non-aqueous solvent in which a lithium salt is dissolved is preferably used.
- a non-aqueous solvent in which a lithium salt is dissolved examples include cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and dipropyl carbonate, methyl formate, methyl acetate and propionic acid.
- Aliper carboxylic acid esters such as methyl and ethyl propionate, lactones such as ⁇ -butyrolactone and ⁇ -valerolactone, and chain ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and ethoxymethoxyethane.
- chain ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and ethoxymethoxyethane.
- chain ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and ethoxymethoxyethane.
- cyclic ethers such as tetrahydrofuran and 2-methyltetraethane. These can be used alone or in combination of two or more.
- Examples of the lithium salt dissolved in a non-aqueous solvent include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCl, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 3 SO 2 ) 2 , Examples thereof include LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiB 10 Cl 10 , lower lithium aliphatic carboxylate, LiCl, LiBr, LiI, lithium chloroborane, lithium tetraphenylborate, lithium imide salt and the like. These can be used alone or in combination of two or more.
- the amount of the lithium salt dissolved in the non-aqueous solvent is not particularly limited, but is preferably 0.2 to 2 mol / L, and more preferably 0.5 to 1.5 mol / L.
- additives may be further added to the non-aqueous electrolytic solution for the purpose of improving the charge / discharge characteristics of the power storage device.
- additives include vinylene carbonate, vinylethylene carbonate, phosphazene and fluorobenzene, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glime, pyridine, hexaphosphate triamide, nitrobenzene derivative, and crown ethers. , Quaternary ammonium salt, ethylene glycol dialkyl ether and the like.
- These additives are preferably blended in an amount of about 0.5 to 10% by mass of the non-aqueous electrolytic solution.
- an insulating microporous thin film conventionally used in lithium ion batteries can be used as a separator.
- the microporous thin film preferably has a function of closing the pores at a certain temperature or higher and increasing the resistance.
- polyolefins such as polypropylene and polyethylene having excellent organic solvent resistance and hydrophobicity are preferably used.
- sheets, non-woven fabrics, woven fabrics and the like made of glass fibers and the like are also used.
- the shape of the power storage device of the present invention is not particularly limited, and for example, a coin type, a button type, a sheet type, a cylindrical type, a flat type, a square type, or the like can be applied.
- the shape of the power storage device is a coin type or a button type
- the negative electrode mixture is mainly compressed into a pellet shape and used.
- the thickness and diameter of the pellet may be determined by the size of the power storage device.
- the winding body of the electrode in the present invention does not necessarily have to be a true cylinder, and may have a prismatic shape such as a long cylinder having an elliptical cross section or a rectangle.
- the power storage device of the present invention includes a negative electrode having a high charge / discharge capacity and capable of realizing excellent cycle characteristics, its capacity is sufficient even in the so-called all-solid-state battery mode in which no electrolytic solution is used. It can be used effectively.
- Polyimide-based binder (precursor composition): UPIA (registered trademark) -LB-2001 (polyamic acid varnish manufactured by Ube Industries, Ltd. (solvent: water))
- CMC Carboxymethyl Cellulose EC: Ethylene Carbonate
- DEC Diethyl Carbonate
- This negative electrode mixture paste for a power storage device was applied onto a nickel-plated steel foil (thickness 10 ⁇ m) as a current collector, and pre-dried at 80 ° C. for 10 minutes. Then, it was roll-pressed, placed in a vacuum dryer and heat-treated at 150 ° C. for 7 hours to prepare a negative electrode for evaluation (capacity density: 3 mAh / cm 2). By changing the press line pressure, a negative electrode for evaluation having a negative electrode active material layer having a different porosity was prepared.
- Example 1 When the charge / discharge cycle characteristics of the produced evaluation battery (porousness of the negative electrode active material layer: 47%) were confirmed, the capacity retention rate after 30 cycles was 98%. The initial charge / discharge efficiency was 85%.
- Example 2 When the charge / discharge cycle characteristics of the produced evaluation battery (porousness of the negative electrode active material layer: 45%) were confirmed, the capacity retention rate after 30 cycles was 96%. The initial charge / discharge efficiency was 85%.
- Example 3 When the charge / discharge cycle characteristics of the produced evaluation battery (porousness of the negative electrode active material layer: 41%) were confirmed, the capacity retention rate after 30 cycles was 97%. The initial charge / discharge efficiency was 85%.
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Abstract
Description
1. カーボン粒子、
シリコンを成分として含み、リチウムイオンを吸蔵・放出可能なシリコン系粒子、および
主鎖にイミド結合を有する有機高分子であるポリイミド系バインダー
を含有し、多孔度が40%より大きい、負極活物質層。
2. 前記シリコン系粒子の平均粒子径が10μm未満である、上記項1に記載の負極活物質層。
3. 前記カーボン粒子が黒鉛粒子である、上記項1または2に記載の負極活物質層。
4. さらにポリイミド系バインダー以外のポリマー系バインダーを含む、上記項1~3のいずれか一項に記載の負極活物質層。
5. 前記ポリイミド系バインダーを形成するための前駆体が、下記化学式(I)で表される繰り返し単位を含むポリアミック酸である、上記項1~4のいずれか一項に記載の負極活物質層。
6. 上記項1~5のいずれか一項に記載の負極活物質層を形成するために用いられる蓄電デバイス負極用電極合剤ペースト。
7. 集電体上に、上記項6に記載の蓄電デバイス負極用電極合剤ペーストを流延または塗布し、加熱処理することによって形成される負極活物質層の製造方法。
8. 上記項1~5のいずれか一項に記載の負極活物質層を有する蓄電デバイス用負極。
9. 上記項8に記載の蓄電デバイス用負極を有する蓄電デバイス。
本発明の実施形態の一つである負極活物質層は、カーボン粒子及びリチウムイオンを吸蔵・放出可能なシリコン系粒子を含む負極活物質と、主鎖にイミド結合を有する有機高分子であるポリイミド系バインダーとを含有する。加えて、本発明の負極活物質層の多孔度は40%より大きいことが特徴である。
本発明の負極活物質層中に含有されるポリイミド系バインダーは、主鎖にイミド結合を有する有機高分子である。ポリイミド系バインダーは特には限定されず、電極バインダーに用いられる公知のポリイミド系バインダーを使用してよい。具体的には例えばポリイミド、ポリアミドイミド、ポリエステルイミド等の主鎖にイミド結合を有する有機高分子が挙げられる。また、本発明において、負極活物質層中の「ポリイミド系バインダー」を形成するための物質を、「前駆体」といい、「前駆体」と溶媒、必要によりその他の化合物を含有するものを「前駆体組成物」という。前駆体組成物は、「ワニス」とよばれることもある。
本発明の負極活物質層は、カーボン粒子及びシリコン系粒子を含む。
本発明におけるカーボン粒子は、通常、リチウムイオン電池などの負極活物質層中に添加されるものであれば特に制限されず、例えば、天然黒鉛および人造黒鉛等の黒鉛、並びに、アセチレンブラック、カーボンブラック等を挙げることができる。特に、負極活物質としてリチウムイオンを吸蔵・放出可能で貯蔵容量の大きいものが好ましく、天然黒鉛、人造黒鉛等の黒鉛粒子が好ましく、その中でも、人造黒鉛を好適に用いることができる。本発明では、カーボン粒子を単独で用いて使用してもよく、2種類以上を使用してもよい。
本発明におけるシリコン系粒子は、シリコンを成分として含み、リチウムイオンを吸蔵・放出可能な粒子である。シリコン系粒子としては、例えば、シリコン、シリコン金属複合体(シリコンと他の金属との合金を含む)、酸化シリコン、シリコン・二酸化ケイ素複合体等を挙げることができ、これらは単独で使用してもよく、2種類以上を使用してもよい。
カーボン粒子の場合、その平均粒子径は特に制限されるものではなく、例えば0.1μm~20μm、中でも1μm~15μm、さらに5μm~15μmであることが好ましい。
またシリコン系粒子の場合、その平均粒子径は特に制限されるものではないが、例えば10μm未満であることが好ましく、より優れたサイクル特性を確保する観点から、中でも5μm以下、さらに3μm以下、特に1μm以下であることが好ましい。また、平均粒子径は例えば0.01μm以上である。こうした平均粒子径を有する負極活物質は、各々、1種類からなるものであってもよいし、2種類以上のものを混ぜることにより平均粒子径を調製したものでもよい。
ここで、平均粒子径とは、負極活物質の1次粒子に関する値であって、カーボン粒子粉末、シリコン系粒子粉末の平均粒子径をいい、例えば、レーザー回折式粒度分布測定装置により測定することができる。なお、この平均粒子径は、負極活物質を用いて負極を作製した後、その表面の走査型電子顕微鏡(SEM)画像から確認してもよい。粒子が球状でない場合には、粒子径は粒子の最も長い部分(長径)をいうものとする。
なお、シリコン系粒子が2種類以上含む場合、その総量をシリコン系粒子の配合量とする。同様に、カーボン粒子が2種類以上含む場合、その総量をカーボン粒子の配合量とする。
なお、上記負極活物質(カーボン粒子及びシリコン系粒子)とその他の活物質との配合割合は特に限定されず、充放電容量やその他蓄電デバイスの特性を考慮して適宜追加することができるが、1実施形態においてはその他の活物質の添加量が、負極活物質全体に対して好ましくは15質量%以下、より好ましくは10質量%以下、さらにより好ましくは5質量%以下であり、その他の活物質を含まないことも好ましい。
本発明では、負極活物質層の多孔度が40%より大きいことを特徴とする。好ましくは42%以上である。また上記多孔度は、少なくとも70%以下であり、好ましくは60%以下、より好ましくは50%以下である。
多孔度を上記のように設定することにより、負極活物質の充放電に伴う体積変化により発生する活物質層へのストレスをこの孔により吸収し、充放電の際に負極活物質層に亀裂が生じることを防ぐことができる。
多孔度(%)=100-N(WA1/DA1+WA2/DA2+・・・WAn/DAn+WB1/DB1+WB2/DB2+・・・+WBm/DBm)
多孔度(%)=100-N(WA1/DA1+WA2/DA2+WB1/DB1+WB2/DB2)
なお、ポリイミド系バインダーを2種以上使用した場合は、各々の成分について真密度と質量を考慮する必要がある。その他の活物質、その他のポリマーについても同様に、成分ごとに考慮するものとする。本実施例で明らかにされているように、本発明で規定する多孔度を満足することによって、高容量化と優れたサイクル特性の両方を具備することが可能となる。
本発明では、上記ポリイミド系バインダー以外のポリマー系バインダーを含んでいてもよい。このようなポリマー系バインダーとしては、ポリイミド系バインダーおよび負極活物質の機能を阻害するものでなければ特に制限されず、例えば、ポリ(メタ)アクリル酸、ポリスルホン酸、およびこれらの塩などのアニオン系ポリマー、カルボキシアルキルセルロース、ヒドロキシアルキルセルロースなどの水溶性セルロース誘導体、ポリビニルアルコール、ポリアルキレングリコール、ポリビニルピロリドン、これらの塩、およびアルギン酸塩などの水溶性ポリマー、アクリル樹脂、合成ゴム、ポリアミド、シリコーン系樹脂(シリコーンオイル含む)等を挙げることができる。また、これらに限定されず、電極バインダーとして公知のものも使用できる。
本発明の負極活物質層はカーボン粒子を含有するので、カーボン粒子とは別に導電助剤を添加しなくてもよいが、必要に応じて導電助剤を含んでいてもよい場合もある。このような導電助剤としては、従来公知の導電助剤を使用することができ、目的とする負極活物質層や蓄電デバイスの特性に応じて、1種または2種類以上を使用することができる。このような導電助剤としては、従来公知の導電助剤であれば特に制限されるものではなく、例えば銀、銅、ニッケル、これらの合金等の金属系導電助剤を用いることができる。
本発明の負極活物質層は、必要に応じて、その他添加剤を配合することができる。その他の添加剤としては、本発明の効果を損なわない範囲で使用することができ、具体的には、触媒(例えば、アミン化合物、イミダゾール化合物);化学イミド化剤(例えば、無水酢酸等の酸無水物やピリジン、イソキノリン等のアミン化合物);酸化防止剤(例えば、フェノール系、リン系酸化防止剤);光安定剤(例えば、ヒンダードアミン系安定剤);帯電防止剤(例えば、界面活性剤、カーボン、金属酸化物);可塑剤(例えば、エステル系可塑剤、エポキシか植物油);油溶性溶媒(例えば、1-アセトナフトン、アセトフェノン、ベンジルアセトン、メチルアセトフェノン、ジメチルアセトフェノン、プロピオフェノン、バレロフェノン、アニソール、安息香酸メチル、安息香酸ベンジル);防錆剤(例えば、亜鉛化合物、鉛化合物、ジフェニルアミン等、アジピン酸、エタノールアミンおよびモノエタノールアミン、エチレングリコールモノエチルエーテル,トリメチルアミン、ノニルフェノール、ヘキサメチレンジアミン,ペンタエリスリトール等、ジシクロヘキシルアンモニュームナイトライト、ジイソプロピルアンモニュームナイトライトおよびこれらの混合物等、ジシクロヘキシルアンモニュームのカプレート、ラウレート、カーボネート等、ベンゾトリアゾールおよびアルキルベンゾトリアゾール等、アミン塩類,低級脂肪酸およびこれらの塩類等);シランカップリング剤;チタンカップリング剤;難燃材(例えば、臭素系難燃剤、リン系難燃剤、酸化アンチモン、水酸化アルミニウム等);消泡剤(例えば、シリコーン系消泡剤、アクリル系消泡剤、フッ素系消泡材);レベリング剤(例えば、シリコーン系レベリング剤、アクリル系レベリング剤);平滑化剤(例えば、ベンジルアルコール、2-フェニルエチルアルコール、4-メチルベンジルアルコール、4-メトキシベンジルアルコール、4-クロルベンジルアルコール、4-ニトロベンジルアルコール、フェノキシ-2-エタノール、シンナミルアルコール、フルフリルアルコールおよびナフチルカルビノールポリエチレングリコール、クマリン、2-ブチン-1,4-ジオール、2-プロピン-1-オール、3-フェニルプロピオン酸等);レオロジーコントロール剤(流動制御目的の添加剤);粘度調整剤;剥離剤;界面活性剤(例えば、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、ノニオン性界面活性剤);金属石鹸(例えば、ステアリン酸、ラウリン酸、リシノール酸、オクチル酸等の脂肪酸と、リチウム、マグネシウム、カルシウム、バリウム、亜鉛等の金属との塩);支持電解質(例えば、アルカリ金属のハロゲン化物や硝酸塩等、テトラアルキルアンモニウムの過塩素酸塩やテトラフルオロホウ酸等の強酸との塩)等が挙げられる。
本発明の実施形態の一つである蓄電デバイス負極用電極合剤ペーストは、上述した負極活物質層を形成するために用いられるものである。
この蓄電デバイス負極用電極合剤ペーストは、負極活物質、ポリイミド系バインダー、その他任意成分を含有するものである。これら各成分については、上記負極活物質層の項に開示したものと同様のものを使用すればよい。さらに本発明の蓄電デバイス負極用電極合剤ペーストは、必要に応じて各種添加剤を含むことができる。
本発明の蓄電デバイス負極用電極合剤ペーストは、必要に応じて溶媒を含んでいてもよい。このような溶媒としては、目的とする蓄電デバイス、電極合剤ペースト等に応じて適宜選択でき、例えば、有機溶媒、水系溶媒(水又は水を含む溶媒)、又はこれらの混合物を使用できる。中でも、ポリイミド系バインダー(ポリアミック酸、ポリイミド樹脂等)の調製の際に用いる溶剤を好適に使用することができる。
本発明の実施形態の一つである負極活物質層の製造方法としては、目的とする負極活物質層を製造できれば特に制限されるものではない。一例としては、集電体上に、蓄電デバイス負極用電極合剤ペーストを流延あるいは塗布し、加熱処理することによって負極活物質層を形成する方法が挙げられる。なお、ポリアミック酸は、加熱処理あるいはイミド化剤等の化学的処理によって、容易にポリイミドになる。以下、この一例に沿って、負極活物質層の製造方法を詳細に説明する。
本発明に用いられる集電体としては、一般的な化学変化を起こさない電子伝導体を用いることができる。これらの集電体を形成する材料としては、例えば、アルミニウム、銅、銅合金、鉄、ステンレス鋼、ニッケル、チタンなどが挙げられ、アルミニウム、銅、銅合金、鉄、ステンレス鋼の表面にカーボン、ニッケル、チタン、銀等で処理されたもの(薄膜が形成されたもの)も用いることができる。中でも、アルミニウム、銅、銅合金、ニッケルメッキ鋼、ステンレス鋼等を好適に用いることができる。
本発明の実施形態の一つである蓄電デバイス用負極は、上述した負極活物質層を有するものである。より具体的には、集電体上に本発明の負極活物質層を有するものである。蓄電デバイス用負極を製造する方法は、上述のように、集電体上に負極活物質層を形成する方法を採用すればよい。また、上記蓄電デバイス用負極は、蓄電デバイスの態様に応じて、負極活物質層上に各種機能層が1種または2種以上積層されていてもよい。
本発明の実施形態の一つである蓄電デバイスは、上述した負極活物質層を有する蓄電デバイス用負極を備えるものである。上述した本発明の蓄電デバイス用負極は、公知の方法にしたがって、好適に蓄電デバイスとすることができる。例えば、得られた蓄電デバイス用負極と正極とを、ポリオレフィン多孔質体等のセパレータを挟み込みながら、円筒状に巻き取り、この円筒状の電極体を円筒状のままで或いは押しつぶして扁平状にして、この電極体と非水電解液とを外装体内に挿入することによって、好適に蓄電デバイスを得ることができる。
なお、正極に使用される集電体は、一般的に使用されるものを用いることができる。
ポリイミド系バインダー(前駆体組成物):UPIA(登録商標)-LB-2001(宇部興産株式会社製ポリアミック酸ワニス(溶媒:水))
CMC:カルボキシメチルセルロース
EC:エチレンカーボネート
DEC:ジエチルカーボネート
負極活物質として、容量が600mAh/gになるようにケイ素単体(Si)(平均粒子径5μm)、ケイ素酸化物(SiO)(平均粒子径1μm)及び人造黒鉛(平均粒子径6μm)を配合した。配合した負極活物質とUPIA(登録商標)-LB-2001及びCMC(ポリアミック酸固形分質量:CMC質量=50:50)を95:5(質量%)になるように配合し、スラリー濃度が約60質量%になるように水を加え、蓄電デバイス用負極電極合剤ペーストを調製した。この蓄電デバイス用負極電極合剤ペーストを集電体であるニッケルメッキ鋼箔(厚み10μm)上に塗布し、80℃で10分プレ乾燥を行った。その後、ロールプレスし、真空乾燥機に入れて150℃で7時間加熱処理し、評価用負極(容量密度:3mAh/cm2)を作製した。なお、プレス線圧を変更することで、異なる多孔度の負極活物質層を有する評価用負極を作成した。
上記(1)で得られた評価用負極を用い、下記の構成で評価用電池を作製した。
・対極:リチウム箔(金属リチウム)
・電解液:1M LiPF6/EC:DEC=1:1(体積%)
以下の条件で繰り返し充放電を実施し、サイクル特性を評価した。
・測定温度:30℃
・充放電範囲:0.001~1.0V
・充放電電流値:0.1C
初期充放電効率は、(初回の放電容量)÷(初回の充電容量)により算出した。
容量維持率は、(サイクル試験後の放電容量)÷(初回の放電容量)により算出した。
尚、ここでは「評価用負極」にLiが吸蔵されることを「充電」、「評価用負極」からLiが放出されることを「放電」というものとする。
作製した評価用電池(負極活物質層の多孔度:47%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が98%であった。また、初期充放電効率は85%であった。
作製した評価用電池(負極活物質層の多孔度:45%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が96%であった。また、初期充放電効率は85%であった。
作製した評価用電池(負極活物質層の多孔度:41%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が97%であった。また、初期充放電効率は85%であった。
作製した評価用電池(負極活物質層の多孔度:33%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が75%であった。また、初期充放電効率は75%であった。
作製した評価用電池(負極活物質層の多孔度:30%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が70%であった。また、初期充放電効率は70%であった。
作製した評価用電池(負極活物質層の多孔度:25%)の充放電サイクル特性を確認したところ、30サイクル後の容量維持率が73%であった。また、初期充放電効率は65%であった。
Claims (9)
- カーボン粒子、
シリコンを成分として含み、リチウムイオンを吸蔵・放出可能なシリコン系粒子、および
主鎖にイミド結合を有する有機高分子であるポリイミド系バインダー
を含有し、多孔度が40%より大きい、負極活物質層。 - 前記シリコン系粒子の平均粒子径が10μm未満である、請求項1に記載の負極活物質層。
- 前記カーボン粒子が黒鉛粒子である、請求項1または2に記載の負極活物質層。
- さらにポリイミド系バインダー以外のポリマー系バインダーを含む、請求項1~3のいずれか一項に記載の負極活物質層。
- 請求項1~5のいずれか一項に記載の負極活物質層を形成するために用いられる蓄電デバイス負極用電極合剤ペースト。
- 集電体上に、請求項6に記載の蓄電デバイス負極用電極合剤ペーストを流延または塗布し、加熱処理することによって形成される負極活物質層の製造方法。
- 請求項1~5のいずれか一項に記載の負極活物質層を有する蓄電デバイス用負極。
- 請求項8に記載の蓄電デバイス用負極を有する蓄電デバイス。
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CN114747043A (zh) | 2022-07-12 |
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US20220384810A1 (en) | 2022-12-01 |
EP4040532A1 (en) | 2022-08-10 |
TWI755882B (zh) | 2022-02-21 |
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KR20220075362A (ko) | 2022-06-08 |
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