WO2020137403A1 - Liquide de dispersion de matériau carboné pour électrodes de batterie secondaire, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires et batterie secondaire - Google Patents

Liquide de dispersion de matériau carboné pour électrodes de batterie secondaire, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires et batterie secondaire Download PDF

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WO2020137403A1
WO2020137403A1 PCT/JP2019/047460 JP2019047460W WO2020137403A1 WO 2020137403 A1 WO2020137403 A1 WO 2020137403A1 JP 2019047460 W JP2019047460 W JP 2019047460W WO 2020137403 A1 WO2020137403 A1 WO 2020137403A1
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secondary battery
electrode
carbon material
dispersion liquid
slurry composition
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PCT/JP2019/047460
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English (en)
Japanese (ja)
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高橋　直樹
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日本ゼオン株式会社
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Publication of WO2020137403A1 publication Critical patent/WO2020137403A1/fr

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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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a carbon material dispersion liquid for a secondary battery electrode, a slurry composition for a secondary battery electrode, an electrode for a secondary battery, and a secondary battery.
  • Secondary batteries such as lithium-ion secondary batteries are small and lightweight, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of secondary batteries.
  • an electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector. Then, the electrode mixture layer, for example, an electrode active material, a conductive material, a binder or the like is dispersed or dissolved in a dispersion medium, an electrode slurry composition is applied onto a current collector, dried to form an electrode. It is formed by binding an active material and a conductive material with a binder.
  • the electrode mixture layer for example, an electrode active material, a conductive material, a binder or the like is dispersed or dissolved in a dispersion medium, an electrode slurry composition is applied onto a current collector, dried to form an electrode. It is formed by binding an active material and a conductive material with a binder.
  • a carbon material dispersion liquid obtained by dispersing a conductive material made of a carbon material having conductivity such as carbon black in a dispersion medium.
  • Patent Documents 1 and 2 as a carbon material dispersion having excellent dispersibility and storage stability, a carbon black having a predetermined BET specific surface area and a dispersant comprising a polyvinyl alcohol resin having a predetermined saponification degree are disclosed.
  • a carbon black dispersion liquid containing N-methyl-2-pyrrolidone as a dispersion medium is disclosed.
  • the conventional carbon material dispersion liquid for a secondary battery electrode is improved in rate characteristics and high temperature storage characteristics of a secondary battery including an electrode formed by using the carbon material dispersion liquid for a secondary battery electrode. There was room for improvement.
  • the present invention provides a secondary battery electrode capable of exhibiting excellent rate characteristics and high temperature storage characteristics in a secondary battery, and a carbon material dispersion liquid for a secondary battery electrode capable of forming the secondary battery electrode, It is an object to provide a slurry composition for a secondary battery electrode. Another object of the present invention is to provide a secondary battery that is excellent in both rate characteristics and high temperature storage characteristics.
  • the present inventor has conducted extensive studies in order to achieve the above object. Then, the present inventor has determined a median diameter (D50) of a dispersoid to be a predetermined value in a carbon material dispersion liquid for a secondary battery electrode in which a carbon material is dispersed in an organic dispersion medium using a polyvinyl alcohol-based polymer as a dispersant. Within the range, it was found that a secondary battery using an electrode formed by using the carbon material dispersion liquid for a secondary battery electrode can exhibit excellent rate characteristics and high temperature storage characteristics, and completed the present invention. It was
  • the present invention is intended to advantageously solve the above problems, the carbon material dispersion liquid for a secondary battery electrode of the present invention, a carbon material, a polyvinyl alcohol-based polymer, an organic dispersion medium.
  • the median diameter (D50) of the dispersoid is 0.90 ⁇ m or more and 10 ⁇ m or less.
  • the carbon material dispersion for the secondary battery electrode is dispersed.
  • a secondary battery including an electrode having an electrode mixture layer formed using a liquid can exhibit excellent rate characteristics and high-temperature storage characteristics.
  • the “median diameter (D50) of dispersoid” can be measured by the method described in Examples of the present specification.
  • the carbon material is at least one selected from the group consisting of acetylene black, furnace black, Ketjen black, carbon fibers, carbon nanotubes and graphene. It is preferable to include. If at least one selected from the group consisting of acetylene black, furnace black, Ketjen black, carbon fiber, carbon nanotube, and graphene is used as the carbon material, the rate characteristics of the secondary battery can be further improved.
  • the saponification degree of the polyvinyl alcohol-based polymer in the carbon material dispersion liquid for a secondary battery electrode of the present invention is preferably more than 60 mol% and 99.5 mol% or less.
  • the “saponification degree of the polyvinyl alcohol polymer” can be measured in accordance with JIS K0070.
  • the present invention is intended to advantageously solve the above problems, the secondary battery electrode slurry composition of the present invention, any of the above secondary battery electrode carbon material dispersion, It is characterized by containing an electrode active material and a binder.
  • the carbon material dispersion liquid for a secondary battery electrode described above is contained, it is possible to form a secondary battery electrode capable of exhibiting excellent rate characteristics and high temperature storage characteristics in a secondary battery.
  • the electrode for secondary batteries of this invention is the electrode mixture material formed using the slurry composition for secondary battery electrodes mentioned above. It is characterized by having a layer.
  • the secondary battery electrode including the electrode mixture layer formed by using the above-described secondary battery electrode slurry composition the secondary battery can exhibit excellent rate characteristics and high temperature storage characteristics. ..
  • the secondary battery of this invention is equipped with a positive electrode, a negative electrode, an electrolytic solution, and a separator, and at least one of the said positive electrode and a negative electrode is the above-mentioned. It is a secondary battery electrode as described above.
  • a secondary battery including the above-described secondary battery electrode can exhibit excellent rate characteristics and high temperature storage characteristics.
  • the carbon material dispersion liquid for a secondary battery electrode and the slurry composition for a secondary battery electrode of the present invention it is possible to form a secondary battery electrode capable of exhibiting excellent rate characteristics and high temperature storage characteristics in a secondary battery. You can Further, according to the secondary battery electrode of the present invention, the secondary battery can exhibit excellent rate characteristics and high temperature storage characteristics. Furthermore, the secondary battery of the present invention is excellent in both rate characteristics and high temperature storage characteristics.
  • the carbon material dispersion liquid for a secondary battery electrode of the present invention can be used when preparing a slurry composition for a secondary battery electrode.
  • the slurry composition for secondary battery electrodes prepared by using the carbon material dispersion liquid for secondary battery electrodes of the present invention can be used when forming electrodes of secondary batteries such as lithium ion secondary batteries. ..
  • the secondary battery of the present invention is characterized by using an electrode for a secondary battery formed by using the slurry composition for an electrode of the secondary battery of the present invention.
  • the carbon material dispersion liquid for a secondary battery electrode and the slurry composition for a secondary battery electrode of the present invention can be particularly preferably used when forming a positive electrode of a secondary battery.
  • the carbon material dispersion liquid for a secondary battery electrode of the present invention contains a carbon material, a polyvinyl alcohol-based polymer, and an organic dispersion medium, and optionally further contains other components that can be blended in the electrode of the secondary battery. To do. Furthermore, the carbon material dispersion liquid for secondary battery electrodes of the present invention requires that the median diameter (D50) of the dispersoid be 0.90 ⁇ m or more and 10 ⁇ m or less. The carbon material dispersion liquid for a secondary battery electrode usually does not contain an electrode active material.
  • the carbon material dispersion liquid for a secondary battery electrode of the present invention contains a polyvinyl alcohol-based polymer, and further, the median diameter (D50) of the dispersoid is 0.90 ⁇ m or more and 10 ⁇ m or less.
  • a secondary battery including an electrode having an electrode mixture layer formed by using the carbon material dispersion liquid for use can exhibit excellent rate characteristics and high-temperature storage characteristics.
  • the median diameter of the dispersoid is The rate property is improved by having an appropriate size, and the electrode mixture layer due to the stress generated during high temperature storage is obtained by further containing a polyvinyl alcohol polymer and adjusting the median diameter of the dispersoid to an appropriate size. It is presumed that this is because the structural change of is suppressed.
  • the carbon material is not particularly limited as long as it can be used as a conductive material in the electrode of the secondary battery, and a known carbon material can be used.
  • the carbon material is at least selected from the group consisting of acetylene black, furnace black, Ketjen Black (registered trademark), carbon fiber, carbon nanotube, and graphene. It is preferable to use one kind, more preferably to use at least one kind selected from the group consisting of acetylene black, Ketjen black and carbon nanotubes, and further preferable to use acetylene black and/or carbon nanotubes.
  • the amount of the carbon material contained in the carbon material dispersion liquid for secondary battery electrodes (100% by mass) is usually 1% by mass or more and 30% by mass or less, and 3% by mass or more and 30% by mass or less. It is preferable.
  • the polyvinyl alcohol-based polymer has the following formula: It is a polymer containing the vinyl alcohol structural unit represented by and optionally further containing other structural units derived from other monomers.
  • the polyvinyl alcohol-based polymer is, for example, a polyvinyl ester obtained by polymerizing one or more kinds of vinyl ester-based monomers and other monomers which can be optionally copolymerized with the vinyl ester-based monomers. It can be produced by saponifying a polymer.
  • vinyl ester-based monomer for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, etc. Can be used. Of these, vinyl acetate is preferable.
  • vinyl ester-based monomer examples include, for example, ethylene, propylene, 1-butene, isobutene and other olefins having 2 to 30 carbon atoms; (meth)acrylic acid and Salts thereof; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate i -(Meth)acrylic acid ester such as -butyl, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate; (meth)acrylonitrile, etc.
  • (meth)acrylic acid refers to acrylic acid and/or methacrylic acid
  • (meth)acrylonitrile refers to acrylonitrile and/or methacrylonitrile
  • the polyvinyl ester-based polymer can be obtained by polymerizing the above-mentioned monomers by a conventionally known method, and is a copolymer of one or more kinds of vinyl ester-based monomers and other monomers. Or a polymer obtained by using only a vinyl ester-based monomer.
  • the proportion of structural units derived from other monomers (other structural units) in all structural units contained in the polyvinyl ester-based polymer is preferably 50% by mass or less, and 30% by mass.
  • the content is more preferably the following or less, still more preferably 5% by mass or less, and further preferably 0% by mass (that is, the polyvinyl ester-based polymer is a polymer obtained by using only a vinyl ester-based monomer). Is particularly preferable. It is even more preferable that the polyvinyl ester polymer is a polymer obtained by using only one type of vinyl ester monomer.
  • the saponification of the polyvinyl ester-based polymer is not particularly limited, and can be performed according to a known saponification method using a base such as sodium hydroxide or potassium hydroxide.
  • the degree of saponification of the polyvinyl alcohol-based polymer obtained by saponifying the polyvinyl ester-based polymer is not particularly limited, and is preferably more than 60 mol%, more preferably more than 70 mol%, and 85 mol%. % Is more preferable, it is particularly preferable that it is more than 95 mol%, and it is preferable that it is 99.5 mol% or less.
  • the saponification degree of the polyvinyl alcohol polymer is within the above range, the high temperature storage characteristics of the secondary battery can be further improved.
  • the amount of the polyvinyl alcohol-based polymer contained in the carbon material dispersion liquid for secondary battery electrode is preferably more than 0.1 parts by mass, and more than 1 part by mass, per 100 parts by mass of the carbon material. More preferably, more preferably more than 3 parts by mass, particularly preferably 10 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, 30 It is more preferable that the amount is not more than parts by mass.
  • the amount of the polyvinyl alcohol polymer is within the above range, the rate characteristics and the high temperature storage characteristics of the secondary battery can be further improved while the carbon material is well dispersed.
  • the organic dispersion medium is not particularly limited, and a known organic solvent used in the field of secondary batteries can be used.
  • a known organic solvent used in the field of secondary batteries can be used.
  • the organic dispersion medium alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol; acetone , Ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, dioxane and tetrahydrofuran; amides such as N,N-dimethylformamide and N-methyl-2-pyrrolidone (NMP) System polar organic solvents; aromatic
  • the carbon material dispersion liquid for a secondary battery electrode requires that the median diameter of the dispersoid be 0.90 ⁇ m or more and 10 ⁇ m or less, preferably 1.2 ⁇ m or more, and 1.5 ⁇ m or more. Is more preferable, 3.0 ⁇ m or more is more preferable, 7.0 ⁇ m or less is preferable, 5.0 ⁇ m or less is more preferable, and 4.0 ⁇ m or less is further preferable.
  • the median diameter of the dispersoid is at least the above lower limit, the rate characteristics and high temperature storage characteristics of the secondary battery can be further improved.
  • the rate characteristic of the secondary battery can be further improved.
  • the dispersoid contains a carbon material and a polyvinyl alcohol polymer adsorbed on the carbon material. Then, the median diameter of the dispersoid can be adjusted, for example, by changing the particle diameter of the carbon material, the type and amount of the polyvinyl alcohol-based polymer, and the preparation conditions of the carbon material dispersion liquid for secondary battery electrodes. it can.
  • carbon material dispersion liquid for secondary battery electrodes may optionally contain are not particularly limited, and examples thereof include a reinforcing material, a leveling agent, a viscosity modifier, and an electrolyte solution additive. These are not particularly limited as long as they do not affect the battery reaction, and known ones such as those described in International Publication No. 2012/115096 can be used. Moreover, these components may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.
  • the carbon material dispersion liquid for a secondary battery electrode can be prepared by mixing the above components by a known method and dispersing the carbon material or the like in an organic dispersion medium.
  • the mixing of the components described above is not particularly limited, propeller mixer, high speed mixer, dissolver, homogenizer, artemizer, wet jet mill, colloid mill, mass colloider, bead mill, sand mill, ball mill, sand grinder, It can be carried out using a mixing and dispersing machine such as an in-line mixer or a medialess type high speed stirring and dispersing machine. Among them, from the viewpoint of easy adjustment of the median diameter of the dispersoid, it is preferable to use a media stirring type mixing/dispersing machine such as a bead mill.
  • the outer diameter (media diameter) of the media used is preferably 0.1 mm or more, more preferably 0.5 mm or more, and 3 mm or less. It is preferably 2 mm or less, more preferably 1 mm or less.
  • the slurry composition for a secondary battery electrode of the present invention contains the above-mentioned carbon material dispersion liquid for a secondary battery electrode, an electrode active material, and a binder, and can be optionally blended in an electrode of a secondary battery. It further contains components. That is, the secondary battery electrode slurry composition contains a carbon material, a polyvinyl alcohol-based polymer, an organic dispersion medium, an electrode active material, and a binder, and optionally further contains other components. Since the secondary battery electrode slurry composition of the present invention contains the above-described secondary battery electrode carbon material dispersion liquid, an electrode mixture formed using the secondary battery electrode slurry composition. The electrode provided with the layer can exhibit excellent rate characteristics and high temperature storage characteristics in the secondary battery.
  • the carbon material dispersion liquid for secondary battery electrodes the carbon material dispersion liquid for secondary battery electrodes of the present invention described above can be used.
  • the amount of the secondary battery electrode carbon material dispersion liquid used for the preparation of the secondary battery electrode slurry composition is not particularly limited, for example, the amount of the carbon material contained in the slurry composition is the electrode active material. The amount can be 0.5 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the substance.
  • the electrode active material is a material that exchanges electrons in the electrode of the secondary battery. Then, for example, when the secondary battery is a lithium-ion secondary battery, a substance capable of inserting and extracting lithium is usually used as the electrode active material.
  • the slurry composition for secondary battery electrodes is a slurry composition for lithium ion secondary battery electrodes is demonstrated below as an example, this invention is not limited to the following examples.
  • the positive electrode active material for a lithium ion secondary battery is not particularly limited, and lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2 ). ), Co-Ni-Mn lithium-containing composite oxide (Li(Co Mn Ni)O 2 ), Ni-Mn-Al lithium-containing composite oxide, Ni-Co-Al lithium-containing composite oxide, olivine type Represented by lithium iron phosphate (LiFePO 4 ), olivine-type lithium manganese phosphate (LiMnPO 4 ), Li 2 MnO 3 —LiNiO 2 based solid solution, Li 1+x Mn 2-x O 4 (0 ⁇ X ⁇ 2)
  • Examples of known positive electrode active materials include lithium-excess spinel compounds, Li[Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ]O 2 and LiNi 0.5 Mn 1.5 O 4 .
  • examples of the negative electrode active material for a lithium ion secondary battery include a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material combining these.
  • the carbon-based negative electrode active material refers to an active material having lithium as a main skeleton into which lithium can be inserted (also referred to as “dope”).
  • examples of the carbon-based negative electrode active material include a carbonaceous material and graphite. Quality materials.
  • Examples of the carbonaceous material include easily graphitizable carbon and non-graphitizable carbon having a structure close to an amorphous structure represented by glassy carbon.
  • examples of the graphitizable carbon include a carbon material obtained from tar pitch obtained from petroleum or coal as a raw material. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, and pyrolytic vapor growth carbon fiber.
  • Examples of the non-graphitizable carbon include, for example, a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), hard carbon and the like.
  • examples of the graphite material include natural graphite and artificial graphite.
  • artificial graphite for example, artificial graphite obtained by heat-treating carbon containing easily graphitizable carbon at 2800° C. or higher, graphitized MCMB obtained by heat-treating MCMB at 2000° C. or higher, and mesophase pitch-based carbon fiber at 2000° C.
  • the graphitized mesophase pitch-based carbon fiber heat-treated as described above can be used.
  • the metal-based negative electrode active material is an active material containing a metal, and usually has a structure containing an element capable of inserting lithium, and has a theoretical electric capacity of 500 mAh/unit mass per unit mass when lithium is inserted.
  • the metal-based active material include lithium metal and elemental metals capable of forming a lithium alloy (eg, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn). , Sr, Zn, Ti, etc.) and alloys thereof, and their oxides, sulfides, nitrides, silicides, carbides, phosphides and the like.
  • the metal-based negative electrode active material is preferably an active material containing silicon (silicon-based negative electrode active material). This is because the lithium-ion secondary battery can have a high capacity by using the silicon-based negative electrode active material.
  • silicon-based negative electrode active material examples include silicon (Si), alloys containing silicon, SiO, SiO x , and a compound of Si-containing material and conductive carbon obtained by coating or compounding Si-containing material with conductive carbon. And so on.
  • the above electrode active materials may be used alone or in combination of two or more.
  • the binder is not particularly limited as long as it can function as a binder for binding the electrode active material, the carbon material, etc., and a known binder used in the field of secondary batteries can be used. it can.
  • the binder is not particularly limited, but a fluorine-containing polymer such as polyvinylidene fluoride; a polymer containing a conjugated diene monomer unit such as acrylonitrile-butadiene copolymer or styrene-butadiene copolymer is used.
  • a compound (conjugated diene polymer) and its hydride; a polymer containing a (meth)acrylic acid ester monomer unit (acrylic polymer); and the like can be used.
  • One of these polymers may be used alone, or two or more of them may be used in combination.
  • the amount of the binder contained in the secondary battery electrode slurry composition is not particularly limited and can be, for example, 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the electrode active material.
  • the other components that can be added to the slurry composition are not particularly limited, and include the same components as the other components that can be added to the carbon material dispersion liquid for secondary battery electrode described above. Further, other components may be used alone or in combination of two or more at an arbitrary ratio.
  • the slurry composition for secondary battery electrodes can be manufactured by mixing the electrode active material, the binder, the above-mentioned carbon material dispersion liquid for secondary battery electrodes, and any other components.
  • the mixing of the above-mentioned components is not particularly limited, and a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a mixer such as a fill mix is used. Can be done by The mixing may be performed by newly adding an organic dispersion medium.
  • the order of mixing the above-mentioned components is not particularly limited, and all the components may be mixed together, for example, only one of the electrode active material and the binder is used as a carbon material dispersion liquid for a secondary battery electrode. After mixing, the remaining ingredients may be further mixed.
  • the secondary battery electrode of the present invention includes an electrode mixture layer formed using the above-described secondary battery electrode slurry composition. Therefore, the electrode mixture layer contains at least an electrode active material, a binder, a carbon material, a polyvinyl alcohol-based polymer, and any other component.
  • the respective components contained in the electrode mixture layer were those contained in the slurry composition for a secondary battery electrode, and the preferable abundance ratio of these components is in the slurry composition. It is the same as the preferable abundance ratio of each component.
  • the secondary battery electrode of the present invention since the electrode mixture layer is formed using the above-described secondary battery electrode slurry composition, the conductive path is well formed, and at the time of storage at high temperature. The structural change of the electrode composite material layer due to the generated stress is suppressed. Therefore, when the secondary battery electrode of the present invention is used, the secondary battery can exhibit excellent rate characteristics and high temperature storage characteristics.
  • the electrode mixture layer of the secondary battery electrode of the present invention includes, for example, a step of applying the above-mentioned slurry composition on a current collector (application step) and a slurry composition applied on the current collector. It can be formed on the current collector through a step of drying the material to form an electrode mixture layer on the current collector (drying step).
  • the method for applying the slurry composition onto the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dipping method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method or the like can be used. At this time, the slurry composition may be applied to only one surface of the current collector, or may be applied to both surfaces. The thickness of the slurry film on the current collector after coating and before drying can be appropriately set according to the thickness of the electrode mixture layer obtained by drying.
  • the current collector for applying the slurry composition a material having electrical conductivity and electrochemical durability is used.
  • a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used.
  • the above materials may be used alone or in combination of two or more at an arbitrary ratio.
  • the method for drying the slurry composition on the current collector is not particularly limited, and known methods can be used, for example, hot air, hot air, low-humid air drying method, vacuum drying method, infrared ray, electron beam, and the like. A drying method by irradiation can be mentioned.
  • an electrode mixture layer is formed on the current collector, and a secondary battery electrode including the current collector and the electrode mixture layer can be obtained. it can.
  • the electrode mixture layer may be subjected to a pressure treatment using a die press or roll press.
  • the pressure treatment can improve the adhesion between the electrode mixture layer and the current collector.
  • the electrode mixture layer contains a curable polymer, it is preferable to cure the polymer after forming the electrode mixture layer.
  • the secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and uses the secondary battery electrode described above as at least one of the positive electrode and the negative electrode. Since the secondary battery of the present invention uses the above-described secondary battery electrode as at least one of the positive electrode and the negative electrode, it can exhibit excellent rate characteristics and high temperature storage characteristics.
  • the secondary battery is a lithium ion secondary battery will be described below as an example, the present invention is not limited to the following example.
  • the electrodes other than the above-mentioned secondary battery electrodes that can be used in the secondary battery of the present invention are not particularly limited, and known electrodes used in the production of secondary batteries can be used. You can Specifically, as the electrodes other than the secondary battery electrode described above, an electrode obtained by forming an electrode mixture layer on a current collector by using a known manufacturing method can be used.
  • an organic electrolytic solution prepared by dissolving a supporting electrolyte in an organic solvent is usually used.
  • a lithium salt is used as the supporting electrolyte of the lithium ion secondary battery.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi. , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 )NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable, because it is easily dissolved in a solvent and exhibits a high dissociation degree.
  • the electrolytes may be used alone or in combination of two or more at an arbitrary ratio.
  • the lithium ion conductivity tends to be higher as the supporting electrolyte having a higher dissociation degree is used, and thus the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, and examples thereof include dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), Carbonates such as butylene carbonate (BC) and ethylmethyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide And the like are preferably used. Further, a mixed solution of these solvents may be used. Of these, carbonates are preferably used because they have a high dielectric constant and a wide stable potential region. The concentration of the electrolyte in the electrolytic solution can be adjusted appropriately. Further, known additives can be added to the electrolytic solution.
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl
  • the separator is not particularly limited, and for example, those described in JP 2012-204303 A can be used. Among these, the film thickness of the entire separator can be reduced, and thus the capacity per volume can be increased by increasing the ratio of the electrode active material in the secondary battery, and thus the polyolefin-based ( A microporous membrane made of a resin of polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferable.
  • the secondary battery is, for example, a positive electrode and a negative electrode are stacked via a separator, which is wound or folded according to the shape of the battery as required and put into a battery container, and the electrolytic solution is placed in the battery container. It can be manufactured by injecting and sealing.
  • the above-mentioned secondary battery electrode is used as at least one of the positive electrode and the negative electrode.
  • the secondary battery of the present invention may include a fuse, an overcurrent prevention element such as a PTC element, and an expanded metal, if necessary, in order to prevent an increase in internal pressure of the secondary battery and the occurrence of overcharging/discharging.
  • a lead plate or the like may be provided.
  • the shape of the secondary battery may be, for example, a coin type, a button type, a sheet type, a cylindrical type, a prismatic type, a flat type or the like.
  • ⁇ Saponification degree> About 1 g of the polyvinyl alcohol polymer was precisely weighed to the order of 1 mg (the precision value is S), put in a 300 mL Erlenmeyer flask, and 25 mL of 0.5 mol/L potassium hydroxide ethanol solution was added using a pipette. .. Subsequently, a cooling tube was attached to the Erlenmeyer flask and reacted at 40° C. for 30 minutes while stirring. After completion of the reaction, the mixture was cooled, 1 mL of a phenolphthalein solution was added as an indicator, and titration was performed using a 0.5 mol/L hydrochloric acid aqueous solution.
  • the amount of hydrochloric acid at this time is A.
  • the blank test was performed without adding the polyvinyl alcohol polymer.
  • the amount of hydrochloric acid at this time is B.
  • the saponification value X was calculated from the following formula.
  • f is a factor of the 0.5 mol/L hydrochloric acid aqueous solution used.
  • Saponification value X ⁇ (BA) ⁇ f ⁇ 28.05 ⁇ /S
  • the saponification degree was calculated from the following equation, where Y is the number of moles of vinyl ester monomer units contained in 1 g of the polymer (polyvinyl ester polymer) before saponification.
  • Saponification degree [ ⁇ 1-(X/0.0561) ⁇ /Y] ⁇ 100 ⁇ Median diameter>
  • the prepared carbon material dispersion liquid for a secondary battery electrode was diluted to an appropriate concentration and then subjected to ultrasonic treatment for 1 minute (output: 70 W, frequency: 35 kHz, temperature: 25° C.) to obtain a measurement sample.
  • the particle size distribution (volume basis) was measured with the solvent refractive index of 1.47 (N-methyl-2-pyrrolidone), and the median diameter (D50) was calculated. I asked.
  • the concentration of the measurement sample was set so that the absorbance at the measuring device was 0.2 or less.
  • the manufactured secondary battery was charged at a temperature of 25° C. to 4.2 V by the constant current charging method (charging rate: 0.2 C) and then charged by the constant voltage charging method until the current value became 0.02 C. After that, the capacity when discharged to 3.0 V by the constant current method with a discharge rate of 0.2 C was defined as C1. Then, the charging conditions were the same, the capacity was measured in the same manner except that the discharge rate was 2.0 C, and the capacity at this time was C2. Then, the rate characteristic was calculated from the following formula and evaluated according to the following criteria. The larger the value, the lower the battery resistance and the better the rate characteristics.
  • Rate characteristic (C2/C1) ⁇ 100 (%)
  • the manufactured secondary battery was charged at a temperature of 25° C. to 4.2 V by the constant current charging method (charging rate: 0.2 C) and then charged by the constant voltage charging method until the current value became 0.02 C. Then, the charged secondary battery was stored in a constant temperature bath at 60° C. for 30 days. After the secondary battery stored in the constant temperature bath was cooled to a temperature of 25° C., the capacity when discharged to 3.0 V by a constant current method with a discharge rate of 0.2 C was defined as C3.
  • High temperature storage characteristics (C3/C1) ⁇ 100 (%)
  • Example 1 ⁇ Preparation of carbon material dispersion liquid for positive electrode>
  • a premixing tank of a bead mill with a crushing chamber capacity of 0.6 L 2640 g of N-methyl-2-pyrrolidone (NMP) as an organic dispersion medium and 300 g of acetylene black as a carbon material (specific surface area: 39 m 2 /g)
  • NMP N-methyl-2-pyrrolidone
  • acetylene black as a carbon material (specific surface area: 39 m 2 /g)
  • 60 g of polyvinyl alcohol (saponification degree: 98 mol%) as a polyvinyl alcohol-based polymer were added and premixing was performed to obtain a preliminary dispersion liquid.
  • the peripheral speed of the bead mill was set to 12 m/sec, the preliminary dispersion was mixed while feeding at a speed of 300 g/min, and the dispersion treatment was carried out when the median diameter of the dispersoid in the dispersion became 3.4 ⁇ m.
  • the beads used were zirconia beads having a diameter of 1.0 mm.
  • PVdF polyvinylidene fluoride
  • the amount of NMP added is such that the viscosity of the obtained slurry composition for a positive electrode (measured with a single cylindrical rotary viscometer at a temperature of 25° C. and a rotation speed of 60 rpm according to JIS Z8803:1991) is 4,000 to 5,000 mPa. It was adjusted to fall within the range of s.
  • An aluminum foil having a thickness of 20 ⁇ m was prepared as a current collector.
  • the slurry composition for a positive electrode was applied on an aluminum foil with a comma coater so that the basis weight after drying was 20 mg/cm 2 , dried at 90° C. for 20 minutes and 120° C. for 20 minutes, and then at 60° C.
  • the obtained positive electrode raw material was rolled by a roll press to produce a sheet-shaped positive electrode composed of a positive electrode mixture layer having a density of 3.2 g/cm 3 and an aluminum foil.
  • the thickness of the sheet-shaped positive electrode was 70 ⁇ m. This sheet-shaped positive electrode was cut into a width of 4.8 mm and a length of 50 cm to obtain a positive electrode for a lithium ion secondary battery.
  • ⁇ Production of negative electrode> A mixture of 90 parts of spherical artificial graphite (volume average particle size: 12 ⁇ m) and 10 parts of SiO X (volume average particle size: 10 ⁇ m) as a negative electrode active material, 1 part of a styrene-butadiene copolymer as a binder, and a thickening agent. 1 part of carboxymethyl cellulose as an agent and an appropriate amount of water as a dispersion medium were stirred with a planetary mixer to prepare a slurry composition for a negative electrode. Next, a copper foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the above negative electrode slurry composition was applied onto both surfaces of a copper foil so that the applied amount after drying was 10 mg/cm 2 , and dried at 60° C. for 20 minutes and 120° C. for 20 minutes. Then, it heat-processed at 150 degreeC for 2 hours, and obtained the negative electrode original fabric.
  • This negative electrode raw material was rolled by a roll press to produce a sheet-shaped negative electrode composed of a negative electrode mixture layer (both sides) having a density of 1.7 g/cm 3 and a copper foil. Then, the sheet-shaped negative electrode was cut into a width 5.0 mm and a length 52 cm to obtain a negative electrode for a lithium ion secondary battery.
  • the positive electrode and the negative electrode were wound using a core having a diameter of 20 mm with a separator (a microporous polypropylene film having a thickness of 15 ⁇ m) interposed therebetween to obtain a wound body. Then, the obtained wound body was compressed from one direction at a speed of 10 mm/sec until the thickness became 4.5 mm.
  • the wound body after compression had an elliptical shape in plan view, and the ratio of the major axis to the minor axis (major axis/minor axis) was 7.7.
  • the compressed wound body was accommodated in an aluminum laminate case together with 3.2 g of the electrolytic solution.
  • a nickel lead wire was connected to a predetermined part of the negative electrode and an aluminum lead wire was connected to a predetermined part of the positive electrode, and then the opening of the case was sealed with heat to obtain a lithium ion secondary battery.
  • This lithium-ion secondary battery was a pouch type with a width of 35 mm, a height of 48 mm, and a thickness of 5 mm, and the nominal capacity of the battery was 700 mAh.
  • the rate characteristics and the high temperature storage characteristics of the obtained lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • Example 2 When preparing the carbon material dispersion liquid for the positive electrode, polyvinyl alcohol having a saponification degree of 80 mol% was used in place of polyvinyl alcohol (saponification degree: 98 mol %), and the dispersion treatment was stopped when the median diameter reached 3.2 ⁇ m.
  • a positive electrode carbon material dispersion liquid, a positive electrode slurry composition, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 At the time of preparing the carbon material dispersion liquid for the positive electrode, the amount of NMP was set to 2595 g, the amount of polyvinyl alcohol was set to 105 g, and the dispersion treatment was stopped at the time when the median diameter reached 3.3 ⁇ m. A carbon material dispersion liquid for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 When preparing the carbon material dispersion liquid for the positive electrode, the carbon material dispersion liquid for the positive electrode, the slurry composition for the positive electrode, and the positive electrode were prepared in the same manner as in Example 1 except that the dispersion treatment was stopped when the median diameter reached 1.8 ⁇ m. A negative electrode and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 The positive electrode was prepared in the same manner as in Example 1 except that the rotor peripheral speed of the bead mill was changed to 8 m/sec and the dispersion treatment was stopped when the median diameter reached 8.4 ⁇ m when the carbon material dispersion liquid for positive electrode was prepared. A carbon material dispersion liquid, a positive electrode slurry composition, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 Except that the zirconia beads having a diameter of 0.5 mm were used instead of the zirconia beads having a diameter of 1.0 mm when the dispersion of the carbon material for the positive electrode was prepared, and the dispersion treatment was stopped when the median diameter became 0.95 ⁇ m.
  • a positive electrode carbon material dispersion liquid, a positive electrode slurry composition, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 When preparing the carbon material dispersion liquid for the positive electrode, 150 g of multi-walled carbon nanotubes (specific surface area: 90 m 2 /g) was used instead of 300 g of acetylene black (specific surface area: 39 m 2 /g), and the amount of NMP was 2585 g. The amount of alcohol was 37.5 g, and the carbon material dispersion liquid for the positive electrode, the slurry composition for the positive electrode, the positive electrode, which was the same as in Example 1, except that the dispersion treatment was stopped when the median diameter reached 1.2 ⁇ m. A negative electrode and a lithium ion secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 8 When preparing the carbon material dispersion liquid for the positive electrode, 150 g of Ketjen black (specific surface area: 300 m 2 /g) was used instead of 300 g of acetylene black (specific surface area: 39 m 2 /g), and the amount of NMP was 2585 g. The amount of alcohol was 45 g, and the carbon material dispersion for positive electrode, positive electrode slurry composition, positive electrode, negative electrode, and the like were prepared in the same manner as in Example 1 except that the dispersion treatment was stopped at the time when the median diameter became 1.6 ⁇ m. A lithium ion secondary battery was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • the secondary batteries prepared using the carbon material dispersion liquids for secondary battery electrodes of Examples 1 to 8 are excellent in both rate characteristics and high temperature storage characteristics.
  • the secondary batteries produced using the carbon material dispersion liquids for secondary battery electrodes of Comparative Examples 1 to 3 in which the median diameter (D50) of the dispersoid is less than 0.90 ⁇ m or more than 10 ⁇ m have rate characteristics. It can be seen that
  • the carbon material dispersion liquid for a secondary battery electrode and the slurry composition for a secondary battery electrode of the present invention it is possible to form a secondary battery electrode capable of exhibiting excellent rate characteristics and high temperature storage characteristics in a secondary battery. You can Further, according to the secondary battery electrode of the present invention, the secondary battery can exhibit excellent rate characteristics and high temperature storage characteristics. Furthermore, the secondary battery of the present invention is excellent in both rate characteristics and high temperature storage characteristics.

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Abstract

La présente invention concerne un liquide de dispersion de matériau carboné d'électrode de batterie secondaire capable de former une électrode de batterie secondaire qui peut amener une batterie secondaire à présenter d'excellentes caractéristiques de régime et d'excellentes caractéristiques de stockage à haute température. Ce liquide de dispersion de matériau carboné pour électrodes de batterie secondaire contient un matériau carboné, un polymère à base d'alcool polyvinylique et un milieu de dispersion organique, le diamètre médian (D50) des dispersoïdes étant compris entre 0,90 et 10 µm.
PCT/JP2019/047460 2018-12-27 2019-12-04 Liquide de dispersion de matériau carboné pour électrodes de batterie secondaire, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires et batterie secondaire WO2020137403A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112489882A (zh) * 2020-11-16 2021-03-12 哈尔滨万鑫石墨谷科技有限公司 一种石墨烯导电浆料的制备方法及其制备得到的导电浆料和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014194001A (ja) * 2013-02-27 2014-10-09 Toyo Ink Sc Holdings Co Ltd カーボンブラック分散液およびその利用
JP2016514080A (ja) * 2013-02-22 2016-05-19 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ カーボンナノチューブ含有分散液および電極の製造におけるその使用
JP2018534747A (ja) * 2015-10-28 2018-11-22 エルジー・ケム・リミテッド 導電材分散液およびこれを用いて製造したリチウム二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016514080A (ja) * 2013-02-22 2016-05-19 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ カーボンナノチューブ含有分散液および電極の製造におけるその使用
JP2014194001A (ja) * 2013-02-27 2014-10-09 Toyo Ink Sc Holdings Co Ltd カーボンブラック分散液およびその利用
JP2018534747A (ja) * 2015-10-28 2018-11-22 エルジー・ケム・リミテッド 導電材分散液およびこれを用いて製造したリチウム二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112489882A (zh) * 2020-11-16 2021-03-12 哈尔滨万鑫石墨谷科技有限公司 一种石墨烯导电浆料的制备方法及其制备得到的导电浆料和应用
CN112489882B (zh) * 2020-11-16 2022-08-23 哈尔滨万鑫石墨谷科技有限公司 一种石墨烯导电浆料的制备方法及其制备得到的导电浆料和应用

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