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WO2016072090A1 - Collecteur de courant pour batterie secondaire au lithium-ion, son procédé de fabrication, et batterie secondaire à électrolyte non aqueux - Google Patents

Collecteur de courant pour batterie secondaire au lithium-ion, son procédé de fabrication, et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2016072090A1
WO2016072090A1 PCT/JP2015/005521 JP2015005521W WO2016072090A1 WO 2016072090 A1 WO2016072090 A1 WO 2016072090A1 JP 2015005521 W JP2015005521 W JP 2015005521W WO 2016072090 A1 WO2016072090 A1 WO 2016072090A1
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WO
WIPO (PCT)
Prior art keywords
current collector
positive electrode
active material
secondary battery
protective layer
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Ceased
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PCT/JP2015/005521
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English (en)
Japanese (ja)
Inventor
達哉 江口
金田　潤
三好　学
一輝 山内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Industries Corp
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Toyota Industries Corp
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Priority to JP2016557455A priority Critical patent/JPWO2016072090A1/ja
Publication of WO2016072090A1 publication Critical patent/WO2016072090A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a current collector for a lithium ion secondary battery, a method for producing the same, and a non-aqueous electrolyte secondary battery.
  • a positive electrode current collector of a lithium ion secondary battery it is common to use a metal such as Al which forms a stable passive film on the surface in order to resist corrosion by electrolytic salt.
  • a metal such as Al which forms a stable passive film on the surface in order to resist corrosion by electrolytic salt.
  • Al when Al is used as a current collector, a passive film of Al 2 O 3 , AlF 3 or the like is formed on the surface.
  • the current collector of Al has the above-mentioned passive film formed on the surface, so it is difficult to be corroded and it is easy to maintain the current collection function.
  • lithium ion secondary batteries are desired to be able to be used well even in a high voltage use environment.
  • corrosion of the current collector of Al progresses gradually, and the storage characteristics and cycle characteristics of the lithium ion secondary battery having the current collector of Al deteriorate. I have a concern.
  • a protective layer on the current collector In order to maintain various battery characteristics of a lithium ion secondary battery under a high voltage use environment, studies are being made to form a protective layer on the current collector. For example, forming a protective layer by a dry process such as an ion sputtering method or a vacuum evaporation method is considered. In addition, it is also studied to form a protective layer by a wet process using an organic solvent. Furthermore, forming a protective layer using a water-based solvent that is environmentally friendly by a wet process has been studied.
  • Patent Document 1 describes a protective layer containing tin-doped indium oxide (ITO) or tin oxide, and specifically discloses a protective layer containing ITO fine particles and a polyester-based resin. There is.
  • Patent Document 2 discloses an aqueous slurry and a protective layer containing a polysaccharide polymer, a hydrophobic filler, and a polybasic acid, and the aqueous slurry is less likely to cause sedimentation of the hydrophobic filler and has high dispersibility. It is disclosed.
  • Patent Document 2 discloses at least one polymer selected from derivatives of cellulose, derivatives of alginic acid, derivatives of chitin and derivatives of chitosan, polyallylamine and polyvinylamine as polysaccharide-based polymers, and as a hydrophobic filler Acetylene black and ketjen black are disclosed, and as polybasic acids, 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid are disclosed.
  • non-aqueous electrolyte secondary batteries are steadily increasing, and in general, non-aqueous electrolyte secondary batteries are recognized as essential in portable devices such as mobile phones and laptop computers .
  • non-aqueous electrolyte secondary batteries lithium ion secondary batteries are generally used because of their small size and large capacity, and are also used in aircraft and automobiles.
  • researches on a lithium ion secondary battery are actively conducted.
  • Patent Document 4 describes a lithium ion secondary battery which does not continuously generate heat even when a nail penetration test is performed.
  • the electrode is divided into sheets of a specific shape.
  • the area and shape of the sheet obtained by dividing the electrode, and the distance between the positive electrode current collector and the negative electrode current collector are specified by a constant relational expression, and the lithium ion secondary battery Several limitations were imposed on the components.
  • the positive electrode current collector made of aluminum which is easy to obtain and has excellent conductivity.
  • the positive electrode current collector made of aluminum may contact and react with the positive electrode active material containing a metal oxide particularly in an abnormal state such as a nail penetration test. This reaction is considered to be difficult to suppress by the aluminum oxide film on the surface of the positive electrode current collector.
  • it is considered that the stability of the film is insufficient in an abnormal state, and it is presumed that the above reaction is also difficult to suppress.
  • Patent Document 6 CaSi 2 is reacted with an acid to synthesize a layered silicon compound having layered polysilane as a main component, and the layered silicon compound is heated at 300 ° C. or higher to manufacture a silicon material. And, a lithium ion secondary battery including the silicon material as an active material is described.
  • the present invention has been made in view of such circumstances, and a first object thereof is to provide a current collector for a lithium ion secondary battery having a novel protective layer and a method for producing the same.
  • the second object is to provide a non-aqueous electrolyte secondary battery having a positive electrode current collector made of aluminum, which has high stability at the time of internal short circuit.
  • the current collector for a lithium ion secondary battery of the present invention comprises a current collector body and a protective layer disposed on the surface of the current collector body, and the protective layer comprises antimony-doped tin oxide and an acrylic resin. It is characterized by including.
  • the method for producing a current collector for a lithium ion secondary battery according to the present invention is a method for producing the current collector for a lithium ion secondary battery, which comprises an aqueous dispersion containing antimony-doped tin oxide under stirring.
  • a process for preparing a composition for forming a protective layer which prepares a composition for forming a protective layer by adding a binder-containing water, and a composition for forming a protective layer are applied to a current collector body, and dried by heating.
  • the non-aqueous electrolyte secondary battery of the present invention is a reaction that is disposed on the surface of a positive electrode current collector made of aluminum and the surface of a positive electrode current collector, and suppresses the reaction between the positive electrode current collector and the positive electrode active material.
  • the reaction suppression layer comprises conductive particles and A binder for a reaction suppression layer
  • the positive electrode active material contains a metal oxide
  • the conductive particles are indium oxide, zinc oxide, zinc peroxide, tin (II) oxide, tin (IV) oxide, tin oxide (VI), germanium nitride, titanium nitride, zirconium nitride, hafnium nitride, tantalum nitride, niobium nitride, vanadium nitride, tungsten nitride, element X doped indium oxide (element X is Zn, Mo, W, Ti, Zr, Sn and H
  • a small number selected from Element Y-doped tin (IV) oxide (element Y is at least
  • the negative electrode active material preferably contains a Si-based active material.
  • the conductive particles are preferably antimony-doped tin oxide (IV) in which the doping ratio of Sb (antimony) is more than 0% by mass and 20% by mass or less.
  • the positive electrode preferably has a positive electrode tab portion, and the positive electrode tab portion preferably has a positive electrode current collector and a reaction suppression layer disposed on a part of the positive electrode current collector.
  • the thickness of the reaction suppression layer is preferably 10 nm to 1000 nm.
  • the current collector for a lithium ion secondary battery of the present invention has a novel protective layer containing antimony-doped tin oxide and an acrylic resin.
  • the collector body of the current collector for a lithium ion secondary battery of the present invention is well protected by the protective layer.
  • a novel protective layer containing antimony-doped tin oxide and an acrylic resin can be easily formed on the current collector body.
  • the non-aqueous electrolyte secondary battery of the present invention since the reaction suppression layer for suppressing the reaction between the positive electrode active material and the current collector made of aluminum is provided on the positive electrode, the reaction between the positive electrode active material and the current collector for the positive electrode Is suppressed. Therefore, the non-aqueous electrolyte secondary battery of the present invention can obtain good results in the nail penetration test and is excellent in stability even at the time of internal short circuit.
  • the numerical range “a to b” described in the present specification includes the lower limit a and the upper limit b in that range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range. Further, numerical values arbitrarily selected from within the numerical value range can be used as upper limit and lower limit numerical values.
  • the current collector for a lithium ion secondary battery of the present invention has a current collector body and a protective layer.
  • the current collector body When a protective layer is formed on the current collector body, the current collector body is defined in a high voltage operating environment (herein, use at a voltage of 4.3 V or higher is defined as high voltage use). Is well protected from electrolytes and the like.
  • the protective layer since the protective layer is disposed on the surface of the current collector body, it is difficult to form a passive film of Al 2 O 3 , AlF 3 or the like on the surface of the current collector body. Therefore, this protective layer can suppress the formation of a high resistance layer made of a passive film on the surface of the current collector body.
  • FIG. 1 The schematic diagram explaining the collector for lithium ion secondary batteries of this embodiment in FIG. 1 is shown.
  • a protective layer 2 is disposed on the current collector body 1.
  • the current collector body refers to a chemically inactive electron conductor for keeping current flowing to the electrode during discharge or charge of the lithium ion secondary battery.
  • the material of the current collector body examples include metal materials such as stainless steel, titanium, nickel, aluminum, copper and the like, and conductive resins.
  • the material of the current collector main body is preferably made of aluminum.
  • To be made of aluminum refers to being made of pure aluminum or an aluminum alloy.
  • Aluminum having a purity of 99.0% or more is referred to as pure aluminum, and an alloy obtained by adding various elements to aluminum is referred to as an aluminum alloy.
  • the aluminum alloy include Al-Cu-based, Al-Mn-based, Al-Fe-based, Al-Si-based, Al-Mg-based, AL-Mg-Si-based and Al-Zn-Mg-based.
  • aluminum alloys include A1000 series alloys (pure aluminum series) such as JIS A 1085 and A1 N30, A3000 series alloys (Al-Mn series) such as JIS A 3003 and A 3004, and A 8000 series alloys (Al-Al alloy such as JIS A 8079 and A 8021). Fe series can be mentioned.
  • the shape of the current collector body can be in the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh or the like.
  • a foil can be suitably used as the shape of the current collector body.
  • the thickness of the current collector body is preferably 10 ⁇ m to 100 ⁇ m, and more preferably 15 ⁇ m to 25 ⁇ m.
  • the current collector body it is preferable to use a degreased current collector body.
  • the degreasing treatment include heat treatment, corona treatment, plasma treatment and the like.
  • the material manufactured by the electrolytic method it is preferable to use the material manufactured by the electrolytic method as a collector body from the point which degreasing processing is unnecessary.
  • the protective layer is disposed on the surface of the current collector body and includes antimony-doped tin oxide and an acrylic resin.
  • Antimony-doped tin oxide (hereinafter sometimes referred to as ATO) is tin oxide doped with antimony. Tin oxide is resistant to atmospheric oxygen, electrolytes and electrolytes, and also maintains its resistance well even in high voltage operating environments. Tin oxide is also excellent in oxidation resistance. While having the characteristics of tin oxide, ATO has a significantly improved conductivity compared to tin oxide.
  • the doping amount of antimony is not particularly limited. As the ATO, for example, one doped with 0.1% by mass to 2% by mass of antimony with respect to tin oxide can be favorably used.
  • antimony-doped tin oxide coated oxide (hereinafter referred to as ATO coated oxide) can also be used, including ATO.
  • Examples of the ATO coating oxide include titanium oxide whose surface is coated with ATO, zirconium oxide whose surface is coated with ATO, and cerium oxide whose surface is coated with ATO.
  • the oxide coated on the surface with ATO has higher conductivity than that of the oxide before coating because the conductivity of ATO is high.
  • ATO particles are preferred.
  • the ATO particles are composed not only of the particle surface but also of the inside of the particle from ATO having high electron conductivity. Therefore, ATO particles have higher electron conductivity than ATO-coated oxide particles, and the volume resistivity of ATO particles is comparable to that of ATO-coated oxide particles in terms of volume resistivity of powder. It is about 1/3 to 1/2 of the volume resistance value.
  • the shape of the ATO and ATO coated oxide is not particularly limited, and examples thereof include spherical particle shape and needle-like particle shape.
  • SN-100P spherical powder
  • SN-100D spherical water dispersion
  • SNS-10M spherical methyl ethyl ketone dispersion
  • FS-10P manufactured by Ishihara Sangyo Co., Ltd. as a material containing ATO particles (Needle-like powder), FS-10D (needle-like water dispersion), T-1 (spherical powder) and TDL-1 (spherical water dispersion) manufactured by Mitsubishi Materials Electronics Chemical Corporation.
  • ATO coating oxide particles specifically, for example, Ishihara Sangyo Kaisha Ltd. ET-300 W (spherical ATO coating TiO 2), ET-500 W (spherical ATO coating TiO 2), ET-600W (spherical ATO coated TiO 2 And FT-1000 (needle-like ATO coated TiO 2 ), FT-2000 (needle-like ATO coated TiO 2 ), and FT-3000 (needle-like ATO coated TiO 2 ).
  • the average particle diameter of the primary particles is preferably 50 nm or less. If the average particle size of the primary particles is larger than 50 nm, the thickness of the protective layer may be too thick.
  • the average particle size of the primary particles can be determined by directly measuring the particle sizes of 20 to 30 particles from the observation image by an electron microscope and taking the average value.
  • the cumulant average particle diameter of the ATO particles or ATO coated oxide particles is preferably 200 nm or less, and more preferably about 100 nm.
  • the cumulant average particle size is a numerical value calculated by measuring the particle size of particles in a liquid by the dynamic light scattering method and analyzing the obtained data by the Cumulant method.
  • the cumulant average particle diameter of the particles is larger than 200 nm, the particles may be significantly aggregated, and it is difficult to coat the composition for forming a protective layer on the current collector body, and the thickness of the protective layer becomes too thick There is a fear.
  • the compounding amount of the particles can be smaller than that of the spherical shape particles.
  • the needle-shaped particles can create long conductive paths in the protective layer even if the number of particles contained in the protective layer is small. Therefore, the needle-like shaped particles can ensure the same conductivity with a smaller blending amount than spherical shaped particles.
  • the needle-shaped particles preferably have a minor axis of 300 nm or less. If the minor axis of the needle-like shaped particles is larger than 300 nm, the particles themselves become very large and easily precipitate, which may make it impossible to maintain the dispersion stability of the composition for forming a protective layer.
  • the major axis is preferably 0.2 ⁇ m to 20 ⁇ m
  • the minor axis is 0.01 ⁇ m to 0.3 ⁇ m
  • the aspect ratio (major axis / minor axis) is preferably 10 to 30.
  • Acrylic resin is a general term for polymers containing monomers of acrylic acid, methacrylic acid and their derivatives, and those obtained by heat-drying polymers.
  • acrylic acid and methacrylic acid are generically referred to as (meth) acrylic acid.
  • Examples of the derivative of (meth) acrylic acid include salts of (meth) acrylic acid ester, (meth) acrylic acid amide and (meth) acrylic acid.
  • (meth) acrylic acid esters examples include (meth) acrylic acid alkyl esters and (meth) acrylic acid hydroxyalkyl esters.
  • As (meth) acrylic acid alkyl ester for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, pentyl (meth) acrylic acid Examples thereof include esters, hexyl ester of (meth) acrylic acid, heptyl ester of (meth) acrylic acid and octyl ester of (meth) acrylic acid.
  • the (meth) acrylic acid alkyl esters may be used singly or in combination of two or more.
  • (meth) acrylic acid hydroxyalkyl ester those in which a hydroxy group is substituted by the alkyl group of the (meth) acrylic acid alkyl ester can be mentioned.
  • the (meth) acrylic acid hydroxyalkyl esters may be used alone or in combination of two or more.
  • salts of (meth) acrylic acid include sodium salts of (meth) acrylic acid and ammonium salts of (meth) acrylic acid.
  • the acrylic resin acts as a binder for the protective layer which bonds the ATOs and between the ATO and the current collector body.
  • Acrylic resin is excellent in adhesion to ATO and adhesion to the current collector body.
  • the composition for protective layer formation containing an acrylic resin has good dispersibility of ATO, and an acrylic resin and ATO are easy to be mixed uniformly.
  • the acrylic resin can be dissolved or dispersed in an environmentally friendly aqueous solvent.
  • (Meth) acrylic acid has a carboxyl group, and the polymer is very hydrophilic.
  • poly (meth) acrylic acid can be used as a water soluble binder.
  • Acrylic emulsions can also be used as water dispersible binders.
  • poly (meth) acrylic acid having a mass average molecular weight (hereinafter referred to as weight average molecular weight) of 3000 or more and 10000 or less as the acrylic resin. If the weight average molecular weight of the poly (meth) acrylic acid is too large, the storage stability of the coating liquid may be deteriorated, and a precipitate may be precipitated during storage of the coating liquid. If the weight-average molecular weight of poly (meth) acrylic acid is too small, the adhesion to the current collector after coating and drying will be reduced, and there is a risk of dissolution and peeling due to the solvent when coating the electrode mixture layer.
  • poly (meth) acrylic acid is preferable because it has a large amount of carboxylic acid groups and has high adhesion to the current collector body after coating and drying.
  • an acrylic resin is a dispersion in which particles of acrylic resin are dispersed in water.
  • Acrylic emulsions are of non-reactive type, reactive type, self-crosslinking type, etc., and have a wide range of polymer composition and glass transition point (hereinafter referred to as Tg).
  • the non-reaction type is one in which the emulsions are bound together by the caking properties of the acrylic emulsion itself.
  • the acrylic emulsion has a reactive functional group, and the emulsions are crosslinked by blending a crosslinking agent.
  • a self-crosslinking functional group is introduced into the acrylic emulsion, and the emulsions are crosslinked alone.
  • acrylic resin in the acrylic emulsion examples include polymers of (meth) acrylic acid derivatives, and copolymers of (meth) acrylic acid or its derivatives and an ethylenically unsaturated monomer.
  • Ethylenically unsaturated monomers include itaconic acid, fumaric acid, maleic acid, styrene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, butadiene.
  • the acrylic emulsion includes not only acrylic resin but also those modified with other resins such as epoxy resin, ester resin, urethane resin, etc.
  • the modified acrylic emulsion has heat resistance and water resistance depending on the constitution of the resin to be modified. It is possible to widely control the physical properties of the coating film, such as chemical resistance and alkali resistance.
  • a commercial item can be used suitably as an acryl-type emulsion.
  • the acrylic emulsion modified with an ester resin under the trade names Joncryl PDX-7341 and Joncryl PDX-7430 (all are BASF Japan Ltd.) have good compatibility with ATO particles, and aluminum current collectors. Adhesion to the body is also high, which is preferable.
  • the thickness of the protective layer may be too thick. 0.5 micrometer or less is preferable and, as for the average particle diameter of the acrylic resin in an acryl-type emulsion, 0.2 micrometer or less is more preferable.
  • Acrylic emulsions are known to be defined at the minimum film forming temperature.
  • the minimum film formation temperature is the temperature required for the emulsions themselves to bind to each other to form a film. If it is an acrylic emulsion having a low minimum film-forming temperature, it becomes an acrylic resin that acts as a binder at a low heat-drying temperature, and is suitably used for the current collector for a lithium ion secondary battery of the present invention.
  • a preferred minimum film-forming temperature range -20 ° C to 80 ° C can be exemplified.
  • the pH of the acrylic emulsion is preferably about 7 to 9.
  • mixing can be performed without significantly changing the zeta potential of the ATO particles when mixed with ATO particles, and the storage stability of the slurry after being mixed is also good.
  • the Tg of the acrylic emulsion is preferably 5 ° C. or more and 50 ° C. or less. If it is an acrylic emulsion having a low Tg, it becomes an acrylic resin that acts as a binder at a low heat drying temperature, and is suitably used for the current collector for a lithium ion secondary battery of the present invention.
  • the thickness of the protective layer is preferably 50 nm or more and 1000 nm or less, more preferably 50 nm or more and less than 275 nm, and more preferably 50 nm or more and less than 100 nm. If the thickness of the protective layer is too thick, the lithium ion secondary battery using the current collector having the protective layer as an electrode may have high resistance. If the thickness of the protective layer is too thin, the protective effect of the current collector by the protective layer may not be obtained. When the thickness of the protective layer is less than 100 nm, the electrode resistance increase rate can be further suppressed.
  • the method for forming the protective layer on the current collector body is not particularly limited, and any known method can be used.
  • the protective layer can be favorably formed on the current collector body by using the following method for producing a current collector for a lithium ion secondary battery of the present invention.
  • the method for producing a current collector for a lithium ion secondary battery of the present invention has a step of preparing a composition for forming a protective layer, and a step of forming a protective layer.
  • the composition preparation step for forming a protective layer is a step of preparing a composition for forming a protective layer by adding an aqueous binder-containing water to an aqueous dispersion containing antimony-doped tin oxide under stirring.
  • an aqueous dispersion containing antimony-doped tin oxide is used.
  • the water dispersion refers to one in which particles are dispersed in water.
  • dispersion means that particles are uniformly dispersed in the form of fine particles in water.
  • the water in the aqueous dispersion is preferably one from which impurities such as distilled water and ion exchanged water have been removed.
  • An alcohol may be added to the water in the aqueous dispersion. Examples of the alcohol include methanol, ethanol and isopropanol.
  • ATO particles or ATO coated oxide particles are highly hydrophilic. When ATO particles or ATO coated oxide particles are mixed with water, an aqueous dispersion can be obtained. Furthermore, the aqueous dispersion may contain a dispersant in order to achieve a more stable dispersion state.
  • the content of particles in the aqueous dispersion of ATO particles or ATO coated oxide particles is preferably 1.0% by mass or more and 40.0% by mass or less based on 100% by mass of the entire aqueous dispersion, More preferably, it is 3.0% by mass or more and 30.0% by mass or less. If the content of the particles is less than 1.0% by mass, the content of water is large, and thus the coatability may be deteriorated and the drying efficiency may also be reduced. When the content of the particles is more than 40.0% by mass, it is difficult to maintain the dispersion stability of the particles, and the particles may be easily aggregated or precipitated.
  • the aqueous binder-containing water is a poly (meth) acrylic acid aqueous solution or an acrylic emulsion.
  • the water in the water-based binder-containing water is preferably one from which impurities such as distilled water and ion-exchanged water have been removed.
  • An alcohol may be added to the water in the aqueous binder-containing water. Examples of the alcohol include methanol, ethanol and isopropanol.
  • the content of the aqueous binder in the aqueous binder-containing water is preferably 0.1% by mass to 50.0% by mass, and more preferably 0.5% by mass to 10.0% by mass. If the content of the water-based binder is too small, the solid content becomes too small when the composition for forming a protective layer is produced, the coatability may deteriorate, and the drying efficiency may decrease. In addition, when the content of the aqueous binder is too large, the viscosity of the aqueous binder-containing water becomes very high, and the mixing property may be deteriorated when it is mixed with the ATO particles or the aqueous dispersion of ATO coated oxide particles.
  • the aqueous dispersion and the aqueous binder-containing water are mixed by adding the aqueous binder-containing water to the aqueous dispersion while stirring the aqueous dispersion of ATO particles or ATO-coated oxide particles with a stirrer at a rotational speed of 1000 rpm or more. It is preferable to do.
  • a stirrer is a stirring device.
  • the stirrer include a homodisper, a homomixer and a homogenizer.
  • the stirrer is preferably a homodisper having high mixing performance and high-speed stirring even with high viscosity.
  • a stirring condition it is preferable to set it as the rotation speed of 1000 rpm-6000 rpm, and it is more preferable to set it as the rotation speed of 1500 rpm-3000 rpm. Agitation at a rotational speed less than 1000 rpm may lead to agglomeration of the ATO particles or ATO coated oxide particles.
  • Aqueous dispersions of ATO particles or ATO-coated oxide particles may aggregate at abrupt pH changes.
  • the aqueous binder-containing water is a poly (meth) acrylic acid aqueous solution exhibiting acidity
  • the aqueous binder-containing water is added to the aqueous dispersion while the aqueous dispersion of ATO particles or ATO coated oxide particles is stirred at high speed with a stirrer. Is preferably added gradually.
  • the addition order is reversed and the aqueous dispersion of ATO particles or ATO coated oxide particles is added to the aqueous poly (meth) acrylic acid solution, the ATO particles or ATO coated oxide particles tend to aggregate.
  • water-based binder-containing water to the aqueous dispersion of ATO particles or ATO coated oxide particles can suppress abrupt pH change of the mixed system by gradually adding it over a while rather than adding it at once.
  • the aggregation behavior of ATO particles or ATO coated oxide particles can be suppressed.
  • an aqueous dispersion of ATO particles or ATO-coated oxide particles having 1.0% by mass or more and 40.0% by mass or less It is preferable to add 60 g to 90 g of water containing an aqueous binder having a content of the aqueous binder of 0.1% by mass to 50.0% by mass in 5 to 60 minutes to 10 g to 40 g.
  • the content ratio of the water-based binder in the protective layer is preferably 0.1% by mass or more and 20% by mass or less.
  • the content of the aqueous binder is too large, the content of the ATO particles or ATO coated oxide particles may be reduced to lower the conductivity of the protective layer, and if the content of the aqueous binder is too small, the ATO particles or ATO may be contained. There is a possibility that the binder effect of binding the coated oxide particles to the current collector body may not be obtained.
  • the protective layer forming step is a step of applying a composition for forming a protective layer on the current collector body and drying by heating to form a protective layer on the surface of the current collector body.
  • composition for forming a protective layer As a method of applying the composition for forming a protective layer, conventionally known methods such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, a curtain coating method, and a gravure coating method may be used.
  • the current collector body on which the composition for forming a protective layer is applied is dried by heating to arrange the protective layer on the surface of the current collector body.
  • the heat drying plays a role of evaporating water from the composition for forming a protective layer and binding the ATO particles or ATO coated oxide particles to the current collector main body with an acrylic resin.
  • the heating and drying temperature is preferably such that the water can be evaporated and the temperature is higher than the minimum film forming temperature of the acrylic resin used.
  • the heating and drying conditions vary depending on the acrylic resin used, but for example, the heating and drying can be performed at 40 ° C. to 120 ° C. for 1 minute to 15 minutes.
  • the protective layer forming step may be performed under reduced pressure.
  • the lithium ion secondary battery of the present invention has the above current collector for a lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, a separator, and an electrolyte as battery components.
  • the positive electrode has a current collector and a positive electrode active material layer disposed on the current collector.
  • the current collector those described for the current collector body and the above-described current collector for a lithium ion secondary battery can be used. It is preferable to use the said collector for lithium ion secondary batteries as a collector of a positive electrode.
  • the positive electrode active material layer contains a positive electrode active material and a binder.
  • the positive electrode active material layer may further contain a conductive aid, if necessary.
  • a material containing a lithium-containing compound or another metal compound can be used.
  • the positive electrode active material is preferably made of a lithium-containing oxide represented by the chemical formula: LiMO 2 (M is at least one selected from Ni, Co and Mn), and further, lithium cobalt having a layered structure as described above It is preferable to consist of a containing complex metal oxide.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0. 3 O 2 , LiCoO 2 , LiNi 0.8 Co 0.2 O 2 , LiCoMnO 2 can be used.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and LiNi 0.5 Co 0.2 Mn 0.3 O 2 are preferable in view of thermal stability.
  • the positive electrode active material is preferably in the form of powder having an average particle diameter D 50 of 1 ⁇ m to 20 ⁇ m.
  • the average particle diameter D 50 of the positive electrode active material is small, the specific surface area of the positive electrode active material is increased.
  • the reaction area of the average particle diameter D 50 of the positive electrode active material is too small and the positive electrode active material and the electrolyte becomes excessive increase it, as a result, are accelerated decomposition of the electrolytic solution, the lithium ion secondary Battery cycle characteristics may be degraded.
  • the average particle diameter D 50 of the positive electrode active material is too large resistance of the lithium ion secondary battery increases, there is a possibility that the output characteristics of the lithium ion secondary battery decreases.
  • the average particle diameter D 50 is that the particle size cumulative value of the volume distribution in the particle size distribution measurement by laser diffraction method is equivalent to 50%. That is, the average particle diameter D 50 means the median size measured by volume.
  • the binder plays a role of securing the positive electrode active material and the conductive auxiliary agent to the current collector.
  • the binder for example, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (abbr. FEP), fluorine-containing resin such as fluororubber, thermoplastic resin such as polypropylene, polyethylene, polyimide, Imide-based resins such as polyamideimide, acrylic resins such as poly (meth) acrylic acid, alkoxysilyl group-containing resins, styrene butadiene rubber, carboxymethyl cellulose, polyethylene glycol, and polyacrylonitrile can be exemplified.
  • the compounding ratio of the binder in the positive electrode active material layer is, in mass ratio, preferably: positive electrode active material: binder 1: 0.001 to 1: 0.3.
  • the positive electrode active material: binder is more preferably 1: 0.005 to 1: 0.2, and still more preferably 1: 0.01 to 1: 0.15. If the amount of the binder is too small, the formability of the electrode may be reduced. If the amount of the binder is too large, the energy density of the electrode may be reduced.
  • a conductive aid is added as needed to enhance the conductivity of the electrode.
  • carbon black fine particles such as carbon black, graphite, acetylene black (AB), ketjen black (registered trademark) (KB), vapor grown carbon fiber (VGCF), etc. are used singly or in combination of two or more. It can be used.
  • the amount of the conductive aid used is not particularly limited, but can be, for example, about 1 to 30 parts by mass with respect to 100 parts by mass of the active material contained in the positive electrode.
  • the conventional methods such as roll coating, dip coating, doctor blade, spray coating, curtain coating, lip coating, comma coating, die coating, etc.
  • a known method may be used.
  • a composition for forming a positive electrode active material layer containing a positive electrode active material, a binder and, if necessary, a conductive auxiliary agent is prepared, and a suitable solvent is added to the composition to form a slurry.
  • the binder may be used as a solution or a suspension in which the binder is previously dissolved in a solvent.
  • the solvent include water, N-methyl-2-pyrrolidone (NMP), methanol and methyl isobutyl ketone (MIBK).
  • NMP N-methyl-2-pyrrolidone
  • MIBK methyl isobutyl ketone
  • the drying temperature may be set appropriately, and a temperature above the boiling point of the solvent is preferable.
  • the drying time may be appropriately set according to the amount of application and the drying temperature.
  • a compression step may be added to the current collector after forming the positive electrode active material layer by drying.
  • the negative electrode includes a current collector and a negative electrode active material layer bonded to the surface of the current collector.
  • the negative electrode active material layer contains a negative electrode active material and a binder, and optionally contains a conductive auxiliary.
  • the current collector, the binder, and the conductive additive are the same as those described for the positive electrode.
  • a carbon-based material capable of occluding and releasing lithium an element capable of alloying with lithium, a compound having an element capable of alloying with lithium, a polymer material, or the like can be used.
  • the carbon-based material examples include non-graphitizable carbon, artificial graphite, natural graphite, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, activated carbon or carbon blacks.
  • the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenol or furan at an appropriate temperature.
  • the elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn At least one of Pb, Sb, and Bi.
  • an element capable of being alloyed with lithium is preferably silicon (Si) or tin (Sn).
  • a compound having an element capable of alloying with lithium for example, ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2, CrSi 2, Cu 5 Si , FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2) SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO 2 or LiSnO.
  • a silicon compound or a tin compound is preferable.
  • a silicon compound SiO x (0.5 ⁇ x ⁇ 1.6) is preferable.
  • tin compounds include tin alloys (Cu-Sn alloy, Co-Sn alloy, etc.).
  • the silicon-based active material a silicon material having a structure in which a plate-like silicon body described in the second embodiment below is laminated in the thickness direction can be mentioned.
  • polymer material examples include polyacetylene and polypyrrole.
  • the negative electrode active material is preferably in the form of powder. If the anode active material is in powder form, it is preferable that the average particle size D 50 of the negative electrode active material is 0.5 ⁇ m or more 30 ⁇ m or less, and more preferably 1 ⁇ m or more 20 ⁇ m or less. When the average particle diameter D 50 of the negative electrode active material is too small, the specific surface area of the powder of the negative electrode active material increases, the contact area between the powder of the negative electrode active material and the electrolyte increases, and decomposition of the electrolyte proceeds. As a result, the cycle characteristics of the lithium ion secondary battery may be deteriorated. When the average particle diameter D 50 of the negative electrode active material is too large, conductivity of the whole electrode becomes uneven, charging and discharging characteristics may deteriorate.
  • the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass while preventing the short circuit of the current due to the contact of the both electrodes.
  • the separator may be, for example, a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene or polyethylene, or a porous film made of ceramic.
  • the electrolytic solution contains a solvent and an electrolyte dissolved in the solvent.
  • cyclic esters linear esters, ethers
  • cyclic esters for example, ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone and gamma valerolactone
  • chain esters for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, acetic acid alkyl ester can be used.
  • ethers for example, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane can be used.
  • lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 can be used.
  • an electrolytic solution for example, 0.5 mol / l to 1.7 mol / l of lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 and the like in a solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethyl carbonate It is possible to use solutions dissolved at a certain concentration.
  • a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body.
  • the electrode body may be any of a laminated type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are wound.
  • the lithium ion secondary battery can be mounted on a vehicle.
  • Any vehicle may be used as long as it uses electric energy from batteries for all or part of the power source.
  • electric vehicles for example, electric vehicles, hybrid vehicles, plug-in hybrid vehicles, hybrid railway vehicles, electric forklifts, electric wheelchairs, electric assists There are bicycles and electric motorcycles.
  • the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode having a positive electrode current collector, a reaction suppression layer, and a positive electrode active material layer, and a negative electrode.
  • the positive electrode of the non-aqueous electrolyte secondary battery of the present invention comprises a current collector for a positive electrode, a reaction suppression layer disposed on the surface of the current collector for the positive electrode, and a positive electrode active material layer disposed on the surface of the reaction suppression layer.
  • the positive electrode current collector is made of aluminum and made of pure aluminum or an aluminum alloy.
  • Aluminum having a purity of 99.0% or more is referred to as pure aluminum, and an alloy obtained by adding various elements to aluminum is referred to as an aluminum alloy.
  • the aluminum alloy include Al-Cu-based, Al-Mn-based, Al-Fe-based, Al-Si-based, Al-Mg-based, AL-Mg-Si-based and Al-Zn-Mg-based.
  • aluminum alloys include A1000 series alloys (pure aluminum series) such as JIS A 1085 and A1 N30, A3000 series alloys (Al-Mn series) such as JIS A 3003 and A 3004, and A 8000 series alloys (Al-Al alloy such as JIS A 8079 and A 8021). Fe series can be mentioned.
  • the shape of the positive electrode current collector can be in the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like.
  • a positive electrode current collector for example, a foil can be suitably used.
  • the thickness of the current collector for the positive electrode is preferably 10 ⁇ m to 100 ⁇ m, and more preferably 15 ⁇ m to 25 ⁇ m.
  • the current collector refers to a chemically inactive electron high conductor for keeping current flow to the electrode during discharge or charge of the non-aqueous electrolyte secondary battery.
  • Pure aluminum or an aluminum alloy is also stable in a non-aqueous electrolyte under high voltage use environment (herein, use at a voltage of 4.3 V or higher is defined as high voltage use). Therefore, an aluminum current collector made of pure aluminum or an aluminum alloy is preferably used for the positive electrode of the non-aqueous electrolyte secondary battery.
  • reaction suppression layer is disposed on the surface of the positive electrode current collector, and suppresses the reaction between the positive electrode current collector and the positive electrode active material.
  • a reaction suppression layer is provided on the surface of the current collector for the positive electrode.
  • the reaction suppression layer has conductive particles and a binder for the reaction suppression layer.
  • the conductive particles include indium oxide, zinc oxide, zinc peroxide, tin (II) oxide, tin (IV) oxide, tin (VI) oxide, germanium nitride, titanium nitride, zirconium nitride, hafnium nitride, tantalum nitride, niobium nitride Vanadium nitride, tungsten nitride, element X-doped indium oxide (element X is at least one selected from Zn, Mo, W, Ti, Zr, Sn and H), element Y-doped tin (IV) oxide (element Y is At least one selected from F, W, Ta, Sb, P and B) and element Z-doped zinc oxide (element Z is at least one selected from Ga, Al and B) .
  • the conductive particles are conductive, resistant to organic solvents, corrosion resistant to oxidation-reduction reactions, and low in reaction activity. In addition, the conductive particles are less likely to burn by themselves and to be less likely to react with aluminum. The conductive particles are conductive, and thus are unlikely to be resistant to the non-aqueous electrolyte secondary battery.
  • the conductive particles may be used alone or in combination of two or more.
  • antimony-doped tin oxide (IV) (abbr. ATO) in which Sb 2 O 3 is added to tin oxide (IV) is preferable.
  • ATO has high electrical conductivity, is resistant to atmospheric oxygen, electrolytes and salts, and exhibits high resistance even at high voltages. It is preferable that the conductivity of the conductive particles is higher because the increase in the resistance of the positive electrode can be suppressed and the decrease in the capacity of the non-aqueous electrolyte secondary battery can be suppressed.
  • the proportion of the doped amount of antimony in ATO is preferably more than 0% by mass and 20% by mass or less, and more preferably 5% by mass to 16% by mass.
  • the ratio of the doping amount of antimony is large because the electrical conductivity of ATO is high.
  • the electrical conductivity of ATO does not increase in proportion to the amount of antimony even if the proportion of the doped amount of antimony exceeds 20% by mass.
  • the average particle size D 50 of the conductive particles is preferably 10 nm to 1000 nm, more preferably 20 nm to 100 nm, and still more preferably 50 nm to 80 nm.
  • the average particle diameter D 50 can be measured by particle size distribution measurement method.
  • the average particle diameter D 50 is that the particle size cumulative value of the volume distribution in the particle size distribution measurement by laser diffraction method is equivalent to 50%. That is, the average particle diameter D 50 means the median size measured by volume.
  • the binder for reaction suppression layer bonds the conductive particles to each other, and bonds the conductive particles and the current collector for the positive electrode.
  • the binder for the reaction suppression layer is not particularly limited as long as it is a binder that can be used for the non-aqueous electrolyte secondary battery.
  • a binder for the reaction suppression layer for example, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (abbr. FEP), fluorine-containing resin such as fluororubber, thermoplastic resin such as polypropylene, polyethylene, etc.
  • fluorine-containing resin such as fluororubber
  • thermoplastic resin such as polypropylene, polyethylene, etc.
  • examples thereof include polyimide, imide resins such as polyamideimide, acrylic resins such as poly (meth) acrylic acid, alkoxysilyl group-containing resins, styrene butadiene rubber, carboxymethyl cellulose, polyethylene glycol and polyacrylonitrile.
  • binders for reaction suppression layer can be used individually or in combination of 2 or more types.
  • polyacrylic acid polytetrafluoroethylene and polyethylene glycol are preferably used. These binders for reaction suppression layer are excellent in adhesion to the current collector for the positive electrode, and excellent in coatability on the current collector for the positive electrode.
  • the compounding ratio of the conductive particles to the binder for the reaction suppression layer is preferably such that the mass ratio of conductive particles to the binder for the reaction suppression layer is 1: 1 to 100: 1. If the compounding ratio is within this range, the conductive particles and the conductive particles and the positive electrode current collector are favorably bound in the reaction suppression layer. Moreover, if it is this compounding ratio, it can suppress that resistance of an electrode rises excessively by the reaction suppression layer.
  • the thickness of the reaction suppression layer is preferably 10 nm to 1000 nm, and more preferably 20 nm to 500 nm. If the thickness of the reaction suppression layer is too small, it may be difficult to obtain the effect of the reaction suppression between the positive electrode active material and the positive electrode current collector by the reaction suppression layer. If the thickness of the reaction suppression layer is too large, the volume occupied by the reaction suppression layer in the non-aqueous electrolyte secondary battery becomes too large, and the amount of the active material has to be reduced, which may lower the battery capacity.
  • the method for arranging the reaction suppression layer on the positive electrode current collector is not particularly limited, but the following method can be employed.
  • a binder for reaction suppression layer and conductive particles are mixed with a solvent to obtain a slurry for reaction suppression layer.
  • the solvent can be water or an organic solvent.
  • the organic solvent ethanol, methanol, benzene, dichloromethane and the like can be used.
  • Water contains a small amount of inorganic salts and the like, and the pH can be used even in the range of pH 4 to pH 9.
  • water preferably has a pH of 6 to 8 from which impurities have been removed, such as distilled water or ion-exchanged water.
  • the conductive particles are preferably dispersed in the reaction suppression layer slurry.
  • the conductive particles are easily disposed in the entire reaction suppression layer in the completed reaction suppression layer.
  • the addition amount of the reaction suppression layer binder which is an organic substance, may be appropriately adjusted so that the conductive particles do not aggregate.
  • the slurry for the reaction suppression layer is applied to the positive electrode current collector.
  • a coating method conventionally known methods such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, a curtain coating method, and a gravure coating method may be used.
  • the positive electrode current collector coated with the reaction suppression layer slurry is dried, and the reaction suppression layer is disposed on the surface of the positive electrode current collector.
  • the positive electrode active material layer is disposed on the surface of the reaction suppression layer and has a positive electrode active material containing a metal oxide.
  • the positive electrode active material layer may contain a binder and a conductive additive as needed.
  • a lithium ion secondary battery will be described as an example of a non-aqueous electrolyte secondary battery.
  • the positive electrode active material contains a metal oxide.
  • Metal oxides include lithium-containing oxides or other metal oxides.
  • a titanium oxide, a vanadium oxide, or manganese dioxide is mentioned, for example.
  • LiMO 2 is at least one selected from Ni, Co and Mn
  • D is at least one selected from Al, Mg, Ti, Sn, Zn
  • LiMO 2 As a lithium-containing oxide represented by a chemical formula: LiMO 2 (M is at least one selected from Ni, Co and Mn), for example, LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiCoO 2 , LiNi 0.8 Co 0.2 O 2 , LiCoMnO 2 and the like. Among them, LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and LiNi 0.5 Co 0.2 Mn 0.3 O 2 are preferable in view of thermal stability.
  • the positive electrode active material may contain another positive electrode active material in addition to the metal oxide.
  • positive electrode active materials include elemental sulfur (S), compounds in which sulfur and carbon are complexed, and metal sulfides such as TiS 2 .
  • the positive electrode active material is preferably in the form of powder having an average particle diameter D 50 of 1 ⁇ m to 20 ⁇ m.
  • the average particle diameter D 50 of the positive electrode active material is small, the specific surface area of the positive electrode active material is increased. Therefore, if the average particle size D 50 of the positive electrode active material is too small, the reaction area between the positive electrode active material and the electrolyte solution will be excessively increased, and as a result, the decomposition of the electrolyte solution is promoted. The cycle characteristics of the secondary battery may be deteriorated. Resistance of the average particle diameter D 50 is too the nonaqueous electrolyte secondary battery size of the positive electrode active material becomes large, there is a possibility that the output characteristics of the nonaqueous electrolyte secondary battery decreases.
  • the binding agent plays a role of fixing the positive electrode active material to the reaction suppression layer.
  • the binder for example, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (abbr. FEP), fluorine-containing resin such as fluororubber, thermoplastic resin such as polypropylene, polyethylene, polyimide, Imide-based resins such as polyamideimide, acrylic resins such as poly (meth) acrylic acid, alkoxysilyl group-containing resins, styrene butadiene rubber, carboxymethyl cellulose, polyethylene glycol, and polyacrylonitrile can be exemplified.
  • the compounding ratio of the binder in the positive electrode active material layer is, in mass ratio, preferably: positive electrode active material: binder 1: 0.001 to 1: 0.3.
  • the positive electrode active material: binder is more preferably 1: 0.005 to 1: 0.2, and still more preferably 1: 0.01 to 1: 0.15. If the amount of the binder is too small, the formability of the electrode may be reduced. If the amount of the binder is too large, the energy density of the electrode may be reduced.
  • the conductive aid is added to the positive electrode active material layer as needed to enhance the conductivity of the electrode.
  • carbon black fine particles such as carbon black, graphite, acetylene black (abbr. AB), ketjen black (registered trademark) (abbr. KB), vapor grown carbon fiber (abbr. VGCF), etc. alone or in combination
  • the above can be used in combination.
  • the amount of the conductive aid used is not particularly limited, but can be, for example, about 1 to 30 parts by mass with respect to 100 parts by mass of the active material contained in the electrode.
  • a composition for forming a positive electrode active material layer containing a positive electrode active material and a binder, and optionally a conductive auxiliary agent is prepared, and this composition is further provided.
  • a suitable solvent may be added to form a paste, and the paste may be applied to the surface of the reaction suppression layer and then dried. If necessary, the positive electrode current collector on which the positive electrode active material layer is disposed may be compressed to increase the electrode density.
  • composition for forming the positive electrode active material layer may be applied by any of the conventionally known methods such as roll coating, dip coating, doctor blade, spray coating, curtain coating, lip coating, comma coating, and die coating. The method may be used.
  • water N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone and the like can be used.
  • FIG. 3 The schematic diagram explaining the positive electrode for non-aqueous electrolyte secondary batteries of 2nd embodiment is shown in FIG.
  • the reaction suppression layer 4 is disposed on the positive electrode current collector 3
  • the positive electrode active material layer 5 is disposed on the surface of the reaction suppression layer 4.
  • the negative electrode has a current collector for the negative electrode and a negative electrode active material layer disposed on the surface of the current collector for the negative electrode.
  • the negative electrode active material layer contains a negative electrode active material and a binder, and optionally contains a conductive auxiliary.
  • the binder and the conductive additive are the same as those described for the positive electrode.
  • the material of the current collector for the negative electrode examples include metal materials such as stainless steel, titanium, nickel, aluminum and copper, and conductive resins.
  • copper or stainless steel is preferable as the material of the current collector for the negative electrode from the viewpoint of electrical conductivity, processability and cost.
  • the form of the current collector for the negative electrode can be in the form of a foil, a sheet, a film, a line, a rod, a mesh or the like.
  • metal foils such as copper foil, nickel foil, aluminum foil, stainless steel foil, can be used suitably, for example.
  • the thickness of the current collector for the negative electrode is preferably 8 ⁇ m to 100 ⁇ m.
  • a carbon-based material capable of occluding and releasing lithium an element capable of alloying with lithium, a compound having an element capable of alloying with lithium, a polymer material, or the like can be used.
  • the carbon-based material examples include graphite, non-graphitizable carbon, cokes, graphites, glassy carbons, an organic polymer compound fired body, carbon fiber, activated carbon and carbon blacks.
  • the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenol or furan at an appropriate temperature.
  • the elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn At least one of Pb, Sb, and Bi.
  • an element capable of being alloyed with lithium is preferably silicon (Si) or tin (Sn).
  • a compound having an element capable of alloying with lithium for example, ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2, CrSi 2, Cu 5 Si , FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO or LiSnO can be used.
  • a silicon compound or a tin compound is preferable.
  • a silicon compound SiO x (0.5 ⁇ x ⁇ 1.5) is preferable.
  • a tin compound for example, a tin alloy (Cu-Sn alloy, Co-Sn alloy, etc.) can be used.
  • Examples of the Si-based active material include a silicon material having a structure in which a plate-like silicon body is stacked in the thickness direction.
  • the structure of the silicon material having a structure in which the plate-like silicon bodies are stacked in the thickness direction can be confirmed by observation with a scanning electron microscope or the like.
  • the plate-like silicon body has a thickness in the range of 10 nm to 100 nm for efficient insertion and desorption reaction of lithium ions. Are preferable, and those in the range of 20 nm to 50 nm are more preferable.
  • the length of the plate-like silicon body in the long axis direction is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
  • the plate-like silicon body preferably has a (longitudinal direction length) / (thickness) in the range of 2 to 1,000.
  • the silicon material may be pulverized or classified into particles having a constant particle size distribution.
  • D 50 can be in the range of 1 ⁇ m to 30 ⁇ m, as measured by a general laser diffraction type particle size distribution measuring device.
  • the silicon material is subjected to X-ray diffraction measurement (XRD measurement), and the silicon crystallite size is calculated from Scheller's equation using the half value width of the diffraction peak of the Si (111) plane of the obtained XRD chart.
  • the size of the silicon crystallite is preferably nano-sized.
  • the silicon crystallite size is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, still more preferably in the range of 1 nm to 50 nm, particularly preferably in the range of 1 nm to 10 nm preferable.
  • the silicon material can be manufactured by the following manufacturing process.
  • the manufacturing process includes a process of reacting CaSi 2 with an acid to manufacture a layered silicon compound containing layered polysilane as a main component, and a process of manufacturing the silicon material by heating the layered silicon compound at 300 ° C. or higher.
  • CaSi 2 generally has a structure in which a Ca layer and a Si layer are laminated.
  • CaSi 2 may be synthesized by a known production method, or a commercially available one may be adopted.
  • CaSi 2 used for manufacturing the layered silicon compound it is preferable to preliminarily pulverized.
  • the acid hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid, fluoro Antimonic acid, hexafluorosilicic acid, hexafluorogermanic acid, hexafluorotin (IV) acid, trifluoroacetic acid, hexafluorotitanic acid, hexafluorozirconic acid, trifluoromethanesulfonic acid and fluorosulfonic acid are exemplified. These acids may be used alone or in combination.
  • the acid is preferably used in the form of an aqueous solution from the viewpoint of the simplicity and safety of operation and the removal of by-products.
  • the acid may be used in an amount capable of supplying two or more equivalents of proton to CaSi 2 . Therefore, in the case of a monovalent acid, 2 moles or more of the acid may be used with respect to 1 mole of CaSi 2 .
  • the reaction conditions are preferably reduced pressure conditions such as vacuum or under an inert gas atmosphere, and temperature conditions below room temperature such as an ice bath are preferable.
  • the reaction time may be set appropriately.
  • reaction formula in the case of using hydrogen chloride as an acid is as follows.
  • Si 6 H 6 which is a polysilane corresponds to an ideal layered silicon compound. This reaction can also be considered to form a Si—H bond while Ca in layered CaSi 2 is replaced by 2H.
  • the layered silicon compound is layered because the basic skeleton of the Si layer in the raw material CaSi 2 is maintained.
  • the acid is preferably used as an aqueous solution in the reaction step of reacting CaSi 2 with the acid.
  • Si 6 H 6 can react with water, normally, a layered silicon compound is hardly obtained only with a compound of Si 6 H 6 and contains an element derived from oxygen or an acid.
  • a silicon material manufacturing process By heating the layered silicon compound at 300 ° C. or higher, hydrogen and the like are released to form a silicon material.
  • the process of heating the layered silicon compound at 300 ° C. or higher may be hereinafter referred to as a silicon material manufacturing process.
  • the silicon material manufacturing process can be represented by the following ideal reaction equation. Si 6 H 6 ⁇ 6 Si + 3 H 2 ⁇
  • the silicon material to be actually obtained also contains an element derived from oxygen or acid, Furthermore, it also contains unavoidable impurities.
  • the molar amount of the oxygen element is preferably 50 or less, and more preferably 40 or less, when the molar amount of silicon is 100.
  • the molar amount of the acid-derived element is preferably 8 or less, and particularly preferably 5 or less.
  • the silicon material production process is preferably carried out in a non-oxidizing atmosphere having a lower oxygen content than in the normal atmosphere.
  • a reduced pressure atmosphere including vacuum and an inert gas atmosphere can be exemplified.
  • the heating temperature is preferably in the range of 350 ° C. to 1200 ° C., and more preferably in the range of 400 ° C. to 1200 ° C. If the heating temperature is too low, desorption of hydrogen may not be sufficient, while if the heating temperature is too high, energy is wasted.
  • the heating time may be appropriately set in accordance with the heating temperature, and it is also preferable to determine the heating time while measuring the amount of hydrogen and the like which leaks out of the reaction system.
  • the ratio of amorphous silicon and silicon crystallite contained in the silicon material to be manufactured, and the size of silicon crystallite can also be adjusted, and further, manufactured
  • the shape and size of a nano-level thick layer including amorphous silicon and silicon crystallite included in silicon material can also be prepared.
  • a silicon material is used as a negative electrode active material of a secondary battery such as a lithium ion secondary battery, it is preferable to use the silicon material coated with carbon.
  • the carbon may be only amorphous carbon or only crystalline carbon, or amorphous carbon and crystalline carbon may be mixed.
  • the method for coating the silicon material with carbon is not particularly limited.
  • a carbon coating method a method of mixing carbon powder and silicon material (for example, mechanical milling), a method of heat treating a mixture obtained from compounding of resin and silicon material to carbonize resin, non-oxidizing silicon material The method (thermal CVD method) etc. which carbonize organic substance gas by making it contact with organic substance gas under atmosphere, and carbonize are mentioned.
  • polyacetylene polypyrrole and the like can be used as the polymer material.
  • the non-aqueous electrolyte secondary battery in which the negative electrode active material is made of a carbon-based material has an effect of suppressing the continuous heat generation of the non-aqueous electrolyte secondary battery in the abnormal state of the nail sticking test.
  • the carbon-based material at the negative electrode in the abnormal state of thermal runaway consumes oxygen.
  • the carbon-based material consumes oxygen, a high temperature reaction in which aluminum becomes aluminum oxide is suppressed. Therefore, the non-aqueous electrolyte secondary battery can suppress the continuous heat generation.
  • the negative electrode active material preferably contains a carbon-based material. When the negative electrode active material is 100% by mass, the carbon-based material is preferably 15% by mass or more and 70% by mass or less, and more preferably 20% by mass or more and 65% by mass or less.
  • non-aqueous electrolyte secondary batteries in which the negative electrode active material is a material that reacts more slowly with oxygen than carbon-based materials, it is difficult to consume oxygen during thermal runaway, so carbon-based materials are used under abnormal conditions of the nail penetration test. As compared with the non-aqueous electrolyte secondary battery, heat generation continues more easily.
  • the non-aqueous electrolyte secondary battery of the present invention has the effect of suppressing the continuous heat generation at the time of the nail penetration test, even if the negative electrode active material uses the negative electrode active material whose reaction with oxygen is slower than the carbon-based material. It is presumed that this is because the reaction suppressing layer suppresses the reaction between the positive electrode active material and the positive electrode current collector made of aluminum.
  • Examples of negative electrode active materials that react more slowly with oxygen than carbon-based materials include Si-based active materials and Sn-based active materials. When these active materials are used as negative electrode active materials, the effects of the present invention are significantly exhibited.
  • Examples of the Si-based active material include the above-described silicon and silicon compounds.
  • Examples of the Sn-based active material include the above-mentioned tin and tin compounds.
  • the content of the Si-based active material is preferably 30% by mass or more and 50% by mass or less.
  • the negative electrode active material is preferably in the form of powder. If the anode active material is in powder form, it is preferable that the average particle size D 50 of the negative electrode active material is 0.5 ⁇ m or more 30 ⁇ m or less, and more preferably 1 ⁇ m or more 20 ⁇ m or less. When the average particle diameter D 50 of the negative electrode active material is too small, the specific surface area of the powder of the negative electrode active material increases, the contact area between the powder of the negative electrode active material and the electrolyte increases, and decomposition of the electrolyte proceeds. As a result, the cycle characteristics of the non-aqueous electrolyte secondary battery may be deteriorated. When the average particle diameter D 50 of the negative electrode active material is too large, conductivity of the whole electrode becomes uneven, charging and discharging characteristics may deteriorate.
  • the lithium ion secondary battery which is an example of 2nd embodiment of this invention has a separator and electrolyte solution in addition to the above-mentioned positive electrode and negative electrode as a battery structural element.
  • the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass while preventing the short circuit of the current due to the contact of the both electrodes.
  • a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene or polyethylene, or a porous film made of ceramic can be used.
  • the electrolytic solution contains a solvent and an electrolyte dissolved in the solvent.
  • cyclic esters linear esters, ethers
  • cyclic esters for example, ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone and gamma valerolactone
  • chain esters that can be used include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, alkyl propionic acid esters, malonic acid dialkyl esters and acetic acid alkyl esters.
  • ethers for example, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane can be used.
  • lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 can be used.
  • an electrolytic solution for example, 0.5 mol / l to 1.7 mol / l of lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 and the like in a solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethyl carbonate It is possible to use solutions dissolved at a certain concentration.
  • a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body.
  • the electrode body may be any of a laminated type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are wound.
  • the positive electrode tab portion has a positive electrode current collector and a reaction suppression layer disposed on a part of the positive electrode current collector.
  • the reaction suppression layer is not disposed at a portion connected to the current collection lead or the like.
  • a reaction suppression layer is disposed on the positive electrode current collector other than the connection portion such as the current collection lead in the positive electrode tab portion, and all the positive electrode current collectors other than the connection portion such as the current collector lead.
  • the reaction suppression layer is disposed on the In the positive electrode tab portion, the reaction suppressing layer is disposed on a part of the surface of the positive electrode current collector, whereby the continuous heat generation is further suppressed in the abnormal state of the nail sticking test.
  • FIG. 4 The schematic diagram explaining the positive electrode tab part of this embodiment in FIG. 4 is shown.
  • the reaction suppression layer 4 is disposed on a part of the surface of the positive electrode current collector 3 in the positive electrode tab portion 7.
  • the positive electrode active material layer 5 is not disposed on the surface of the reaction suppression layer 4.
  • the shape of the lithium ion secondary battery is not particularly limited, and various shapes such as cylindrical, square, coin, and laminate types can be adopted.
  • the lithium ion secondary battery can be mounted on a vehicle. Since the lithium ion secondary battery is highly safe, a vehicle equipped with the lithium ion secondary battery is highly safe.
  • Any vehicle may be used as long as it uses electric energy from batteries for all or part of the power source.
  • electric vehicles for example, electric vehicles, hybrid vehicles, plug-in hybrid vehicles, hybrid railway vehicles, electric forklifts, electric wheelchairs, electric assists There are bicycles and electric motorcycles.
  • non-aqueous electrolyte secondary battery of the present invention has been described by taking the lithium ion secondary battery as an example, but the present invention is not limited to the above embodiment. In the range which does not deviate from the summary of the present invention, it can carry out with various forms which gave change, improvement, etc. which a person skilled in the art can make.
  • the protective layer or the reaction suppression layer is not disposed at the conductive connection between the current collectors or between the current collector and the other conductive member in the current collector main body. . If the protective layer or the reaction suppression layer is disposed at the conductive connection point, the connection may be disturbed. Therefore, it is preferable that a place where the protective layer or the reaction suppression layer is not disposed, that is, an uncoated part of the protective layer or the reaction suppression layer be present on the current collector body. Furthermore, it is preferable to ensure that the active material layer is disposed on the protective layer or the reaction suppression layer.
  • the active material layer When the active material layer is disposed on the current collector main body in which the protective layer or the reaction suppression layer is not disposed, the effect of the protective layer or the reaction suppression layer may be reduced. Therefore, in order to apply the active material layer continuously to the current collector having the protective layer or the reaction suppression layer disposed on a part of the surface of the current collector main body, the following apparatus is used. preferable.
  • coating an active material layer to the collector body in which the protective layer or reaction suppression layer was formed in the partial surface of a collector body in FIG. 5 is shown.
  • the coating device 14 includes a coating unit 11, a detection unit 12, and a control unit 13.
  • the current collector body 1 is conveyed in a fixed direction by the conveying means not described in FIG.
  • the current collector body 1 is conveyed in a state of being supported by the roller 10 in the arrow direction shown in FIG. 5.
  • a protective layer or a reaction suppression layer 8 is applied to a part of the current collector body 1. That is, the protective layer or the reaction suppression layer 8 is applied to the central region excluding both ends in the width direction of the current collector body 1. That is, the protective layer or the reaction suppression layer 8 is not applied to both ends in the width direction of the current collector body 1.
  • both end portions in the width direction of the current collector body 1 are used as conductive connection points between the current collectors or between the current collector and another conductive member.
  • the detection unit 12 detects the arrangement position of the protective layer or the reaction suppression layer 8 in the current collector body 1.
  • the detection unit 12 has a resistance measuring instrument 120.
  • the resistance measuring device 120 measures the resistance of the surface of the current collector body 1 and the protective layer or reaction suppression layer 8. Note that the number of resistance measuring instruments 120 installed can be changed as appropriate, and may be more than one as needed.
  • the detection unit 12 outputs a signal of the detected resistance value to the control unit 13.
  • the control unit 13 controls the coating position of the coating unit 11 based on the resistance value sent from the detection unit 12 as follows.
  • the resistance of the protective layer or reaction suppression layer 8 is higher than the resistance of the current collector body 1. Therefore, when the resistance value is higher than the preset reference value, the control unit 13 determines that the protective layer or the reaction suppression layer 8 is coated, and the position and the range of the protective layer or the reaction suppression layer 8 Identify
  • the coating unit 11 has a die coating device 110.
  • a die head portion is illustrated as the die coating apparatus 110.
  • the die coating apparatus 110 has a coating liquid tank and a liquid supply pump not shown.
  • the coating liquid is conveyed from the coating liquid tank to the die head through the liquid supply pump, pushed out from the slit in the die head, and applied according to the specified width of the slit.
  • the die head of the die coating apparatus 110 is movable in the width direction of the current collector body 1.
  • the coating range of the coating liquid is determined in accordance with the position in the width direction of the current collector body 1 of the die head.
  • the control unit 13 moves the position in the width direction of the current collector body 1 of the die head of the die coating apparatus 110 to control the die coating apparatus 110.
  • the die coating apparatus 110 controlled by the control unit 13 forms the active material layer 9 within the range in which the protective layer or the reaction suppression layer 8 is disposed.
  • the means for detecting the arrangement of the protective layer or the reaction suppression layer 8 may be a photodetector which is a non-contact detection device.
  • the photodetector measures the reflection of light of the current collector body 1 and the protective layer or reaction suppression layer 8.
  • the light emitted by the illumination of the room is reflected to the current collector body 1 and the protective layer or reaction suppression layer 8 and is sent to the light receiving element of the light detector.
  • the light detector calculates the luminance value of each position based on the detected light quantity.
  • the detection unit 12 outputs the detected luminance value to the control unit 13. Since the luminance value of the current collector body 1 and the luminance value of the protective layer or the reaction suppression layer 8 are different, the control unit 13 controls the protective layer or the reaction suppression layer when the luminance value is higher or lower than a preset value. Judging that 8 is disposed, the position and range of the protective layer or reaction suppression layer 8 are specified.
  • the coating on one side of the current collector main body 1 is described, but in the case of coating on both sides of the current collector main body 1, collection is performed using a plurality of coating units, a detection unit, and a control unit. Coating may be performed on both sides of the main body 1 at a time or on one side.
  • the protective layer or the reaction suppression layer 8 and the active material layer 9 are coated on both sides of the current collector body 1 first, the positions of the protective layer or the reaction suppression layer 8 are first aligned on both sides of the current collector body 1 Is preferred. In that case, first, the protective layer or the reaction suppression layer 8 is coated on one surface of the current collector body 1. And it is preferable to detect the position of the protective layer or reaction suppression layer 8 of one side, and to apply the protective layer or reaction suppression layer 8 to the other side according to it.
  • the detection unit on one side detects the position of the protective layer or reaction suppression layer 8 on one side, sends the information obtained from the detection unit 12 to the control unit 13 on the other side, and sends the information
  • the control unit 13 may control the coating unit 11 on the other surface side, and the controlled coating unit 11 may coat the protective layer or the reaction suppression layer 8 on the other surface.
  • the coating part 11 can be intermittently coated, and the active material layer 9 can be formed in the range in which the protective layer or the reaction suppression layer 8 is disposed.
  • the coating unit 11 is not limited to the die coating apparatus 110.
  • the coating part 11 should just be a coating apparatus which can form a film on metal foil.
  • Examples 1 to 9, Comparative Examples 1 to 3, Test Examples 1 to 3 ⁇ Preparation of protective layer formation>
  • An aluminum foil (made by UACJ Co., Ltd.) having a thickness of 15 ⁇ m was prepared.
  • the prepared aluminum foil was subjected to a degreasing treatment such as a heat treatment, a corona treatment, a plasma treatment, a washing treatment with a solvent to reduce fats and oils on the surface of the aluminum foil.
  • an ATO water dispersion (TDL-1 (spherical particles having a primary particle diameter of 50 nm or less, solid content 17.5% by mass) manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. was prepared.
  • a water-soluble acrylic resin, an acrylic emulsion and a fluorine emulsion were prepared as binders for the protective layer.
  • the emulsion it is an acrylic emulsion BASF Japan Ltd.
  • John Krill PDX7341 which is an acrylic emulsion
  • John Flour PDX 7430 which is an acrylic emulsion
  • PTFE fluorine-based emulsion Daikin Industries polytetrafluoroethylene
  • PDX7341 nonvolatile content: 49.0%, viscosity: 400 (mPa ⁇ a), pH: 8.4, solid content acid value: 51 (mg KOH / g), Tg: 15 ° C., minimum film forming temperature: ⁇ 5 ° C.
  • PDX 7430 normal temperature self-crosslinking type, nonvolatile content: 38.0%, viscosity: 50 (mPa ⁇ a), pH: 8.0, solid content acid value: 30 (mg KOH / g), Tg: 34 ° C., minimum film formation Temperature: 44 ° C., average particle size: 0.12 ⁇ m, molecular weight (MW):> 2 ⁇ 10 6 , specific gravity: 1.04 (g / cc)
  • composition A for forming a protective layer A total of 514.3 parts by mass of the ATO aqueous dispersion and 2,834 parts by mass of distilled water were weighed in a plastic container, and a diluted product was prepared by diluting the ATO aqueous dispersion with distilled water.
  • composition B for forming a protective layer A composition B for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except that a 10% aqueous solution of PAA (weight average molecular weight 250,000) was used instead of a 10% aqueous solution of PAA (weight average molecular weight 5000). .
  • PAA weight average molecular weight 250,000
  • composition for forming a protective layer C A composition C for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except that a 10% aqueous solution of PAA (weight average molecular weight 1,000,000) was used instead of a 10% aqueous solution of PAA (weight average molecular weight 5000). .
  • PAA weight average molecular weight 1,000,000
  • composition D for forming a protective layer A composition D for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except that a 10% aqueous solution of PAANa (weight average molecular weight 5500) was used instead of a 10% aqueous solution of PAA (weight average molecular weight 5000). .
  • composition E for forming a protective layer A protective layer is formed in the same manner as the composition A for forming a protective layer except that a 10% aqueous solution of acrylic acid / maleic acid copolymer (weight average molecular weight 5000) is used instead of the 10% aqueous solution of PAA (weight average molecular weight 5000). Composition E was obtained.
  • composition F for forming a protective layer It is protected in the same manner as the composition A for forming a protective layer except that a 10% aqueous solution of acrylic acid / sulfonic acid monomer copolymer salt (weight average molecular weight 5000) is used instead of a 10% aqueous solution of PAA (weight average molecular weight 5000).
  • the composition F for layer formation was obtained.
  • a composition G for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except that the composition was changed to .5.
  • a composition H for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except that the composition was changed to .5.
  • a composition I for forming a protective layer was obtained in the same manner as the composition A for forming a protective layer except for the above.
  • composition for protective layer formation manufactured as mentioned above was left still at 25 degreeC for 3 days, and it observed visually whether the precipitate could be seen.
  • composition B for forming a protective layer In the composition B for forming a protective layer and the composition C for forming a protective layer, a large amount of precipitate was observed. In the compositions A and D to I for forming a protective layer, no precipitate was observed. From this result, it was found that the presence of PAA having an excessively large weight average molecular weight causes the ATO particles to aggregate, and the storage stability of the composition for forming a protective layer is poor.
  • a collector for a lithium ion secondary battery was produced using compositions A and DI for forming a protective layer, in which no precipitate was observed in storage stability evaluation.
  • Example 1 The composition A for protective layer formation was coated on a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater so that the thickness of the protective layer would be 75 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 1.
  • Example 2 Composition A for protective layer formation was applied to a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater so that the thickness of the protective layer would be 125 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 2.
  • Example 3 Composition A for protective layer formation was applied to a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater so that the thickness of the protective layer would be 150 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 3.
  • Example 4 Composition A for protective layer formation was applied to a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater so that the thickness of the protective layer would be 275 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 4.
  • Example 5 The composition A for forming a protective layer was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 500 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 5.
  • Example 6 Composition G for protective layer formation was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 75 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain a current collector of Example 6.
  • Example 7 Composition G for protective layer formation was applied to a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater so that the thickness of the protective layer would be 150 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Example 7.
  • Example 8 The composition H for protective layer formation was coated on a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 75 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain a current collector of Example 8.
  • Example 9 The composition H for protective layer formation was coated on a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 150 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain a current collector of Example 9.
  • composition I for protective layer formation was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 75 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain the current collector of Comparative Example 1.
  • composition I for protective layer formation was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater so that the thickness of the protective layer would be 150 nm.
  • the aluminum foil after application of the composition for protective layer formation was dried at 100 degreeC for 2 minutes. The same process was performed on the back surface of the aluminum foil to obtain a current collector of Comparative Example 2.
  • composition D for forming a protective layer was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater, but the composition D for forming a protective layer was significantly repelled on the surface of the aluminum foil, and the protective layer was It could not be formed.
  • composition E for protective layer formation was applied to a degreased 15 ⁇ m thick aluminum foil using a microgravure coater, but the composition E for protective layer formation was significantly repelled on the surface of the aluminum foil, and the protective layer was It could not be formed.
  • composition F for protective layer formation was applied to a degreased aluminum foil having a thickness of 15 ⁇ m using a microgravure coater, but the composition F for protective layer formation was significantly repelled on the surface of the aluminum foil, and the protective layer It could not be formed.
  • compositions A and G to I for forming a protective layer had good wettability with the aluminum foil and good coatability.
  • ⁇ Adhesiveness test of protective layer> The surfaces of the protective layers of the current collectors of Examples 1 to 9 and Comparative Examples 1 and 2 were rubbed with a cotton swab, and the adhesion of the protective layers was evaluated. In the current collector of Comparative Example 1 and the current collector of Comparative Example 2, the protective layer was peeled off. The current collectors of Examples 1 to 9 did not have the protective layer peeled off, and the adhesion of the protective layers of the current collectors of Examples 1 to 9 was good. From this result, it was found that an acrylic resin is suitable as a binder in the protective layer.
  • the positive electrode of Example 1 using the current collector of Example 1 as a current collector for positive electrode was produced as follows. First, 94 parts by mass and 3 parts by mass of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a positive electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride (PVDF) as a binder, respectively The mixture was mixed as 3 parts by mass, and the mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (NMP) to prepare a slurry for a positive electrode active material layer.
  • NMP N-methyl-2-pyrrolidone
  • the slurry for the positive electrode active material layer was placed on the current collector of Example 1 and applied to the current collector of Test Example 1 using a doctor blade so that the slurry became a film.
  • the slurry-coated current collector is dried at 80 ° C. for 20 minutes to volatilize and remove NMP, and then the coated material on the current collector of Example 1 and the current collector of Example 1 is used by a roll press. Tightly bonded together. At this time, the density of the positive electrode active material layer was adjusted to 3.2 g / cm 3 .
  • the density of the positive electrode active material layer referred to here is the mass (g) of the positive electrode active material layer ⁇ the thickness (cm) of the positive electrode active material layer ⁇ the area (cm 2 ) of the positive electrode active material layer.
  • the joined product was heated at 120 ° C. for 6 hours in a vacuum dryer, and then cut into a predetermined shape (a rectangular shape with a positive electrode active material layer area of 25 mm ⁇ 30 mm) to obtain a positive electrode having a thickness of about 90 ⁇ m. . This was used as the positive electrode of Example 1.
  • Example 2 A positive electrode of Example 2 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 2 was used instead of the current collector of Example 1.
  • Patent electrode of Example 3 A positive electrode of Example 3 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 3 was changed to the current collector of Example 1.
  • Patent electrode of Example 4 A positive electrode of Example 4 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 4 was used instead of the current collector of Example 1.
  • Patent electrode of Example 5 A positive electrode of Example 5 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 5 was used instead of the current collector of Example 1.
  • Example 6 A positive electrode of Example 6 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 6 was used instead of the current collector of Example 1.
  • Patent electrode of Example 7 A positive electrode of Example 7 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 7 was changed to the current collector of Example 1.
  • Patent electrode of Example 8 A positive electrode of Example 8 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 8 was used instead of the current collector of Example 1.
  • Positive electrode of Example 9 A positive electrode of Example 9 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Example 9 was changed to the current collector of Example 1.
  • (Positive electrode of Comparative Example 1) A positive electrode of Comparative Example 1 was obtained in the same manner as the positive electrode of Example 1, except that the current collector of Test Example 1 was changed to an aluminum foil having no protective layer formed thereon.
  • (Positive electrode of Comparative Example 2) A positive electrode of Comparative Example 2 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Comparative Example 1 was used instead of the current collector of Example 1.
  • Patent electrode of Comparative Example 3 A positive electrode of Comparative Example 3 was obtained in the same manner as the positive electrode of Example 1 except that the current collector of Comparative Example 2 was used instead of the current collector of Example 1.
  • Electrode resistance increase rate (((electrode resistivity of each positive electrode-electrode resistivity of positive electrode of Comparative Example 1) / electrode resistivity of positive electrode of Comparative Example 1)) ⁇ 100 The results are shown in Table 1.
  • the positive electrode of Comparative Example 2 and Comparative Example 3 using PTFE as a binder for the protective layer has a higher rate of increase in electrode resistance as compared with the positive electrodes of Examples 1, 3 and 6 to 9 each having the same thickness of the protective layer. I understand.
  • FIG. 2 is a graph showing the relationship between the thickness of the protective layer and the rate of increase in electrode resistance, using the electrode resistance increase rates of the positive electrodes of Examples 1, 2, 4 and 5 and the positive electrode of Comparative Example 1 and the thickness of the protective layer. Show.
  • the electrode resistance increase rate decreases.
  • the electrode resistance increase rate is less than 100%, which is more preferable.
  • a laminate type lithium ion secondary battery of Example 1 using the positive electrode of Example 1 was produced as follows.
  • the average particle diameter D 50 of SiO 2 and an average particle diameter D 50 of 4 ⁇ m was prepared 20 ⁇ m natural graphite.
  • a polyamideimide resin was prepared as a binder resin.
  • Acetylene black was prepared as a conduction aid.
  • An appropriate amount of NMP as a solvent was added to the mixture to prepare a slurry for a negative electrode active material layer.
  • This slurry was coated on one side of a copper foil having a thickness of 20 ⁇ m, which is a current collector for a negative electrode, using a doctor blade to form a film.
  • the current collector coated with the slurry was dried at 100 ° C. for 10 minutes, and then the NMP was volatilized and removed, followed by pressing with a roll press to obtain a bonded product.
  • the density of the negative electrode active material layer was made to be 1.6 g / cm 3 .
  • the density of the negative electrode active material layer referred to here is the mass (g) of the negative electrode active material layer ⁇ the thickness (cm) of the negative electrode active material layer ⁇ the area (cm 2 ) of the negative electrode active material layer.
  • the joined product was heated at 200 ° C. for 2 hours in a vacuum dryer, and then cut into a predetermined shape (a rectangular shape with a negative electrode active material layer area of 25 mm ⁇ 30 mm) to make a negative electrode with a thickness of 50 ⁇ m.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • a solution dissolved to be mol / l was used. After that, the remaining one side was sealed, and the four sides were airtightly sealed, to obtain a laminate type lithium ion secondary battery in which the electrode plate group and the electrolytic solution were sealed.
  • the positive electrode and the negative electrode are provided with a tab electrically connectable to the outside, and a part of the tab extends to the outside of the laminated lithium ion secondary battery.
  • Example 2 (Laminated lithium ion secondary battery of Example 2) A laminated lithium ion secondary battery of Example 2 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 2 was used instead of the positive electrode of Example 1.
  • Example 3 (Laminated lithium ion secondary battery of Example 3) A laminated lithium ion secondary battery of Example 3 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 3 was used instead of the positive electrode of Example 1.
  • Example 4 (Laminated lithium ion secondary battery of Example 4) A laminated lithium ion secondary battery of Example 4 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 4 was used instead of the positive electrode of Example 1.
  • Example 5 (Laminated lithium ion secondary battery of Example 5) A laminated lithium ion secondary battery of Example 5 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 5 was used instead of the positive electrode of Example 1.
  • Example 6 (Laminated Lithium Ion Secondary Battery of Example 6) A laminated lithium ion secondary battery of Example 6 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 6 was used instead of the positive electrode of Example 1.
  • Example 7 (Laminated lithium ion secondary battery of Example 7) A laminated lithium ion secondary battery of Example 7 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 7 was used instead of the positive electrode of Example 1.
  • Example 8 (Laminated Lithium Ion Secondary Battery of Example 8) A laminated lithium ion secondary battery of Example 8 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 8 was used instead of the positive electrode of Example 1.
  • Example 9 (Laminated Lithium Ion Secondary Battery of Example 9) A laminated lithium ion secondary battery of Example 9 was produced in the same manner as the laminated lithium ion secondary battery of Example 1 except that the positive electrode of Example 9 was used instead of the positive electrode of Example 1.
  • ⁇ Measurement of Al content of negative electrode> The amount of Al of the negative electrode after the charge and discharge cycle test was measured for the laminated lithium ion secondary batteries of Examples 1, 2, 4, 5 and Comparative Example 1.
  • the Al content of the negative electrode was measured as follows. Each laminate type lithium ion secondary battery after the charge and discharge cycle test was disassembled to separate each negative electrode. The separated negative electrode was washed with dimethyl carbonate (abbreviated DMC), and the amount of Al in the negative electrode was measured with an inductively coupled plasma analyzer (abbreviated ICP).
  • DMC dimethyl carbonate
  • ICP inductively coupled plasma analyzer
  • CC charge constant current charge
  • CC discharge constant current discharge
  • Al elution rate (%) (Al elution amount of each battery / Al elution amount of the battery of Comparative Example 1) ⁇ 100
  • the average particle diameter D 50 was prepared 30nm of antimony-doped tin oxide (hereinafter referred to as ATO).
  • ATO antimony-doped tin oxide
  • PAA polyacrylic acid
  • PTFE polytetrafluoroethylene
  • PEG polyethylene glycol having an average molecular weight of 20,000
  • ATO, PAA, and ion-exchanged water were mixed so that the mass ratio of ATO: PAA was 90:10, to prepare a slurry for a reaction suppression layer.
  • the slurry for the reaction suppression layer was placed on an aluminum foil and applied using a microgravure coater. The application was carried out on both sides of the aluminum foil, and the aluminum foil after application of the slurry for reaction suppression layer was dried at 200 ° C., and this was taken as a current collector A.
  • the current collector A is composed of an aluminum foil as a current collector for the positive electrode and a reaction suppression layer disposed on both sides of the surface of the aluminum foil. The thickness of the reaction suppression layer of the current collector A was 100 nm on one side.
  • a current collector B was produced in the same manner as the current collector A except that a slurry for the reaction suppression layer was produced such that the mass ratio of ATO: PTFE was 90:10.
  • a current collector C was produced in the same manner as the current collector A except that a slurry for the reaction suppression layer was produced such that the mass ratio of ATO: PEG was 90:10.
  • a current collector E was produced in the same manner as the current collector A except that a slurry for a reaction suppression layer was applied to an aluminum foil which was masked to narrow the coating width using a microgravure coater. The reaction suppression layer is not disposed at the masked portion of the current collector E. By using the current collector E, it is possible to produce a positive electrode in which the reaction suppression layer is not formed on the surface of the positive electrode tab portion.
  • Example 10 ⁇ Production of laminate type lithium ion secondary battery> (Example 10) A laminate type lithium ion secondary battery of Example 10 was produced as follows.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 having an average particle diameter D 50 of 6 ⁇ m, acetylene black as a conductive additive, and polyvinylidene fluoride (hereinafter referred to as PVDF) as a binder were mixed in proportions of 94 parts by mass, 3 parts by mass, and 3 parts by mass, respectively, and this mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to prepare a slurry for positive electrode active material layer did.
  • NMP N-methyl-2-pyrrolidone
  • the slurry for the positive electrode active material layer was applied in the form of a film on the surface of the current collector A using a comma coater. The coating is carried out on both sides, and the current collector A coated with the slurry for positive electrode active material layer is dried at 100 ° C. for 5 minutes to volatilize and remove NMP, and then pressed by a roll press to bond I got a thing. At this time, the density of the positive electrode active material layer was adjusted to 3.2 g / cm 3 .
  • the density of the positive electrode active material layer referred to here is the mass (g) of the positive electrode active material layer ⁇ the thickness (cm) of the positive electrode active material layer ⁇ the area (cm 2 ) of the positive electrode active material layer.
  • the joined product After heating the joined product at 120 ° C. for 6 hours with a vacuum dryer, it is cut into a predetermined shape (a rectangular shape with a positive electrode active material layer area of 40 mm ⁇ 80 mm), and a positive electrode A having a thickness of about 90 ⁇ m on one side And
  • the average particle diameter D 50 of SiO 2 and an average particle diameter D 50 of 4 ⁇ m was prepared 20 ⁇ m natural graphite.
  • a polyamideimide resin was prepared as a binder resin.
  • Acetylene black was prepared as a conduction aid.
  • An appropriate amount of NMP as a solvent was added to the mixture to prepare a slurry for a negative electrode active material layer.
  • the negative electrode active material was 100% by mass, the carbon-based material was 61% by mass.
  • a copper foil of 20 ⁇ m was prepared as a current collector for a negative electrode, and the slurry for the negative electrode active material layer was applied in a film shape using a comma coater on the copper foil. The coating is carried out on both sides, and the copper foil coated with the slurry for the negative electrode active material layer is dried at 80 ° C. for 5 minutes to volatilize and remove NMP, and then pressed with a roll press to obtain a bonded product. Obtained. At this time, the density of the negative electrode active material layer was made to be 1.6 g / cm 3 .
  • the density of the negative electrode active material layer referred to here is the mass (g) of the negative electrode active material layer ⁇ the thickness (cm) of the negative electrode active material layer ⁇ the area (cm 2 ) of the negative electrode active material layer.
  • a laminated type lithium ion secondary battery was manufactured using the above 30 positive electrodes A and 31 negative electrodes A. Specifically, a rectangular sheet (48 mm ⁇ 88 mm, 25 ⁇ m thickness) made of polyethylene resin as a separator is sandwiched between each positive electrode A and each negative electrode A, and 30 pairs of them are laminated to form an electrode plate group. The electrode plate group was covered with a pair of laminate films, the three sides were sealed, and then an electrolytic solution was injected into the bag-like laminate film.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • a solution dissolved to give l was used. After that, the remaining one side was sealed, and the four sides were airtightly sealed, to obtain a laminate type lithium ion secondary battery in which the electrode plate group and the electrolytic solution were sealed.
  • the positive electrode and the negative electrode are provided with tab portions that can be electrically connected to the outside, and a part of the tab portions extends to the outside of the laminated lithium ion secondary battery.
  • Example 11 A laminated lithium ion secondary battery of Example 11 was produced in the same manner as in Example 10 except that the current collector B was used instead of the current collector A in Example 10.
  • Example 12 A laminated lithium ion secondary battery of Example 12 was produced in the same manner as in Example 10 except that a current collector C was used instead of the current collector A in Example 10.
  • Example 13 A laminated lithium ion secondary battery of Example 13 was produced in the same manner as in Example 10 except that a current collector E was used instead of the current collector A in Example 10. A reaction suppression layer is not formed on the surface of the positive electrode tab portion of the laminate type lithium ion secondary battery of Example 13.
  • a laminate-type lithium ion secondary battery of Comparative Example 4 was produced in the same manner as in Example 10 except for the exception of the above.
  • the negative electrode active material of the laminate type lithium ion secondary battery of Comparative Example 4 is only graphite.
  • Comparative example 5 A laminate-type lithium ion secondary battery of Comparative Example 5 was produced in the same manner as in Example 10 except that a current collector D was used instead of the current collector A in Example 10.
  • the negative electrode active material of the laminate type lithium ion secondary battery of Comparative Example 5 is SiO and graphite.
  • ⁇ Tail test> The laminated lithium ion secondary batteries of Examples 10 to 13 and Comparative Examples 4 to 5 were evaluated for safety by a nail penetration test. Specifically, each battery was charged at a constant current (CC) until it reached 4.5 V at a current value of 3.0 A. Thereafter, charging was continued so as to maintain the voltage within 4.5 V ⁇ 0.02 V, and charging was stopped when the total charging time reached 5 hours.
  • the capacity of each laminate type lithium ion secondary battery was 6 Ah.
  • Each of the laminated lithium ion secondary batteries subjected to the above-mentioned charge treatment was placed on a restraint plate having a hole of 20 mm in diameter.
  • the restraint plate was placed on a press machine with nails attached to the top.
  • the nail was moved from the top to the bottom at a speed of 20 mm / sec until the nail penetrated the laminated lithium ion secondary battery on the restraint plate and the tip of the nail was located inside the hole of the restraint plate.
  • the laminated lithium ion secondary battery was attached with a temperature measurement device capable of measuring the surface temperature.
  • the nail was made of stainless steel (S45C specified by JIS G 4051), and had a diameter of 8 mm and a tip angle of 60 ° of the nail.
  • the nail penetration test was carried out while measuring the surface temperature of the laminated lithium ion secondary battery at room temperature and in the air. By this nail penetration test, the positive electrode and the negative electrode of the laminate type lithium ion secondary battery were shorted
  • the surface temperature of the laminated lithium ion secondary battery at the time of internal short circuit was measured, and the appearance of the battery was observed.
  • the surface temperature of each battery after penetration of the nail gradually decreased after rising once. Table 3 shows the highest temperature among the observed surface temperatures.
  • Table 3 and FIG. 6 show the nail penetration test results of the laminated lithium ion secondary batteries of Examples 10 to 12 and Comparative Examples 4 to 5.
  • the surface temperature is hard to lower, and the case where heat generation is continued is indicated by x, and the case where smoke is generated is indicated by ⁇ .
  • a reaction suppression layer was formed on the surface of the positive electrode tab portion.
  • Table 4 shows the nail penetration test results of the laminate type lithium ion secondary battery of Example 10, the laminate type lithium ion secondary battery of Example 13, and the laminate type lithium ion secondary battery of Comparative Example 4.
  • Table 4 shows the number of cells in which continuous heat generation has occurred among the number of test cells.
  • Example 14 A laminate type lithium ion secondary battery of Example 14 was produced as follows.
  • LiNi is 6 ⁇ m 0.5 Co 0.2 Mn 0.3 O 2 ( hereinafter, referred to as NCM) and that the average particle size D 50 whose surface is a carbon-coated as a cathode active material 67 parts by mass, 27 parts by mass, 3 parts by mass, and 3 parts by mass of 1.5 ⁇ m of LiFePO 4 (hereinafter referred to as LFP), acetylene black as a conductive additive, and PVDF as a binder
  • LFP LiFePO 4
  • acetylene black as a conductive additive
  • PVDF as a binder
  • the slurry for the positive electrode active material layer was applied in the form of a film on the surface of the current collector A using a comma coater. The coating is carried out on both sides, and the current collector A coated with the slurry for positive electrode active material layer is dried at 100 ° C. for 5 minutes to volatilize and remove NMP, and then pressed by a roll press to bond I got a thing. At this time, the density of the positive electrode active material layer was adjusted to 3.2 g / cm 3 . After heating the joined product at 120 ° C. for 6 hours with a vacuum dryer, it is cut into a predetermined shape (a rectangular shape with a positive electrode active material layer area of 40 mm ⁇ 80 mm), and a positive electrode B having a thickness of about 90 ⁇ m on one side And
  • a mixed solution of 7 ml of a 46% by weight aqueous solution of HF and 56 ml of a 36% by weight aqueous solution of HCl was brought to 0 ° C. in an ice bath, and 3.3 g of CaSi 2 was added thereto in an argon gas stream and stirred. . After confirming that the foaming was completed, the mixed solution was warmed to room temperature and stirred at room temperature for another 2 hours, and then 20 ml of distilled water was added and the mixture was further stirred for 10 minutes. At this time, yellow powder floated.
  • the obtained mixed solution was filtered, and the obtained residue was washed with 10 ml of distilled water and then with 10 ml of ethanol. The washed residue was vacuum dried to obtain 2.5 g of layered polysilane.
  • the obtained silicon material was placed in a rotary kiln type reactor, and a carbonization step by thermal CVD was performed under a propane gas flow at 850 ° C. and a residence time of 5 minutes to obtain a carbon-coated silicon material.
  • a carbonization step by thermal CVD was performed under a propane gas flow at 850 ° C. and a residence time of 5 minutes to obtain a carbon-coated silicon material.
  • the rotational speed of the reactor was 1 rpm.
  • the average particle diameter D 50 of the silicon material coated with this carbon was 5 [mu] m.
  • a silicon material coated with the above carbon and natural graphite having an average particle diameter D 50 of 20 ⁇ m were prepared.
  • a polyamideimide resin was prepared as a binder resin.
  • Acetylene black was prepared as a conduction aid.
  • An appropriate amount of NMP as a solvent was added to the mixture to prepare a slurry for a negative electrode active material layer.
  • the negative electrode active material was 100% by mass, the carbon-based material was 38% by mass.
  • a copper foil of 20 ⁇ m was prepared as a current collector for a negative electrode, and the slurry for the negative electrode active material layer was applied in a film shape using a comma coater on the copper foil.
  • the coating is carried out on both sides, and the copper foil coated with the slurry for the negative electrode active material layer is dried at 80 ° C. for 5 minutes to volatilize and remove NMP, and then pressed with a roll press to obtain a bonded product. Obtained.
  • the density of the negative electrode active material layer was adjusted to 1.2 g / cm 3 . After heating the joined product at 200 ° C. for 2 hours with a vacuum dryer, it is cut into a predetermined shape (a rectangular shape with a negative electrode active material layer area of 44 mm ⁇ 84 mm), and a negative electrode B with a thickness of 50 ⁇ m on one side did.
  • a laminated lithium ion secondary battery was manufactured using the above 30 positive electrodes B and 31 negative electrodes B. Specifically, a rectangular sheet (48 mm ⁇ 88 mm, 25 ⁇ m thickness) made of polyethylene resin as a separator is sandwiched between each positive electrode B and each negative electrode B, and 30 pairs of them are laminated to form an electrode plate group. The electrode plate group was covered with a pair of laminate films, the three sides were sealed, and then an electrolytic solution was injected into the bag-like laminate film.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the positive electrode and the negative electrode are provided with tab portions that can be electrically connected to the outside, and a part of the tab portions extends to the outside of the laminated lithium ion secondary battery.
  • An appropriate amount of NMP as a solvent was added to the mixture to prepare a slurry for a negative electrode active material layer.
  • the carbon-based material was 18% by mass.
  • a negative electrode C was produced in the same manner as the negative electrode B except for this. At this time, the thickness of the negative electrode active material layer of the negative electrode C was about 50 ⁇ m.
  • the density of the negative electrode active material layer of the negative electrode C was 1.2 g / cm 3 .
  • a laminated lithium ion secondary battery of Example 15 was produced in the same manner as in Example 14 except that this negative electrode C was used instead of the negative electrode B.
  • Table 5 shows the nail penetration test results of the laminated lithium ion secondary batteries of Examples 14 and 15.
  • Example 14 when the negative electrode active material is 100% by mass, the carbon-based material is 38% by mass, and in Example 15, when the negative electrode active material is 100% by mass, the carbon-based material is 18% by mass. there were.

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Abstract

L'invention concerne un collecteur de courant pour batterie secondaire au lithium-ion qui possède une nouvelle couche de protection, et une batterie secondaire à électrolyte non aqueux qui est très stable pendant un court-circuit interne. Ce collecteur de courant pour batterie secondaire au lithium-ion est caractérisé en ce qu'il comprend un corps principal de collecteur de courant et une couche de protection disposée sur la surface du corps principal de collecteur de courant, et en ce que la couche de protection contient des oxydes d'étain dopé à l'antimoine et une résine acrylique. La batterie secondaire à électrolyte non aqueux est caractérisée en ce qu'elle comprend une électrode positive qui possède un collecteur de courant d'électrode positive en aluminium, une couche de suppression de réaction qui est placée sur la surface du collecteur de courant d'électrode positive et qui supprime les réactions entre le collecteur de courant d'électrode positive et une substance active d'électrode positive, et une couche de substance active d'électrode positive qui est disposée sur la surface de la couche de suppression de réaction et qui comprend une substance active d'électrode positive, et une électrode négative qui comprend une substance active d'électrode négative, et est caractérisée en ce que la couche de suppression de réaction comprend des particules conductrices prescrites et un liant de couche de suppression de réaction.
PCT/JP2015/005521 2014-11-06 2015-11-04 Collecteur de courant pour batterie secondaire au lithium-ion, son procédé de fabrication, et batterie secondaire à électrolyte non aqueux Ceased WO2016072090A1 (fr)

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WO2023130888A1 (fr) * 2022-01-05 2023-07-13 宁德时代新能源科技股份有限公司 Batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2024088245A1 (fr) * 2022-10-24 2024-05-02 珠海冠宇电池股份有限公司 Feuille positive et batterie au lithium-ion
EP4503169A4 (fr) * 2022-10-24 2025-11-05 Zhuhai Cosmx Battery Co Ltd Feuille positive et batterie au lithium-ion
JP2025522205A (ja) * 2022-11-07 2025-07-11 エルジー エナジー ソリューション リミテッド 正極およびそれを用いて製造されたリチウム二次電池
JP7798436B2 (ja) 2022-11-07 2026-01-14 エルジー エナジー ソリューション リミテッド 正極およびそれを用いて製造されたリチウム二次電池
JP2024155024A (ja) * 2023-04-20 2024-10-31 トヨタ自動車株式会社 固体電池の製造方法、及び負極活物質層
WO2025036075A1 (fr) * 2023-08-16 2025-02-20 珠海冠宇电池股份有限公司 Feuille d'électrode, élément de batterie et batterie

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