WO2013132864A1 - Pâte de mélange d'électrode et électrode pour batterie rechargeable au lithium-ion, et batterie rechargeable au lithium-ion - Google Patents

Pâte de mélange d'électrode et électrode pour batterie rechargeable au lithium-ion, et batterie rechargeable au lithium-ion Download PDF

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Publication number
WO2013132864A1
WO2013132864A1 PCT/JP2013/001463 JP2013001463W WO2013132864A1 WO 2013132864 A1 WO2013132864 A1 WO 2013132864A1 JP 2013001463 W JP2013001463 W JP 2013001463W WO 2013132864 A1 WO2013132864 A1 WO 2013132864A1
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Prior art keywords
lithium ion
ion secondary
secondary battery
active material
negative electrode
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PCT/JP2013/001463
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English (en)
Japanese (ja)
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克典 西浦
功 鷲尾
鳥井田　昌弘
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三井化学株式会社
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Priority to JP2013529500A priority Critical patent/JP5358754B1/ja
Publication of WO2013132864A1 publication Critical patent/WO2013132864A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode mixture paste and electrode used to form an electrode of a lithium ion secondary battery by forming an active material layer containing an active material, and a lithium ion secondary battery.
  • a secondary battery uses chemical energy generated by a chemical reaction between a positive electrode active material and a negative electrode active material via an electrolyte as electrical energy.
  • lithium ion secondary batteries have been put into practical use as those having a high energy density.
  • a lithium-containing metal composite oxide such as lithium cobalt composite oxide is mainly used as a positive electrode active material of a lithium ion secondary battery, and a carbon material is mainly used as a negative electrode active material.
  • PVdF polyvinylidene fluoride
  • Patent Document 1 proposes a negative electrode material for a secondary battery using polyimide as a binder, but only describes a negative electrode active material made of carbonaceous powder, and includes a silicon atom, a tin atom, or a germanium atom. Application to the negative electrode active material is not suggested.
  • Patent Document 2 proposes a negative electrode binder containing polyimide and an acrylic-silica hybrid resin. According to Patent Document 2, an increase in resistance accompanying an increase in the number of cycles can be effectively suppressed by combining polyimide and an acrylic-silica hybrid resin. However, in this method, the mechanical strength of the binder is excessively lowered due to the composite, the active material particles cannot be held firmly, and the dropping of the active material particles cannot be sufficiently suppressed.
  • Patent Documents 3 and 4 propose a polyimide binder containing a siloxane monomer having a high affinity for silicon.
  • the binding property to the active material is improved, and the pulverization and desorption of the active material are suppressed, so that the cycle characteristics are improved.
  • the flexibility of the polyimide molecular skeleton is increased, and the mechanical strength of the resin, particularly the elastic modulus, is excessively decreased. Therefore, when Si repeatedly expands and contracts, the resin gradually expands. As a result, there is a problem that the active material particles cannot be held firmly in the end, and the dropping of the active material particles cannot be sufficiently suppressed.
  • Patent Document 5 proposes to use a binder resin having specific mechanical properties for an active material made of an alloy containing silicon atoms and tin atoms.
  • a binder resin having a high tensile elastic modulus when used, when the active material particles expand and contract due to charge and discharge, the electrode active material layer is hardly deformed. The contact state between the substance particles can be kept good.
  • a resin having a relatively high breaking elongation is desirable as a binder together with the tensile modulus. This is because if the elongation at break is too low, the active material cannot withstand expansion, and the electrode active material layer is easily broken, the contact state between the active material particles is deteriorated, and the current collector is easily peeled off.
  • the active material that has a very large volume change due to insertion and extraction of lithium ions such as silicon atoms and tin atoms has excellent binding properties to the active material, and both tensile modulus and elongation at break are excellent.
  • Resins exhibiting high values are suitable as binders.
  • Patent Document 5 proposes to use a binder resin having specific mechanical properties for an active material made of an alloy containing silicon atoms and tin atoms, but also discloses a specific chemical structure of the resin. There is no specific proposal for improving the binding property.
  • Patent Documents 6 and 7 propose resin binders that specifically disclose the chemical structure of polyimide.
  • Patent Documents 6 and 7 show either a high value of either the tensile modulus or the elongation at break, but the other physical property is insufficient, The binding property to the active material was insufficient.
  • carbon materials such as graphite and amorphous carbon have been studied as a negative electrode active material, a negative electrode active material using a silicon atom, a tin atom, or the like, which is a next-generation negative electrode active material. The study was insufficient.
  • Patent Document 8 discloses a polyimide resin that desirably contains a predetermined diamine in an amount of 40% by mass or less of the total diamine, but has not yet solved the above-described problem.
  • An object of the present invention is to provide an electrode mixture paste and electrode for a lithium ion secondary battery excellent in the balance between tensile elastic modulus and elongation at break, and a lithium ion secondary battery excellent in cycle characteristics comprising the same. .
  • the present inventors have found that when a resin composition having a specific chemical structure is used, it has excellent binding properties to an active material, a large tensile elastic modulus, and excellent toughness (large elongation at break and It was found that a new binder resin composition for electrodes having a breaking energy) was obtained, and the present invention was achieved. That is, the present invention relates to the following items.
  • N is an integer of 1 to 4).
  • the aromatic tetracarboxylic dianhydride has the following chemical formula 2 (Chemical formula 2) (Y is a tetravalent aromatic group having 6 to 27 carbon atoms, and is an aromatic ring, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member.
  • An electrode mixture paste for a lithium ion secondary battery which is a compound represented by:
  • X 1 is the chemical formula 3 (Chemical formula 3) (Wherein A 2 represents a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group and / or a sulfonyl group. N is an integer of 1 to 4).
  • a 2 represents a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group and / or a sulfonyl group.
  • N is an integer of 1 to 4).
  • the electrode mixture paste for lithium ion secondary batteries according to [1].
  • a lithium ion secondary battery including a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte, wherein the negative electrode is an electrode for a lithium ion secondary battery according to [6] Secondary battery.
  • the lithium ion secondary battery excellent in the cycle characteristic which consists of the electrode compound paste and electrode for lithium ion secondary batteries which were excellent in the balance of tensile elasticity modulus and elongation at breakage, and these was further provided.
  • a 1 represents a divalent group selected from a direct bond (that is, an aromatic ring is directly bonded), an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and / or a sulfonyl group. .
  • a different diamine unit of A 1 may be copolymerized.
  • a 1 is preferably a direct bond or a sulfonyl group.
  • n is an integer of 1 to 4.
  • n is preferably 1 or 2, particularly preferably 1.
  • Aromatic diamine compounds include 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3- Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, Bis [4- (3-aminophenoxy) phenyl] sulfone is preferred, and 4,4′-bis (3-aminophenoxy) biphenyl and bis [4- (3-aminophenoxy) phenyl] sulfone are particularly preferred.
  • the aromatic diamine compound used in the embodiment comprises 25 to 100 mol% of the unit represented by (Chemical Formula 1) and 75 to 0 mol% of p-phenylenediamine unit.
  • the unit represented by (Chemical Formula 1) is preferably 50 to 100 mol%, particularly preferably 70 to 100 mol%, and the p-phenylenediamine unit is 50 to 0 mol%, particularly preferably. Is preferably used at 30 to 0 mol%. The more p-phenylenediamine units, the better the tensile modulus of the binder resin composition.
  • the unit represented by (Chemical Formula 1) is preferably 25 to 80 mol%, particularly preferably 25 to 50 mol%, and the p-phenylenediamine unit is 75 to 20 mol%, particularly preferably. Is preferably used at 75 to 50 mol%.
  • Aromatic tetracarboxylic dianhydride The aromatic tetracarboxylic dianhydride used in the embodiment is represented by (Chemical Formula 2).
  • (Chemical formula 2) Y in Chemical Formula 2 is a tetravalent aromatic group having 6 to 27 carbon atoms, and is an aromatic ring, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridging member Selected from the formula aromatic groups.
  • non-condensed polycyclic aromatic groups in which aromatic rings are connected to each other by a direct bond are preferable.
  • aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, merophanic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 , 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3 4-Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis
  • Aromatic Polyamic Acid used in the embodiment can be obtained by condensing the aromatic diamine compound and the aromatic tetracarboxylic dianhydride described above.
  • the polyamic acid represented by the general formula (1) is (1)
  • a diamine represented by the following general formula (2), (2) Tetracarboxylic dianhydride represented by the following general formula (3) (3) It is obtained by reacting.
  • M1: M2 is more preferably 0.92 to 1.08: 1.00, and further preferably 0.95 to 1.05: 1.00.
  • the weight average molecular weight of the aromatic polyamic acid is preferably 1.0 ⁇ 10 3 to 5.0 ⁇ 10 5 .
  • the weight average molecular weight of the polyimide or its precursor can be measured by gel permeation chromatography (GPC).
  • the aromatic polyamic acid includes silane coupling agents such as aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, trimethoxyvinylsilane, and trimethoxyglycidoxysilane, triazine compounds, phenanthroline compounds, and triazole compounds.
  • a compound or the like may be contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the aromatic polyamic acid. By containing these, adhesiveness with an active material and a collector can further be improved.
  • silane coupling agents 3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane are preferred.
  • the electrode mixture paste for a lithium ion secondary battery according to the embodiment comprises the binder resin composition and the negative electrode active material described above.
  • the electrode mixture paste for a lithium ion secondary battery according to the embodiment is prepared by adding a conductive additive, an active material, a solvent, etc. to an electrode binder resin composition for a lithium ion secondary battery or a varnish containing the same, and stirring or kneading. Can be manufactured. Examples of the mixing method of the raw materials include the following two methods, but are not limited thereto.
  • a conductive additive is added and kneaded to the varnish containing the electrode binder resin composition for a lithium ion secondary battery.
  • An active material and a solvent are added to the obtained kneaded material to obtain an electrode mixture paste.
  • a conductive additive is added to a varnish containing an electrode binder resin composition for a lithium ion secondary battery, and an active material is further added and kneaded.
  • a solvent is added to the kneaded material obtained and stirred to obtain an electrode mixture paste.
  • the stirring may be normal stirring using a stirring blade or the like, or stirring using a rotation / revolution mixer or the like.
  • a kneader or the like can be used for the kneading operation.
  • Negative electrode active material Although it does not specifically limit as a negative electrode active material, A thing with a volume expansion coefficient more than 110% at the time of lithium ion occlusion and / or insertion can be used preferably.
  • the volume expansion coefficient of the negative electrode active material is preferably 150% or more, and more preferably 200% or more. Even if the volume expansion coefficient accompanying charging / discharging is large, the resin for binders used for embodiment shows favorable binding property.
  • the value of the volume expansion coefficient is published in, for example, “Development Trends of Automotive Lithium Ion Batteries”, Kinki University Faculty of Engineering Research Public Forum, October 27, 2010, etc.
  • an active material containing a silicon atom, a tin atom or a germanium atom having a large charge / discharge capacity can be preferably used. Since the volume change accompanying charging / discharging is large in these, the effect of this invention is exhibited more. Among these, silicon particles and / or silicon alloys are more preferable.
  • Examples of the negative electrode active material containing silicon atoms include (i) silicon fine particles, (ii) tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, Examples thereof include alloys with silicon, (iii) compounds of boron, nitrogen, oxygen or carbon and silicon, and those having the metal exemplified in (ii).
  • silicon alloys or compounds include SiB 4 , SiB 6 , Mg 2 Si, 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, SiOx (0 ⁇ x ⁇ 2) or LiSiO.
  • Examples of the negative electrode active material containing tin atoms include (i) alloys of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium and tin, ( ii) Oxygen or a compound of carbon and tin, and those having the metal exemplified in (i).
  • Examples of tin alloys or compounds include SnOw (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, Mg 2 Sn, and the like.
  • Examples of the negative electrode active material containing germanium include germanium oxide, carbide, nitride, and carbonitride.
  • the negative electrode active material may be used by mixing with an active material having a volume expansion coefficient of 110% or less, and can be preferably used as long as the volume expansion coefficient of the entire mixture is greater than 110%.
  • Examples of the active material having a volume expansion coefficient of 110% or less include graphite and lithium titanate. Of these, one or two of them can be mixed with the negative electrode active material.
  • the surface of these negative electrode active materials may be covered with a conductive material such as carbon or copper for the purpose of improving the conductivity.
  • the average particle size of the active material is preferably 0.1 to 10 ⁇ m.
  • the surface of the active material may be treated with a silane coupling agent or the like.
  • the electrode mixture paste for a lithium ion secondary battery according to the embodiment may contain a solvent.
  • the type of the solvent is not particularly limited as long as it can uniformly dissolve or disperse the electrode binder resin composition for a lithium ion secondary battery and the active material.
  • an aprotic polar solvent is preferable, and an aprotic amide solvent is more preferable.
  • aprotic amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazo Lysinone etc. are included. These solvents may be used alone or in combination of two or more.
  • solvents may coexist as necessary.
  • examples of other solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-cresol, m-cresol, p-cresol, o-chlorotoluene, m-chlorotoluene, p- Examples include chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, chlorobenzene, bromobenzene, methanol, ethanol, n-propanol, isopropyl alcohol and n-butanol.
  • the amount of the solvent is appropriately selected in consideration of the viscosity of the electrode mixture paste for lithium ion secondary batteries. Usually, it is preferable to blend 50 to 900 parts by mass, and more preferably 65 to 500 parts by mass with respect to 100 parts by mass of the solid content contained in the composite paste.
  • the electrode mixture paste for lithium ion secondary batteries according to the embodiment may contain a conductive auxiliary agent together with an active material.
  • the conductive assistant is blended for the purpose of reducing the electrical resistance of the electrode.
  • a carbon material can be used as the conductive assistant.
  • Examples of pyrolysis products of organic matter include coal-based coke; petroleum-based coke; carbides from coal-based pitch; carbides from petroleum-based pitch; or carbides obtained by oxidizing these pitches; needle coke; pitch coke; phenol resin, crystalline cellulose And carbon materials obtained by partially graphitizing these; furnace black; acetylene black; pitch-based carbon fiber; and the like.
  • graphite is preferable, and artificial graphite, purified natural graphite, or those obtained by subjecting these graphites to various surface treatments, which are produced by subjecting easy-graphite pitches obtained from various raw materials to high-temperature heat treatment, are particularly preferable.
  • the electrode mixture paste for lithium ion secondary batteries contains metal oxides such as tin oxide, sulfides and nitrides, lithium alloys such as lithium alone and lithium aluminum alloys, and the like. Also good.
  • materials other than these carbon materials one kind may be used alone, or two or more kinds may be used in combination. Moreover, you may use in combination with the above-mentioned carbon material.
  • the blending amount (mass) of the conductive assistant with respect to the total amount (mass) of the solid content in the electrode mixture paste for lithium ion secondary batteries is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, More preferably, it is 0.1 mass% or more. Moreover, 20 mass% or less is preferable normally, More preferably, it is 10 mass% or less.
  • the electrode for a lithium ion secondary battery according to the embodiment is a laminate of a current collector and a negative electrode active material layer.
  • This active material layer is a cured product of an electrode mixture paste for a lithium ion secondary battery containing a binder resin composition.
  • the electrode for a lithium ion secondary battery includes a sheet-like electrode.
  • the material of the negative electrode current collector includes metal materials such as silicon and / or silicon alloys, tin and alloys thereof, silicon-copper alloys, copper, nickel, stainless steel, nickel-plated steel, carbon cloth, and carbon paper. A carbon material such as is used.
  • Examples of the shape of the negative electrode current collector include a metal foil, a metal cylinder, a metal coil, a metal plate, and a metal thin film in the case of a metal material, and a carbon plate, a carbon thin film, and a carbon cylinder in the case of a carbon material.
  • the thickness of the current collector is not particularly limited, but is usually, for example, 5 ⁇ m to 30 ⁇ m, and preferably 9 to 20 ⁇ m.
  • Negative electrode active material layer The active material layer is obtained by applying an electrode mixture paste for a lithium ion secondary battery containing a binder resin composition to a current collector and curing it by heating.
  • the electrode mixture paste can be applied by, for example, screen printing, roll coating, slit coating, or the like. At this time, the electrode mixture paste may be applied onto the pattern so that the binder (cured product) has a mesh shape.
  • the thickness of the active material layer is not particularly limited, and for example, the thickness after curing is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more. Moreover, it is preferable to set it as 200 micrometers or less, More preferably, it is 100 micrometers or less, More preferably, it is 75 micrometers or less. When the active material layer is too thin, the practicality as a positive electrode or a negative electrode is lacking from the balance with the particle size of the active material. On the other hand, if the thickness is too thick, it may be difficult to obtain a sufficient Li storage / release function for high-density current values.
  • Heating and curing of the electrode mixture paste can usually be performed under atmospheric pressure, but may be performed under pressure or under vacuum.
  • the atmosphere at the time of heating and drying is not particularly limited, but is usually preferably performed in an atmosphere of air, nitrogen, helium, neon, argon, or the like, and more preferably in an atmosphere of nitrogen or argon as an inert gas.
  • the heating temperature in the heat curing of the electrode mixture paste is usually 150 ° C. to 500 ° C. for 1 minute to 24 hours to perform a ring closure reaction of the polyimide precursor to the polyimide, thereby obtaining a reliable negative electrode. be able to.
  • it is 200 ° C. to 450 ° C. for 5 minutes to 20 hours.
  • the negative electrode thus obtained can be used for a lithium ion secondary battery.
  • the basic configuration of the lithium ion secondary battery according to the embodiment is the same as that of a conventionally known lithium ion secondary battery, and usually includes a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte.
  • cured material of the binder resin composition mentioned above is good also as any active material layer of a positive electrode and a negative electrode, and may be used only for any one.
  • the form of the lithium ion secondary battery according to the embodiment is not particularly limited.
  • Examples of the form of the lithium ion secondary battery include a cylinder type in which the sheet electrode and the separator are spiral, a cylinder type having an inside-out structure in which the pellet electrode and the separator are combined, a coin type in which the pellet electrode and the separator are stacked, and the like. It is done. Moreover, it is good also as arbitrary shapes, such as a coin shape, a cylindrical shape, and a square shape, by accommodating the battery of these forms in arbitrary exterior cases.
  • the procedure for assembling the lithium ion secondary battery according to the embodiment is not particularly limited, and may be assembled by an appropriate procedure according to the structure of the battery.
  • a negative electrode is placed on an outer case, an electrolyte and a separator are provided on the outer case, and a positive electrode is placed so as to face the negative electrode.
  • the battery is then caulked together with a gasket and a sealing plate.
  • Electrolytic solution As an electrolytic solution for a lithium ion secondary battery, a non-aqueous electrolytic solution in which a lithium salt is dissolved in a non-aqueous solvent, or a non-aqueous electrolytic solution gelled, rubbery, or solid sheet with an organic polymer compound or the like The one made into a shape is used.
  • a non-aqueous solvent in which a lithium salt is dissolved is used for the electrolytic solution.
  • the lithium salt can be appropriately selected from known lithium salts.
  • halides such as LiCl and LiBr; perhalogenates such as LiClO 4 , LiBrO 4 and LiClO 4 ; inorganic fluoride salts such as LiPF 6 , LiBF 4 and LiAsF 6 ; lithium bis (oxalatoborate) LiBC 4 O
  • Inorganic lithium salts such as 8 ; perfluoroalkane sulfonates such as LiCF 3 SO 3 and LiC 4 F 9 SO 3 ; perfluoroalkane sulfonic acid imides such as Li trifluorosulfonimide ((CF 3 SO 2 ) 2 NLi)
  • fluorine-containing organic lithium salts such as salts; Lithium salts may be used alone or in combination of two or more.
  • non-aqueous solvents examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), cyclic carbonates such as vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • VC vinylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl ethyl
  • Chain carbonates such as methyl carbonate (EMC) and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, methyl propionate and ethyl propionate, and ⁇ -lactones such as ⁇ -butyrolactone
  • Chain ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyls Ruxoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsul
  • organic polymer compound in the electrolytic solution to form a gel, rubber, or solid sheet.
  • organic polymer compounds include polyether polymer compounds such as polyethylene oxide and polypropylene oxide; crosslinked polymers of polyether polymer compounds; vinyl alcohol polymers such as polyvinyl alcohol and polyvinyl butyral.
  • the electrolyte solution may further contain a film forming agent.
  • a film forming agent include vinylene carbonate, vinyl ethylene carbonate, vinyl ethyl carbonate, methyl phenyl carbonate and other carbonate compounds, fluoroethylene carbonate, difluoroethylene carbonate, trifluoromethyl ethylene carbonate, bis (trifluoromethyl) ethylene carbonate.
  • the content thereof is usually 10% by mass or less, particularly 8% by mass or less, more preferably 5% by mass or less, based on the total amount (mass) of the constituent components of the electrolytic solution. In particular, it is preferably 2% by mass or less. If the content of the film forming agent is too large, other battery characteristics such as an increase in initial irreversible capacity, low temperature characteristics, and deterioration in rate characteristics of the lithium ion secondary battery may be adversely affected.
  • Positive electrode may have a structure in which a current collector and a positive electrode active material layer are laminated.
  • material for the positive electrode current collector metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum, and carbon materials such as carbon cloth and carbon paper are usually used. Of these, metal materials are preferable, and aluminum is particularly preferable.
  • shape in the case of a metal material, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, etc., and in the case of a carbon material, a carbon plate, a carbon thin film, a carbon cylinder Etc.
  • the thickness is arbitrary, but the lower limit is usually 1 ⁇ m, preferably 3 ⁇ m, more preferably 5 ⁇ m, and the upper limit is usually 100 mm, preferably 1 mm, more preferably 50 ⁇ m. It is a range. If the thickness is less than the above range, the strength required for the current collector may be insufficient. On the other hand, if it is thicker than the above range, the handleability may be impaired.
  • Examples of the positive electrode active material include metal chalcogen compounds that can occlude and release alkali metal cations such as lithium ions during charge and discharge.
  • metal chalcogen compounds include transition metal oxides such as vanadium oxide, molybdenum oxide, manganese oxide, chromium oxide, titanium oxide, and tungsten oxide; phosphate compound with olivine structure; vanadium sulfide, sulfides of molybdenum, sulfides of titanium, transition metal sulfides such as CuS; NiPS 3, FePS 3 phosphate of a transition metal such as - sulfur compounds; VSe 2, NbSe 3 selenium compounds of transition metals, such as; Transition metal composite oxides such as Fe 0.25 V 0.75 S 2 and Na 0.1 CrS 2 ; composite metal sulfides such as LiCoS 2 and LiNiS 2 ; Among these, V 2 O 5, V 5 O 13, VO 2, Cr 2 O 5, MnO 2, TiO, MoV 2 O 8,
  • the lower limit of the content ratio of the positive electrode active material in the positive electrode active material layer is usually 10% by mass, preferably 30% by mass, more preferably 50% by mass, and the upper limit is usually 99.9% by mass, preferably 99%. % By mass.
  • the binder resin for binding the positive electrode active material a known resin can be arbitrarily selected and used in addition to the binder resin composition described above.
  • examples of such include inorganic compounds such as silicate and water glass, Teflon (registered trademark), and polymers having no unsaturated bond.
  • the lower limit of the weight average molecular weight of these polymers is usually 10,000, preferably 100,000, and the upper limit is usually 3 million, preferably 1 million.
  • the lower limit is usually 0.1% by mass, preferably 1% by mass, more preferably 5% by mass
  • the upper limit is usually 80%. % By mass, preferably 60% by mass, more preferably 40% by mass, particularly preferably 10% by mass.
  • the ratio of the binder resin is too low, the positive electrode active material cannot be sufficiently retained, and the mechanical strength of the positive electrode is insufficient, which may deteriorate battery performance such as cycle characteristics.
  • the ratio of binder resin is too high, there exists a possibility of leading to a battery capacity and electroconductivity fall.
  • the positive electrode active material layer may contain a conductive material in order to improve the conductivity of the electrode.
  • the conductive agent is not particularly limited as long as it can be mixed with an active material in an appropriate amount to impart conductivity, but is usually carbon powder such as acetylene black, carbon black, and graphite, various metal fibers, powder, and foil. Etc.
  • the thickness of the positive electrode active material layer is usually about 10 to 200 ⁇ m.
  • the positive electrode is obtained by forming a positive electrode active material and a binder resin composition containing the binder resin on a current collector.
  • the positive electrode active material layer is usually formed by mixing a positive electrode material, a binder, and a conductive material and a thickener, which are used if necessary, in a dry form into a sheet shape, and then pressing the positive electrode current collector on the positive electrode current collector. Alternatively, these materials are dissolved or dispersed in a liquid medium to form a paste, which is then applied to the positive electrode current collector and dried. Note that the positive electrode active material layer obtained by applying and drying the paste on the positive electrode current collector is preferably consolidated by a roller press or the like in order to increase the packing density of the positive electrode active material.
  • a positive electrode active material, a binder resin, and a conductive material and a thickener that can be used as necessary can be dissolved or dispersed in the solvent, in particular.
  • a solvent there is no restriction, and either an aqueous solvent or an organic solvent may be used.
  • the aqueous solvent include water and alcohol.
  • organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N -N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran (THF), toluene, acetone, dimethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, etc. be able to.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone cyclohexanone
  • methyl acetate methyl acrylate
  • diethyltriamine N -N-dimethylaminopropylamine
  • a dispersant is added in addition to the thickener, and a paste is formed using a latex such as SBR.
  • these solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • a porous separator such as a porous film or a nonwoven fabric is interposed between the positive electrode and the negative electrode in order to prevent a short circuit between the electrodes.
  • a separator for example, a microporous film having excellent ion permeability, a glass fiber sheet, a nonwoven fabric, a woven fabric, or the like is used.
  • polypropylene, polyethylene, polyphenylene sulfide, polyethylene terephthalate, polyethylene naphthalate, polymethylpentene, polyamide, polyimide, or the like is used. These may be used alone or in combination of two or more.
  • polypropylene is usually used, but when reflow resistance is imparted to the lithium ion secondary battery, among these, polypropylene sulfide, polyethylene terephthalate, polyamide, polyimide, etc. having a heat distortion temperature of 230 ° C. or higher are used. It is preferable.
  • the thickness of the separator is, for example, 10 to 300 ⁇ m.
  • the porosity of the separator may be determined as appropriate according to the permeability of electrons and ions, the material of the separator, and the like, but is generally preferably 30 to 80%.
  • NMP N-methyl-2-pyrrolidone p-PD: p-phenylenediamine m-BP: 4,4′-bis (3-aminophenoxy) biphenyl m-BS: bis (4- (3-aminophenoxy) phenyl) Sulfone 4,4′-BAPB: 4,4′-bis (4-aminophenoxy) biphenyl 1,4-APB: 1,4-bis (3-aminophenoxy) benzene BPDA: 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride
  • the measuring method of the characteristic used in the Example is shown below.
  • the sample solution was diluted to a concentration of 0.5 g / dl (solvent is NMP) based on the solid content concentration.
  • the flow down time (T1) of this diluted solution was measured at 35 ° C. using an automatic kinematic viscosity measuring device PVS manufactured by Lauda.
  • the logarithmic viscosity was calculated from the following equation using the flow time (T0) of blank NMP.
  • Logarithmic viscosity [dl / g] ⁇ ln (T1 / T0) ⁇ / 0.5 ⁇ Resin characteristics (tensile modulus, breaking elongation, breaking energy)>
  • the resin properties were measured using a small desktop tensile tester EZ-S manufactured by Shimadzu Corporation.
  • Electrode binder resin composition (Reference Example 1) -Preparation of electrode binder resin composition
  • a container equipped with a stirrer and a nitrogen introduction tube was charged with 14.74 g of m-BP and 127.1 g of NMP as a solvent. After stirring until m-BP was dissolved, 11.65 g of BPDA was added over about 30 minutes, 54.5 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 12% by mass and a logarithmic viscosity of 1.4 dl / g.
  • This electrode paste was applied to a copper foil as a current collector (rolled copper foil manufactured by Nippon Foil Co., Ltd., thickness: 18 ⁇ m) using an applicator, and cured by performing a heat treatment at 330 ° C. for 30 minutes in a nitrogen atmosphere. To produce a negative electrode. At this time, the concentration and the coating amount of the electrode paste were adjusted so that the thickness of the negative electrode active material layer on the current collector after the heat treatment was about 20 ⁇ m. The peel strength of the negative electrode active material layer is shown in Table 1.
  • Electrode binder resin composition had a solid content concentration of 12.3% by mass and a logarithmic viscosity of 1.3 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 15 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 1 A container equipped with a stirrer and a nitrogen introduction tube was charged with 3.24 g of p-PD, 11.05 g of m-BP, and 150.5 g of NMP as a solvent, and the temperature of the solution was adjusted to 50 ° C. The mixture was warmed and stirred until p-PD and m-BP were dissolved. After the temperature of the solution was lowered to room temperature, 17.48 g of BPDA was added over about 30 minutes, 64.5 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 12% by mass and a logarithmic viscosity of 1.3 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 16 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 2 A vessel equipped with a stirrer and a nitrogen introduction tube was charged with 4.87 g of p-PD, 5.53 g of m-BP, and 130.5 g of NMP as a solvent, and the temperature of the solution was adjusted to 50 ° C. The mixture was warmed and stirred until p-PD and m-BP were dissolved. After the temperature of the solution was lowered to room temperature, 17.48 g of BPDA was added over about 30 minutes, 55.9 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 12% by mass and a logarithmic viscosity of 1.4 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 15 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • the obtained electrode binder resin composition had a solid content concentration of 12.1% by mass and a logarithmic viscosity of 1.2 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 15 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 3 A container equipped with a stirrer and a nitrogen introduction tube was charged with 3.24 g of p-PD, 12.97 g of m-BS, and 160.4 g of NMP as a solvent, and the temperature of the solution was adjusted to 50 ° C. The mixture was warmed and stirred until p-PD and m-BS were dissolved. After the temperature of the solution was lowered to room temperature, 17.48 g of BPDA was added over about 30 minutes, 68.7 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 12% by mass and a logarithmic viscosity of 1.4 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 16 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 4 A vessel equipped with a stirrer and a nitrogen inlet tube was charged with 4.87 g of p-PD, 6.49 g of m-BS, and 135.4 g of NMP as a solvent, and the temperature of the solution was adjusted to 50 ° C. The mixture was warmed and stirred until p-PD and m-BS were dissolved. After the temperature of the solution was lowered to room temperature, 17.48 g of BPDA was added over about 30 minutes, 58.0 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 12.2% by mass and a logarithmic viscosity of 1.3 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 16 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 1 A container equipped with a stirrer and a nitrogen inlet tube was charged with 14.74 g of 4,4′-BAPB and 231 g of NMP as a solvent. After stirring until 4,4′-BAPB was dissolved, 11.65 g of BPDA was added over about 30 minutes, 99 g of NMP was further added, and the mixture was stirred for 20 hours to obtain an electrode binder resin composition.
  • the obtained electrode binder resin composition had a solid content concentration of 6.9% by mass and a logarithmic viscosity of 3.0 dl / g.
  • the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 13 ⁇ m. The properties of the obtained film are shown in Table 1. Further, a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1. The peel strength of the negative electrode active material layer is shown in Table 1.
  • the obtained electrode binder resin composition had a solid content concentration of 12.1% by mass and a logarithmic viscosity of 1.2 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 13 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • the obtained electrode binder resin composition had a solid content concentration of 6% by mass and a logarithmic viscosity of 2.7 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 14 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • the obtained electrode binder resin composition had a solid content concentration of 7% by mass and a logarithmic viscosity of 2.5 dl / g.
  • the binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 14 ⁇ m.
  • the properties of the obtained film are shown in Table 1.
  • a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1.
  • the peel strength of the negative electrode active material layer is shown in Table 1.
  • Example 5 A container equipped with a stirrer and a nitrogen inlet tube was charged with 11.69 g of 1,4-APB and 111.4 NMP as a solvent. After stirring until 1,4-APB was dissolved, 11.65 g of BPDA was added over about 30 minutes, and 47.8 g of NMP was further added, followed by stirring for 20 hours to obtain an electrode binder resin composition. .
  • the obtained electrode binder resin composition had a solid content concentration of 12% by mass and a logarithmic viscosity of 1.2 dl / g.
  • the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to form a binder resin film having a thickness of 15 ⁇ m. The properties of the obtained film are shown in Table 1. Further, a negative electrode having a negative electrode active material layer thickness of about 20 ⁇ m was produced in the same manner as in Example 1. The peel strength of the negative electrode active material layer is shown in Table 1.
  • p-PD p-phenylenediamine m-BP: 4,4′-bis (3-aminophenoxy) biphenyl m-BS: bis (4- (3-aminophenoxy) phenyl) sulfone 4,4′-BAPB: 4 , 4′-bis (4-aminophenoxy) biphenyl 1,4-APB: 1,4-bis (3-aminophenoxy) benzene
  • Table 1 when the blending ratio of p-PD is the same, chemical formula 1 In Examples 1-4 and Reference Example 1-4 using the diamine compound represented by formula (1), the elongation at break was higher than that of Comparative Example 2-5 using no diamine compound represented by formula (1). .
  • the breaking energy shown in Table 1 refers to the total energy required from when the film starts to stretch until it breaks. The higher the breaking strength and the higher the breaking elongation, the larger the numerical value. That is, it can be said that the larger this value is, the less likely to break.
  • Example 1-4 and Reference Example 1-4 using the diamine compound represented by Chemical Formula 1 are different from Comparative Example 2-5 in which the diamine compound represented by Chemical Formula 1 is not used. By comparison, it is understood that the resin shows a higher breaking energy and is more difficult to break.
  • Examples 1-4 and Reference Examples 1-4 using the diamine compound represented by Chemical Formula 1 are more active materials / binders than Comparative Examples 1-4 not using the diamine compound represented by Chemical Formula 1.
  • Example 1-4 as compared with Reference Example 1-4, the higher the p-PD blending ratio, the higher the tensile elastic modulus.
  • the peel strength was measured using a negative electrode active material containing a tin atom or a germanium atom as the negative electrode active material, the same tendency results as in the above-mentioned Examples, Reference Examples, and Comparative Examples were obtained. It was.
  • This application is accompanied by a priority claim based on a Japanese patent application previously filed by the same applicant, ie, Japanese Patent Application No. 2012-51024 (filing date: March 7, 2012), The contents of which are incorporated herein as part of the present invention.

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Abstract

La présente invention concerne une pâte de mélange d'électrode pour une batterie rechargeable au lithium-ion, comprenant : (i) une composition de résine pour un liant, qui comprend un acide polyamique aromatique produit par réaction d'un composé diamine aromatique avec un dianhydride d'acide tétracarboxylique aromatique représenté par la formule chimique (2), le composé de diamine aromatique étant composé de 75 à 50 % en moles de p-phénylènediamine et de 25 à 50 % en moles d'un composé représenté par la formule chimique (1) ; et (ii) un matériau actif d'électrode négative contenant au moins un atome choisi parmi un atome de silicium, un atome d'étain et un atome de germanium. La pâte selon la présente invention présente un excellent équilibre entre le module d'élasticité à la traction et l'allongement de rupture.
PCT/JP2013/001463 2012-03-07 2013-03-07 Pâte de mélange d'électrode et électrode pour batterie rechargeable au lithium-ion, et batterie rechargeable au lithium-ion WO2013132864A1 (fr)

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JP2014096327A (ja) * 2012-11-12 2014-05-22 Toyota Industries Corp 硫黄系活物質とその製造方法及びリチウムイオン二次電池用電極
JP2016114578A (ja) * 2014-12-18 2016-06-23 国立大学法人三重大学 赤外分光分析セル
JP2017050203A (ja) * 2015-09-03 2017-03-09 株式会社日立製作所 リチウムイオン二次電池
EP3605674A4 (fr) * 2017-03-24 2020-03-25 Nissan Motor Co., Ltd. Matériau d'électrode négative de batterie secondaire à électrolyte non aqueux, et électrode négative et batterie secondaire à électrolyte non aqueux utilisant un matériau d'électrode négative de batterie secondaire à électrolyte non aqueux
EP3605668A4 (fr) * 2017-03-24 2020-04-01 Nissan Motor Co., Ltd. Électrode négative de batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux l'utilisant
CN117117170A (zh) * 2023-08-30 2023-11-24 安徽皓飞新材料有限公司 一种三元正极浆料及其制备方法和应用

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KR20240107050A (ko) * 2022-12-29 2024-07-08 주식회사 엘지에너지솔루션 전극, 이를 포함하는 이차전지, 및 이의 제조 방법

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JP2014096327A (ja) * 2012-11-12 2014-05-22 Toyota Industries Corp 硫黄系活物質とその製造方法及びリチウムイオン二次電池用電極
JP2016114578A (ja) * 2014-12-18 2016-06-23 国立大学法人三重大学 赤外分光分析セル
JP2017050203A (ja) * 2015-09-03 2017-03-09 株式会社日立製作所 リチウムイオン二次電池
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EP3605674A4 (fr) * 2017-03-24 2020-03-25 Nissan Motor Co., Ltd. Matériau d'électrode négative de batterie secondaire à électrolyte non aqueux, et électrode négative et batterie secondaire à électrolyte non aqueux utilisant un matériau d'électrode négative de batterie secondaire à électrolyte non aqueux
EP3605668A4 (fr) * 2017-03-24 2020-04-01 Nissan Motor Co., Ltd. Électrode négative de batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux l'utilisant
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US11664489B2 (en) 2017-03-24 2023-05-30 Nissan Motor Co., Ltd. Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
CN117117170A (zh) * 2023-08-30 2023-11-24 安徽皓飞新材料有限公司 一种三元正极浆料及其制备方法和应用

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