WO2018084319A1 - Électrode négative pour batterie lithium-ion, et batterie lithium-ion - Google Patents

Électrode négative pour batterie lithium-ion, et batterie lithium-ion Download PDF

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WO2018084319A1
WO2018084319A1 PCT/JP2017/040163 JP2017040163W WO2018084319A1 WO 2018084319 A1 WO2018084319 A1 WO 2018084319A1 JP 2017040163 W JP2017040163 W JP 2017040163W WO 2018084319 A1 WO2018084319 A1 WO 2018084319A1
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negative electrode
active material
electrode active
group
ion battery
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PCT/JP2017/040163
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English (en)
Japanese (ja)
Inventor
南　和也
勇輔 中嶋
大澤　康彦
雄樹 草地
佐藤　一
赤間　弘
堀江　英明
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日産自動車株式会社
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Priority claimed from JP2017213671A external-priority patent/JP7143069B2/ja
Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to CN201780068741.5A priority Critical patent/CN109923699B/zh
Priority to US16/346,707 priority patent/US10930920B2/en
Priority to EP17866935.4A priority patent/EP3537513B1/fr
Publication of WO2018084319A1 publication Critical patent/WO2018084319A1/fr

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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H01M2300/0022—Room temperature molten salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode for a lithium ion battery and a lithium ion battery.
  • lithium ion secondary batteries As for lithium ion secondary batteries, various studies have been conducted in order to further improve battery characteristics such as output. For example, as lithium ion secondary batteries capable of increasing capacity, nano-sized oxidation is performed on conductive carbon powder. A battery using a negative electrode active material on which tin particles are supported is known (see JP 2011-253620 A).
  • a thin film is also formed on components other than the electrode active material layer (positive electrode active material layer or negative electrode active material layer), such as separators and current collectors. It is necessary to make it. However, if the separator is made too thin, there is a problem that an internal short circuit is likely to occur due to precipitated lithium, and if the current collector is made too thin, there is a problem that the internal resistance of the battery increases.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a negative electrode for a lithium ion battery having high energy density and excellent quick charge characteristics.
  • the present invention is a lithium battery comprising a negative electrode current collector, a negative electrode active material layer formed on the surface of the negative electrode current collector, a nonaqueous electrolyte solution containing an electrolyte containing lithium ions and a nonaqueous solvent.
  • the negative electrode for an ion battery wherein the negative electrode active material layer includes a negative electrode active material and a void, and the void is filled with the non-aqueous electrolyte, and the battery capacity based on the total amount of the negative electrode active material
  • a negative electrode for a lithium ion battery wherein the ratio of the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer is 3 to 17%; and
  • the present invention relates to a lithium ion battery.
  • a lithium ion battery includes a lithium ion secondary battery.
  • the present invention relates to a lithium ion battery comprising a negative electrode current collector, a negative electrode active material layer formed on the surface of the negative electrode current collector, a nonaqueous electrolyte solution containing an electrolyte containing lithium ions and a nonaqueous solvent.
  • the negative electrode active material layer includes a negative electrode active material and a void, and the void is filled with the non-aqueous electrolyte, and the battery capacity based on the total amount of the negative electrode active material is A negative electrode for a lithium ion battery, wherein a ratio of a battery capacity based on a total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer is 3 to 17%.
  • X to Y indicating a range includes X and Y, and means “X or more and Y or less”.
  • the problem with rapid charging is the movement rate of lithium ions from the positive electrode to the negative electrode inside the lithium ion battery (also called the diffusion rate), but there is a sufficient amount of lithium ions around the negative electrode active material.
  • the charging reaction when the charging reaction is started, first, lithium ions present around the negative electrode active material are taken into the negative electrode active material. In the case where charging does not end even when lithium ions around the negative electrode active material are taken into the negative electrode active material, it is considered that lithium ions desorbed from the positive electrode are taken into the negative electrode active material and the charging reaction proceeds.
  • the lithium ions existing around the negative electrode active material before the start of charging can respond to rapid charging because the distance between the lithium ions and the negative electrode active material is very close.
  • the diffusion rate of lithium ions is rate-limiting and cannot be used for rapid charging.
  • the non-aqueous electrolyte is filled in the voids present around the negative electrode active material, and the negative electrode active material layer with respect to the battery capacity based on the total amount of the negative electrode active material Since the battery capacity ratio (battery capacity ratio) based on the total amount of lithium ions in the non-aqueous electrolyte present in the battery is 3 to 17%, lithium that can be rapidly charged around the negative electrode active material It can be said that there are enough ions.
  • the ratio of the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer is less than 3%, there are not enough lithium ions that can be used for rapid charging around the negative electrode active material. If it exceeds 17%, the rapid charge characteristics deteriorate due to an increase in solution resistance due to the increase in the concentration of the electrolyte and precipitation of lithium salts.
  • the battery capacity ratio is preferably 5 to 17%, more preferably 10 to 17%.
  • the negative electrode active material in the negative electrode for a lithium ion battery of the present invention since a sufficient amount of lithium ions is present around the negative electrode active material in the negative electrode for a lithium ion battery of the present invention, it is not necessary to consider the diffusion rate of lithium ions between the positive electrode and the negative electrode in rapid charging. That is, in the negative electrode for a lithium ion battery of the present invention, even if the energy density is increased by increasing the amount of the negative electrode active material, the diffusion rate of lithium ions between the positive electrode and the negative electrode does not affect the charging rate. Therefore, the quick charge characteristic is not deteriorated.
  • the lithium ion battery using the negative electrode for the lithium ion battery of the present invention can achieve both rapid charging and improved energy density.
  • the battery capacity based on the total amount of the negative electrode active material is a theoretical battery capacity based on the weight of the negative electrode active material constituting the negative electrode active material layer.
  • the theoretical value of the battery capacity refers to that which can withstand repeated charge and discharge, and excludes the initial charge capacity when repeated charge and discharge is difficult due to irreversible reaction.
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer means that all the lithium ions in the non-aqueous electrolyte contained in the negative electrode active material layer are converted into the negative electrode active material. It is the battery capacity when inserted.
  • the battery capacity based on the total amount of the negative electrode active material is calculated according to the following formula.
  • Battery capacity [mAh / cm 2 ] negative electrode active material capacity [mAh / g] ⁇ negative electrode active material basis weight [mg / cm 2 ] / 10 3
  • the negative electrode active material capacity [mAh / g] represents the negative electrode active material (in the case where the negative electrode active material is a coated negative electrode active material coated with a coating layer containing a polymer compound), ethylene carbonate
  • a mixture of non-aqueous electrolyte prepared by dissolving LiN (FSO 2 ) 2 at a ratio of 3 mol / L in a mixed solvent of (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) to form an aramid
  • a separator manufactured by Japan Vilene Co., Ltd.
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer can be uniquely derived from the thickness of the negative electrode active material layer, the porosity, and the electrolyte concentration of the non-aqueous electrolyte. It can be adjusted by combining them in a timely manner.
  • the calculation formula is as follows.
  • Battery capacity [mAh / cm 2 ] based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer electrode void volume [cm 3 ] ⁇ the electrolyte concentration of the non-aqueous electrolyte [mol / L] / 10 3 ⁇ capacity conversion constant [mAh / mol] / electrode area [cm 2 ] Capacity conversion constant [mAh / mol]: 26806 The capacity conversion constant represents the battery capacity per lithium ion.
  • Electrode void volume [cm 3 ] Porosity [volume%] ⁇ Electrode film thickness [ ⁇ m] / 10 4 ⁇ electrode area [cm 2 ]
  • the battery capacity ratio (battery capacity ratio) based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer with respect to the battery capacity based on the total amount of negative electrode active material is the type of negative electrode active material, negative electrode active It can be controlled by the weight of the negative electrode active material in the material layer, the porosity of the negative electrode active material layer, the electrolyte concentration of the non-aqueous electrolyte, and the like.
  • the battery capacity based on the total amount of the negative electrode active material is increased and the battery capacity ratio is decreased.
  • increasing the electrolyte concentration of the non-aqueous electrolyte or increasing the porosity of the negative electrode active material layer increases the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer. As a result, the battery capacity ratio increases.
  • the negative electrode active material constituting the negative electrode for a lithium ion battery of the present invention those conventionally used as an active material for a negative electrode of a lithium ion battery can be suitably used.
  • the negative electrode active material examples include carbon-based materials [for example, graphite, non-graphitizable carbon, amorphous carbon, resin fired bodies (for example, those obtained by firing and carbonizing phenol resin, furan resin, etc.), cokes (for example, pitch coke, Needle coke and petroleum coke etc.), silicon carbide and carbon fiber etc.], conductive polymers (eg polyacetylene and polypyrrole etc.), metals (tin, silicon, aluminum, zirconium and titanium etc.), metal oxides (titanium oxide, Lithium-titanium oxide, silicon oxide, etc.) and metal alloys (for example, lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy and lithium-aluminum-manganese alloy). Two or more negative electrode active materials may be used in combination.
  • carbon-based materials for example, graphite, non-graphitizable carbon, amorphous carbon, resin fired bodies (for example, those obtained by firing and carbonizing phenol resin
  • those that do not contain lithium or lithium ions may be subjected to a pre-doping treatment in which lithium or lithium ions are included in part or all of the active material in advance.
  • a carbon-based material or a metal oxide is preferably used as the negative electrode active material.
  • the volume average particle diameter of the negative electrode active material is preferably from 0.01 to 100 ⁇ m, more preferably from 0.1 to 20 ⁇ m, and even more preferably from 2 to 20 ⁇ m, from the viewpoint of the electric characteristics of the battery.
  • the volume average particle diameter of the negative electrode active material means a particle diameter (Dv50) at an integrated value of 50% in a particle size distribution obtained by a microtrack method (laser diffraction / scattering method).
  • the microtrack method is a method for obtaining a particle size distribution using scattered light obtained by irradiating particles with laser light.
  • the Nikkiso Co., Ltd. microtrack etc. can be used for the measurement of a volume average particle diameter.
  • the negative electrode active material layer includes a negative electrode active material and voids.
  • a sufficient amount of lithium ions can be disposed around the negative electrode active material by filling the voids with the non-aqueous electrolyte containing lithium ions in the negative electrode active material layer.
  • the void volume in the negative electrode active material layer is such that the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer is 3 to 17% of the battery capacity based on the total amount of negative electrode active material.
  • the total volume of the voids is preferably 35 to 60% by volume, more preferably 35 to 50% by volume, based on the total volume of the negative electrode active material layer.
  • voids of 35 to 60% by volume of the total volume are formed in the negative electrode active material layer, a sufficient amount of lithium ions is arranged around the negative electrode active material by filling the voids with a non-aqueous electrolyte. can do.
  • the void refers to a void included in the negative electrode active material layer in a state where the negative electrode is not impregnated with the non-aqueous electrolyte.
  • the porosity can also be obtained by image analysis of the cross section of the negative electrode active material layer by X-ray computed tomography (CT) or the like.
  • the measurement is performed by the following method.
  • the porosity is the total volume value of each component obtained by dividing the weight of each solid component (excluding the electrolyte) constituting the negative electrode active material layer having a constant volume by the true density of each component. The value obtained by subtracting from the volume of can be calculated by further dividing by the volume of the negative electrode active material layer.
  • the weight and true density of each solid component can be determined by solid-liquid separation of a cleaning solution obtained by cleaning the negative electrode with a non-aqueous solvent, and removing the non-aqueous solvent.
  • the solid component is not separated into a component that dissolves in a non-aqueous solvent and a component that does not dissolve, and as a mixture of solid components, the weight is divided by the true density to obtain the volume of the entire solid component, You may replace with the method of measuring a weight and a true density for every component.
  • the thickness of the negative electrode active material layer (hereinafter also simply referred to as “film thickness”) is not particularly limited, but is preferably 100 ⁇ m or more and 1500 ⁇ m or less, and preferably 150 ⁇ m or more and 1200 ⁇ m from the viewpoint of achieving both energy density and input / output characteristics. Or less, more preferably 200 ⁇ m or more and 800 ⁇ m or less.
  • the amount of the non-aqueous electrolyte that the negative electrode active material layer can hold per unit area is not particularly limited, but is preferably 6 to 120 ⁇ L / cm 2 .
  • the reference surface per unit area is a surface parallel to the surface of the negative electrode current collector.
  • the amount of the non-aqueous electrolyte that the negative electrode active material layer can hold per unit area is 6 ⁇ L / cm 2 or more, the total amount of lithium ions present around the negative electrode active material is sufficiently obtained, and the rate characteristics are excellent.
  • the amount of the non-aqueous electrolyte solution that can be held per unit area can be determined by calculating from the porosity and film thickness of the negative electrode active material layer.
  • the negative electrode current collector is not particularly limited, but copper, aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer (polymer having an electron conductive skeleton) or non-conductive polymer material as a resin Examples thereof include a material to which a conductive material is added if necessary, and a foil containing a conductive material such as conductive glass. Among these, from the viewpoint of safety, it is preferable to use a resin current collector containing a conductive material and a resin as the negative electrode current collector.
  • the conductive material contained in the resin current collector is selected from conductive materials. Specifically, metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, etc.], carbon [graphite and carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), etc. , And mixtures thereof, but are not limited thereto. These conductive materials may be used alone or in combination of two or more. Alternatively, an alloy or metal oxide of the above metal may be used. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, copper, titanium and a mixture thereof are preferable, silver, aluminum, stainless steel and carbon are more preferable, and carbon is more preferable. In addition, as these conductive materials, a particulate ceramic material or a resin material may be coated with a conductive material (a metal material among the above-described conductive materials) by plating or the like.
  • a conductive material a metal material among the above-described conductive materials
  • the average particle diameter of the conductive material is not particularly limited, but is preferably from 0.01 to 10 ⁇ m, more preferably from 0.02 to 5 ⁇ m, from the viewpoint of the electric characteristics of the battery. More preferably, the thickness is 03 to 1 ⁇ m.
  • the “particle diameter of the conductive material” means the maximum distance among any two points on the contour line of the conductive material.
  • the value of “average particle size” is the average value of the particle size of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
  • the shape (form) of the conductive material is not limited to the particle form, and may be a form other than the particle form, and in a form that is put into practical use as a so-called filler-based conductive resin composition such as carbon nanofiller and carbon nanotube. There may be.
  • the conductive material may be a conductive fiber having a fibrous shape.
  • conductive fibers include carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, conductive fibers obtained by uniformly dispersing highly conductive metal and graphite in synthetic fibers, and metals such as stainless steel.
  • examples thereof include fiberized metal fibers, conductive fibers in which the surface of organic fiber is coated with metal, and conductive fibers in which the surface of organic fiber is coated with a resin containing a conductive substance.
  • carbon fibers are preferable.
  • a polypropylene resin in which graphene is kneaded is also preferable.
  • the average fiber diameter is preferably 0.1 to 20 ⁇ m.
  • the resins contained in the resin current collector include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), polyethylene terephthalate (PET), polyether nitrile (PEN), polytetra Fluoroethylene (PTFE), styrene butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVdF), epoxy resin, silicone resin or a mixture thereof Is mentioned.
  • PE polyethylene
  • PP polypropylene
  • PMP polymethylpentene
  • PCO polycycloolefin
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PTFE polytetra Fluoroethylene
  • SBR styrene butadiene rubber
  • PAN polyacrylonitrile
  • PMA polymethyl acrylate
  • PMMA polymethyl methacryl
  • polyethylene (PE), polypropylene (PP), polymethylpentene (PMP) and polycycloolefin (PCO) are preferable, and polyethylene (PE), polypropylene (PP) and polymethylpentene are more preferable. (PMP).
  • non-aqueous electrolyte a non-aqueous electrolyte containing an electrolyte and a non-aqueous solvent used in the production of a lithium ion battery can be used.
  • electrolyte those used in known electrolyte solutions can be used, and preferable examples include lithium salt electrolytes of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 and LiClO 4 , A sulfonylimide-based electrolyte having fluorine atoms such as LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2, and a fluorine atom such as LiC (CF 3 SO 2 ) 3 are used. Examples thereof include a sulfonylmethide-based electrolyte.
  • a sulfonylimide-based electrolyte having a fluorine atom is preferable from the viewpoint of ion conductivity at a high concentration and a thermal decomposition temperature, and LiN (FSO 2 ) 2 is more preferable.
  • LiN (FSO 2 ) 2 may be used in combination with other electrolytes, but is more preferably used alone.
  • the electrolyte concentration of the non-aqueous electrolyte is not particularly limited, but is preferably 1 to 5 mol / L, and preferably 1.5 to 4 mol / L from the viewpoints of the handleability of the non-aqueous electrolyte and battery capacity. More preferably, it is 2 to 3 mol / L.
  • non-aqueous solvent those used in known non-aqueous electrolytes can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphate esters. , Nitrile compounds, amide compounds, sulfones and the like and mixtures thereof.
  • lactone compound examples include 5-membered rings (such as ⁇ -butyrolactone and ⁇ -valerolactone) and 6-membered lactone compounds (such as ⁇ -valerolactone).
  • cyclic carbonate examples include propylene carbonate, ethylene carbonate and butylene carbonate.
  • chain carbonate examples include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
  • chain carboxylic acid ester examples include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate.
  • cyclic ether examples include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane and the like.
  • chain ether examples include dimethoxymethane and 1,2-dimethoxyethane.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, tri (trichloromethyl) phosphate, Tri (trifluoroethyl) phosphate, tri (triperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphosphoran-2-one, 2-trifluoroethoxy-1,3,2- Examples include dioxaphospholan-2-one and 2-methoxyethoxy-1,3,2-dioxaphosphoran-2-one.
  • nitrile compounds include acetonitrile.
  • amide compound examples include N, N-dimethylformamide (hereinafter referred to as DMF).
  • sulfone include chain sulfones such as dimethyl sulfone and diethyl sulfone, and cyclic sulfones such as sulfolane.
  • the non-aqueous solvent may be used alone or in combination of two or more.
  • lactone compounds, cyclic carbonates, chain carbonates, and phosphates are preferable from the viewpoint of battery output and charge / discharge cycle characteristics, and preferably do not contain a nitrile compound. More preferred are lactone compounds, cyclic carbonates and chain carbonates, and particularly preferred is a mixture of cyclic carbonate and chain carbonate. Most preferred is a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) or a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the negative electrode active material layer may further contain a conductive material.
  • the conductive material include conductive fibers.
  • the negative electrode active material layer further includes a conductive fiber
  • the conductive fiber can function to assist electronic conduction in the negative electrode active material layer, and the conductive fiber described above with respect to the resin current collector is used as the conductive fiber.
  • the same thing as a property fiber can be used.
  • the negative electrode active material layer further contains conductive fibers, it is preferable to use a coated negative electrode active material described later as the negative electrode active material.
  • the content of the conductive fibers contained in the negative electrode active material layer is preferably 25% by weight or less with respect to the total weight of the negative electrode active material layer.
  • a conductive agent having no fibrous form may be used.
  • a conductive agent having a particulate (for example, spherical) form can be used.
  • the shape of the particles is not particularly limited, and may be any shape such as powder, sphere, plate, column, indefinite shape, flake shape, and spindle shape.
  • the conductive agent having a particulate (for example, spherical) form the same conductive material as that described for the resin current collector can be used.
  • the negative electrode active material is preferably partially or entirely covered with a coating layer containing a polymer compound.
  • a negative electrode active material in which part or all of the surface is coated with a coating layer is also referred to as a coated negative electrode active material.
  • the surface of the negative electrode active material is coated with the coating layer, the volume change of the negative electrode is relieved and the negative electrode can be prevented from expanding. Furthermore, the wettability of the negative electrode active material with respect to the non-aqueous solvent can be improved.
  • Examples of the polymer compound constituting the coating layer include a polymer compound having a liquid absorption rate of 10% or more when immersed in a non-aqueous electrolyte and a tensile elongation at break in a saturated liquid absorption state of 10% or more. preferable.
  • the liquid absorption rate when immersed in the non-aqueous electrolyte is obtained by the following equation by measuring the weight of the polymer compound before and after being immersed in the non-aqueous electrolyte.
  • Absorption rate (%) [(weight of polymer compound after immersion in non-aqueous electrolyte ⁇ weight of polymer compound before immersion in non-aqueous electrolyte) / weight of polymer compound before immersion in non-aqueous electrolyte] ⁇ 100
  • a nonaqueous electrolytic solution dissolved to a concentration of L is used.
  • the saturated liquid absorption state refers to a state in which the weight of the polymer compound does not increase even when immersed in the non-aqueous electrolyte.
  • non-aqueous electrolyte used when manufacturing a lithium ion battery is not limited to the said non-aqueous electrolyte, You may use another non-aqueous electrolyte.
  • the polymer compound sufficiently absorbs the non-aqueous electrolyte, and lithium ions can easily permeate the polymer compound. The movement of lithium ions between electrolytes is not hindered. If the liquid absorption rate is less than 10%, the non-aqueous electrolyte does not easily penetrate into the polymer compound, so that the lithium ion conductivity is lowered and the performance as a lithium ion battery may not be sufficiently exhibited.
  • the liquid absorption is more preferably 20% or more, and further preferably 30% or more.
  • a preferable upper limit of a liquid absorption rate it is 400%, and as a more preferable upper limit, it is 300%.
  • the tensile elongation at break in the saturated liquid absorption state is obtained by punching the polymer compound into a dumbbell shape and immersing in a non-aqueous electrolyte at 50 ° C. for 3 days in the same manner as the measurement of the liquid absorption rate described above to saturate the polymer compound.
  • As a liquid absorption state it can measure based on ASTM D683 (test piece shape Type II).
  • the tensile elongation at break is a value obtained by calculating the elongation until the test piece breaks in the tensile test according to the following formula.
  • Tensile elongation at break (%) [(length of specimen at break ⁇ length of specimen before test) / length of specimen before test] ⁇ 100
  • the tensile elongation at break is more preferably 20% or more, and further preferably 30% or more.
  • the preferable upper limit value of the tensile elongation at break is 400%, and the more preferable upper limit value is 300%.
  • the polymer compound constituting the coating layer examples include thermoplastic resins and thermosetting resins, such as vinyl resins, urethane resins, polyester resins, polyamide resins, epoxy resins, polyimide resins, silicone resins, phenol resins, Examples include melamine resins, urea resins, aniline resins, ionomer resins, polycarbonates, polysaccharides (such as sodium alginate), and mixtures thereof. Of these, vinyl resins are preferred.
  • the vinyl resin is a resin comprising a polymer (A1) having the vinyl monomer (a) as an essential constituent monomer.
  • the polymer (A1) is a monomer containing a vinyl monomer (a1) having a carboxyl group or an acid anhydride group as the vinyl monomer (a) and a vinyl monomer (a2) represented by the following general formula (1).
  • a polymer of the composition is preferred.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a straight chain or branched alkyl group having 4 to 36 carbon atoms.
  • vinyl resins those having a liquid absorption rate of 10% or more when immersed in a non-aqueous electrolyte and a tensile elongation at break in a saturated liquid absorption state of 10% or more are more preferable.
  • Examples of the vinyl monomer (a1) having a carboxyl group or an acid anhydride group include monocarboxylic acids having 3 to 15 carbon atoms such as (meth) acrylic acid (a11), crotonic acid and cinnamic acid; (anhydrous) maleic acid, fumaric acid Dicarboxylic acids having 4 to 24 carbon atoms such as acid, (anhydrous) itaconic acid, citraconic acid and mesaconic acid; polycarboxylic acids having 6 to 24 carbon atoms such as aconitic acid and the like having a valence of 3 to 4 or more. Is mentioned. Among these, (meth) acrylic acid (a11) is preferable, and methacrylic acid is more preferable. In addition, (meth) acrylic acid shows acrylic acid and / or methacrylic acid.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 1 is preferably a methyl group.
  • R 2 is preferably a linear or branched alkyl group having 4 to 12 carbon atoms or a branched alkyl group having 13 to 36 carbon atoms.
  • (A21) R 2 is a linear or branched alkyl group having 4 to 12 carbon atoms.
  • Examples of the linear alkyl group having 4 to 12 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group can be mentioned.
  • Examples of the branched alkyl group having 4 to 12 carbon atoms include 1-methylpropyl group (sec-butyl group), 2-methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), 1-methylbutyl group, 1 , 1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group 1-methylhexyl group, 2-methylhexyl group, 2-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethy
  • R 2 is a branched alkyl group having 13 to 36 carbon atoms.
  • the branched alkyl group having 13 to 36 carbon atoms include a 1-alkylalkyl group [1-methyldodecyl group, 1-butyleicosyl group, 1-hexyloctadecyl group, 1-octylhexadecyl group, 1-decyltetradecyl group, 1-undecyltridecyl group, etc.], 2-alkylalkyl group [2-methyldodecyl group, 2-hexyloctadecyl group, 2- Octylhexadecyl group, 2-decyltetradecyl group, 2-undecyltridecyl group, 2-dodecylhexadecyl group, 2-tridecylpentadecyl group, 2-decyloctadecyl group, 2-te
  • the polymer (A1) preferably further contains an ester compound (a3) of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid.
  • Examples of the monovalent aliphatic alcohol having 1 to 3 carbon atoms constituting the ester compound (a3) include methanol, ethanol, 1-propanol and 2-propanol.
  • the content of the ester compound (a3) is preferably 10 to 60% by weight, and preferably 15 to 55% by weight based on the total weight of the polymer (A1) from the viewpoint of suppressing volume change of the negative electrode active material. More preferred is 20 to 50% by weight.
  • the polymer (A1) may further contain an anionic monomer salt (a4) having a polymerizable unsaturated double bond and an anionic group.
  • Examples of the structure having a polymerizable unsaturated double bond include a vinyl group, an allyl group, a styryl group, and a (meth) acryloyl group.
  • anionic group examples include a sulfonic acid group and a carboxyl group.
  • An anionic monomer having a polymerizable unsaturated double bond and an anionic group is a compound obtained by a combination thereof, such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid and (meth) acrylic acid. It is done.
  • the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • Examples of the cation constituting the salt (a4) of the anionic monomer include lithium ion, sodium ion, potassium ion and ammonium ion.
  • the anionic monomer salt (a4) When the anionic monomer salt (a4) is contained, its content is preferably 0.1 to 15% by weight based on the total weight of the polymer compound from the viewpoint of internal resistance and the like. It is more preferably ⁇ 15% by weight, and further preferably 2-10% by weight.
  • the polymer (A1) preferably contains (meth) acrylic acid (a11) and an ester compound (a21), and more preferably contains an ester compound (a3).
  • methacrylic acid is used as (meth) acrylic acid (a11)
  • 2-ethylhexyl methacrylate is used as ester compound (a21)
  • methyl methacrylate is used as ester compound (a3).
  • Methacrylic acid, 2-ethylhexyl Most preferred is a copolymer of methacrylate and methyl methacrylate.
  • the polymer compound includes (meth) acrylic acid (a11), the above vinyl monomer (a2), an ester compound (a3) of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid, and if necessary.
  • a monomer composition comprising a salt (a4) of an anionic monomer having a polymerizable unsaturated double bond and an anionic group to be used is polymerized, and the vinyl monomer (a2) and the (meta ) Acrylic acid (a11) weight ratio [the ester compound (a21) / (meth) acrylic acid (a11)] is preferably 10/90 to 90/10.
  • the weight ratio of vinyl monomer (a2) to (meth) acrylic acid (a11) is 10/90 to 90/10, the polymer obtained by polymerizing this has good adhesion to the negative electrode active material and is peeled off. It becomes difficult to do.
  • the weight ratio is, for example, 20/80 to 85/15, preferably 30/70 to 85/15, and more preferably 40/60 to 70/30.
  • the monomer constituting the polymer (A1) includes a vinyl monomer (a1) having a carboxyl group or an acid anhydride group, a vinyl monomer (a2) represented by the above general formula (1), and a carbon number of 1
  • a vinyl monomer (a1) having a carboxyl group or an acid anhydride group a vinyl monomer (a2) represented by the above general formula (1)
  • a carbon number of 1 In addition to the ester compound (a3) of a monovalent aliphatic alcohol of 1 to 3 and (meth) acrylic acid and a salt of an anionic monomer having a polymerizable unsaturated double bond and an anionic group (a4)
  • the vinyl monomer (a1), the vinyl monomer (a2) represented by the general formula (1), and a monovalent aliphatic alcohol having 1 to 3 carbon atoms It can be copolymerized with an ester compound (a3) with (meth) acrylic acid and may contain a radical polymerizable monomer (a5).
  • the radical polymerizable monomer (a5) is preferably a monomer not containing active hydrogen, and the following monomers (a51) to (a58) can be used.
  • the monool (i) linear aliphatic monool (tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol Etc.), (ii) alicyclic monools (cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol etc.), (iii) araliphatic monools (benzyl alcohol etc.) and mixtures of two or more thereof Can be mentioned.
  • (A52) Poly (n 2 to 30) oxyalkylene (carbon number 2 to 4) alkyl (carbon number 1 to 18) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meta ) Propylene oxide of acrylate, methanol (hereinafter abbreviated as PO), 10 mol adduct (meth) acrylate, etc.]
  • (a54) Vinyl hydrocarbon (a54-1) Aliphatic vinyl hydrocarbon Olefin having 2 to 18 or more carbon atoms (ethylene, propylene, Butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.), diene having 4 to 10 or more carbon atoms (butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7- Octadiene etc.) (a54-2) Alicyclic vinyl hydrocarbon charcoal Cyclic unsaturated compounds having 4 to 18 or more primes, such as cycloalkene (eg cyclohexene), (di) cycloalkadiene [eg (di) cyclopentadiene], terpene (eg pinene and limonene), indene (a54-3) Aromatic vinyl hydrocarbons C8-20 aromatic unsaturated
  • a vinyl monomer (a1) having a carboxyl group or an acid anhydride group a vinyl monomer (a2) represented by the above general formula (1), a monovalent aliphatic alcohol having 1 to 3 carbon atoms And (meth) acrylic acid ester compound (a3), a salt of an anionic monomer having a polymerizable unsaturated double bond and an anionic group (a4), and a radically polymerizable monomer containing no active hydrogen (a5) )
  • (a1) is 0.1 to 80% by weight
  • (a2) is 0.1 to 99.9% by weight
  • (a3) is 0 to 60% by weight.
  • (a4) is 0 to 15% by weight, and (a5) is 0 to 99.8% by weight.
  • the content of the monomer is within the above range, the liquid absorptivity to the non-aqueous electrolyte is good.
  • the preferable lower limit of the number average molecular weight of the polymer (A1) is 3,000, more preferably 50,000, still more preferably 100,000, particularly preferably 200,000, and the preferable upper limit is 2,000,000. It is preferably 1,500,000, more preferably 1,000,000, and particularly preferably 800,000.
  • the number average molecular weight of the polymer (A1) can be determined by gel permeation chromatography (hereinafter abbreviated as GPC) measurement under the following conditions.
  • GPC gel permeation chromatography
  • Apparatus Alliance GPC V2000 (manufactured by Waters) Solvent: Orthodichlorobenzene Reference material: Polystyrene detector: RI Sample concentration: 3 mg / ml
  • Column stationary phase PLgel 10 ⁇ m, MIXED-B 2 in series (manufactured by Polymer Laboratories) Column temperature: 135 ° C.
  • the polymer (A1) is a known polymerization initiator ⁇ azo initiator [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile, etc.)], peroxide-based initiators (benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.), etc. ⁇ (Bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
  • the amount of the polymerization initiator used is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the monomers, from the viewpoint of adjusting the number average molecular weight within a preferable range. More preferably, it is 0.1 to 1.5% by weight, and the polymerization temperature and polymerization time are adjusted according to the type of the polymerization initiator, etc., but the polymerization temperature is preferably -5 to 150 ° C. (more preferably 30 to 120 ° C.), and the reaction time is preferably 0.1 to 50 hours (more preferably 2 to 24 hours).
  • Examples of the solvent used in the solution polymerization include esters (having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate), alcohols (having 1 to 8 carbon atoms such as methanol, ethanol and octanol), hydrocarbons (having carbon atoms).
  • the amount used is preferably 5 to 900% by weight, more preferably 10 to 400% by weight, based on the total weight of the monomers. More preferably, it is 30 to 300% by weight, and the monomer concentration is 10 to 9 Preferably wt%, more preferably 20 to 90 wt%, more preferably 30 to 80 wt%.
  • Examples of the dispersion medium in emulsion polymerization and suspension polymerization include water, alcohol (for example, ethanol), ester (for example, ethyl propionate), light naphtha and the like, and examples of the emulsifier include higher fatty acid (carbon number 10 to 24) metal salt.
  • alcohol for example, ethanol
  • ester for example, ethyl propionate
  • emulsifier include higher fatty acid (carbon number 10 to 24) metal salt.
  • sulfate metal salt for example, sodium lauryl sulfate
  • ethoxylated tetramethyldecynediol sodium sulfoethyl methacrylate, dimethylaminomethyl methacrylate, etc.
  • the monomer concentration of the solution or dispersion is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, more preferably 30 to 80% by weight.
  • the amount of the polymerization initiator used in the solution or dispersion is The content is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the above.
  • chain transfer agents such as mercapto compounds (such as dodecyl mercaptan and n-butyl mercaptan) and / or halogenated hydrocarbons (such as carbon tetrachloride, carbon tetrabromide and benzyl chloride) can be used.
  • mercapto compounds such as dodecyl mercaptan and n-butyl mercaptan
  • halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and benzyl chloride
  • the polymer (A1) contained in the vinyl resin is a crosslinking agent (A ′) having a reactive functional group that reacts the polymer (A1) with a carboxyl group ⁇ preferably a polyepoxy compound (a′1) [polyglycidyl ether].
  • Examples of the method of crosslinking the polymer (A1) using the crosslinking agent (A ′) include a method of crosslinking after coating the negative electrode active material with the polymer (A1). Specifically, a negative electrode active material and a resin solution containing the polymer (A1) are mixed and removed to produce a coated negative electrode active material in which the negative electrode active material is coated with the polymer (A1), and then crosslinked. The solution containing the agent (A ′) is mixed with the coated negative electrode active material and heated to cause solvent removal and a crosslinking reaction, and the polymer (A1) is crosslinked by the crosslinking agent (A ′). A method of causing a reaction to be a molecular compound on the surface of the negative electrode active material is exemplified.
  • heating temperature is adjusted according to the kind of crosslinking agent, when using a polyepoxy compound (a'1) as a crosslinking agent, 70 degreeC or more is preferable, and when using a polyol compound (a'2), it is 120 degreeC. The above is preferable.
  • the coating layer may further contain a conductive agent, and as the conductive agent that can be contained in the coating layer, the same conductive material as that contained in the resin current collector can be suitably used. The same applies to preferred forms, average particle diameters, and the like.
  • the ratio of the total weight of the polymer compound and the conductive agent contained in the coating layer is not particularly limited, but is preferably 0 to 25% by weight with respect to the weight of the negative electrode active material.
  • the ratio of the weight of the polymer compound to the weight of the negative electrode active material is not particularly limited, but is preferably 0.1 to 11% by weight.
  • the ratio of the weight of the conductive agent to the weight of the negative electrode active material is not particularly limited, but is preferably 0 to 14% by weight.
  • the coated negative electrode active material can be produced, for example, by mixing a polymer compound and a negative electrode active material.
  • the coating layer contains a conductive agent, it may be produced, for example, by mixing a polymer compound, a conductive agent, and a negative electrode active material.
  • a coating material was prepared by mixing a polymer compound and a conductive agent. Then, you may manufacture by mixing this coating
  • at least a part of the surface of the negative electrode active material is coated with the coating layer containing the polymer compound.
  • negative electrode active material and the polymer compound those described for the coated negative electrode active material can be preferably used.
  • the coated negative electrode active material is prepared by, for example, dropping and mixing a polymer solution containing a polymer compound over a period of 1 to 90 minutes in a state where the negative electrode active material is put in a universal mixer and stirred at 300 to 1000 rpm. Stir further. Further, if necessary, a conductive agent is mixed, and then, if necessary, stirring is continued for 10 minutes to 1 hour. After reducing the pressure to 0.007 to 0.04 MPa while stirring, the stirring and the degree of vacuum are maintained. It can be obtained by raising the temperature to 50 to 200 ° C. and holding for 10 minutes to 10 hours, preferably 1 to 10 hours. Thereafter, the coated negative electrode active material obtained as a powder may be classified.
  • Examples of the method for producing a negative electrode for a lithium ion battery according to the present invention include, for example, a negative electrode active material and a conductive agent to be used as needed, based on the weight of a non-aqueous electrolyte or a non-aqueous solvent of the non-aqueous electrolyte.
  • a coating device such as a bar coater
  • Examples include a method in which a negative electrode active material layer obtained by removing a solvent and the like is pressed with a press if necessary, and the obtained negative electrode active material layer is impregnated with a predetermined amount of a non-aqueous electrolyte.
  • the negative electrode active material layer obtained from the dispersion does not need to be directly formed on the negative electrode current collector, for example, a negative electrode active material layer obtained by applying the dispersion on the surface of an aramid separator or the like, You may arrange
  • the drying performed as necessary after applying the dispersion liquid can be performed using a known dryer such as a forward air dryer, and the drying temperature is determined by the dispersion medium (non-aqueous electrolyte or It can be adjusted according to the type of nonaqueous solvent of the nonaqueous electrolytic solution.
  • a binder such as polyvinylidene fluoride (PVdF) contained in a known negative electrode for a lithium ion battery may be added to the dispersion, but the negative electrode active material is the above-described coated negative electrode active material. It is preferable not to add a binder.
  • the binder content is preferably 1% by weight or less, more preferably 0.5% by weight or less, with respect to 100% by weight of the total solid content contained in the negative electrode active material layer.
  • the amount is preferably 0.2% by weight or less, particularly preferably 0.1% by weight or less, and most preferably 0% by weight.
  • the binder is a polymer material added to bind the negative electrode active material particles and other members and maintain the structure of the negative electrode active material layer, and is a polymer compound for the coating layer contained in the coating layer.
  • the binder is an insulating material that does not cause a side reaction (oxidation-reduction reaction) during charge and discharge, and generally satisfies the following three points: (1) A slurry used for the production of an active material layer is stable. Maintaining the state (having a dispersing action and a thickening action); (2) Electrode active particles, conductive assistants, etc. are adhered to each other, the mechanical strength as an electrode is maintained, and the particles are electrically Keeping contact; (3) Has adhesion (binding force) to the current collector.
  • a negative electrode for a lithium ion battery it is necessary to maintain a conductive path by fixing a negative electrode active material in the negative electrode with a binder.
  • the coated negative electrode active material it is not necessary to add a binder because the conductive path can be maintained without fixing the negative electrode active material in the negative electrode by the action of the coating layer.
  • the amount of addition is determined from the point that the active material layer can be molded while a sufficient amount of voids are formed in the negative electrode active material layer. It is preferably 0.1 to 20% by weight based on the minute weight.
  • binder examples include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene, and polypropylene.
  • the pressure at which the dried slurry is pressed is not particularly limited. However, if the pressure is too high, a sufficient amount of voids cannot be formed in the negative electrode active material layer. Since it is not observed, it is preferable to press at 1 to 200 MPa.
  • the preferred form of the negative electrode current collector is as described above.
  • the dispersion medium is a non-aqueous electrolyte or a non-aqueous solvent of the non-aqueous electrolyte, and when the applied dispersion is dried, the negative electrode active material layer obtained after drying
  • the weight of the non-aqueous electrolyte obtained by impregnating the non-aqueous electrolyte into the negative electrode active material layer depends on the amount of voids in the negative electrode active material layer and the electrolyte concentration of the non-aqueous electrolyte. Can be adjusted.
  • the impregnation of the non-aqueous electrolyte with respect to the negative electrode active material layer is performed by a method in which the non-aqueous electrolyte is dropped and impregnated on the surface of the negative electrode active material layer formed by the above method using a dropper or the like. Can do.
  • the lithium ion battery of the present invention is a battery using the above-described negative electrode for lithium ion battery, and is combined with an electrode serving as a counter electrode of the above negative electrode for lithium ion battery, and stored in a cell container together with a separator, It can be manufactured by a method of injecting and sealing the cell container.
  • a positive electrode active material layer containing the positive electrode active material is formed on the other surface of the negative electrode current collector. It is also possible to produce a bipolar electrode by laminating the bipolar electrode with a separator and storing it in a cell container, injecting a non-aqueous electrolyte, and sealing the cell container.
  • separator examples include a microporous film made of polyethylene or polypropylene, a laminated film of a porous polyethylene film and porous polypropylene, a nonwoven fabric containing synthetic fibers (such as polyester fibers and aramid fibers) or glass fibers, and silica on the surface thereof.
  • synthetic fibers such as polyester fibers and aramid fibers
  • glass fibers such as glass fibers, and silica on the surface thereof.
  • separators for lithium ion batteries such as those to which ceramic fine particles such as alumina and titania are attached, may be mentioned.
  • non-aqueous electrolyte those described in the negative electrode for lithium ion batteries of the present invention can be suitably used.
  • the positive electrode used for a known lithium ion battery can be used as the electrode (positive electrode) that is the counter electrode of the negative electrode for the lithium ion battery.
  • the lithium ion battery of the present invention is characterized by using the negative electrode for a lithium ion battery of the present invention. Since the lithium ion battery of the present invention uses the negative electrode for a lithium ion battery of the present invention, it is possible to obtain a lithium ion battery that can be rapidly charged and has a high energy density.
  • ⁇ Production Example 2 Production of coated negative electrode active material particles> It was obtained in Production Example 1 with 100 parts of non-graphitizable carbon powder 1 (volume average particle diameter 20 ⁇ m) being put into a universal mixer high speed mixer FS25 [manufactured by Earth Technica Co., Ltd.] and stirred at room temperature at 720 rpm. 6.1 parts of the polymer compound solution for coating layer was added dropwise over 2 minutes, and the mixture was further stirred for 5 minutes.
  • a universal mixer high speed mixer FS25 manufactured by Earth Technica Co., Ltd.
  • acetylene black [DENKA BLACK (registered trademark) manufactured by Denka Co., Ltd.], which is a conductive agent, was added in 2 minutes while stirring, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining the stirring, and then the temperature was raised to 140 ° C. while maintaining the stirring and the degree of vacuum, and the volatile matter was distilled off by maintaining the stirring, the degree of vacuum and the temperature for 8 hours. . The obtained powder was classified with a sieve having an opening of 212 ⁇ m to obtain coated negative electrode active material particles.
  • ⁇ Production Example 3 Production of coated negative electrode active material particles>
  • the non-graphitizable carbon powder 1 volume average particle diameter 20 ⁇ m
  • artificial graphite volume average particle diameter 18 ⁇ m
  • SiO silicon oxide
  • Example 1 [Preparation of negative electrode active material slurry for lithium ion battery] 20 parts of non-aqueous electrolyte prepared by dissolving LiN (FSO 2 ) 2 at a rate of 3 mol / L in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) and carbon fiber [ Osaka Gas Chemical Co., Ltd. Donakabo Milled S-243: average fiber length 500 ⁇ m, average fiber diameter 13 ⁇ m: electrical conductivity 200 mS / cm 2 parts and planetary agitation type mixing kneader ⁇ Awatori Kentaro [Sinky Co., Ltd.
  • the obtained negative electrode active material slurry was applied to one side of an aramid separator [manufactured by Japan Vilene Co., Ltd.], pressed at a pressure of 10 MPa for about 10 seconds, and a negative electrode active material layer having a thickness of about 250 ⁇ m on the aramid separator (3 cm ⁇ 3 cm) was fixed.
  • the basis weight (also referred to as basis weight) of the negative electrode active material layer was determined from the weight change of the aramid separator before and after forming the negative electrode active material layer, and found to be 20.7 mg / cm 2 .
  • an X-ray CT image is obtained as a cross-sectional image in two directions: a thickness direction of an aramid separator and a direction perpendicular thereto. Thereafter, for the 50 ⁇ m ⁇ 50 ⁇ m region extracted at 10 random locations in the cross-sectional images in each direction, the area occupied by the voids in the entire region was determined, and the average value thereof was taken as the porosity.
  • Laminated copper foil (3cm x 3cm, thickness 50 ⁇ m) is laminated in the same direction in the direction of two terminals, and sandwiched between two commercially available heat-sealing aluminum laminate films (8cm x 8cm) The one side where the terminal comes out was heat-sealed to produce a laminate cell for negative electrode evaluation.
  • an aramid separator (3 cm ⁇ 3 cm) having a negative electrode active material layer fixed between one copper foil and the separator is inserted so that the negative electrode active material layer and the copper foil are in contact with each other, and an electrode (3 cm ⁇ 3 cm negative electrode active material)
  • the negative electrode for a lithium ion battery according to Example 1 was prepared by injecting 70 ⁇ L of the non-aqueous electrolyte into the layer) and causing the electrode to absorb the non-aqueous electrolyte.
  • 70 ⁇ L of nonaqueous electrolyte was injected onto the separator. Thereafter, a lithium foil was inserted between the separator and the other copper foil, and two sides orthogonal to the one side heat-sealed first were heat sealed.
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the negative electrode active material layer is compared with the battery capacity based on the total amount of the negative electrode active material.
  • the ratio hereinafter also referred to as battery capacity ratio
  • Example 2 A lithium ion battery negative electrode and a negative electrode evaluation lithium ion battery 2 according to Example 2 were prepared in the same procedure as in Example 1 except that the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 1 mol / L. .
  • the porosity of the negative electrode active material layer was the same as in Example 1.
  • the battery capacity ratio was 3.3%.
  • Example 3 A lithium ion battery negative electrode and a negative electrode evaluation lithium ion battery 3 according to Example 3 were prepared in the same procedure as in Example 1, except that the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 5 mol / L. .
  • the porosity of the negative electrode active material layer was the same as in Example 1.
  • the battery capacity ratio was 16.7%.
  • Example 4 The same procedure as in Example 1 was followed to Example 4 except that the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 2 mol / L and the type of electrolyte was changed from LiN (FSO 2 ) 2 to LiPF 6.
  • the negative electrode for lithium ion batteries and the lithium ion battery 4 for negative electrode evaluation were produced.
  • the porosity of the negative electrode active material layer was the same as in Example 1.
  • the battery capacity ratio was 6.7%.
  • Example 5 was performed in the same manner as in Example 1 except that the mixture was changed to a mixture, and the basis weight of the negative electrode active material was changed from 20.7 mg / cm 2 to 38.4 mg / cm 2 to change the film thickness to 445 ⁇ m.
  • the negative electrode for lithium ion batteries which concerns on this, and the lithium ion battery 5 for negative electrode evaluation were produced.
  • the porosity of the negative electrode active material layer was the same as in Example 1.
  • the battery capacity ratio was 6.6%.
  • Example 6> For a lithium ion battery according to Example 6 in the same procedure as in Example 1 except that the basis weight of the negative electrode active material was changed from 20.7 mg / cm 2 to 8.6 mg / cm 2 and the film thickness was changed to 100 ⁇ m. A negative electrode and a lithium ion battery 6 for negative electrode evaluation were prepared. The porosity of the negative electrode active material layer was the same as in Example 1. The battery capacity ratio was 9.7%.
  • Example 7> For a lithium ion battery according to Example 7 in the same procedure as in Example 1 except that the basis weight of the negative electrode active material was changed from 20.7 mg / cm 2 to 103.2 mg / cm 2 and the film thickness was changed to 1200 ⁇ m. A negative electrode and a lithium ion battery 7 for negative electrode evaluation were prepared. The porosity of the negative electrode active material layer was the same as in Example 1. The battery capacity ratio was 9.7%.
  • Example 8> A negative electrode for a lithium ion battery according to Example 8 according to the same procedure as in Example 1 except that the basis weight of the negative electrode active material was changed from 20.7 mg / cm 2 to 6 mg / cm 2 and the film thickness was changed to 70 ⁇ m. A lithium ion battery 8 for negative electrode evaluation was produced. The porosity of the negative electrode active material layer was the same as in Example 1. The battery capacity ratio was 9.6%.
  • Example 9 The electrolyte concentration of the non-aqueous electrolyte is changed from 3 mol / L to 1 mol / L, and the negative electrode active material slurry is placed on the aramid separator so that the film thickness of the negative electrode active material layer is 306 ⁇ m and the porosity is 55% by volume.
  • a negative electrode for a lithium ion battery and a lithium ion battery 9 for negative electrode evaluation according to Example 9 were produced in the same procedure as in Example 1 except that the press condition after coating was changed to about 10 seconds at 4 MPa.
  • the film thickness of the negative electrode active material layer was 306 ⁇ m, and the porosity was 55% by volume.
  • the battery capacity ratio was 5.0%.
  • Example 10> instead of the coated negative electrode active material particles produced in Production Example 2, the coated negative electrode active material particles produced in Production Example 3 were used, and the press conditions after applying the negative electrode active material slurry on the aramid separator were 15 MPa.
  • a lithium ion battery negative electrode and a negative electrode evaluation lithium ion battery 10 according to Example 10 were produced in the same procedure as in Example 1 except that the time was changed to about 10 seconds.
  • the basis weight of the negative electrode active material layer was 50 mg / cm 2
  • the film thickness of the negative electrode active material layer was 380 ⁇ m
  • the porosity 40% by volume.
  • the battery capacity ratio was 8.1%.
  • Example 11 Instead of 98 parts of the coated negative electrode active material particles produced in Production Example 2 used in the production of the negative electrode active material slurry for a lithium ion battery, 98 parts of the negative electrode active material particles prepared in Production Example 4 were used, and a non-aqueous electrolyte solution was used.
  • a lithium ion battery negative electrode and a negative electrode evaluation lithium ion battery 11 according to Example 11 were prepared in the same procedure as in Example 1 except that the electrolyte concentration was changed to 2 mol / L.
  • the basis weight of the negative electrode active material layer was 33.2 mg / cm 2 , the film thickness of the negative electrode active material layer was 323 ⁇ m, and the porosity was 45% by volume.
  • the battery capacity ratio was 4.8%.
  • Example 2 In Example 1, the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 5.5 mol / L, but the electrolyte salt was precipitated in the electrolyte, and a non-aqueous electrolyte that could be used for a battery could not be produced. The battery was not manufactured. Note that the battery capacity ratio is 18.1% when it is assumed that a battery is manufactured in the same manner as in Example 1 using a non-aqueous electrolyte having an electrolyte concentration of 5.5 mol / L.
  • a negative electrode for a lithium ion battery and a lithium ion battery 4 for comparative evaluation of negative electrode according to Comparative Example 4 were prepared in the same procedure as in Example 1 except that the pressing conditions after the change were changed to about 10 seconds at 50 MPa.
  • the film thickness of the negative electrode active material layer was 214 ⁇ m, and the porosity was 30% by volume.
  • the battery capacity ratio was 1.9%.
  • the coated negative electrode active material particles prepared in Production Examples 2 and 3 and the negative electrode active material particles prepared in Production Example 4 were respectively mixed with ethylene carbonate (EC) and diethyl carbonate (DEC) in a mixed solvent (volume ratio 1: 1) with LiN. (FSO 2 ) 2 was mixed with a non-aqueous electrolyte prepared by dissolving at a rate of 3 mol / L to form a slurry, which was applied to one side of an aramid separator [manufactured by Japan Vilene Co., Ltd.] and then 10 seconds at a pressure of 10 MPa.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the electrode was produced by pressing and incorporated into the battery pack, and the discharge capacity when discharged from 0.0 V to 1.5 V was measured with a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Corporation], and The discharge capacity (0.0 V ⁇ 1.5 V discharge capacity) of the negative electrode active material was determined.
  • the coated negative electrode active material prepared in Production Example 2 was 434 mAh / g
  • the coated negative electrode active material prepared in Production Example 3 was 300 mAh / g
  • the negative electrode active material particles prepared in Production Example 4 was 492 mAh / g. It was.
  • the lithium ion batteries 1 to 11 for negative electrode evaluation and the lithium ion batteries 1, 3 and 4 for comparative evaluation of negative electrode were charged to 4.2 V at a current of 2.0 C, respectively, and the capacity at the time of charging (2.0 C charge capacity) was measured.
  • the lithium ion battery using the negative electrode for a lithium ion battery of the present invention has high energy density and excellent quick charge characteristics.
  • the negative electrode for lithium ion batteries of the present invention is particularly useful as a negative electrode for bipolar secondary batteries and lithium ion secondary batteries used for mobile phones, personal computers, hybrid vehicles and electric vehicles.

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Abstract

L'invention aborde le problème de la réalisation d'une électrode négative pour une batterie lithium-ion ayant une haute densité d'énergie et d'excellentes caractéristiques de charge rapide. La solution selon l'invention consiste en une électrode négative pour une batterie lithium-ion, l'électrode négative comprenant : un collecteur d'électrode négative ; une couche de matériau actif d'électrode négative formée sur la surface du collecteur d'électrode négative ; et une solution d'électrolyte non aqueux contenant un solvant non aqueux et un électrolyte incluant des ions lithium. L'électrode négative pour une batterie lithium-ion est caractérisée en ce que la couche de matériau actif d'électrode négative contient un matériau actif d'électrode négative et des lacunes, en ce que les lacunes sont remplies par la solution d'électrolyte non aqueux, et en ce que le ratio de la capacité de la batterie sur la base de la quantité totale d'ions lithium dans la solution d'électrolyte non aqueux présente dans la couche de matériau actif d'électrode négative par rapport à la capacité de la batterie sur la base de la quantité totale du matériau actif d'électrode négative est compris entre 3 et 17 %.
PCT/JP2017/040163 2016-11-07 2017-11-07 Électrode négative pour batterie lithium-ion, et batterie lithium-ion WO2018084319A1 (fr)

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CN201780068741.5A CN109923699B (zh) 2016-11-07 2017-11-07 锂离子电池用负极和锂离子电池
US16/346,707 US10930920B2 (en) 2016-11-07 2017-11-07 Negative electrode for lithium ion battery and lithium ion battery
EP17866935.4A EP3537513B1 (fr) 2016-11-07 2017-11-07 Électrode négative pour batterie lithium-ion et batterie lithium-ion

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CN110459810A (zh) * 2019-08-15 2019-11-15 萨姆蒂萨（天津）数据信息技术有限公司 一种锂电池的制备方法
CN112420998B (zh) * 2019-08-22 2022-03-01 宁德时代新能源科技股份有限公司 一种二次电池
CN113224297A (zh) * 2020-02-06 2021-08-06 宁德新能源科技有限公司 负极极片、应用所述负极极片的电池以及电子装置
CN114024021B (zh) * 2021-10-25 2022-08-30 珠海冠宇电池股份有限公司 一种电池

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