WO2013118380A1 - Batterie rechargeable lithium-ion et procédé pour sa fabrication - Google Patents

Batterie rechargeable lithium-ion et procédé pour sa fabrication Download PDF

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WO2013118380A1
WO2013118380A1 PCT/JP2012/081731 JP2012081731W WO2013118380A1 WO 2013118380 A1 WO2013118380 A1 WO 2013118380A1 JP 2012081731 W JP2012081731 W JP 2012081731W WO 2013118380 A1 WO2013118380 A1 WO 2013118380A1
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Prior art keywords
binder
protective film
electrode film
film
slurry
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PCT/JP2012/081731
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English (en)
Japanese (ja)
Inventor
千恵美 窪田
昌作 石原
菊池　廣
桂司 佐藤
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株式会社日立製作所
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Priority to CN201280067434.2A priority Critical patent/CN104067420A/zh
Publication of WO2013118380A1 publication Critical patent/WO2013118380A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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 lithium ion secondary battery and a manufacturing method thereof.
  • Patent Document 1 JP-A-7-220759 (Patent Document 1) as background art in this technical field.
  • Patent Document 1 states that “the protective layer formed on the surface of the active material layer can prevent the active material from dropping and reattaching after the active material layer is formed and before the electrode is housed in the battery can. The internal short circuit of the battery induced by the active material reattached to the electrode surface can be prevented, and a highly reliable and safe non-aqueous electrolyte secondary battery can be obtained.
  • Lithium ion secondary batteries have the advantages described above, and are therefore widely used in portable electronic devices such as digital cameras, notebook personal computers, and mobile phones.
  • lithium ion secondary batteries capable of realizing high capacity, high output, and high energy density as electric vehicle batteries and power storage batteries.
  • development of an electric vehicle that uses a motor as a power source and a hybrid vehicle that uses both an engine (internal combustion engine) and a motor as a power source are in progress.
  • Lithium ion secondary batteries have attracted attention as power sources for such electric vehicles and hybrid vehicles.
  • a step of winding a positive electrode plate and a negative electrode plate made of metal foil a step of welding and fixing an electrode winding body to an outer container, and an electrolyte solution in an outer container
  • a process of injecting into the inside For example, in the step of winding a positive electrode plate or a negative electrode plate, metal fine powder may be generated when the positive electrode plate or the negative electrode plate, which is a metal foil, is wound.
  • metallic foreign matter may be scattered during welding.
  • the porous and insulating protective film described in Patent Document 1 is provided on the surface of the electrode film, it is possible to prevent the adhesion of the metal foreign object to the electrode surface. The internal short circuit due to can be suppressed.
  • a method for forming such a protective film a method of applying a slurry made of insulating particles and a binder component on the surface of the electrode film and drying it can be employed.
  • the binder distribution in the protective film is generated, the adhesion with the electrode film is lowered, and the protective film is easily dropped during the transportation of the electrode plate or the manufacturing process of the electrode winding body.
  • it is necessary to increase the binder content When the content of the binder is excessively increased, the battery capacity is lowered, and it is difficult to achieve both improvement in reliability and improvement in battery capacity.
  • the present invention provides a lithium ion secondary battery capable of improving battery capacity without reducing reliability by using an electrode film with a protective layer having high adhesion to the electrode film, and a method for manufacturing the lithium ion secondary battery The purpose is to provide.
  • the present invention provides an electrode film that is formed on the surface of a current collector foil and includes a binder that adheres to the current collector foil, and a binder that is formed on the surface of the electrode film and adheres to the electrode film. And a protective film containing insulating particles, wherein the concentration of the binder on the electrode film side in the protective film is higher than the concentration of the binder on the opposite side of the electrode film I will provide a.
  • the present invention also includes a first step of applying a liquid protective film slurry containing a binder that adheres to the electrode film on the electrode film formed on the surface of the current collector foil; and a solvent containing a solidified liquid is added to the protective film.
  • a lithium ion secondary battery comprising: a second step of bringing the protective film slurry into contact with a slurry and solidifying the protective film slurry; and a third step of removing a liquid component from the solidified protective film slurry and drying the solid film.
  • a lithium ion secondary battery capable of improving battery capacity without reducing reliability by an electrode film with a protective layer having high adhesion to the electrode film, and a method for manufacturing the lithium ion secondary battery. Can do.
  • FIG. 1 It is a figure showing the protective film formation process in the conventional method. It is a figure which shows the concentration to the protective film surface side of the binder after the conventional protective film drying. It is a figure showing the formation process of the protective film in this invention embodiment. It is a figure which shows binder distribution of a protective film at the time of forming a protective film in the shape of an electrode film by sequential lamination
  • the lithium ion secondary battery in the present embodiment is wound or laminated via a separator that prevents contact between the positive electrode plate and the negative electrode plate.
  • the electrolytic solution is injected into the outer container.
  • the positive electrode plate and the negative electrode plate have a structure in which an electrode film 9 is formed on a current collector foil 6 that is a metal foil as a current collector, and a protective film 8 is formed on the surface of the electrode film 9. ing.
  • the electrode film 9 is an electrode film slurry containing an active material 3 capable of releasing and occluding lithium ions by charge and discharge, a binder 4 for bonding the current collector foil 6 and the electrode film 9, and a solvent 2 in which the conductive material 5 is dissolved. It is formed by solidifying and drying.
  • the protective film 8 is formed by solidifying and drying the protective film slurry containing the solvent 2 in which the insulating particles 1, the electrode 4 and the binder 4 that bonds the protective film 8 are dissolved.
  • the electrode film slurry containing the active material 3, the binder 4, the conductive material 4, and the first solvent is applied to the current collector foil 6, and the second solvent containing the solidified liquid 11 is brought into contact with the first electrode film slurry.
  • the electrode film 9 is formed by solidifying, removing the liquid component, and drying.
  • the protective film slurry containing the insulating particles 1, the binder 4, and the first solvent is applied to the electrode film 9, and the second solvent containing the solidified liquid 11 is brought into contact with the protective film slurry to solidify the liquid component.
  • the protective film 8 is formed by removing and drying.
  • a separator made of a porous insulating material that allows lithium ions to pass through is sandwiched between the positive electrode plate and the negative electrode plate while preventing contact between the positive electrode plate and the negative electrode plate, and the positive electrode plate, the separator, and the negative electrode plate are wound.
  • the electrode winding body which consists of the wound positive electrode plate, separator, and negative electrode plate can be formed.
  • electrolyte solution is inject
  • a lithium ion secondary battery can be manufactured by cap-sealing an exterior container.
  • a conventional method for forming the protective film 8 will be described with reference to FIGS.
  • a liquid protective film slurry is applied to the surface of the electrode film 9 formed on the surface of the current collector foil 6 and introduced into a drying chamber as it is to be dried.
  • the solvent 2 in the applied protective film 8 evaporates and dries, but the protective film 8 is applied to the surface of the electrode film 9.
  • the solvent 2 evaporates from the surface of the protective film 8 (opposite side of the electrode film 9).
  • the solvent 2 on the electrode film 9 side moves to the surface of the protective film 8 (opposite side of the electrode film 9) and evaporates from the surface of the protective film 8 (opposite side of the electrode film 9).
  • the binder 4 dissolved in the solvent 2 moves together with the solvent 2 toward the surface of the protective film 8 in the direction of the arrow in FIG.
  • the moved solvent 2 evaporates as a solvent 7 evaporated from the surface, but the dissolved binder 4 is deposited and remains with the evaporation of the solvent 2.
  • the binder 4 is concentrated on the surface side of the protective film 8 (opposite side of the electrode film 9), as shown in FIG.
  • a method of forming the protective film 8 in this embodiment will be described with reference to FIG.
  • a step of solidifying the applied protective film slurry is added, and the solidified protective film 8 is dried.
  • the decrease in the adhesion of the protective film 8 is eliminated.
  • the decrease in the adhesion of the protective film 8 causes the binder distribution in the protective film 8 to become non-uniform during the drying process, and the binder concentration on the electrode film 9 side becomes lower than the binder concentration on the surface side (opposite side of the electrode film 9). This is what happens.
  • the binder concentration on the electrode film 9 side can be increased also on the surface side (opposite side of the electrode film 9).
  • the difference between the binder concentration on the electrode film 9 side and the binder concentration on the surface side (opposite side of the electrode film 9) can be 50% or less of the binder concentration on the surface side (opposite side of the electrode film 9), It is possible to prevent the binder distribution in the protective film 8 from becoming non-uniform.
  • the decrease in the adhesion of the electrode film 9 is eliminated.
  • the decrease in the adhesion between the current collector foil 6 and the electrode film 9 causes the binder distribution in the electrode film 9 to be non-uniform during the drying process, and the binder concentration on the current collector foil 6 side is lower than the binder concentration on the protective film 8 side. This is what happens.
  • the binder concentration on the current collector foil 6 side can be made higher than the binder concentration on the protective film 8 side.
  • the difference between the binder concentration on the current collector foil 6 side and the binder concentration on the protective film 8 side can be 50% or less of the binder concentration on the protective film 8 side, and the binder distribution in the electrode film 8 becomes non-uniform. Can be suppressed.
  • the second solvent containing the solidified liquid 11 of the present embodiment is applied to the coating protective film 8 held on the surface of the electrode film 9 containing the first solvent of the present embodiment. What is necessary is just to deposit the binder 4 by making it contact. Accordingly, a method of passing the coating film held on the surface of the electrode film 9 through the liquid tank storing the second solvent, a method of spraying the second solvent on the coating film held on the surface of the electrode film 9, Although the system etc. which supply the solvent of 2 while flowing down are included, it is not limited to these.
  • the binder distribution is basically the same as that of the protective film slurry for coating when the solidification is instantaneous, that is, the binder 4. Is uniformly distributed in the protective film 8.
  • the solidified liquid 11 penetrates from the surface of the protective film 8 as shown by the arrows in FIG. 3, and the binder 4 dissolved in the first solvent is precipitated by the solidified liquid 11. That is, the precipitation of the binder 4 proceeds from the surface to the electrode film 9 side, and the binder concentration on the electrode film 9 side increases.
  • the binder distribution increases on the electrode film 9 side. A good protective film 8 is obtained.
  • the solidified liquid 11 permeates from the surface of the electrode film 9, and the binder 4 dissolved in the first solvent is precipitated by the solidified liquid 11. That is, the precipitation of the binder 4 proceeds from the surface to the current collector foil 6 side, and the binder concentration on the current collector foil 6 side increases. Contrary to the large amount of binder 4 on the surface side (protective film 8 side) of the conventional electrode screen 9, this binder distribution increases the amount of binder 4 on the current collector foil 6 side, so that the adhesion to the current collector foil 6 is improved. A good electrode film 9 is obtained.
  • the lower limit of the contact time required for solidification generally requires time for the first solvent and the second solvent to interdiffuse and replace in the coating film, but the thickness of the protective film 8 is 1 mm. If it is below, the contact time is preferably 1 to 100 seconds, more preferably 2 to 50 seconds, and even more preferably 5 to 20 seconds.
  • the method of drying the protective film 8 is not limited to general hot air drying.
  • a heating method that irradiates electromagnetic waves such as infrared rays, far-infrared rays, or visible light may be used, or a dielectric heating method that uses a high-frequency electric field, or an induction heating method that uses a change in magnetic flux may be used.
  • a contact heating method using a heating roll or a hot plate incorporating a heater can also be used.
  • the insulating particles 1 constituting the protective film 8 used in the present embodiment various inorganic particles and / or resin particles exhibiting insulating properties (non-conductive properties) can be used. From the viewpoint of durability and reliability, it is preferable to use inorganic particles.
  • the inorganic particles may be metal element or non-metal element oxides, carbides, silicides, and nitrides. From the viewpoint of chemical stability and material cost, it is preferable to use oxide particles such as alumina (Al 2 O 3 ) and silica (SiO 2 ).
  • the average particle diameter of the insulating particles 1 to be used is related to the thickness of the protective film 8 formed on the surface of the electrode film 9, but is preferably about 0.1 to 10 ⁇ m, more preferably about 0.3 to 5 ⁇ m. It becomes. Moreover, the insulating particle
  • a polyvinylidene fluoride polymer (vinylidene fluoride which is a main component monomer) is used as a polymer material having the property of binding the insulating particles 1 described above.
  • Polymers of fluorine-containing monomers containing 80% by mass or more), rubber-based polymers, etc. are preferably used. Two or more of the above polymers may be used in combination.
  • Examples of the fluorine-containing monomer group for synthesizing the polyvinylidene fluoride-based polymer include vinylidene fluoride; a mixture of vinylidene fluoride and other monomers, and a monomer mixture containing 80% by mass or more of vinylidene fluoride; Can be mentioned.
  • Examples of other monomers include vinyl fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
  • Examples of the rubber polymer include styrene butadiene rubber (SBR), ethylene propylene diene rubber, and fluorine rubber.
  • SBR styrene butadiene rubber
  • ethylene propylene diene rubber examples include fluorine rubber.
  • the binder 4 of the present embodiment may be added separately from the component having the performance as the solidifying liquid 11, or the binder 4 itself may have a function as the solidifying liquid 11.
  • the binder 4 is added separately from the component having the performance as the solidifying liquid 11, the above polymer material having the property of binding the insulating particles 1 is preferably used as the binder 4, but the solution dissolved in the solvent 2 is not necessarily used. However, it may be in the form of an emulsion in which a polymer material is dispersed in a liquid.
  • the binder 4 used for forming the electrode film 9 and the binder 4 used for forming the protective film 8 is the same.
  • the binder 4 used for both the electrode film 9 and the protective film 8 is more preferably a polymer material having the properties of the solidified liquid 11 in this embodiment.
  • the content of the binder 4 in the protective film 8 is 0.1% by mass or more, more preferably 0.5% by mass or more and 20% by mass or less, more preferably 10%, based on the protective film 8 after drying. It is desirable that it is less than mass%. If the content of the binder 4 is too small, not only is the solidification in the solidification step of this embodiment insufficient, but the mechanical strength of the mixture layer after drying is insufficient, and the protective film 8 is peeled off from the electrode film 9. May fall. Moreover, when there is too much content of the binder 4, the pore formed with the insulating particle 1 will be obstruct
  • the solvent 2 of the present embodiment is used by appropriately selecting the first solvent and the second solvent.
  • the solvent 2 should be selected from the solubility of the solidified liquid 11 of the present embodiment or the component of the binder 4 that also serves as the solidified liquid 11 and the mutual solubility of the solvent.
  • As the first solvent N-methylpyrrolidone, dimethylsulfoxide
  • An aprotic polar solvent typified by propylene carbonate, dimethylformamide, ⁇ -butyrolactone or a mixture thereof can be selected.
  • a protic solvent typified by water, ethanol, isopropyl alcohol, acetic acid or the like, or a mixed solution thereof can be selected, but is not limited to the examples given here.
  • aliphatic saturated hydrocarbons, aliphatic amines, esters, ethers, various halogen-based solvents, and the like can be selected as the second solvent. Further, in some cases, it is possible to select to exchange the first solvent and the second solvent.
  • the selection of the solvent 2 in this embodiment depends on the selection of the solidifying component used for the protective film 8 and the combination of the two types of solvents 2 that match the selection.
  • the solvent used for the electrode film slurry and the protective film slurry may be the same or different.
  • the same solvent as the electrode film 9 slurry can be preferably used as the solvent of the protective film slurry (first solvent in the present embodiment).
  • the protective film 8 is formed by bringing the second solvent into contact with the coating protective film 8 held on the surface of the electrode film 9 containing the first solvent, and precipitating and solidifying the binder 4. Since the second solvent also contacts the electrode film 9, an event that affects the state of the electrode film 9 can be avoided by selecting a solvent that does not melt or swell the material of the binder 4 contained in the electrode film 9. .
  • various application methods such as an extrusion coater, a reverse roller, a doctor blade, an applicator and the like can be employed.
  • the positive electrode active material used for the positive electrode lithium cobaltate, a lithium-containing composite oxide having a spinel structure containing manganese, a composite oxide containing nickel, cobalt, manganese, or olivine
  • An olivine type compound represented by type iron phosphate is used, but is not limited thereto. Since the lithium-containing composite oxide having a spinel structure containing manganese is excellent in thermal stability, for example, a highly safe battery can be configured.
  • the positive electrode active material only a lithium-containing composite oxide having a spinel structure containing manganese may be used, but another positive electrode active material may be used in combination.
  • An oxide containing Ni and Mn (LiMn1 / 3Ni1 / 3Co1 / 3O2, LiMn5 / 12Ni5 / 12Co1 / 6O2, LiNi3 / 5Mn1 / 5Co1 / 5O2, etc.) can be used.
  • examples of the negative electrode active material used for the negative electrode include graphite materials such as natural graphite (flaky graphite), artificial graphite, and expanded graphite; graphitizable properties such as coke obtained by firing pitch.
  • Carbonaceous materials Carbon materials such as non-graphitizable carbonaceous materials such as amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin (PFA), polyparaphenylene (PPP), and phenol resin.
  • lithium or a lithium-containing compound can also be used as the negative electrode active material.
  • examples of the lithium-containing compound include a lithium alloy such as Li—Al, and an alloy containing an element that can be alloyed with lithium such as Si and Sn.
  • oxide-based materials such as Sn oxide and Si oxide can also be used.
  • the conductive material 5 is usually used as an electron conduction aid to be contained in the positive electrode film, and is preferably a carbon material such as carbon black, acetylene black, ketjen black, graphite, carbon fiber, or carbon nanotube.
  • a carbon material such as carbon black, acetylene black, ketjen black, graphite, carbon fiber, or carbon nanotube.
  • acetylene black or ketjen black is particularly preferable from the viewpoint of the amount of addition and conductivity, and the productivity of the positive electrode mixture slurry for coating.
  • Such a conductive material 5 can be contained in the negative electrode film, and may be preferable.
  • the current collector foil 6 used in the present embodiment is representatively shown, and is not limited to a sheet-like foil.
  • the substrate include pure aluminum, copper, stainless steel, titanium, and the like.
  • a metal, an alloy conductive material, or a net, a punched metal, a foam metal, a foil processed into a plate shape, or the like is used.
  • As the thickness of the conductive substrate for example, 5 to 30 ⁇ m, more preferably 8 to 16 ⁇ m is selected.
  • the lithium ion secondary battery that can be provided by the present embodiment can be manufactured in the same manner as a conventional secondary battery except that it includes a positive electrode and a negative electrode manufactured by the above-described method.
  • a positive electrode and a negative electrode manufactured by the above-described method There is no particular limitation on the structure and size of the battery container or the structure of the electrode body having positive and negative electrodes as main components.
  • the positive electrode film slurry was prepared by the following method.
  • the active material 3 a lithium transition metal composite oxide lithium manganese cobalt nickel composite oxide powder was used.
  • the lithium manganese cobalt nickel composite oxide was mixed as a positive electrode mixture by mixing 9 parts by weight of graphite powder and 2 parts by weight of carbon black as the conductive material 5 with respect to 85 parts by weight.
  • NMP N-methyl-2-pyrrolidone
  • bin polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • the slurry for the positive electrode film prepared above is applied to the surface of the current collector foil 6 formed of aluminum using a die coater.
  • the coated electrode film 9 was immersed in pure water for 5 seconds to solidify the binder 4 and then dried at 120 ° C. at a temperature rising rate of 3 ° / second in a warm air drying furnace to form a positive electrode film.
  • the protective film slurry was produced by the following method.
  • Silica particles having an average particle diameter of 1 ⁇ m were used as the insulating particles 1.
  • NMP N-methyl-2-pyrrolidone
  • PVDF polyvinylidene fluoride
  • the solution was added and dispersed in NMP to form a slurry.
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side is increased compared to the vicinity of the surface (opposite side of the electrode film 9), and the electrode film 9 of the protective film 8.
  • the binder concentration on the side of the protective film 8 is 4.2%
  • the binder concentration on the surface side of the protective film 8 (the side opposite to the electrode film 9) is 3.5%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8.
  • the binder concentration on the surface side (opposite side of the electrode film 9) was 20% higher than the binder concentration on the surface side (opposite side of the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the side of the current collector foil 6 is increased compared to the vicinity of the surface (protective film 8 side), and the binder concentration on the side of the current collector foil 6 of the electrode film 9 is 4.
  • the binder concentration on the surface side of the electrode film 9 (protective film 8 side) is 3.7%, and the binder concentration on the current collector foil 6 side of the electrode film 9 is on the surface side of the electrode film 9 (protective film 8).
  • the binder concentration on the surface side of the electrode film 9 (protective film 8 side) was 19% higher than the binder concentration on the side).
  • Example 1 Comparative Example 1
  • the slurry for the positive electrode film of Example 1 is applied to the surface of the current collector foil 6 formed of aluminum using a die coater. Subsequently, the coated positive electrode film was dried at 120 ° C. in a warm air drying oven at a temperature increase rate of 3 ° C./second to form a positive electrode film. Thereafter, the protective layer slurry of Example 1 was applied onto the positive electrode film using a die coater, and the protective film 8 was dried at 120 ° C. at a temperature rising rate of 3 ° / second in the hot air drying path. .
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side decreases compared to the vicinity of the surface (opposite side to the electrode film 9), and the electrode film 9 of the protective film 8.
  • the binder concentration on the side of the protective film 8 is 3.6%
  • the binder concentration on the surface side of the protective film 8 (the side opposite to the electrode film 9) is 4.9%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8.
  • the binder concentration on the surface side (opposite side of the electrode film 9) was 27% lower than the binder concentration on the surface side (opposite side of the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the side of the current collector foil 6 is reduced as compared with the vicinity of the surface (protective film 8 side), and the binder concentration on the side of the current collector foil 6 of the electrode film 9 is 2.
  • the binder concentration on the surface side of the electrode film 9 (protective film 8 side) is 5.3%, and the binder concentration on the current collector foil 6 side of the electrode film 9 is on the surface side of the electrode film 9 (protective film 8 side) ) Was 47% less than the binder concentration on the surface side (protective film 8 side).
  • the difference between the binder concentration on the electrode film 9 side of the protective film 8 and the binder concentration on the surface side (opposite side of the electrode film 9) is set to 50% or less of the binder concentration on the surface side (opposite side of the electrode film 9). be able to. Furthermore, the difference between the binder concentration on the current collector foil 6 side of the electrode film 9 and the binder concentration on the protective film 8 side can be 50% or less of the binder concentration on the protective film 8 side. Thereby, since the part where a binder density
  • the slurry for the positive electrode film produced in the same manner as in Example 1 is applied to the surface of the current collector foil 6 formed of aluminum using a die coater. Then, the protective film slurry produced similarly to Example 1 is apply
  • the method of applying the protective film slurry after first applying the positive electrode film slurry has been described. However, for example, multilayer coating in which the positive electrode slurry and the protective film slurry are simultaneously applied can also be used.
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side is increased compared to the vicinity of the surface (opposite side to the electrode film 9).
  • the binder concentration on the side of the protective film 8 is 3.8%
  • the binder concentration on the surface side of the protective film 8 (the side opposite to the electrode film 9) is 3.3%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8.
  • the binder concentration on the surface side (opposite side of the electrode film 9) was 15% higher than the amount of field inter on the surface side (opposite side of the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the current collector foil 6 side is increased compared to the vicinity of the surface (protective film 8 side), and the binder concentration on the current collector foil 6 side of the electrode film 9 is 3.
  • the binder concentration on the surface side of the electrode film 9 (protective film 8 side) is 4.4%
  • the binder concentration on the current collector foil 6 side of the electrode film 9 is on the surface side of the electrode film 9 (protective film 8 side) ) And 13% higher than the binder concentration.
  • the slurry for the positive electrode film of Example 2 is applied to the surface of the current collector foil 6 formed of aluminum using a die coater.
  • the protective film slurry of Example 2 is coated on the coated positive electrode film using a die coater.
  • the coated positive electrode film and the protective film 8 were dried at 120 ° C. in a warm air drying furnace at a temperature rising rate of 3 ° C./second to produce an electrode film 9 on which the protective film 8 was formed.
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side is reduced as compared with the vicinity of the surface (opposite side to the electrode film 9).
  • the binder concentration on the side of the protective film 8 is 4.8%
  • the binder concentration on the surface side of the protective film 8 (the side opposite to the electrode film 9) is 5.6%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8. 14% of the binder concentration on the surface side (opposite side of the electrode film 9) was smaller than the amount of field inter on the surface side (opposite side of the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the side of the current collector foil 6 is reduced as compared with the vicinity of the surface (protective film 8 side), and the binder concentration on the side of the current collector foil 6 of the electrode film 9 is 2. 3%, the surface side of the electrode film 9 (protective film 8 side) is 4.8%, and the binder concentration on the current collector foil 6 side of the electrode film 9 is the binder on the surface side of the electrode film 9 (protective film 8 side) 52% less than the concentration.
  • Example 2 since mixing of particles due to solvent movement during drying as in Comparative Example 2 can be prevented, the thickness of the protective film 8 can be reduced.
  • the amount of the positive electrode active material can be increased, and the capacity of the electrode film 9 on which the protective film 8 is formed can be increased.
  • the positive electrode film of Example 2 it is possible to obtain a lithium ion secondary battery having excellent reliability such as short circuit resistance and a high capacity.
  • the positive electrode film of the electrode film 9 and the protective film 8 are collectively formed, and the binder 4 in the protective film 8 is double the binder in the positive electrode film of the electrode film. State.
  • the slurry for the positive electrode film produced in the same manner as in Examples 1 and 2 is applied to the surface of the current collector foil 6 formed of aluminum using a die coater.
  • the protective film slurry produced similarly to Example 1, 2 is apply
  • the coated positive electrode film and the protective film 8 are immersed in pure water for 5 seconds to solidify the binder 4 and then dried at 120 ° C. in a warm air drying furnace at a temperature rising rate of 3 ° C./second. A positive electrode film in which was formed was produced.
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side is increased compared to the vicinity of the surface (opposite side to the electrode film 9).
  • the binder concentration on the side of the protective film 8 is 8.4%
  • the binder concentration on the surface side of the protective film 8 (the side opposite to the electrode film 9) is 7.8%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8.
  • the binder concentration on the surface side (the side opposite to the electrode film 9) was 7.7% higher than the binder concentration on the surface side (the side opposite to the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the side of the current collector foil 8 is increased compared with the vicinity of the surface (protective film 8 side), and the binder concentration on the side of the current collector foil of the electrode film 9 is 4.4. %, The binder concentration on the surface side of the electrode film 9 (protective film 8 side) is 4.0%, and the binder concentration on the current collector foil 6 side of the electrode film 9 is the surface side of the electrode film 9 (protective film 8 side) 10% higher than the binder concentration.
  • the slurry for the positive electrode film of Example 3 is applied to the surface of the current collector foil 6 formed of aluminum using a die coater.
  • the protective film slurry of Example 3 is coated on the coated positive electrode film using a die coater.
  • the coated positive electrode film and the protective film 8 were dried at 120 ° C. in a warm air drying furnace at a temperature rising rate of 3 ° C./second to produce an electrode film 9 on which the protective film 8 was formed.
  • the protective film slurry of Example 3 was applied onto the positive electrode film using a die coater, and the protective film 8 was dried at 120 ° C. at a temperature rising rate of 3 ° / second in the hot air drying path. In the dried electrode film 9, many cracks and peeling were observed in the protective film 8. As shown in FIG.
  • the binder distribution of the produced protective film 8 is such that the binder concentration on the electrode film 9 side is reduced compared to the vicinity of the surface (opposite side of the electrode film 9), and the electrode film 9 of the protective film 8.
  • the binder concentration on the side of the protective film 8 is 7.1%
  • the binder concentration on the surface side of the protective film 8 (opposite to the electrode film 9) is 9.0%
  • the binder concentration on the electrode film 9 side of the protective film 8 is the protective film 8.
  • the binder concentration on the surface side (opposite side of the electrode film 9) was 21% lower than the binder concentration on the surface side (opposite side of the electrode film 9).
  • the binder distribution of the electrode film 9 is such that the binder concentration on the side of the current collector foil 8 is reduced compared with the vicinity of the surface (protective film 8 side), and the binder concentration on the side of the current collector foil 8 of the electrode film 9 is 2.
  • the binder concentration on the surface side of the electrode film 9 (protective film 8 side) is 6.5%, and the binder concentration on the current collector foil 6 side of the electrode film 9 is on the surface side of the electrode film 9 (protective film 8 side) ) And the binder concentration was 57% less.
  • Example 3 (Effect of Example 3) In the case where drying is performed after the binder 4 is solidified as in Example 3, compared to the case where the hot air drying is performed without solidifying the binder 4 in Comparative Example 3, the same as in Examples 1 and 2. The effect is obtained. Further, in Example 3, since the stress due to the difference in drying shrinkage due to the difference in binder concentration between the protective film 8 and the electrode film 9 can be relaxed, it is possible to prevent the peeling from the electrode film 9.

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Abstract

La présente invention a pour objet de réaliser : une batterie rechargeable lithium-ion capable d'améliorer la capacité de la batterie sans diminuer la fiabilité du fait d'un film d'électrode comprenant une couche protectrice présentant une forte adhérence au film d'électrode ; et un procédé de fabrication de la batterie rechargeable lithium-ion. La présente invention concerne une batterie rechargeable lithium-ion caractérisée en ce qu'elle comporte : un film d'électrode qui est formé sur la surface d'une feuille de collecteur et qui contient un liant qui lie le film d'électrode à la feuille de collecteur ; et un film protecteur qui est formé sur la surface du film d'électrode et qui contient des particules isolantes et un liant qui lie le film protecteur au film d'électrode. Cette batterie rechargeable lithium-ion est également caractérisée en ce que la concentration en liant dans le film protecteur du côté du film d'électrode est supérieure à la concentration en liant du côté opposé au film d'électrode.
PCT/JP2012/081731 2012-02-09 2012-12-07 Batterie rechargeable lithium-ion et procédé pour sa fabrication WO2013118380A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014141547A1 (fr) * 2013-03-13 2014-09-18 株式会社日立製作所 Dispositif et procédé de production d'une batterie secondaire au lithium-ion

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
JP6081333B2 (ja) * 2013-09-27 2017-02-15 株式会社日立ハイテクノロジーズ リチウムイオン二次電池の製造方法およびリチウムイオン二次電池の製造装置
WO2015045533A1 (fr) * 2013-09-27 2015-04-02 株式会社日立ハイテクノロジーズ Procédé de fabrication de batterie secondaire au lithium-ion, dispositif de fabrication de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion
JP6021775B2 (ja) * 2013-09-30 2016-11-09 株式会社日立ハイテクノロジーズ リチウムイオン二次電池の製造方法およびリチウムイオン二次電池の製造装置
CN106505264A (zh) * 2017-01-05 2017-03-15 梁伟 一种简单高效提高可充电池续航力的方法及高效能电池续航贴

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000058044A (ja) * 1998-08-06 2000-02-25 Japan Storage Battery Co Ltd 有孔性ポリマー電解質を備えた電極の製造方法およびその電極を用いた非水電解質二次電池
JP2000195522A (ja) * 1998-12-28 2000-07-14 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2006147185A (ja) * 2004-11-16 2006-06-08 Hitachi Maxell Ltd 捲回電極およびその製造方法、並びにそれを用いた電池
WO2010089898A1 (fr) * 2009-02-09 2010-08-12 トヨタ自動車株式会社 Batterie secondaire au lithium
JP2011108516A (ja) * 2009-11-18 2011-06-02 Teijin Ltd 非水系二次電池用電極シート及びそれを用いた非水系二次電池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005104270A1 (fr) * 2004-04-19 2005-11-03 Matsushita Electric Industrial Co., Ltd. Batterie secondaire ion-lithium et sa méthode de production
JP4519796B2 (ja) * 2005-04-15 2010-08-04 パナソニック株式会社 角型リチウム二次電池
JP5219621B2 (ja) * 2007-08-22 2013-06-26 三洋電機株式会社 非水電解質電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000058044A (ja) * 1998-08-06 2000-02-25 Japan Storage Battery Co Ltd 有孔性ポリマー電解質を備えた電極の製造方法およびその電極を用いた非水電解質二次電池
JP2000195522A (ja) * 1998-12-28 2000-07-14 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2006147185A (ja) * 2004-11-16 2006-06-08 Hitachi Maxell Ltd 捲回電極およびその製造方法、並びにそれを用いた電池
WO2010089898A1 (fr) * 2009-02-09 2010-08-12 トヨタ自動車株式会社 Batterie secondaire au lithium
JP2011108516A (ja) * 2009-11-18 2011-06-02 Teijin Ltd 非水系二次電池用電極シート及びそれを用いた非水系二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014141547A1 (fr) * 2013-03-13 2014-09-18 株式会社日立製作所 Dispositif et procédé de production d'une batterie secondaire au lithium-ion

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