WO2018051850A1 - Procédé et dispositif de fabrication d'électrode de batterie, électrode de batterie et batterie - Google Patents

Procédé et dispositif de fabrication d'électrode de batterie, électrode de batterie et batterie Download PDF

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Publication number
WO2018051850A1
WO2018051850A1 PCT/JP2017/031970 JP2017031970W WO2018051850A1 WO 2018051850 A1 WO2018051850 A1 WO 2018051850A1 JP 2017031970 W JP2017031970 W JP 2017031970W WO 2018051850 A1 WO2018051850 A1 WO 2018051850A1
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Prior art keywords
valve
coating
slurry
opening
battery electrode
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PCT/JP2017/031970
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English (en)
Japanese (ja)
Inventor
秀明 高松
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Ｎｅｃエナジーデバイス株式会社
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Priority to JP2018539644A priority Critical patent/JPWO2018051850A1/ja
Publication of WO2018051850A1 publication Critical patent/WO2018051850A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 battery electrode manufacturing method and a battery electrode manufacturing apparatus manufactured by applying a slurry such as an active material to a sheet base material when manufacturing an electrode of a laminate-type lithium ion secondary battery.
  • the present invention relates to a battery electrode manufactured by the above-described method and a battery including such a battery electrode.
  • Lithium ion secondary batteries can be reduced in size and weight and have a high energy density, so they are used for portable device power supplies, electric bicycles, electric vehicles, and other commercial power backup applications. Various proposals for improving performance can be seen.
  • a slurry containing active material particles is applied continuously or intermittently to the surface of a strip-shaped current collector, dried, and then compressed, so that the active material particles mutually and the active material particles
  • the battery performance is improved by reducing the electrical contact resistance with the current collector and further increasing the energy density.
  • the positive electrode active material layer contains lithium such as lithium manganese composite oxide particles.
  • a composite oxide is used.
  • Patent Document 1 Japanese Patent Laid-Open No. 2015-26471. Is disclosed.
  • FIG. 9 is a diagram schematically showing the coating apparatus 200.
  • FIG. 10 is a diagram for explaining the operation of the coating valve 240 and the return valve 250 in the coating apparatus 200.
  • the flow path of the slurry 205 of the coating apparatus 200 in intermittent coating has a die head 260, a coating valve 240 connected to the die head 260, a pump 230, and a tank 220 for storing the slurry 205. Moreover, it has the return valve 250 located between the said tank 220 and the coating valve 240.
  • the tank 220 is a storage unit for the slurry 205 and a supply unit for supplying the slurry 205 to the die head 260.
  • a tank 220 is preferably configured to receive the supply of the slurry 205 from a main tank (not shown) or the like.
  • the tank 220 is connected to the die head 260 by a pipe 210.
  • the pipe 210 is provided with a pump 230 which is a liquid feeding means. By operating the pump 230, the slurry 205 is sent from the tank 220 to the die head 260 side (in the direction of the arrow in the figure).
  • the piping 210 in the coating apparatus 200 is branched, the branched piping 210 on one side is connected to the die head 260, and the branched piping 210 on the other side is connected to the tank 220.
  • a coating valve 240 is provided in the middle of the branched pipe 210 on one side.
  • a return valve 250 is provided in the middle of the branched pipe 210 on the other side. When the return valve 250 is open, the slurry 205 can be returned to the tank 220 side. Further, when the coating valve 240 is in the open state, the slurry 205 is supplied to the die head 260.
  • the die head 260 for example, a so-called slot die is used.
  • the die head 260 is provided with an inlet 261 through which the slurry 205 is supplied from the pipe 210.
  • the die head 260 is provided with a liquid reservoir called a manifold 263.
  • the slurry 205 supplied from the inlet 261 is discharged from the coating outlet 265 through the manifold 263.
  • the coating outlet 265 has a slit shape with a constant width.
  • the sheet base material 203 is stretched around the back roll 270 in a state where a predetermined tension is applied.
  • the coating apparatus 200 has a conveying means (not shown) such as a rotating roller, and the sheet base material 203 is conveyed by the conveying means in the direction of the arrow in the figure. .
  • the back roll 270 rotates.
  • the coating valve 240 When the coating valve 240 is in the open state, the slurry 205 is coated from the coating outlet 265, and the coating film 207 is formed on the sheet base material 203. A portion where the coating film 207 is formed is referred to as a coating portion. On the other hand, when the coating valve 240 is in the closed state, the slurry 205 is not applied, and an uncoated portion is formed on the sheet base material 203. According to such a coating apparatus 200, the coated part and the uncoated part can be alternately formed on the sheet base material 203. Such a coating method using the coating apparatus 200 is referred to as intermittent coating.
  • the coating valve 240 can accurately change the opening and closing of the valve even during the application of the slurry 205, and realizes a complicated coating state by controlling the flow path of the slurry in combination with the operation of the return valve 250. It becomes possible.
  • the coating valve 240 and the return valve 250 have a common structure, but their operations are independent.
  • the coating valve 240 and the return valve 250 are provided with valve seats 243 and 253 having through holes 242 and 252 at the center inside the valve boxes 241 and 251, and can be contacted and separated from the valve seats 243 and 253.
  • Valve bodies 247 and 257 are arranged.
  • Shafts 246 and 256 are integrally formed on the valve bodies 247 and 257, and cylinders 245 and 255 are connected to the shafts 246 and 256, respectively.
  • the valve bodies 247 and 257 are moved through the shafts 246 and 256 in a direction approaching or leaving the valve seats 243 and 253 (vertical direction in the drawing).
  • the through holes 242 and 252 are opened, and the coating valve 240 and the return valve 250 are opened.
  • the opening degree (opening amount) of the coating valve 240 and the return valve 250 changes according to the distance between the valve bodies 247 and 257 from the valve seats 243 and 253, and passes through the coating valve 240 and the return valve 250.
  • the amount of slurry varies.
  • the coating valve 240 is opened at the timing when the formation of the coating film 207 is started, and at the same time, the return valve 250 is closed, and the slurry 205 is supplied from the coating valve 240 to the die head 260, The slurry 205 is applied to the sheet base material 203 from the application outlet 265 of 260.
  • the valve body 247 is raised and separated from the through hole 242, and in the return valve 250, the valve body 257 is lowered and the through hole 252. The operation that closes the screen is performed.
  • the battery electrode manufacturing method includes a tank for storing slurry and a sheet substrate conveyed by a roller.
  • a head having a discharge outlet for discharging; a coating valve for controlling the amount of slurry flowing into the head by opening and closing; a return valve for controlling the amount of slurry flowing into the tank by opening and closing; and the tank
  • a pipe for supplying slurry fed by pressure to both the coating valve and the return valve, and a battery electrode manufactured by a coating apparatus, wherein the valve body of the return valve is against the valve seat
  • the battery electrode manufacturing method according to the present invention is a valve in which the valve body of the coating valve operates perpendicularly to the valve seat.
  • the coating valve opening when the coating valve opening is increased from 0%, the return valve opening is decreased from 100%.
  • the battery electrode manufacturing method according to the present invention provided a period during which the opening degree of the coating valve was kept constant while the opening degree of the coating valve was increased from 0% to 100%.
  • the battery electrode manufacturing method according to the present invention may be configured such that when the coating valve opening degree is 0%, the opening degree of the coating valve is set so that the opening degree of the return valve is 100%. Decrease and increase the opening of the return valve.
  • the battery electrode manufacturing apparatus includes a tank for storing slurry, a head having a coating outlet for discharging slurry to a sheet substrate conveyed by a roller, and the head by opening and closing.
  • a coating valve that controls the amount of slurry flowing into the tank
  • a return valve that controls the amount of slurry flowing into the tank by opening and closing, and a slurry fed by pressure from the tank to the coating valve and the return valve.
  • An apparatus for manufacturing a battery electrode wherein the valve body of the coating valve is a valve that operates perpendicularly to a valve seat, and the valve body of the return valve is a valve seat Is a valve that operates in a horizontal or rotational direction.
  • the battery electrode manufacturing apparatus reduces the opening degree of the return valve from 100% when the opening degree of the coating valve is increased from 0%.
  • the battery electrode manufacturing apparatus provided a period during which the opening degree of the coating valve was kept constant while the opening degree of the coating valve was increased from 0% to 100%.
  • the battery electrode manufacturing apparatus is configured so that the opening degree of the coating valve is set so that the opening degree of the return valve becomes 100% when the opening degree of the coating valve becomes 0%. Decrease and increase the opening of the return valve.
  • the battery electrode according to the present invention was formed by using the slurry for intermittently provided on the sheet base material by using the battery electrode manufacturing method described above.
  • the active material layer includes a first film thickness portion having a substantially constant thickness and a second film thickness portion having a thickness smaller than the first film thickness portion.
  • the second film thickness portion was disposed at the boundary between the portion where the material layer was provided and the portion where the active material layer was not provided.
  • an insulating member was arranged at the boundary between the portion where the active material layer was provided and the portion where the active material layer was not provided.
  • the battery according to the present invention uses any one of the battery electrodes described above as either a positive electrode or a negative electrode, an electrode laminate in which the positive electrode and the negative electrode are stacked via a separator, an electrolyte solution, Is housed inside the exterior material, and a positive electrode lead tab conductively connected to the positive electrode and a negative electrode lead tab conductively connected to the negative electrode are drawn out of the exterior material.
  • the battery electrode manufacturing method / manufacturing apparatus is a valve in which the valve body of the return valve operates in a horizontal or rotational direction with respect to a valve seat, and the movement of the valve body when the return valve is opened and closed Therefore, according to the battery electrode manufacturing method / manufacturing apparatus of the present invention, the slurry in the die head accompanying the operation of the coating valve and the return valve is not affected. Pressure fluctuations can be suppressed, the amount of slurry applied from the die head can be easily controlled, the desired coating film can be obtained, and the performance of the lithium ion secondary battery can be improved. Can do.
  • the performance of the battery can be improved.
  • FIG. 6 is a diagram illustrating a stacking order of components in an electrode stack 60. It is a figure which shows the structure of the electrode laminated body 60 sealed in the laminate film exterior material 80.
  • FIG. FIG. 3 is a perspective view of a battery 100 that is packaged with a laminate film packaging material 80.
  • FIG. 4 is a diagram illustrating a manufacturing process of positive electrode 20 in battery 100.
  • FIG. 5 is a view showing an X-X ′ cross section in FIG. It is a figure explaining operation
  • FIG. 1 It is a figure explaining operation
  • FIG. 1 It is a figure explaining operation
  • the battery 100 composed of battery electrodes manufactured by the manufacturing method and manufacturing apparatus of the present invention will be described.
  • FIG. 1 illustrates the stacking order of components in an electrode stack 60 obtained by stacking a positive electrode 20, a negative electrode 30 (battery electrode) and a separator 40 manufactured by the manufacturing method and manufacturing apparatus of the present invention. It is a figure to do.
  • FIG. 2 is a diagram showing the configuration of the electrode laminate 60 sealed in the laminate film exterior material 80.
  • FIG. 3 is a perspective view of the battery 100 covered with a laminate film covering material 80.
  • a lithium ion secondary battery which is a kind of electrochemical element in which charging and discharging are performed by moving lithium ions between the negative electrode 30 and the positive electrode 20, will be described as an example.
  • the present invention can also be applied to other types of batteries.
  • a battery 100 according to an embodiment of the present invention includes an electrode laminate 60 in which a plurality of positive electrodes 20 and a plurality of negative electrodes 30 are laminated via a separator 40, and an electrolyte solution (not shown) having a rectangular laminate film exterior material. The structure is accommodated in 80.
  • FIG. 1 is a diagram for explaining the stacking order of the components in the electrode stack 60. As shown in FIG. 1, the positive electrode 20, the negative electrode 30, and the separator 40 are used in configuring the electrode laminate 60.
  • the positive electrode 20 has a rectangular positive electrode current collector body portion 22 and a strip-like positive electrode current collector terminal portion 24 extending from the positive electrode current collector body portion 22.
  • the entire current collector of the positive electrode 20 is made of a thin aluminum plate or the like, and the positive electrode current collector main body 22 is coated with a positive electrode active material layer 26 containing a lithium nickel composite oxide or the like on both sides.
  • the positive electrode current collector terminal portion 24 is an uncoated portion where the positive electrode active material layer 26 is not applied.
  • the negative electrode 30 has a rectangular negative electrode current collector body 32 and a strip-shaped negative electrode current collector terminal 34 extending from the negative electrode current collector main body 32.
  • the entire current collector of the negative electrode 30 is made of a thin plate-like nickel plate or copper plate, and the negative electrode current collector main body 32 is coated with a negative electrode active material layer 36 containing graphite or the like on both sides.
  • the negative electrode current collector terminal portion 34 is an uncoated portion where the negative electrode active material 36 is not applied.
  • materials that can form the positive electrode active material layer 26 are, for example, LiCoO 2 , LiNiO 2 , LiNi (1-x) CoO 2 , LiNi x (CoAl) (1-x) O 2 , Li 2 MnO 3.
  • -LiMO 2 (where M is a transition metal, and examples thereof include Ni, Co, Fe, Cr, etc.), layered oxide materials such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 And spinel materials such as LiMn 2 O 4 , LiMn 1.5 Ni 0.5 O 4 , LiMn (2-x) M x O 4 , olivine materials such as LiMPO 4 , Li 2 MPO 4 F, Li 2 MSiO 4 fluorinated olivine-based material, such as F, such as vanadium oxide-based materials such as V 2 O 5 and the like, can be used singly or a mixture of two or more of these .
  • materials that can form the negative electrode active material layer 36 include carbon materials such as graphite, amorphous carbon, diamond-like carbon, fullerene, carbon nanotube, and carbon nanohorn, lithium metal materials, silicon, tin, and the like. Alloy-based materials, oxide-based materials such as Nb 2 O 5 and TiO 2 , or composites thereof can be used.
  • the material that can constitute the positive electrode active material layer 26 and the negative electrode active material layer 36 may be a mixture to which a binder, a conductive additive, and the like are appropriately added.
  • a conductive support agent 1 type in carbon black, carbon fiber, or graphite, or a combination of 2 or more types can be used.
  • the binder polyvinylidene fluoride (PVDF), styrene butadiene rubber, polytetrafluoroethylene, carboxymethyl cellulose, modified acrylonitrile rubber particles, and the like can be used.
  • the material of the current collector of the positive electrode 20 aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used, and aluminum is particularly preferable. Further, as a material for the current collector of the negative electrode 30, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.
  • an insulating member 28 is disposed at the end on the positive electrode current collector terminal portion 24 side and a part of the positive electrode current collector terminal portion 24.
  • the insulating member 28 covers the boundary between the positive electrode current collector body portion 22 to which the positive electrode active material layer 26 is applied and the positive electrode current collector terminal portion 24 to which the positive electrode active material layer 26 is not applied. It is the structure that is called.
  • the positive electrode 20 is laminated with the negative electrode 30 through the separator 40 to form an electrode laminate 60.
  • the active material layers of the positive electrode 20 and the negative electrode 30 are in contact with each other, and the positive electrode 20 and the negative electrode 30 are short-circuited. Is provided.
  • the insulating member 28 as described above, polyimide, glass fiber, polyester, polypropylene, or a material containing these can be used. Heat is applied to the tape-shaped resin member made of the above-described material at the boundary between the portion where the positive electrode active material layer 26 is applied and the portion where the positive electrode active material layer 26 is not applied.
  • the insulating member 28 can be formed by applying to the boundary and then drying.
  • the separator 40 is a rectangular sheet-like member that can be impregnated with an electrolytic solution, such as a porous film, a microporous film (microporous film), a nonwoven fabric, or a woven fabric, which is made of a thermoplastic resin such as polyolefin.
  • an electrolytic solution such as a porous film, a microporous film (microporous film), a nonwoven fabric, or a woven fabric, which is made of a thermoplastic resin such as polyolefin.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, ethylene methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC)
  • organic solvents such as aliphatic carboxylic acid esters, ⁇ -lactones such as ⁇ -butyrolactone, chain ethers, cyclic ethers, and the like. Mixtures of the above can be used.
  • lithium salts can be dissolved in these organic solvents.
  • the separator 40 is mainly composed of a resin porous film, woven fabric, non-woven fabric, etc., and as its resin component, for example, a polyolefin resin such as polypropylene or polyethylene, a polyester resin, an acrylic resin, a styrene resin, or a nylon resin is used. it can.
  • a polyolefin-based microporous membrane is preferable because of its excellent ion permeability and performance of physically separating the positive electrode and the negative electrode.
  • the separator 40 may be formed with a layer containing inorganic particles. Examples of the inorganic particles may include insulating oxides, nitrides, sulfides, carbides, etc. It is preferable to contain TiO 2 or Al 2 O 3 .
  • all of the positive electrode current collector terminal portions 24 formed on the positive electrode 20 are all of the negative electrode current collector terminal portions 34 formed on the negative electrode 30. Are fixed to each other by ultrasonic welding or the like.
  • the negative electrode current collector terminal portion 34 of the positive electrode 20 is conductively connected to the positive electrode lead tab 120, and the negative electrode terminal portion of the negative electrode 30 is conductively connected to the negative electrode lead tab 130.
  • the positive electrode extraction tab 120 is made of aluminum or an aluminum alloy
  • the negative electrode extraction tab 130 is made of nickel, copper, or copper alloy.
  • nickel plating may be applied to the surface.
  • the two portions on the opposite two sides of the electrode laminate 60 are fixed by the adhesive tape 65 or the like, It is preferable to ensure that the laminated state is maintained.
  • the electrode laminate 60 and the electrolyte solution (not shown) formed as shown in FIG. 2 are sealed in the laminate film exterior member 80 in a state where the positive electrode extraction tab 120 and the negative electrode extraction tab 130 are extracted, A battery 100 as shown in FIG.
  • the laminate film exterior member 80 is composed of two laminate films surrounding and sandwiching the electrode laminate 60 from both sides in the lamination direction, and the first sides of the opposing surfaces that overlap each other around the electrode laminate 60. 111, the second side 112, the third side 113, and the fourth side 114 are heat-welded to form a heat-welded portion (sealing region) 81, so that the electrode stack 60 is sealed together with an electrolyte (not shown). Has been.
  • the positive electrode pull-out tab 120 is pulled out from the first side 111
  • the negative electrode pull-out tab 130 is pulled out from the second side 112.
  • the electrode laminate 60 and the electrolyte solution are sealed with two laminate films.
  • the electrode laminate 60 and the electrolysis are folded so that one laminate film is folded. It is good also as a structure which seals a liquid (not shown).
  • the laminate film exterior material 80 As a laminate film constituting the laminate film exterior material 80, as long as it has flexibility and can seal the electrode laminate 60 and the electrolyte (not shown) so that the electrolyte does not leak,
  • the film generally used for this kind of film-clad battery can be used.
  • a metal thin film layer and a heat-weldable resin layer are laminated, and further, on the surface opposite to the heat-weldable resin layer of the metal thin film layer. Furthermore, the structure which laminated
  • the electrode laminate 60 and the electrolytic solution the electrode laminate 60 is surrounded by facing the heat-welding resin layer.
  • metal thin film layer for example, a foil of Al, Ti, Ti alloy, Fe, stainless steel, Mg alloy or the like having a thickness of 10 ⁇ m to 100 ⁇ m can be used.
  • the resin used for the heat-welding resin layer is not particularly limited as long as it can be heat-welded.
  • polypropylene, polyethylene, acid-modified products thereof, polyphenylene sulfide, polyester such as polyethylene terephthalate, polyamide, An ethylene-vinyl acetate copolymer can be used.
  • the thickness of the heat-welding resin layer is preferably 10 ⁇ m to 200 ⁇ m, more preferably 30 ⁇ m to 100 ⁇ m.
  • the inner surface of the laminate film exterior material 80 becomes the above-described heat-weldable resin layer of the laminate film exterior material 80.
  • the order of lamination is defined so that the outermost layer always becomes the negative electrode 30. Therefore, in the battery 100, the negative electrode 30 of the electrode laminate 60 and the inner surface (heat-weldable resin layer) of the laminate film exterior material 80 are in contact with each other.
  • the manufacturing process of the positive electrode 20 in the battery 100 configured as described above will be described with reference to FIG.
  • the manufacturing process of the positive electrode 20 will be described as an example.
  • the manufacturing process of the negative electrode 30 is the manufacturing of the positive electrode 20 except that the material is changed and the insulating member 28 is not formed. It is almost the same as the process.
  • the positive electrode 20 is manufactured in the order of (A) ⁇ (B) ⁇ (C).
  • the sheet base material 203 is a base material that is a precursor of the current collector of the positive electrode 20 (the positive electrode current collector main body portion 22 and the positive electrode current collector terminal portion 24), and the coating film 207 is formed from the coating device 200. It is a film having a predetermined thickness formed by the slurry 205 to be applied, and is a precursor of the positive electrode active material layer 26 in the positive electrode 20.
  • FIG. 4 only the manufacturing process of the front surface of the sheet base material 203 is shown, but a similar coating film 207 is formed on the back surface of the sheet base material 203 by the coating apparatus 200.
  • the slurry 205 is intermittently applied from the coating apparatus 200, and the coating portion where the coating film 207 is formed and the coating film 207 are formed on the sheet base material 203. It shows how the uncoated parts that are not formed are alternately formed.
  • the coating film 207 is formed by the slurry 205 on the sheet base material 203 having a predetermined film thickness.
  • the sheet base material 203 is set to advance in the direction of the arrow in the figure. Furthermore, the coating apparatus 200 has a die head 260 provided with a coating outlet 265 for coating the slurry 205.
  • the longitudinal direction of the coating outlet 265 is set to be perpendicular to the traveling direction of the sheet base material 203.
  • the process proceeds to a process shown in FIG. 4B through a predetermined drying process and the like.
  • the insulating member 28 is applied to the boundary portion between the coated portion of the coated film 207 and the uncoated portion on the sheet base material 203 by a device (not shown).
  • the insulating member 28 can be formed at the boundary portion by applying heat and welding to a tape-shaped resin member such as polypropylene.
  • FIG. 4C shows a process of obtaining the positive electrode 20 by cutting a range indicated by a dotted line from the sheet base material 203 using a cutting device (not shown).
  • the part referred to as the coating film 207 on the sheet base material 203 is hereinafter referred to as the positive electrode active material layer 26.
  • the sheet base material 203 is referred to as a current collector of the positive electrode 20 (a positive electrode current collector main body 22 and a positive electrode current collector terminal portion 24).
  • FIG. 5 is a view showing an X-X ′ cross section of FIG.
  • the positive electrode active material layer 26 of the positive electrode 20 is a central portion excluding the start and finish of the application of the positive electrode active material layer 26, and is substantially equal to the overall average film thickness and is substantially constant.
  • a first film thickness portion 26a that occupies most of the area of the positive electrode active material layer 26, and a second film thickness portion that is located at one end of the positive electrode active material 26 and is thinner than the first film thickness portion 26a. 26b is illustrated.
  • the second film thickness portion 26 b is applied when the slurry 205 to be the positive electrode active material layer 26 is applied onto the sheet base material 203 that is a precursor of the positive electrode current collector. This is the first part.
  • the sum of the thickness of the second film thickness portion 26b and the thickness of the insulating member 28 partially disposed on the second film thickness portion 26b is equal to or less than the flat thickness of the first film thickness portion 26a.
  • the thicknesses of the first film thickness portion 26a and the second film thickness portion 26b are set. Since the thickness is set in this way, even when a plurality of positive electrodes 20 are used when forming the electrode stack 60, the thickness of the electrode stack 60 due to the insulating member 28 may be uneven. Absent.
  • the second film thickness portion 26b having a thin layer thickness is formed from the uncoated portion. Further, it is necessary to form the coating film 207 in succession, assuming that the first film thickness portion 26a having a large layer thickness is formed. For this reason, it turns out that especially the film thickness control of the coating film 207 by the coating apparatus 200 in the starting end part at the time of forming the coating film 207 is very important.
  • the coating valve 240 is opened, and at the same time, the return valve 250 is closed, and the slurry 205 is supplied from the coating valve 240 to the die head 260.
  • the slurry 205 is applied from the coating outlet 265 of the die head 260 to the sheet base material 203.
  • the valve body 247 is raised and separated from the through hole 242, and in the return valve 250, the valve body 257 is lowered and the through hole 252. The operation that closes the screen is performed.
  • a pressure as indicated by an arrow is applied to the slurry 205, whereby the pressure at which the slurry 205 is applied to the sheet base material 203 from the coating outlet 265 of the die head 260 is higher than expected, and the coating is applied from the die head 260.
  • the amount of the slurry 205 to be dispensed would become unstable.
  • the coating amount of the slurry 205 applied on the sheet base material 203 cannot be controlled, the desired coating film 207 cannot be obtained and the performance of the lithium ion secondary battery may be adversely affected. There was also sex.
  • the control of the coating amount of the slurry 205 at the timing of starting the application of the slurry 205 on the sheet base material 203 and the control of the film thickness of the coating film 207 accompanying the control are uneasy.
  • the second film thickness portion 26b having a small layer thickness is formed, it is necessary to form the coating film 207 by more complicated control.
  • the valve body of the return valve is a valve that operates in a horizontal or rotational direction with respect to the valve seat. It features that what has a valve structure is adopted.
  • FIG. 6 is a view for explaining the operation of the coating valve 240 and the return valve 300 in the coating apparatus 200 used in the battery electrode manufacturing method according to the present invention.
  • the coating valve 240 of the coating apparatus 200 used in the present invention is a valve in which the valve body of the coating valve operates perpendicularly to the valve seat. That is, as the coating valve 240, the valve body 247 closes or opens the through hole 242 provided in the valve seat 243 to control the flow rate, and a ball valve or the like is used.
  • the return valve 300 is a valve in which the valve body of the return valve operates in a horizontal or rotational direction with respect to the valve seat, and includes a gate valve and a ball valve.
  • FIG. 6 schematically shows a gate valve.
  • the return valve 300 is a gate valve that is provided in the valve box 301 and controls the flow rate by partitioning the flow of the slurry 205 in the valve box 301 by the gate valve body 307. Is used. It is clear that such a gate valve not only does not easily generate a high pressure such as a water hammer effect in the control of the flow rate, but can also extremely reduce the fluctuation of the flow rate to the coating valve connected through the piping. It was.
  • the flow rate of the slurry 205 is controlled by inserting and removing the gate valve body 307 from a substantially vertical direction with respect to the flow of the slurry 205.
  • the pressure as shown by the arrow in FIG. 10 is not generated in the slurry 205, and the amount of the slurry 205 applied from the die head 260 onto the sheet base material 203 can be easily controlled.
  • FIG. 7 is a diagram illustrating an example of operation timings of the coating valve 240 and the return valve 300 of the coating apparatus 200.
  • the operation timing shown in FIG. 7 is for forming the coating film 207 (positive electrode active material layer 26) shown in FIGS. That is, the second film thickness portion 26b having a thin layer thickness is formed on the sheet base material 203 from the uncoated portion, and the first film thickness portion 26a having a thick layer thickness is formed continuously.
  • the operation timing when forming the coating film 207 is shown.
  • the opening degree 0 [%] means the opening degree of the valve at which the flow path is completely blocked.
  • the opening degree 100 [%] means the opening degree of the valve when the user assumes that the flow rate is 100 [%], and the opening degree 100 [%] as the performance of the valve itself. Not to say.
  • FIG. 7 will be described in time series.
  • the horizontal axis in FIG. 7 represents the time axis. 7 shows the opening degree of the coating valve 240, and the lower part shows the opening degree of the return valve 300.
  • the opening degree of the coating valve 240 is increased from 0% and the opening degree of the return valve 300 is set to 100. It is trying to decrease from%.
  • the opening degree increase in Nurikoben 240 temporarily stopped, the opening degree constant. Thereby, the coating film 207 corresponding to the second film thickness portion 26b is formed.
  • the opening degree of the return valve 300 which has reduced the degree of opening from 100% opening at t 0 is 0% at t 2.
  • Opening which has been a degree of opening fixed in Nurikoben 240 increases again at t 3, 100% opening at t 4, to form a coating film 207 corresponding to the first film thickness portion 26a To.
  • t 5 is slightly earlier than the timing of reducing the degree of opening of Nurikoben 240 from 100% to terminate the period for forming the coating film 207 corresponding to the first film thickness portion 26a, the return valve 300 Increase the opening from 0%.
  • the opening degree of Nurikoben 240 starts the reduction from 100% t 6. Timing the opening of Nurikoben 240 is 0% and, timing the opening of the return valve 300 is 100%, is controlled so as to coincide with t 7.
  • the coating film 207 that assumes the first film thickness portion 26a can be formed.
  • the coating valve 240 is a ball valve
  • the return valve 300 is a gate valve
  • the gate valve body is opened and closed when the gate valve is opened and closed. Since the movement does not affect the coating valve 240, according to the battery electrode manufacturing method and manufacturing apparatus according to the present invention, the operation of the coating valve 240 and the return valve 300 is performed. As a result, fluctuations in the pressure of the slurry 205 in the die head 260 can be suppressed, the amount of the slurry 205 applied from the die head 260 can be easily controlled, and a desired coating film can be obtained. This can contribute to improving the performance of the secondary battery.
  • the performance of the battery 100 can be improved.
  • FIG. 8 is a view for explaining the operation of the coating valve 240 and the return valve 300 in the coating apparatus 200 used in the method for manufacturing a battery electrode according to another embodiment of the present invention.
  • the coating apparatus 200 used in another embodiment is different from the coating apparatus 200 shown in FIG. 6 only in that a plurality of gate valve bodies 307 are provided in the return valve 300, and the other configurations are the same. It is.
  • the two gate valve bodies 307 are configured to partition the flow of the slurry 205 in the valve box 301.
  • the valve is formed by three or more gate valve bodies 307. The flow of the slurry 205 in the box 301 may be partitioned.
  • the plurality of gate valve bodies 307 are inserted / removed from a substantially vertical direction with respect to the flow of the slurry 205, so that the case of the previous embodiment. Therefore, more precise flow rate control is possible.
  • the present invention relates to a method and an apparatus for manufacturing an electrode for a battery such as a lithium ion secondary battery that can be reduced in size and weight and has a large energy density.
  • a manufacturing method and manufacturing apparatus for battery electrodes when applying a slurry containing active material particles onto a sheet substrate such as a current collector, it is difficult to control the amount of slurry applied, and the desired coating There was a problem that a film could not be obtained and the performance of the lithium ion secondary battery was adversely affected.
  • the battery electrode manufacturing method and manufacturing apparatus is a valve in which the valve body of the return valve operates in a horizontal or rotational direction with respect to the valve seat, and the valve body at the time of opening and closing the return valve Therefore, according to the battery electrode manufacturing method / manufacturing apparatus of the present invention, the inside of the die head accompanying the operation of the coating valve and the return valve is not affected by the movement of the coating valve.
  • the fluctuation of the slurry pressure can be suppressed, the amount of slurry applied from the die head can be easily controlled, the desired coating film can be obtained, and the performance of the lithium ion secondary battery can be improved. Can contribute.
  • SYMBOLS 20 Positive electrode 22 ... Positive electrode collector main-body part 24 ... Positive electrode collector terminal part 26 ... Positive electrode active material layer 26a ... 1st film thickness part 26b ... 2nd film thickness Portion 28 ... Insulating member 30 ... Negative electrode 32 . Negative electrode current collector body 34 ... Negative electrode current collector terminal 36 ... Negative electrode active material layer 40 ... Separator 60 ... Electrode Laminate 65 ... Adhesive tape 80 ... Laminate film exterior material 81 ... Thermal weld (sealing region) DESCRIPTION OF SYMBOLS 100 ... Battery 110 ... Battery main-body part 111 ... 1st edge 112 ... 2nd edge 113 ... 3rd edge 114 ...

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)

Abstract

La présente invention vise à fournir un procédé de fabrication d'une électrode de batterie, permettant de réguler facilement la quantité d'évacuation d'une bouillie évacuée à partir d'une tête de colorant, d'obtenir un film de revêtement souhaité, et pouvant contribuer à l'amélioration du rendement d'une batterie rechargeable lithium-ion, le procédé de fabrication d'une électrode de batterie mettant en œuvre : un dispositif de revêtement (200) comportant un réservoir (220) servant à stocker une bouillie ; une tête (260) comportant une sortie d'évacuation servant à évacuer la bouillie sur un substrat de feuille (203) transporté par un rouleau (270) ; une soupape de revêtement (240) régulant, par ouverture et fermeture, la quantité de bouillie s'écoulant vers la tête (260) ; une soupape de retour (250) régulant, par ouverture et fermeture, la quantité de bouillie s'écoulant vers le réservoir (220) ; et un tuyau (210) fournissant la bouillie alimentée en pression depuis le réservoir, aussi bien à la soupape de revêtement (240) qu'à la soupape de retour (250), le corps de soupape de la soupape de retour (250) étant une soupape fonctionnant dans un sens horizontal ou de rotation par rapport au siège de soupape et ledit procédé comportant une étape consistant à ajuster la quantité de bouillie évacuée par régulation du degré d'ouverture de la soupape de revêtement (240) et par régulation du degré d'ouverture de la soupape de retour (250).
PCT/JP2017/031970 2016-09-14 2017-09-05 Procédé et dispositif de fabrication d'électrode de batterie, électrode de batterie et batterie WO2018051850A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012047245A (ja) * 2010-08-26 2012-03-08 Hirano Tecseed Co Ltd バルブとそれを用いた塗工装置
JP2014079669A (ja) * 2012-10-15 2014-05-08 Toyota Motor Corp 塗工装置および塗工方法
JP2014188426A (ja) * 2013-03-27 2014-10-06 Nec Corp 間欠塗布装置および塗布方法
JP2014188449A (ja) * 2013-03-27 2014-10-06 Nec Corp 間欠塗布装置及び間欠塗布方法
JP2015010706A (ja) * 2013-07-02 2015-01-19 株式会社テクノスマート バルブ装置及び塗工装置
JP2015062853A (ja) * 2013-09-24 2015-04-09 日本電気株式会社 間欠塗工装置及び間欠塗工方法
JP2015112520A (ja) * 2013-12-10 2015-06-22 株式会社ヒラノテクシード 間欠塗工装置
WO2016063612A1 (fr) * 2014-10-21 2016-04-28 Ｎｅｃエナジーデバイス株式会社 Procédé et appareil de fabrication d'électrode pour batterie rechargeable, électrode pour batterie rechargeable, et batterie rechargeable
JP2017047393A (ja) * 2015-09-04 2017-03-09 Ｎｅｃエナジーデバイス株式会社 塗工装置及びその塗工装置によって製造された電極

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012047245A (ja) * 2010-08-26 2012-03-08 Hirano Tecseed Co Ltd バルブとそれを用いた塗工装置
JP2014079669A (ja) * 2012-10-15 2014-05-08 Toyota Motor Corp 塗工装置および塗工方法
JP2014188426A (ja) * 2013-03-27 2014-10-06 Nec Corp 間欠塗布装置および塗布方法
JP2014188449A (ja) * 2013-03-27 2014-10-06 Nec Corp 間欠塗布装置及び間欠塗布方法
JP2015010706A (ja) * 2013-07-02 2015-01-19 株式会社テクノスマート バルブ装置及び塗工装置
JP2015062853A (ja) * 2013-09-24 2015-04-09 日本電気株式会社 間欠塗工装置及び間欠塗工方法
JP2015112520A (ja) * 2013-12-10 2015-06-22 株式会社ヒラノテクシード 間欠塗工装置
WO2016063612A1 (fr) * 2014-10-21 2016-04-28 Ｎｅｃエナジーデバイス株式会社 Procédé et appareil de fabrication d'électrode pour batterie rechargeable, électrode pour batterie rechargeable, et batterie rechargeable
JP2017047393A (ja) * 2015-09-04 2017-03-09 Ｎｅｃエナジーデバイス株式会社 塗工装置及びその塗工装置によって製造された電極

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