WO2015045533A1 - リチウムイオン二次電池の製造方法、リチウムイオン二次電池の製造装置およびリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池の製造方法、リチウムイオン二次電池の製造装置およびリチウムイオン二次電池 Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for manufacturing a lithium ion secondary battery, a lithium ion secondary battery manufacturing apparatus, and a lithium ion secondary battery, and particularly includes a positive electrode, a negative electrode, and a separator that electrically separates the positive electrode and the negative electrode.
- the present invention relates to a method and apparatus for manufacturing a lithium ion secondary battery, and a technology effective when applied to the lithium ion secondary battery.
- lithium ion secondary batteries have been attracting attention because they have the advantages of high energy density, long cycle life, low self-discharge characteristics, and high operating voltage. 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 using a motor as a power source or a hybrid vehicle using both an engine (internal combustion engine) and a motor as a power source is underway in order to cope with environmental problems.
- Lithium ion secondary batteries have attracted attention as power sources for such electric vehicles and hybrid vehicles.
- lithium ion secondary batteries are becoming increasingly important in applications such as solar power generation or power storage for efficient use of nighttime power.
- the lithium ion secondary battery has a high operating voltage and high energy density, sufficient countermeasures against abnormal heat generation due to an internal short circuit or an external short circuit are required.
- the lithium ion secondary battery is a kind of non-aqueous electrolyte secondary battery, and is a secondary battery in which lithium ions in the electrolyte bear electric conduction.
- a lithium metal oxide is used for the positive electrode material (active material)
- a carbon material such as graphite is used for the negative electrode material (active material)
- an organic solvent such as ethylene carbonate and lithium hexafluorophosphate (LiPF 6 ) are used for the electrolyte.
- lithium salts such as Lithium-ion secondary batteries, for example, electrically separate a positive electrode plate and a negative electrode plate from a strip-shaped positive electrode plate coated with a positive electrode material on a metal foil and a strip-shaped negative electrode plate coated with a negative electrode material on a metal foil. It has the laminated body which piled up through the separator for doing. This laminated body is wound to constitute an electrode winding body having a spiral cross section in the outer can of the lithium ion secondary battery.
- Patent Document 1 Japanese Patent Laid-Open No. 2003-054991.
- a positive electrode sheet containing solution and a solution containing an electrolytic substance and an insulating substance are applied to both surfaces of a positive electrode sheet using a die coater having a solution discharge slit, followed by a heating step. The formation of a positive electrode sheet is described.
- a negative electrode material containing solution and a solution containing an electrolytic substance and an insulating substance are applied to both surfaces of the negative electrode sheet using a die coater, followed by a heating step, followed by a negative electrode sheet material.
- the electrode winding body is formed by laminating both electrode sheets of the positive electrode and the negative electrode.
- a secondary battery manufacturing method and a secondary battery manufacturing apparatus are described in which both electrode sheet-like materials are laminated to form an electrode winding body.
- Patent Document 1 a positive electrode film and a negative electrode film are individually formed, a separator film is laminated on the negative electrode film, and the positive electrode film is laminated on the negative electrode film with a separator to form an electrode winding. It is described to form a body.
- the above configuration can improve the point that it is difficult to uniformly inject a solution-like electric field substance into a current collector in which a plurality of electrode winding bodies are laminated, and the number of manufacturing steps is large. Are listed.
- Lithium ion secondary batteries are, for example, a positive electrode plate coated with a positive electrode active material on the surface of a current collector foil, a negative electrode plate coated with a negative electrode active material on the surface of a current collector foil, and the contact between the positive electrode plate and the negative electrode plate
- the electrode winding body which wound the plate-shaped separator which prevents this is provided.
- each of the positive electrode plate, the negative electrode plate, and the separator is prepared as a separate part, that is, a separate body. In this case, for example, due to the cutting process of the positive electrode plate, between the positive electrode plate and the separator. There arises a problem that a metal foreign substance enters the gap between the positive electrode and the negative electrode, causing a short circuit.
- a positive electrode plate formed by sequentially applying a positive electrode active material and a separator to the surface of the current collector foil, and a negative electrode plate formed by sequentially applying a negative electrode active material and a separator to the surface of another current collector foil To form a lithium ion secondary battery. If it is such a lithium ion secondary battery, it can prevent that the metal foreign material produced by cut
- the electrode material slurry containing the positive electrode active material or the negative electrode active material is applied to the surface of the current collector foil, and the insulating material slurry that becomes the separator continuously is applied on the slurry, the electrode layer and the insulating layer A mixed layer of an electrode material and an insulating material is formed at the interface.
- the insulating material layer functioning as a separator becomes thin, a short circuit between the positive electrode and the negative electrode is likely to occur, thereby causing a problem that the reliability of the lithium ion secondary battery is lowered.
- As a configuration for preventing the short circuit it is conceivable to increase the thickness of the separator, but in this case, it is difficult to reduce the size of the lithium ion secondary battery.
- the positive electrode or the negative electrode material is applied and applied to the surface of the current collector foil as the carrier material. It is conceivable to form an electrode plate by forming a film and applying an insulating material to be a separator on the coating film. Thereby, it is possible to prevent the occurrence of a short circuit problem due to the foreign matter, and it is possible to improve the production efficiency and downsize the manufacturing apparatus.
- the electrode material and the insulating material layer are Since the mixed layer of the insulating material is formed, the layer of the insulating material that functions as a separator is thinned.
- the short circuit of a positive electrode and a negative electrode becomes easy to generate
- As a configuration for preventing the short circuit it is conceivable to increase the thickness of the separator, but in this case, it is difficult to reduce the size of the lithium ion secondary battery.
- a method of manufacturing a lithium ion secondary battery includes a step of applying an electrode material slurry on the surface of a current collector foil using a first coating part, and the electrode material slurry A step of solidifying a surface layer of the electrode material slurry by supplying a first solidified liquid containing a component for precipitating a binder component to the electrode material slurry; and on the electrode material slurry on which the surface layer is solidified. And a step of applying an insulating material slurry using the second coating part, and a step of drying the electrode material slurry and the insulating material slurry.
- a method for manufacturing a lithium ion secondary battery includes a step of applying an electrode material containing a binder on the surface of a current collector foil, and depositing the binder on the electrode material A step of applying an insulating material containing a first component, a step of solidifying the electrode material by supplying a spray liquid containing a second component for precipitating the binder to the electrode material, and the electrode material and the insulating material And a step of drying.
- the lithium ion secondary battery manufacturing apparatus deposits a first coating part for applying an electrode material slurry to the surface of the current collector foil, and a binder component contained in the electrode material slurry.
- a first solidification liquid containing a component to be fed is supplied to the electrode material slurry, whereby a first solidification chamber for solidifying the surface layer of the electrode material slurry, and the electrode material slurry on which the surface layer is solidified,
- a second coating section for applying an insulating material slurry; a drying chamber for drying the electrode material slurry and the insulating material slurry; and the current collector foil, the first coating section, the first solidification chamber, It has a conveyance part which conveys in order of the said 2nd coating part and the said drying chamber.
- the manufacturing apparatus of a lithium ion secondary battery includes a first coating unit that applies an electrode material slurry containing a binder to the surface of the current collector foil, and an electrode material slurry.
- a first coating unit that applies an electrode material slurry containing a binder to the surface of the current collector foil, and an electrode material slurry.
- the reliability of the lithium ion secondary battery can be improved.
- the performance of the lithium ion secondary battery can be improved.
- the graph which shows the relationship between the thickness of a mixed layer and the conveyance speed of current collection foil of each of the lithium ion secondary battery which is Embodiment 3 of this invention, and the lithium ion secondary battery which is a 2nd comparative example It is.
- It is a schematic diagram which shows the structure of a lithium ion secondary battery.
- It is a flowchart which shows the manufacturing process of the lithium ion secondary battery which is a 3rd comparative example.
- It is a schematic diagram which shows the manufacturing apparatus of the lithium ion secondary battery in a 4th comparative example.
- the thickness said in this application refers to the length of each structure in the direction perpendicular
- FIG. 1 is a diagram showing a configuration of a single-side coating type electrode plate manufacturing apparatus according to the present embodiment. That is, FIG. 1 is a schematic diagram showing a lithium ion secondary battery manufacturing apparatus according to the present embodiment.
- the manufacturing apparatus of the lithium ion secondary battery in the present embodiment includes a current collecting metal foil roll RL1 for feeding out the current collecting foil EP and a winding roll RL4 for winding up the current collecting foil EP.
- the current collecting foil EP which is a thin plate-like metal foil, is conveyed between the current collecting metal foil roll RL1 and the take-up roll RL4 while being supported by a plurality of rollers such as rollers RL2 and RL3.
- the plurality of rollers are referred to as a roller conveyance system, that is, a conveyance unit.
- a die coater DC1, a spray nozzle NZ1, a die coater DC2 and a drying chamber DRY in the solidification chamber SD1 are arranged in this order from the current collecting metal foil roll RL1 side to the take-up roll RL4 side in the transport path of the current collecting foil EP. ing.
- the conveyed current collecting foil EP passes between the die coater DC1 and the roller RL2, inside the solidification chamber SD1, between the die coater DC2 and the roller RL3, and inside the drying chamber DRY.
- each of the positive electrode and the negative electrode constituting the lithium ion secondary battery differs in the material of the current collector foil EP and the material of the film applied to the current collector foil EP, but is basically manufactured by the same process. .
- the electrode material ES which is a coating material to be described later, includes a case where it is a positive electrode material and a case where it is a negative electrode material.
- the electrode material ES is composed of different materials.
- the positive electrode manufacturing process the current collector foil EP and the coating material made of the positive electrode material are used, and the material used only in the negative electrode manufacturing process is not used.
- the negative electrode manufacturing process a material used only for the positive electrode manufacturing process is not used.
- the electrode material ES for forming the positive electrode or the negative electrode of the lithium ion secondary battery is adjusted.
- the collected slurry-like electrode material ES is collected from the current-collecting metal foil roll RL1 using the die coater DC1, which is the first coating portion disposed so as to face the roller RL2. Apply thin and evenly on the surface of the foil EP. Below, this process is called a 1st coating process.
- coated on current collection foil EP by the 1st coating process is called a 1st coating film.
- a slit die coater can be used for the first coating part, but another apparatus may be used as an apparatus for supplying the electrode material ES.
- the solidified liquid as used in the present application is a liquid containing a solidifying material contained in a slurry such as a first coating film, that is, a component that precipitates a binder component as a binder. That is, the solidified liquid and the solidified material are different materials, and the solidified material is included in the first coating film, for example, and the solidified liquid supplied from the spray nozzle NZ1 does not include the solidified material.
- the insulating material IF supplied from the die coater DC2, which is the second coating portion provided so as to face the roller RL3, is thinly and uniformly applied on the surface of the first coating film whose surface layer is solidified. Work.
- This process is called a second coating process.
- a film made of the insulating material IF applied on the first coating film in the second coating process is referred to as a second coating film.
- a slit die coater or the like can be used. In FIG. 1, the first coating film and the second coating film are not shown.
- the current collector foil EP coated with the second coating film in the second coating step is conveyed into a drying chamber DRY that is a hot air drying furnace.
- a drying chamber DRY that is a hot air drying furnace.
- the solvent component and the solidified liquid in the first coating film and the second coating film are heated and evaporated to dry and solidify the first coating film and the second coating film, An insulating layer is formed in a lump.
- this process is called a drying process. That is, the first coating film becomes an electrode layer by a drying process, and the second coating film becomes an insulating layer, that is, a separator, by a drying process.
- the electrode plate which consists of the current collection foil EP and the electrode layer and insulating layer which were laminated
- the electrode, the positive electrode, and the negative electrode may be referred to as an electrode plate, a positive electrode plate, and a negative electrode plate, respectively.
- the electrode material ES in the present embodiment includes a positive electrode active material powder or a negative electrode active material powder that can release and occlude lithium ions by charging and discharging.
- the electrode material ES includes a binder component that binds between the powder components after drying, or binds between the powder component and the current collector foil. Further, in some cases, the electrode material ES includes a powder of a conductive additive.
- the solidification liquid used in the pre-solidification step needs to have a property that the binder component contained in the first coating film is insoluble and a property of being mutually dissolved with the solvent in the first coating film.
- the solidified liquid comes into contact with the first coating film, the solidified liquid enters the first coating film while being dissolved in the solvent in the first coating film.
- the solubility of the binder decreases, so that the binder is precipitated and only the surface layer of the first coating film is fixed.
- the present embodiment has a feature that a pre-solidification step is introduced between the first coating step and the second coating step. Thereby, a 2nd coating process can be performed in the state in which the surface of a 1st coating film does not flow. For this reason, as will be described later, it is possible to suppress the generation of a mixed layer formed by applying a coating pressure to the first coating film and the second coating film by the die coater which is the second coating section described above. It becomes.
- the positive electrode active material used in this embodiment includes a lithium-containing composite oxide having a spinel structure containing lithium cobaltate or Mn (manganese), or Ni (nickel), Co (cobalt), or Mn (manganese).
- a composite oxide or the like can be used.
- olivine type compounds such as olivine type iron phosphate, can also be used for a positive electrode active material.
- the positive electrode active material is not limited to these materials, and other materials may be used. 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.
- the other positive electrode active material include olivine type compounds represented by Li 1 + xMO 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1).
- the metal M in this formula include Co (cobalt), Ni (nickel), Mn (manganese), Al (aluminum), Mg (magnesium), Zr (zirconium) or Ti (titanium).
- a lithium-containing transition metal oxide having a layered structure can be used for the positive electrode active material.
- the lithium-containing transition metal oxide having a layered structure include LiCoO 2 or LiNi 1 -xCo x -yAl y O 2 (0.1 ⁇ x ⁇ 0.3, 0.01 ⁇ y ⁇ 0.2).
- an oxide containing at least Co, Ni, and Mn can be used.
- the oxide containing Co, Ni, and Mn include LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , or LiNi 3/5 Examples thereof include Mn 1/5 Co 1/5 O 2 .
- the negative electrode active material used in the present embodiment for example, a graphite material such as natural graphite (flaky graphite), artificial graphite, or expanded graphite can be used.
- a graphite material such as natural graphite (flaky graphite), artificial graphite, or expanded graphite
- an easily graphitizable carbonaceous material such as coke obtained by firing pitch can be used.
- the negative electrode active material includes amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin (PFA: Poly-Furfuryl-Alcohol) or polyparaphenylene (PPP: Poly-Para-Phenylen) and phenol resin
- PFA furfuryl alcohol resin
- PPP Polyparaphenylene
- the non-graphitizable carbonaceous material can be used.
- Li (lithium) or a lithium-containing compound can also be used as the negative electrode active material.
- the lithium-containing compound include a lithium alloy such as Li—Al, or an alloy containing an element that can be alloyed with Li (lithium) such as Si (silicon) or Sn (tin).
- oxide-based materials such as Sn oxide and Si oxide can also be used for the negative electrode active material. This oxide-based material may not contain Li (lithium).
- the conductive aid is used as an electron conductive aid to be contained in the positive electrode film, and is preferably a carbon material such as carbon black, acetylene black, graphite, carbon fiber, or carbon nanotube.
- acetylene black is particularly preferable from the viewpoints of the amount of addition and conductivity, and the productivity of the positive electrode mixture slurry for coating.
- This conductive auxiliary agent can also be contained in the negative electrode film.
- the binder used for the electrode of the present embodiment preferably contains a binder for binding the active material and the conductive additive to each other.
- a binder material for example, a polyvinylidene fluoride polymer or a rubber polymer is preferably used.
- the polyvinylidene fluoride-based polymer is, for example, a polymer of a fluorine-containing monomer group containing 80% by mass or more of vinylidene fluoride whose main component is a monomer. Two or more of the above polymers may be used in combination.
- the binder of the present embodiment is preferably provided in the form of a solution dissolved in a solvent.
- the fluorine-containing monomer group for synthesizing the polyvinylidene fluoride-based polymer includes vinylidene fluoride or a mixture of vinylidene fluoride and another monomer, and a monomer mixture containing 80% by mass or more of vinylidene fluoride. Is mentioned.
- Examples of other monomers include vinyl fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
- Examples of the rubber-based polymer include styrene butadiene rubber (SBR), ethylene propylene diene rubber, or fluorine rubber.
- SBR styrene butadiene rubber
- ethylene propylene diene rubber ethylene propylene diene rubber
- fluorine rubber fluorine rubber
- the content of the binder in the electrode layer, that is, the first coating film is preferably 0.1% by mass or more and 10% by mass or less based on the dried electrode layer. More preferably, the binder content is 0.3% by mass or more and 5% by mass or less. If the binder content is too small, not only will the solidification in the pre-solidification step of the present embodiment be insufficient, but the mechanical strength of the electrode film after drying will be insufficient, and the electrode layer will peel off from the current collector foil. Problems arise. Moreover, when there is too much content of a binder, there exists a possibility that the amount of active materials in an electrode layer may reduce and battery capacity may become low.
- an inorganic oxide such as alumina (Al 2 O 3 ) or silica (SiO 2 ) can be used.
- the insulating layer can be provided with a shutdown property.
- the insulating layer is a porous film, and in the completed lithium ion secondary battery, the electrolytic solution is held in the pores of the insulating layer and constitutes a lithium ion conduction path between the electrodes.
- the shutdown property here refers to a function of melting the insulating layer and closing the hole when the lithium ion secondary battery generates abnormal heat.
- a resin is used as a binder for binding the inorganic oxide particles used for the insulating material IF.
- the binder the above-mentioned polyvinylidene fluoride polymer or rubber polymer is preferably used in the negative electrode as well as the positive electrode.
- the current collector foil EP used in the present embodiment is not limited to a sheet-like foil, and examples of the substrate include pure aluminum (Al), copper (Cu), stainless steel, titanium (Ti), and the like. Metal or alloy conductive materials can be used.
- the current collector foil EP for example, a net, a punched metal, a foam metal, a foil processed into a plate shape, or the like is used.
- the thickness of the conductive substrate constituting the current collector foil EP is, for example, 5 to 30 ⁇ m, and more preferably 8 to 16 ⁇ m.
- the solidifying liquid of the present embodiment is appropriately selected and used for the solvent and binder in the first coating film.
- the solidifying liquid should be selected in consideration of the solubility of the binder component in the first coating film and the mutual solubility of the solvent.
- the solvent in the first coating film used in a general solvent-based slurry is an aprotic polar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, dimethylformamide, or ⁇ -butyrolactone, or a mixture thereof. Liquid.
- water, alcohols such as ethanol and isopropyl alcohol, or a mixture thereof can be selected as the solidified liquid, but are limited to the examples given here. I don't mean.
- the solidified liquid In order to spray the solidified liquid uniformly, the solidified liquid should be selected in consideration of the wettability between the first coating film and the solidified liquid, and it is preferable to use a mixture of water and alcohol. This is because when the wettability between the first coating film and the solidified liquid is poor, the solidified liquid is dispersed at a plurality of locations on the surface of the first coated film and adheres in an island shape, and is uniform on the surface of the first coated film This is because the solidified liquid cannot be supplied to the container.
- the concentration of alcohol in the mixture is desirably 20 to 80%, more preferably 40 to 60%. When the concentration of alcohol is lower than the above concentration range, the wettability between the first coating film and the solidified liquid is deteriorated. If the alcohol concentration is higher than the above concentration range, handling of the solidified liquid becomes difficult due to an increase in the concentration of combustible alcohol, and the risk of explosion in the manufacturing process and the like increases.
- the pre-solidification step of the present embodiment is a step introduced between the first coating step and the second coating step.
- the solidification liquid is sprayed on the surface of the first coating film to solidify the surface layer of the first coating film.
- the surface layer of the first coating film means a first coating film in the vicinity of the surface including the surface of the first coating film.
- the pre-solidification step it is important to perform the pre-solidification step by appropriately selecting the amount of the solidification liquid to be sprayed and the spray particle size of the solidification liquid.
- a one-fluid nozzle that ejects only liquid or a two-fluid nozzle that ejects mixed liquid and gas can be used. From the viewpoint of reducing the impact when water contacts the solidified film by spraying, it is desirable to use a two-fluid nozzle that can spray finer droplets.
- the average particle diameter D50 of the sprayed particles sprayed from the nozzle is 20 ⁇ m or less, more preferably 10 ⁇ m or less, thereby preventing damage such as a coating film defect.
- the coating film defect is the surface of the coating film because the sprayed particles are struck against the surface of the coating film when the spray pressure, spraying force, or average particle size of the droplet sprayed on the surface of the coating film is large. Means that it is recessed. In this case, problems such as variations in insulation between electrodes occur.
- the spray hitting force refers to a pressure that the target receives per unit area by hitting a droplet against the target by spraying.
- the concentration is not more than the solidified solution concentration at which all the binder in the first coating film is deposited. More preferably, the concentration is 40 to 90% of the concentration of the solidified solution in which all the binder in the first coating film is deposited.
- the amount of the solidified liquid to be sprayed is too large, the solidified liquid accumulates on the first coating film, making it difficult to apply the insulating material.
- the amount of the solidified liquid is too small, the solidified liquid spreads on the front surface of the first coating film. There is a risk of not.
- the lithium ion secondary battery that can be provided by the present embodiment is manufactured in the same process as the lithium ion secondary battery of the second comparative example described later, except that it includes the positive electrode and the negative electrode manufactured by the above-described method. can do.
- the manufacturing method of the lithium ion secondary battery of the present embodiment after applying the first coating film to be the first electrode layer as described above, through the step of solidifying only the surface layer of the electrode layer, A second coating film to be a second insulating layer is applied.
- the manufacturing apparatus of the lithium ion secondary battery according to the present embodiment includes the first coating portion that coats the first coating film serving as the first electrode layer as described above, and the second layer insulation. Between the 2nd coating part which coats the 2nd coating film used as a layer, it has a means to solidify only the surface layer of a 1st coating film, It is characterized by the above-mentioned.
- the thickness of the mixed layer generated at the interface between the electrode layer and the insulating layer can be reduced, as described later, and the insulating layer can be made thinner and highly reliable. Can be realized.
- nickel cobalt lithium manganate as a lithium transition metal composite oxide can be used for the positive electrode active material constituting the electrode material ES.
- PVdF polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- the components of the positive electrode active material, the conductive additive, the solidifying material, and the first solvent thus mixed are further kneaded with a planetary mixer to adjust the positive electrode slurry, that is, the electrode material ES.
- the positive electrode active material, graphite powder, acetylene black, and PVdF are mixed in a weight ratio of 85: 8: 2: 5.
- a binder component as a solidifying material is dissolved in NMP, and the slurry is a high-viscosity liquid.
- the viscosity of the slurry measured with a rotational viscometer is about 10 Pa ⁇ s.
- the first coating process is performed.
- an aluminum foil having a thickness of 20 ⁇ m and a width of 200 mm for example, is used for the current collector foil EP to be applied in the first coating process.
- the electrode material ES is applied to the surface of the current collector foil EP with a thickness of 100 ⁇ m and a width of 150 mm using the die coater DC1 which is a slit die coater.
- the 1st coating film which consists of electrode material ES is formed on current collection foil EP.
- the width of the current collector foil EP and the first coating film is a direction orthogonal to the traveling direction of the current collector foil EP being conveyed, and each structure in a direction along the upper surface of the current collector foil EP. Refers to the length of
- a pre-solidification step is performed. That is, the current collector foil EP coated with the first coating film is transported into the solidification chamber SD1, and only the surface layer of the first coating film is solidified.
- 40% ethanol-containing water is used for the solidified liquid supplied from the spray nozzle NZ1.
- the 40% ethanol-containing water is a liquid in which ethanol and water are mixed, and ethanol constitutes 40% of the liquid.
- the spray nozzle NZ1 an internal mixing type two-fluid nozzle is used as the spray nozzle NZ1.
- the average particle diameter D50 of the spray particles that are the solidified liquid ejected from the two-fluid nozzle is 10 ⁇ m.
- the distance from the spray nozzle to the first coating film is adjusted to 100 mm, the spray pressure is adjusted to 0.1 MPa, and the spray hitting force is adjusted to 1 g / cm 2 .
- the spray amount of the solidified liquid was set to an amount that would be 50% of the amount of 40% ethanol-containing water required for the precipitation of PVdF as a binder. That is, the spray amount of the solidified liquid is made half of the amount used for depositing all the binder. Thereby, only the surface layer of the first coating film is solidified.
- the above process is the pre-solidification process of this Embodiment.
- the solidified liquid spray area has a uniform flow distribution. That is, the distribution of the spray amount of the solidified liquid is sprayed in an equal amount within a certain range from the center of the spray nozzle NZ1 in the width direction of the first coating film.
- the solidified liquid is sprayed uniformly over the entire top surface of the first coating film by keeping the entire width of the first coating film within the certain range in which spraying in an equal amount is possible. .
- the position where the flow rate is 50% of the flow rate at the center of the spray nozzle NZ1 is outside the end of the first coating film in the width direction of the first coating film, which is the direction perpendicular to the conveying direction of the current collector foil EP.
- Position. This is because there is a possibility that the solidified liquid cannot be sprayed in an equal amount in a region outside the position where the flow rate is 50% of the total flow rate of the solidified liquid in the width direction from the center of the spray nozzle NZ1. Because there is. That is, the solidified liquid can be sprayed in an equal amount from the center of the spray nozzle NZ1 within a range of 50% of the total flow rate of the solidified liquid.
- Silica (SiO 2 ) powder is used for the insulating material IF.
- the insulating material IF and polyvinylidene fluoride (PVdF) as a binder are mixed at a weight ratio of 90:10, and N-methyl-2-pyrrolidone (NMP) is sequentially added as a solvent.
- NMP N-methyl-2-pyrrolidone
- these components are kneaded with a planetary mixer to adjust the insulating material slurry.
- the insulating material slurry is a high-viscosity liquid, and the viscosity of the slurry measured with a rotational viscometer is about 2 Pa ⁇ s.
- the insulating material slurry that is, the insulating material IF is applied on the first coating film whose surface is solidified by using a die coater DC2 which is a slit die coater so as to have a thickness of 80 ⁇ m and a width of 160 mm.
- the second coating film made of the insulating material IF is formed on the first coating film.
- the above process is the second coating process of the present embodiment.
- a drying process is performed.
- the first coating film and the second coating film are dried by heating at 120 ° C. for 10 minutes in a drying chamber DRY which is a hot air drying furnace.
- the solvent contained in the first coating film and the second coating film is removed by evaporation, so that the entire first coating film and the second coating film are completely solidified.
- a positive electrode plate for a lithium ion secondary battery is manufactured. That is, the positive electrode plate is formed by drying and solidifying the current collector foil EP, the electrode layer formed by drying and solidifying the first coating film containing the electrode material ES, and the second coating film containing the insulating material IF. And an insulating layer.
- the above process is the drying process of the present embodiment in which the solvent component is removed from the electrode material ES and the insulating material IF and the process is dried.
- a film-like positive electrode or negative electrode plate is manufactured by performing a processing step such as compression or cutting on the current collecting foil EP.
- the thickness of the mixed layer formed at the interface between the electrode layer and the insulating layer in the manufacturing method of the present embodiment is evaluated.
- the evaluation is performed by cutting out a cross section of the completed electrode plate and calculating the thickness of the mixed layer from an image observed with a scanning electron microscope (SEM).
- FIG. 3 shows a cross-sectional view of the electrode plate constituting the lithium ion secondary battery.
- an electrode layer EL having a thickness L1 and an insulating layer SEL which is a separator having a thickness L2 are sequentially stacked on the current collector foil EP.
- This configuration is the same for the lithium ion secondary battery of the present embodiment described above and the lithium ion secondary battery of the second comparative example described later.
- a mixed layer MIX having a thickness L3 formed by mixing the constituent material of the electrode layer EL and the constituent material of the insulating layer SEL is formed in the vicinity of the interface between the electrode layer EL and the insulating layer SEL.
- the upper end and the lower end of the mixed layer MIX are indicated by broken lines, respectively.
- the thickness L1 of the electrode layer constituting the positive electrode plate after the drying step is, for example, 50 ⁇ m
- the thickness L2 of the insulating layer is, for example, 40 ⁇ m.
- the mixed layer MIX is a layer formed from the inside of the electrode layer EL to the inside of the insulating layer SEL near the interface between the electrode layer EL and the insulating layer SEL.
- FIG. 4 shows the result of evaluating the film thickness of the mixed layer MIX by the SEM observation based on the cross-sectional view shown in FIG.
- FIG. 4 shows the thickness of each mixed layer MIX (see FIG. 3) of the lithium ion secondary battery of the present embodiment described above and a lithium ion secondary battery of a second comparative example, which will be described later, and a current collector foil.
- It is a graph which shows the relationship with the conveyance speed.
- the vertical axis of the graph shown in FIG. 4 indicates the film thickness of the mixed layer, and the horizontal axis indicates the conveyance speed of the current collector foil.
- the inventors of the present invention determines the thickness L3 (see FIG.
- a positive electrode and a negative electrode having a size required for the battery cell are cut out from the film-like positive electrode plate and negative electrode plate formed by the above process in a process called winding.
- the insulating layer which is a separator for separating the positive electrode plate and the negative electrode plate is cut out together with the positive electrode plate and the negative electrode plate.
- the laminate including the positive electrode plate and the negative electrode plate is put together.
- a group of electrode pairs including the combined positive and negative electrodes is assembled and welded.
- an aluminum ribbon is wound around the positive electrode current collecting tab, and the positive electrode current collecting tab is connected to the aluminum ribbon by ultrasonic welding.
- the welded electrode pair group is placed in the battery can, and then the electrolyte is injected.
- a battery cell of a lithium ion secondary battery is formed by completely sealing the battery can.
- the cells of the lithium ion secondary battery created in the cell assembly process are repeatedly charged and discharged. Thereby, the cell inspection process regarding the performance and reliability of a battery cell is performed.
- the unit cell inspection step for example, the capacity or voltage of the battery cell is inspected, or the current or voltage at the time of charging or discharging is inspected. Thereby, the battery cell of a lithium ion secondary battery, ie, a single battery, is completed.
- FIG. 6 is a flowchart schematically showing specific steps until a lithium ion secondary battery is manufactured.
- the manufacturing process of the lithium ion secondary battery includes a positive electrode plate manufacturing process, a negative electrode plate manufacturing process, and a battery cell assembly process.
- FIG. 5 shows a lithium ion secondary battery manufacturing apparatus of the first comparative example. That is, FIG. 5 is a schematic view showing a lithium ion secondary battery manufacturing apparatus in the first comparative example.
- the electrode material ES is adjusted.
- An electrode material ES used for forming an electrode layer constituting a positive electrode or a negative electrode of a lithium ion secondary battery is composed of an active material capable of releasing and occluding lithium ions by charging and discharging, and a conductive auxiliary powder. It is a high-viscosity slurry-like liquid formed by kneading and dispersing with a binder, a solvent and the like for binding (a kneading and blending step shown in FIG. 6).
- the slurry-like electrode material ES is thinly and uniformly applied on the surface of the current collector foil EP supplied from the current collector metal foil roll RL1 using the die coater DC1 which is a coating part.
- EP is dried and solidified in a hot-air drying furnace which is a drying chamber DRY. In this drying step, the solvent component in the coating film is evaporated by heating, whereby the electrode material is dried and solidified to form the electrode layer.
- an electrode layer is formed on current collection foil EP by performing a series of processes of application of electrode material ES, and a drying process (application process shown in Drawing 6). Then, a film-like positive electrode or negative electrode plate is manufactured by performing a process such as compression on the current collector foil on which the electrode layer is formed.
- the process as described above is performed separately on one surface of the current collector foil EP and the surface opposite to the surface, and on both surfaces of the current collector foil EP.
- a positive electrode plate and a negative electrode plate on which an electrode layer is formed are manufactured.
- a positive electrode and a negative electrode having a size necessary for the battery cell are cut out from the film-like positive electrode plate and negative electrode plate in a process called winding (the processing step shown in FIG. 6). ).
- a separator for separating the positive electrode plate and the negative electrode plate was cut out from the film-like separator material in a size necessary for the battery cell, and cut into the positive electrode plate and the negative electrode plate. After stacking with the separator in between, they are rolled together (winding step shown in FIG. 6).
- the group of electrode pairs of the positive electrode, the negative electrode, and the separator assembled together is assembled and welded (welding / assembly process shown in FIG. 6). Then, after arranging the group of these electrode pairs welded in a battery can, electrolyte solution is inject
- the cells of the lithium ion secondary battery created in the cell assembly process are repeatedly charged and discharged (charge / discharge process shown in FIG. 6).
- inspection regarding the performance and reliability of a battery cell is performed (single cell test process shown in FIG. 6).
- the unit cell inspection step for example, the capacity or voltage of the battery cell is inspected, or the current or voltage at the time of charging or discharging is inspected.
- a battery cell that is, a single battery is completed, and the assembly process of the battery cell of the lithium ion secondary battery is completed.
- the positive electrode plate, the negative electrode plate, and the separator are separate components. For example, there is a gap between the positive electrode plate and the separator.
- the positive electrode plate and the negative electrode plate are cut into a predetermined size (the processing step shown in FIG. 6) before forming the wound body described above, and in addition, the positive electrode and the negative electrode
- the current collecting tab is formed by cutting the positive electrode plate and the negative electrode plate.
- the electrode winding body for example, a step of ultrasonically welding a positive electrode current collecting tab formed on the positive electrode plate to the positive electrode current collecting ring, and a negative electrode current collecting tab formed on the negative electrode plate And a step of ultrasonic welding to the negative electrode current collector ring (welding / assembly step shown in FIG. 6).
- the electrode winding body is inserted into the outer can (container), and after injecting the electrolyte into the outer can, the outer can and the lid are connected by welding or the like to seal the inside of the outer can. Perform the process.
- the positive electrode current collector tab and the positive electrode current collector ring are welded by, for example, attaching an aluminum ribbon to the positive electrode current collector tab and then connecting the positive electrode current collector tab to the aluminum ribbon by ultrasonic welding. It is done by doing.
- the ultrasonic welding used at this time connects the aluminum ribbon and the positive electrode current collector tab by atomic interdiffusion by rubbing the aluminum ribbon and the positive electrode current collector tab.
- a separator by applying a separator directly to the positive electrode plate and the negative electrode plate.
- the positive electrode plate or the negative electrode plate and the separator are continuously formed and integrated with each other, thereby eliminating a gap between the positive electrode plate or the negative electrode plate and the separator.
- the short circuit with a positive electrode and a negative electrode can be prevented.
- a slurry containing a positive electrode active material or a negative electrode active material on a metal, and then applying an insulating material to be a separator it may be possible to improve productivity and reduce manufacturing equipment. it can.
- FIG. 7 is a schematic view showing an apparatus for manufacturing a lithium ion secondary battery in a second comparative example.
- FIG. 7 shows the configuration of the single-side coated electrode plate manufacturing apparatus in the second comparative example.
- the current collector foil EP is fed from the current collector metal foil roll RL1.
- the current collector foil EP is an aluminum foil having a thickness of 20 ⁇ m and a width of 200 mm, for example.
- the electrode material ES supplied from the die coater DC1 facing the roller RL2 is applied on the surface of the current collector foil EP, thereby forming a first coating film.
- the first coating film has a thickness of 100 ⁇ m and a width of 150 mm, for example.
- the second coating film has a thickness of 20 ⁇ m and a width of 160 mm, for example.
- the configuration of the second comparative example includes the die coater DC2 that is the second coating portion as compared with the first comparative example described with reference to FIG. The difference is that a second coating film serving as a separator is directly formed on the coating film.
- a slit die coater is used for the above-described die coater DC1 (see FIG. 7).
- the slit die coater is a coating apparatus used for thick film coating or for applications where a high viscosity material is coated.
- an electrode is connected to the manifold 3 of the base 1 by a metering pump (not shown) from a tank (not shown) in which an electrode material ES as a slurry material is stored. Material ES is supplied.
- the electrode material ES is supplied to the slit 4 provided in the base 1 and discharged.
- the discharged electrode material ES forms an electrode material reservoir 5 called a bead between the base 1 and the current collector foil EP that travels relatively at a constant interval h1, and in this state the current collector foil EP With the running, the electrode material ES is pulled out to form a coating film.
- FIG. 8 is an enlarged cross-sectional view of the die coater DC1 that constitutes the lithium ion secondary battery manufacturing apparatus in the second comparative example.
- a coating film is continuously formed by supplying the same amount of electrode material ES as consumed by the coating film formation from the slit 4.
- the pressure for supplying the positive electrode material to the manifold 3 is slit 4 pressure loss + downstream lip 8 pressure loss of the cap 1 + downstream meniscus 9 pressure. That is, in order to apply the electrode material ES stably, it is necessary to apply a certain pressure from the electrode material ES to the current collector foil EP. This configuration is the same for the die coater DC2.
- the insulating material is continuously applied by the die coater DC2, which is the second coating part.
- the die coating method therefor is the die coater which is the first coating part.
- the conditions are the same as in DC1. That is, a slurry material made of an insulating material discharged from the slit 4 (see FIG. 8) of the die coater DC2, that is, an insulating material IF, is applied onto the electrode material ES applied to the current collector foil EP by the die coater DC1. To do.
- the slurry-like electrode material ES and the insulating material IF shown in FIG. 7 are applied in layers, followed by a heating / drying process in the drying chamber DRY. Since it can be dried and fixed, the manufacturing process is more efficient than the first comparative example. In addition, since processing such as cutting or welding of the electrode can be performed in a state where there is no gap between the electrode layer and the insulating layer which is a separator, an internal short circuit due to intrusion of a metal foreign object can be prevented.
- the mixed layer MIX is a layer generated due to the coating pressure of the slit die coater described with reference to FIG. As shown by the square plot in FIG. 4, the film thickness of the mixed layer MIX (see FIG. 3) generated in the second comparative example varies depending on the conveying speed of the current collector foil.
- the slower the current collecting foil transport speed the longer the time during which the pressure applied by the die coater is applied to the coating film at a specific location, and the thickness of the mixed layer MIX also increases. Even if the conveying speed of the current collector foil is set to a relatively high speed of 100 m / min, the thickness of the mixed layer MIX is 10 ⁇ m or more.
- the insulating layer SEL having an insulating function becomes thinner than originally intended, and when the insulating layer SEL is thinned, the insulating layer There is a problem that the electrode material constituting the mixed layer MIX may be exposed at the top of the SEL.
- the thickness L3 of the mixed layer MIX is larger than 20% of the thickness L2 of the insulating layer SEL that is the separator, the total thickness of the insulating layer SEL between the positive electrode and the negative electrode Among them, since the region where the insulating function is lost becomes large, the insulating property of the insulating layer SEL is lowered, and the problem that a short circuit occurs between the positive electrode and the negative electrode becomes significant.
- the thickness L3 of the mixed layer MIX is 20% or less of the thickness L2 of the insulating layer SEL as a separator. Therefore, when the thickness L2 of the insulating layer SEL is 40 ⁇ m, the thickness L3 of the mixed layer MIX is desirably 8 ⁇ m or less.
- the insulating layer is a thick film of, for example, 50 ⁇ m or more.
- the internal short circuit is prevented by eliminating the gap between the electrode layer and the separator (insulating layer), and the productivity of the lithium ion secondary battery is improved.
- the manufacturing apparatus of the lithium ion secondary battery in this configuration, it is difficult to reduce the thickness of the insulating layer due to the problem of the mixed layer. That is, the second comparative example has a problem that it is difficult to increase the capacity and size of the lithium ion secondary battery.
- the method of manufacturing the lithium ion secondary battery according to the present embodiment applies the first coating film of the first layer to be the electrode layer, and then the surface layer of the first coating film.
- the second coating film of the second layer that becomes the insulating layer is applied through a process of solidifying only the first layer.
- the pre-solidification step is performed, and only the surface layer of the first coating film is solidified, as described with reference to FIGS. 3 and 4.
- the thickness L3 of the layer MIX can be reduced as compared with the second comparative example. Specifically, the thickness of the mixed layer MIX can be 5 ⁇ m or less.
- the thickness L3 of the mixed layer MIX is 10 ⁇ m or more even at a practical speed of transporting the current collector foil. Therefore, when the thickness L2 of the insulating layer SEL is reduced, The possibility of occurrence of a short circuit between the negative electrodes is increased.
- the risk of a short circuit can be prevented even if the separator, which is an insulating layer, is thinned, so that the reliability of the lithium ion secondary battery can be improved. Moreover, since the separator which is an insulating layer can be thinned while preventing a short circuit, the lithium ion secondary battery can be miniaturized. Therefore, the performance of the lithium ion secondary battery can be improved.
- the above effect is not only obtained with the positive electrode plate made of the positive electrode material, but the same effect can be obtained with the negative electrode plate.
- the manufacturing apparatus and the manufacturing method described in this embodiment are merely examples for implementing this embodiment, and various forms can be used without departing from the technical idea or main features thereof. Even in the embodiment, the above effect can be obtained.
- a lithium ion secondary battery has been described as an example, but the effect of this embodiment is not limited to a lithium ion secondary battery.
- the positive electrode, the negative electrode, and the positive electrode and the negative electrode are electrically connected. It can be widely applied to an electricity storage device including a separator that is separated into two. Examples of the power storage device include other types of batteries or capacitors.
- FIG. 2 shows a schematic diagram showing a lithium ion secondary battery manufacturing apparatus of the present embodiment.
- the slurry-like electrode material ES is used by using the die coater DC1 facing the roller RL2. Then, coating is performed on the surface of the current collector foil EP supplied from the current collector metal foil roll. Thereby, the 1st coating film which consists of electrode material ES is formed on current collection foil EP.
- the thickness and width of each of the current collector foil EP and the first coating film are the same as those in the first embodiment.
- a pre-solidification step is performed in the solidification chamber SD1.
- the surface layer of the first coating film is solidified.
- the solidified liquid and spraying conditions are the same as those in the first embodiment.
- a second coating film made of the insulating material IF is applied on the first coating film whose surface is solidified.
- the thickness and width of the second coating film are the same as those in the first embodiment.
- the current collector foil EP coated with the first coating film and the second coating film is carried into the solidification chamber SD2, and the solidification liquid is laminated by using the spray nozzle NZ2 and is composed of the first coating film and the second coating film.
- a step of solidifying the first coating film and the second coating film is performed by spraying on the film.
- this process is called a solidification process.
- 40% ethanol-containing water is used as the solidified liquid.
- water, alcohols such as ethanol or isopropyl alcohol, or a mixed liquid thereof are used in the same manner as the solidification liquid sprayed in the solidification chamber SD1 (see FIG. 1) in the first embodiment. be able to.
- An internal mixing type two-fluid nozzle is used as the spray nozzle NZ2.
- the average particle diameter D50 of the spray particles ejected from the two-fluid nozzle is 10 ⁇ m.
- the distance from the spray nozzle NZ2 to the upper surface of the second coating film is 100 mm
- the spray pressure of the solidified liquid is 0.1 MPa
- the spray hitting force is adjusted to 1 g / cm 2 .
- the amount of the solidified liquid sprayed is 200% of the 40% ethanol-containing water amount in which all PVdF is precipitated in order to completely solidify the first coating film that is the electrode material layer and the second coating film that is along the insulating material. . That is, each coating film is completely solidified by supplying a solidification liquid twice as much as 40% ethanol-containing water, which is a solidification liquid necessary for precipitating PVdF.
- the spray nozzle NZ2 is shown more than the spray nozzle NZ1 in order to increase the number of nozzles and supply a large amount of solidified liquid as described above.
- the first coating film and the second coating film are dried in a drying chamber DRY at 120 ° C. for 10 minutes to evaporate and remove the solvent contained in the first coating film and the second coating film,
- An electrode plate for a lithium ion secondary battery is manufactured.
- the thickness of the electrode layer constituting the electrode plate after the drying step is 50 ⁇ m
- the thickness of the insulating layer on the electrode layer is 40 ⁇ m. Said process is applicable to each manufacturing process of a positive electrode plate and a negative electrode plate.
- the configuration of the present embodiment is almost the same as that of the first embodiment.
- a second solidification chamber SD2 different from the first solidification chamber SD1 is provided between the die coater DC2 which is the second coating part and the drying chamber DRY, and on the current collector foil EP in the solidification chamber SD2.
- This is different from the first embodiment in that the coating film is solidified.
- the pre-solidification step performed in the first solidification chamber SD1 only the surface layer of the first coating film is solidified and the inside of the first coating film is not solidified, whereas the second solidification chamber SD2 is performed.
- the entire structure including the inside of each of the first coating film and the second coating film is solidified. That is, all the binders contained in each of the first coating film and the second coating film are deposited.
- the thickness of the mixed layer MIX (see FIG. 3) formed in the vicinity of the interface between the electrode layer EL and the insulating layer SEL is the same as that of the first embodiment. In addition, it is always 5 ⁇ m or less regardless of the conveying speed of the current collector foil. Therefore, even if the insulating layer SEL is thinned, the possibility of occurrence of a short circuit between the positive electrode and the negative electrode can be reduced.
- each coating film is completely solidified before the drying process as in the present embodiment, the electrode material and the second material in the first coating film can be used even when the drying process is performed at high speed.
- the movement of the insulating material in the coating film can be suppressed. That is, when the solidification process using the second solidification chamber SD2 shown in FIG. 2 is not performed, the inside of the first coating film and the second coating film are in a liquid state at the time of drying, and therefore the binder in each film during the drying process.
- the movement of components such as convection or diffusion occurs in each film. For this reason, the distribution of the electrode material ES after drying may vary. In this case, in order to suppress the convection or diffusion of the electrode material ES, it is necessary to suppress the evaporation rate, which causes a problem that the drying time becomes longer.
- each coating film is completely solidified to the inside before the drying process, it is possible to prevent the electrode material ES from moving during the drying process in the drying chamber DRY. It is possible to increase the evaporation rate of the. Therefore, the drying time can be shortened, and the drying equipment can be downsized. Thereby, the throughput in the manufacturing process of the lithium ion secondary battery can be improved. Further, the manufacturing cost of the lithium ion secondary battery can be reduced by shortening the drying time or downsizing the drying equipment.
- FIG. 9 is a diagram showing a configuration of a single-sided coating type electrode plate manufacturing apparatus according to the present embodiment. That is, FIG. 9 is a schematic diagram showing a lithium-ion secondary battery manufacturing apparatus in the present embodiment.
- the lithium ion secondary battery manufacturing apparatus includes a current collector foil feed roll RL0 that feeds a current collector foil EP that is an electrode plate, and a winding roll that winds the current collector foil EP. RL4.
- the current collector foil EP which is a thin metal foil, is conveyed between the current collector foil feed roll RL0 and the take-up roll RL4 while being supported by a plurality of rollers such as rollers RL2 and RL3.
- the plurality of rollers are referred to as a roller conveyance system, that is, a conveyance unit.
- a coater DC1, a coater DC2, a spray nozzle SPR in the solidification chamber SD, and a drying chamber DRY are arranged in this order from the current collector foil feed roll RL0 side to the take-up roll RL4 side. Yes.
- the conveyed current collecting foil EP passes between the coater DC1 and the roller RL2, between the coater DC2 and the roller RL3, in the solidification chamber SD, and in the drying chamber DRY.
- each of the positive electrode and the negative electrode constituting the lithium ion secondary battery differs in the material of the current collector foil EP and the material of the film applied to the current collector foil EP, but is basically manufactured by the same process. .
- the electrode material ES which is a coating material to be described later, includes a case where it is a positive electrode material and a case where it is a negative electrode material.
- the electrode material ES is composed of different materials.
- the positive electrode manufacturing process the current collector foil EP and the coating material made of the positive electrode material are used, and the material used only in the negative electrode manufacturing process is not used.
- the negative electrode manufacturing process a material used only for the positive electrode manufacturing process is not used.
- the electrode material ES for forming the positive electrode or the negative electrode of the lithium ion secondary battery is adjusted.
- the collected slurry-like electrode material ES is supplied from the collector foil feed roll RL0 using the coater DC1, which is the first coating portion disposed so as to face the roller RL2. Apply thinly and evenly on the surface of the EP. Below, this process is called a 1st coating process.
- coated on current collection foil EP by the 1st coating process is called an electrode material layer or a 1st coating film.
- a slit die coater can be used for the first coating part, but another apparatus may be used as an apparatus for supplying the electrode material ES.
- the insulating material IF1 supplied from the coater DC2, which is the second coating portion provided so as to face the roller RL3, is thinly and uniformly applied.
- This process is called a second coating process.
- the film made of the insulating material IF1 applied on the first coating film in the second coating process is referred to as an insulating material layer or a second coating film.
- a slit die coater or the like can be used for the second coating part. In FIG. 9, the first coating film and the second coating film are not shown.
- the insulating material IF1 contains a component for precipitating the binder component of the surface layer of the first coating film that is the electrode material layer.
- the component which precipitates a binder component is called a solidification material or a solidification liquid.
- the insulating material IF1 includes a solidifying material as described above. In the second coating process, the insulating material IF1 including the solidifying material is in contact with the surface of the first coating film. When the solidifying material comes into contact with the surface layer of the first coating film, the solidified liquid enters the first coating film while dissolving in the solvent in the first coating film.
- the concentration of the solidified liquid in the surface layer of the first coating film is increased, the solubility of the binder in the first coating film is decreased, so that the binder is precipitated and only the surface layer of the first coating film is fixed. That is, the binder of the surface layer of the first coating film is deposited, so that the active material constituting the first coating film that is the electrode material is fixed. Therefore, solidification of the surface layer of the first coating film can prevent the active material constituting the first coating film from being mixed into the second coating film on the first coating film.
- the surface layer of the first coating film means the first coating film in the vicinity of the surface including the surface of the first coating film.
- the binder is a component having a role of binding between the powder components constituting the first coating film and further binding between the powder component and the current collector foil after the first coating film is dried. It is.
- the binder has a role of binding the powder and the conductive additive.
- the powder constituting the first coating film is, for example, a positive electrode active material powder or a negative electrode active material powder.
- a component for precipitating the binder in the electrode material layer that is, the spray liquid LIQ containing the solidifying material is supplied from the spray nozzle SPR in the solidification chamber SD to the laminated film composed of the first coating film and the second coating film.
- the spray liquid LIQ is sprayed from the spray nozzle SPR.
- the binder inside the first coating film that is the electrode material layer is deposited, so that not only the surface layer of the first coating film but also the active material inside the first coating film is fixed. That is, in this solidification step, the entire first coating film that is the electrode material layer is solidified.
- a configuration in which the spray liquid LIQ that is a solidification material is sprayed using the spray nozzle SPR in the solidification chamber SD and the coating film to be sprayed is solidified is referred to as a solidification unit.
- the current collector foil EP is transported into a drying chamber DRY which is a hot air drying furnace.
- the drying chamber DRY the solvent component and the solidified liquid in the first coating film and the second coating film are heated and evaporated to dry and solidify the first coating film and the second coating film, An insulating layer is formed in a lump.
- this process is called a drying process. That is, the first coating film becomes an electrode layer by a drying process, and the second coating film becomes an insulating layer, that is, a separator, by a drying process.
- the electrode plate which consists of the current collection foil EP and the electrode layer and insulating layer which were laminated
- the electrode, the positive electrode, and the negative electrode may be referred to as an electrode plate, a positive electrode plate, and a negative electrode plate, respectively.
- a film-like positive electrode or negative electrode plate is manufactured by performing a processing step such as compression or cutting on the current collecting foil EP.
- a positive electrode and a negative electrode having a size necessary for the battery cell are cut out from the film-like positive electrode plate and negative electrode plate formed by the above process in a process called winding.
- the insulating layer which is a separator for separating the positive electrode plate and the negative electrode plate is cut out together with the positive electrode plate and the negative electrode plate.
- the laminate including the positive electrode plate and the negative electrode plate is put together.
- a group of electrode pairs including the combined positive and negative electrodes is assembled and welded.
- this welding process for example, an aluminum ribbon is wound around the positive electrode current collecting tab, and the positive electrode current collecting tab is connected to the aluminum ribbon by ultrasonic welding. Then, after arranging the group of these electrode pairs welded in the battery can, the electrolyte is injected. Subsequently, a battery cell of a lithium ion secondary battery is formed by completely sealing the battery can.
- the cells of the lithium ion secondary battery created in the cell assembly process are repeatedly charged and discharged. Thereby, the cell inspection process regarding the performance and reliability of a battery cell is performed.
- the unit cell inspection step for example, the capacity or voltage of the battery cell is inspected, or the current or voltage at the time of charging or discharging is inspected. Thereby, the battery cell of a lithium ion secondary battery, ie, a single battery, is completed.
- the electrode material ES in the present embodiment includes a positive electrode active material powder or a negative electrode active material powder that can release and occlude lithium ions by charging and discharging.
- the electrode material ES includes a binder component that binds between the powder components after drying, or binds between the powder component and the current collector foil. Further, in some cases, the electrode material ES includes a powder of a conductive additive.
- the electrode material ES to be applied in the first coating step is, for example, a mixture of an active material made of a lithium-containing composite oxide and carbon as a conductive additive. Is included.
- the positive electrode material is, for example, a slurry obtained by kneading the mixture in a solution in which a binder (binder) made of polyvinylidene fluoride is dissolved in N-methylpyrrolidone (NMP).
- the insulating material IF1 is a binder (binder) made of styrene butadiene rubber, and is added to a component for precipitating the binder component of the surface layer of the electrode material, that is, ethanol-added water which is one of solidifying materials
- a component for precipitating the binder component of the surface layer of the electrode material that is, ethanol-added water which is one of solidifying materials
- a slurry in which silica (SiO 2 ) powder is kneaded is used in the dissolved solution.
- the spray liquid LIQ which is a solidification liquid supplied in the solidification chamber SD which is a solidification part uses a component for precipitating the binder component of the electrode material, that is, ethanol-added water which is one of the solidification materials.
- the electrode material ES applied in the first coating process includes a negative electrode active material made of, for example, a carbon material (carbon material).
- the negative electrode material is, for example, a slurry obtained by kneading the negative electrode active material in a solution in which a binder (binder) made of polyvinylidene fluoride is dissolved in N methylpyrrolidone (NMP).
- a binder (binder) made of styrene butadiene rubber is used as the insulating material IF1 as a component for precipitating the binder component of the surface layer of the electrode material, that is, ethanol-added water which is one of solidifying materials.
- a slurry in which silica (SiO 2 ) powder is kneaded is used in the dissolved solution.
- the spray liquid LIQ which is a solidified liquid supplied in the solidifying chamber SD, uses a component that deposits the binder component of the electrode material, that is, ethanol-added water that is one of the solidified materials.
- the positive electrode active material used in this embodiment includes a lithium-containing composite oxide having a spinel structure containing lithium cobaltate or Mn (manganese), or Ni (nickel), Co (cobalt), or Mn (manganese).
- a composite oxide or the like can be used.
- olivine type compounds such as olivine type iron phosphate, can also be used for a positive electrode active material.
- the positive electrode active material is not limited to these materials, and other materials may be used. 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.
- the other positive electrode active material include olivine type compounds represented by Li 1 + xMO 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1).
- the metal M in this formula include Co (cobalt), Ni (nickel), Mn (manganese), Al (aluminum), Mg (magnesium), Zr (zirconium) or Ti (titanium).
- a lithium-containing transition metal oxide having a layered structure can be used for the positive electrode active material.
- the lithium-containing transition metal oxide having a layered structure include LiCoO 2 or LiNi 1 -xCo x -yAl y O 2 (0.1 ⁇ x ⁇ 0.3, 0.01 ⁇ y ⁇ 0.2).
- an oxide containing at least Co, Ni, and Mn can be used.
- the oxide containing Co, Ni, and Mn include LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , or LiNi 3/5 Examples thereof include Mn 1/5 Co 1/5 O 2 .
- the conductive aid is used as an electron conductive aid to be contained in the positive electrode film, and is preferably a carbon material such as carbon black, acetylene black, graphite, carbon fiber, or carbon nanotube.
- acetylene black is particularly preferable from the viewpoints of the amount of addition and conductivity, and the productivity of the positive electrode mixture slurry for coating.
- This conductive auxiliary agent can also be contained in the negative electrode film.
- the binder as the binder contains a binder for binding the active material and the conductive additive to each other.
- a binder material for example, a polyvinylidene fluoride polymer or a rubber polymer is preferably used.
- the polyvinylidene fluoride-based polymer is, for example, a polymer of a fluorine-containing monomer group containing 80% by mass or more of vinylidene fluoride whose main component is a monomer. Two or more of the above polymers may be used in combination.
- the binder of the present embodiment is preferably provided in the form of a solution dissolved in a solvent.
- the fluorine-containing monomer group for synthesizing the polyvinylidene fluoride-based polymer includes vinylidene fluoride or a mixture of vinylidene fluoride and another monomer, and a monomer mixture containing 80% by mass or more of vinylidene fluoride. Is mentioned.
- Examples of other monomers include vinyl fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
- Examples of the rubber-based polymer include styrene butadiene rubber (SBR), ethylene propylene diene rubber, or fluorine rubber.
- SBR styrene butadiene rubber
- ethylene propylene diene rubber ethylene propylene diene rubber
- fluorine rubber fluorine rubber
- the content of the binder in the electrode material layer is preferably 0.1% by mass or more and 10% by mass or less based on the electrode layer after drying. More preferably, the binder content is 0.3% by mass or more and 5% by mass or less. If the binder content is too small, not only will the solidification in the pre-solidification step of the present embodiment be insufficient, but the mechanical strength of the electrode film after drying will be insufficient, and the electrode layer will peel off from the current collector foil. Problems arise. Moreover, when there is too much content of a binder, there exists a possibility that the amount of active materials in an electrode layer may reduce and battery capacity may become low.
- an inorganic oxide such as alumina (Al 2 O 3 ) or silica (SiO 2 ) can be used.
- the insulating layer can be provided with a shutdown property.
- the insulating layer is a porous film, and in the completed lithium ion secondary battery, the electrolytic solution is held in the pores of the insulating layer and constitutes a lithium ion conduction path between the electrodes.
- the shutdown property here refers to a function of melting the insulating layer and closing the hole when the lithium ion secondary battery generates abnormal heat.
- a resin is used as a binder for fixing the inorganic oxide particles used for the insulating material IF1.
- the binder the above-mentioned polyvinylidene fluoride polymer or rubber polymer is preferably used in the negative electrode as well as the positive electrode.
- the material of the solidified liquid contained in the insulating material IF1 that is appropriately selected with respect to the solvent and binder in the first coating film.
- the solidifying liquid should be selected in consideration of the solubility of the binder component in the first coating film and the mutual solubility of the solvent.
- the solvent in the first coating film used in a general solvent-based slurry is an aprotic polar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, dimethylformamide, or ⁇ -butyrolactone, or a mixture thereof. Liquid.
- water, alcohols such as ethanol and isopropyl alcohol, or a mixture thereof can be selected as the solidified liquid, but are limited to the examples given here. I don't mean.
- the wettability between the solidified liquid and the laminated film composed of the first coating film and the second coating film is also considered.
- a solidified liquid should be selected.
- a mixture of water and alcohol is preferably used as the spray liquid LIQ.
- the concentration of alcohol in the mixture is preferably 20 to 80%, for example. However, more preferably, the concentration of the alcohol is 40 to 60%.
- the concentration of the alcohol is lower than the above concentration range, the wettability between the laminated film and the solidified liquid deteriorates. If the alcohol concentration is higher than the above concentration range, handling of the solidified liquid becomes difficult due to an increase in the concentration of combustible alcohol, and the risk of explosion in the manufacturing process and the like increases.
- the spray liquid LIQ When the solidifying liquid constituting the spray liquid LIQ has high wettability with the surface of the laminated film, that is, the surface of the second coating film, that is, when the affinity is good, the spray liquid LIQ is composed only of water. May be. Further, when the solidified liquid can be handled safely, the spray liquid LIQ may be composed of only alcohol.
- a graphite material such as natural graphite (flaky graphite), artificial graphite, or expanded graphite is used as the negative electrode active material constituting the electrode material ES.
- a graphite material such as natural graphite (flaky graphite), artificial graphite, or expanded graphite is used as the negative electrode active material constituting the electrode material ES.
- an easily graphitizable carbonaceous material such as coke obtained by firing pitch can be used.
- the negative electrode active material includes amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin (PFA: Poly-Furfuryl-Alcohol) or polyparaphenylene (PPP: Poly-Para-Phenylen) and phenol resin
- PFA furfuryl alcohol resin
- PPP Polyparaphenylene
- Li (lithium) or a lithium-containing compound can also be used as the negative electrode active material.
- the lithium-containing compound include a lithium alloy such as Li—Al, or an alloy containing an element that can be alloyed with Li (lithium) such as Si (silicon) or Sn (tin).
- oxide-based materials such as Sn oxide and Si oxide can also be used for the negative electrode active material. This oxide-based material may not contain Li (lithium).
- the current collector foil EP used in the present embodiment is not limited to a sheet-like foil, and examples of the substrate include pure aluminum (Al), copper (Cu), stainless steel, titanium (Ti), and the like. Metal or alloy conductive materials can be used.
- the current collector foil EP for example, a net, a punched metal, a foam metal, a foil processed into a plate shape, or the like is used.
- the thickness of the conductive substrate constituting the current collector foil EP is, for example, 5 to 30 ⁇ m.
- FIG. 10 shows the mixed layer formed at the interface between the electrode layer and the insulating layer in the manufacturing method of the present embodiment
- FIG. 11 shows the result of the evaluation of the thickness of the mixed layer.
- the evaluation is performed by cutting out a cross section of the completed electrode plate and calculating the thickness of the mixed layer from an image observed with a scanning electron microscope (SEM).
- FIG. 10 shows a cross-sectional view of an electrode plate constituting a lithium ion secondary battery.
- an electrode layer EL having a thickness L1 and an insulating layer SEL which is a separator having a thickness L2 are sequentially stacked on the current collector foil EP.
- the electrode layer EL is a film formed by drying the first coating film described above
- the insulating layer SEL is a film formed by drying the second coating film described above.
- a mixed layer MIX having a thickness L3 formed by mixing the constituent material of the electrode layer EL and the constituent material of the insulating layer SEL is formed in the vicinity of the interface between the electrode layer EL and the insulating layer SEL.
- the mixed layer MIX is a region including the interface between the electrode layer EL and the insulating layer SEL, and is formed from the inside of the electrode layer EL to the inside of the insulating layer SEL.
- the thickness L1 of the electrode layer constituting the positive electrode plate after the drying step is, for example, 30 to 500 ⁇ m
- the thickness L2 of the insulating layer is, for example, 10 to 20 ⁇ m.
- FIG. 11 shows the result of evaluating the film thickness of the mixed layer MIX by the SEM observation based on the cross-sectional view shown in FIG.
- FIG. 11 shows the thickness of each mixed layer MIX (see FIG. 10) of the lithium ion secondary battery of the present embodiment described above and a lithium ion secondary battery of a fourth comparative example, which will be described later, and the current collector foil.
- It is a graph which shows the relationship with the conveyance speed.
- the vertical axis of the graph shown in FIG. 11 indicates the film thickness of the mixed layer, and the horizontal axis indicates the conveyance speed of the current collector foil.
- the film thickness of the mixed layer varies depending on the conveying speed of the current collector foil. That is, the thickness of the mixed layer MIX increases as the conveying speed of the current collector foil decreases. On the other hand, even if the conveyance speed of the current collector foil is 100 m / min, the thickness of the mixed layer does not become 10 ⁇ m or less. Moreover, the thickness of the mixed layer is 10 ⁇ m or more even at a practical speed of conveying the current collector foil.
- the mixed layer MIX is a film that has lost its insulating property by mixing the electrode layer EL with the insulating layer SEL.
- the mixed layer MIX is formed with a relatively large thickness, the thickness of the insulating layer SEL having an insulating function may be thinner than originally intended. Further, when the insulating layer SEL is thinned, the electrode material constituting the mixed layer MIX may be exposed above the insulating layer SEL. That is, if the insulating layer is made thin, the possibility of occurrence of a short circuit increases.
- the thickness L3 (see FIG. 10) of the mixed layer MIX in the manufacturing method of the present embodiment is always 4 ⁇ m or less regardless of the conveying speed of the current collector foil. It has become. Therefore, the present inventors can prevent the occurrence of a short circuit when the insulating layer SEL (see FIG. 10) is thinned if the lithium ion secondary battery is formed by the manufacturing method of the present embodiment. I found out that I can.
- FIG. 12 is a schematic diagram showing the structure of a lithium ion secondary battery.
- the lithium ion secondary battery is a kind of non-aqueous electrolyte secondary battery, and is a secondary battery in which lithium ions in the electrolyte bear electric conduction.
- a lithium metal oxide is used for the active material PA that is the amount of the positive electrode material, and a carbon material such as graphite is used for the active material NA that is the negative electrode material.
- an organic solvent such as ethylene carbonate and a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) are used for the electrolyte ELQ made of an electrolyte.
- lithium ions exit from the positive electrode PE and enter the negative electrode NE during charging, and conversely during discharge, the lithium ions exit from the negative electrode NE and enter the positive electrode PE.
- Al foil AF made of Al (aluminum) is used for the current collector foil of the positive electrode PE
- Cu foil CF made of Cu (copper) is used for the current collector foil of the negative electrode NE.
- a positive electrode plate coated with a positive electrode material, a negative electrode plate coated with a negative electrode material, and a separator SP such as a polymer film that prevents contact between the positive electrode plate and the negative electrode plate are wound.
- An electrode winding body is provided.
- the lithium ion secondary battery has a configuration in which the electrode winding body is inserted into the outer can and the electrolyte is injected into the outer can.
- a lithium ion secondary battery has a positive electrode plate coated with a positive electrode material on a metal foil and a negative electrode plate coated with a negative electrode material on a metal foil.
- the positive electrode plate and the negative electrode plate formed into a band shape.
- the laminated body is stacked via separators.
- the electrode winding body having a spiral cross section is formed by winding the laminated body.
- FIG. 13 is a flowchart schematically showing specific steps until a lithium ion secondary battery is manufactured.
- the manufacturing process of the lithium ion secondary battery includes a positive electrode sheet manufacturing process, a negative electrode sheet manufacturing process, a battery cell assembly process, and a module assembly process.
- the electrode material used to form the electrode layer constituting the positive electrode or the negative electrode of the lithium ion secondary battery is composed of an active material capable of releasing and occluding lithium ions by charge and discharge, and a conductive auxiliary powder. It is a high-viscosity slurry-like liquid formed by kneading and dispersing with a binder and a solvent for binding (kneading and blending step shown in FIG. 13).
- the slurry material is applied to a film-like metal foil, and then dried (application process shown in FIG. 13). Thereafter, the metal foil coated with the slurry material is subjected to processing such as compression or cutting (processing step shown in FIG. 13) to form a film-like positive electrode sheet.
- the negative electrode sheet manufacturing process is performed in the same procedure as the positive electrode sheet manufacturing process described above.
- the various materials used in the positive electrode sheet manufacturing process described above may be different from the various materials used in the negative electrode sheet manufacturing process. That is, first, a slurry material (negative electrode material) is prepared by kneading and preparing various materials as raw materials for the negative electrode material (kneading and preparing step shown in FIG. 13). Thereafter, the slurry material is applied to a film-like metal foil and dried (application step shown in FIG. 13). Subsequently, the metal foil coated with the slurry material is subjected to processing such as compression or cutting (processing step shown in FIG. 13) to produce a film-like negative electrode sheet.
- a positive electrode and a negative electrode having a size necessary for the battery cell are cut out from the positive electrode sheet and the negative electrode sheet in a process called winding.
- a separator having a size necessary for the battery cell is cut out from the film-like separator material for separating the positive electrode sheet and the negative electrode sheet, and the cut separator is sandwiched between the positive electrode and the negative electrode. (A winding process shown in FIG. 13).
- a group of electrode pairs composed of the joined positive electrode, negative electrode, and separator is assembled and welded (welding / assembling process shown in FIG. 13).
- the battery can is completely sealed (the sealing step shown in FIG. 13). Thereby, a battery cell is created.
- the cells of the lithium ion secondary battery created in the cell assembly process are repeatedly charged and discharged (charge / discharge process shown in FIG. 13).
- the cell inspection process regarding the performance and reliability of a battery cell is performed (cell inspection process shown in FIG. 13).
- the unit cell inspection step for example, the capacity or voltage of the battery cell is inspected, or the current or voltage at the time of charging or discharging is inspected.
- the battery cell of a lithium ion secondary battery ie, a single battery, is completed.
- module assembly process a plurality of battery cells are combined in series to form a battery module, and a charge / discharge control controller is connected to form a battery system (module assembly process shown in FIG. 13).
- the battery module assembled in the module assembly process is inspected for performance and reliability (module inspection process shown in FIG. 13).
- module inspection process for example, the capacity or voltage of the battery module is inspected, or the current or voltage during charging or discharging is inspected.
- the insulating material layer is applied on the electrode material layer, and then the drying process is performed.
- An electrode plate in which a layer and an insulating layer as a separator are integrated can be formed.
- the step of preparing the processed separator can be omitted in the step of winding the separator in the battery cell assembly step. Thereby, the throughput of the manufacturing process of a lithium ion secondary battery can be improved.
- FIG. 14 is a schematic view showing a lithium ion secondary battery manufacturing apparatus in a fourth comparative example.
- FIG. 14 shows the configuration of a single-side coated electrode plate manufacturing apparatus in the fourth comparative example.
- An example of a manufacturing process in which the electrode material ES and the insulating material IF2 are applied to one surface of the current collector foil EP that is a carrier material will be described.
- coating is performed on one side of the electrode sheet.
- the electrode material ES supplied from the coater DC1 that opposes the roller RL2 is applied to one surface of the current collector foil EP fed from the current collector foil feed roll RL0.
- the insulating material IF2 supplied from the coater DC2 at a position facing the roller RL3 is applied onto the applied electrode material ES.
- the electrode material ES and the insulating material IF2 are dried, wound on the winding roll RL4, and the positive electrode sheet is manufactured.
- the first coating film made of the electrode material ES is dried to form an electrode layer
- the second coating film made of the insulating material IF2 is dried to form an insulating layer, that is, a separator.
- both coating films can be simultaneously dried and fixed through the heating / drying process in the drying chamber DRY.
- the example is more efficient in the manufacturing process than the third comparative example.
- the mixed layer MIX is a layer generated due to the coating pressure of the slit die coater described with reference to FIG. As shown by a square plot in FIG. 11, the film thickness of the mixed layer MIX (see FIG. 10) generated in the fourth comparative example varies depending on the conveying speed of the current collector foil.
- the slower the current collecting foil transport speed the longer the time during which the pressure applied by the coater is applied to the coating film at a specific location, and the thickness of the mixed layer MIX also increases. Even if the conveying speed of the current collector foil is set to a relatively high speed of 100 m / min, the thickness of the mixed layer MIX is 10 ⁇ m or more.
- the insulating layer SEL having an insulating function becomes thinner than originally intended, and when the insulating layer SEL is thinned, the insulating layer There is a problem that the electrode material constituting the mixed layer MIX may be exposed at the top of the SEL.
- the internal short circuit is prevented by eliminating the gap between the electrode layer and the separator (insulating layer), and the productivity of the lithium ion secondary battery is improved.
- the manufacturing apparatus of the lithium ion secondary battery in this configuration, it is difficult to reduce the thickness of the insulating layer due to the problem of the mixed layer. That is, the fourth comparative example has a problem that it is difficult to increase the capacity and size of the lithium ion secondary battery.
- the method of manufacturing the lithium ion secondary battery according to the present embodiment after coating the first coating film of the first layer that becomes the electrode layer, An insulating material IF1 including a solidifying material is applied as the second coating film of the second layer that becomes the insulating layer. Thereby, the surface layer of the first coating film is solidified.
- the insulating material IF1 when the insulating material IF1 is applied, the electrode layer ES and the insulating material IF1 are mixed by solidifying the surface layer of the first coating film, and the mixed layer MIX (see FIG. 10) has a large thickness. Can be prevented.
- the first coating film and the second coating film are supplied by supplying the first coating film and the second coating film with the spray liquid LIQ that is a solidifying material in the solidification chamber SD. Allow the membrane to solidify completely.
- the electrode material ES and the insulating material IF1 are mixed due to the flow of the binder inside each of the electrode material ES and the insulating material IF1, and the mixed layer MIX (FIG. 10) is mixed. Can be prevented from being formed with a large thickness.
- the thickness L3 of the mixed layer MIX shown in FIG. 10 can be reduced as compared with the fourth comparative example. Specifically, the thickness of the mixed layer MIX can be less than 5 ⁇ m. On the other hand, in the fourth comparative example, the thickness L3 of the mixed layer MIX is 10 ⁇ m or more even at a practical speed of transporting the current collector foil. Therefore, when the thickness L2 of the insulating layer SEL is reduced, The possibility of occurrence of a short circuit between the negative electrodes is increased.
- the risk of a short circuit can be prevented even if the separator, which is an insulating layer, is thinned, so that the reliability of the lithium ion secondary battery can be improved. Moreover, since the separator which is an insulating layer can be thinned while preventing a short circuit, the lithium ion secondary battery can be miniaturized. Therefore, the performance of the lithium ion secondary battery can be improved.
- each coating film is completely solidified by supplying the spray liquid LIQ before the drying process, the drying process is performed at a high speed. Even if it exists, the movement of the electrode material in a 1st coating film and the insulating material in a 2nd coating film can be suppressed. That is, when the solidification process using the solidification chamber SD is not performed, the components such as the binder in each film move during the drying process because the inside of the first coating film and the second coating film are liquid during drying. Thus, convection or diffusion occurs in each membrane. For this reason, variations occur in the distribution of the electrode material ES after drying, and the mixed layer MIX (see FIG. 10) may be formed with a large thickness.
- each coating film is completely solidified in the solidification chamber SD before the drying step, it is possible to prevent the electrode material ES from moving during the drying step in the drying chamber DRY. It is possible to increase the evaporation rate of solvents and the like. Therefore, the drying time can be shortened, and the drying equipment can be downsized. Thereby, the throughput in the manufacturing process of the lithium ion secondary battery can be improved. Further, the manufacturing cost of the lithium ion secondary battery can be reduced by shortening the drying time or downsizing the drying equipment.
- the above effect is not only obtained with the positive electrode plate made of the positive electrode material, but the same effect can be obtained with the negative electrode plate.
- the manufacturing apparatus and the manufacturing method described in this embodiment are merely examples for implementing this embodiment, and various forms can be used without departing from the technical idea or main features thereof. Even in the embodiment, the above effect can be obtained.
- a lithium ion secondary battery has been described as an example, but the effect of this embodiment is not limited to a lithium ion secondary battery.
- the positive electrode, the negative electrode, and the positive electrode and the negative electrode are electrically connected. It can be widely applied to an electricity storage device including a separator that is separated into two. Examples of the power storage device include other types of batteries or capacitors.
- the present invention is effective when applied to a manufacturing technology of a lithium ion secondary battery in which an electrode plate is formed by applying an insulating layer on an electrode layer.
- Electrode Material Pool 8 Lip Part 9 Downstream Meniscus (Liquid Bend) AF Al foil CF Cu foil DC1 Die coater, coater (first coating part) DC2 die coater, coater (second coating part) DRY Drying chamber EL Electrode layer ELQ Electrolytic solution EP Current collecting foil ES Electrode material IF Insulating material IF1 Insulating material LIQ Spray liquid MIX Mixed layer NA Active material NE Negative electrode NZ1 Spray nozzle NZ2 Spray nozzle PA Active material PE Positive electrode RL0 Current collecting foil feed roll RL1 Current collecting metal foil roll RL2 Roller RL3 Roller RL4 Winding roll SD Solidification chamber SD1 Solidification chamber SD2 Solidification chamber SEL Insulating layer SP Separator SPR Spray nozzle
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Abstract
Description
3 マニホールド
4 スリット
5 電極材料溜まり
8 リップ部
9 下流側メニスカス(液面の屈曲)
AF Al箔
CF Cu箔
DC1 ダイコータ、コータ(第1の塗工部)
DC2 ダイコータ、コータ(第2の塗工部)
DRY 乾燥室
EL 電極層
ELQ 電解液
EP 集電箔
ES 電極材料
IF 絶縁材料
IF1 絶縁材料
LIQ 噴霧液
MIX 混合層
NA 活物質
NE 負極
NZ1 噴霧ノズル
NZ2 噴霧ノズル
PA 活物質
PE 正極
RL0 集電箔送り出しロール
RL1 集電用金属箔ロール
RL2 ローラ
RL3 ローラ
RL4 巻き取りロール
SD 固化室
SD1 固化室
SD2 固化室
SEL 絶縁層
SP セパレータ
SPR 噴霧ノズル
Claims (20)
- (a1)集電箔の表面上に、第1の塗工部を用いて電極材スラリを塗布する工程、
(b1)前記電極材スラリに含まれるバインダ成分を析出させる成分を含む第1固化液を、前記電極材スラリに供給することで、前記電極材スラリの表面層を固化させる工程、
(c1)前記(b1)工程の後、前記電極材スラリ上に、第2の塗工部を用いて絶縁材スラリを塗布する工程、
(d1)前記電極材スラリおよび前記絶縁材スラリを乾燥させる工程、
を有する、リチウムイオン二次電池の製造方法。 - 請求項1記載のリチウムイオン二次電池の製造方法において、
(c2)前記(c1)工程の後であって、前記(d1)工程の前に、前記電極材スラリおよび前記絶縁材スラリに対し、前記電極材スラリおよび前記絶縁材スラリのそれぞれに含まれるバインダ成分を析出させる成分を含む第2固化液を供給することで、前記電極材スラリおよび前記絶縁材スラリを固化させる工程をさらに有する、リチウムイオン二次電池の製造方法。 - 請求項1記載のリチウムイオン二次電池の製造方法において、
前記電極材スラリに含まれる溶剤は、非プロトン性極性溶剤であり、
前記第1固化液に用いる溶剤は、水もしくはアルコール類またはこれらの混合液である、リチウムイオン二次電池の製造方法。 - 請求項1記載のリチウムイオン二次電池の製造方法において、
前記電極材スラリに含まれる溶剤は、N-メチルピロリドン、ジメチルスルホキシド、プロピレンカーボネート、ジメチルホルムアミド、もしくはγ-ブチロラクトン、またはこれらの混合液であり、
前記第1固化液に用いる溶剤は、水、エタノール、もしくはイソプロピルアルコールまたはこれらの混合液である、リチウムイオン二次電池の製造方法。 - 請求項1記載のリチウムイオン二次電池の製造方法において、
前記(b1)工程で供給される前記第1固化液のアルコール濃度は、20~80%である、リチウムイオン二次電池の製造方法。 - 集電箔の表面に電極材スラリを塗布する第1の塗工部と、
前記電極材スラリに含まれるバインダ成分を析出させる成分を含む第1固化液を、前記電極材スラリに供給することで、前記電極材スラリの表面層を固化させる第1固化室と、
前記表面層が固化された前記電極材スラリ上に、絶縁材スラリを塗布する第2の塗工部と、
前記電極材スラリおよび前記絶縁材スラリを乾燥させる乾燥室と、
前記集電箔を、前記第1の塗工部、前記第1固化室、前記第2の塗工部および前記乾燥室の順に搬送する搬送部と、
を有する、リチウムイオン二次電池の製造装置。 - 請求項6記載のリチウムイオン二次電池の製造装置において、
前記電極材スラリおよび前記絶縁材スラリに対し、前記電極材スラリおよび前記絶縁材スラリに含まれるバインダ成分を析出させる成分を含む第2固化液を供給することで、前記電極材スラリおよび前記絶縁材スラリを固化させる第2固化室をさらに有し、
前記搬送部は、前記集電箔を、前記第1の塗工部、前記第1固化室、前記第2の塗工部、前記第2固化室および前記乾燥室の順に搬送する、リチウムイオン二次電池の製造装置。 - 請求項6記載のリチウムイオン二次電池の製造装置において、
前記電極材スラリに含まれる溶剤は、非プロトン性極性溶剤であり、
前記第1固化液に用いる溶剤は、水もしくはアルコール類またはこれらの混合液である、リチウムイオン二次電池の製造装置。 - 請求項6記載のリチウムイオン二次電池の製造装置において、
前記電極材スラリに含まれる溶剤は、N-メチルピロリドン、ジメチルスルホキシド、プロピレンカーボネート、ジメチルホルムアミド、もしくはγ-ブチロラクトン、またはこれらの混合液であり、
前記第1固化液に用いる溶剤は、水、エタノール、もしくはイソプロピルアルコールまたはこれらの混合液である、リチウムイオン二次電池の製造装置。 - 請求項6記載のリチウムイオン二次電池の製造装置において、
前記第1固化室に備えられた、前記第1固化液を供給する噴霧ノズルは、内部混合型の二流体ノズルであり、
前記噴霧ノズルによる噴霧領域は、均等流量分布を有し、前記噴霧ノズルの中心の流量の50%流量となる位置は、前記集電箔の搬送方向に直交する方向において、前記電極材スラリの端部より外に位置し、
前記噴霧ノズルから供給される前記第1固化液の噴霧粒子径は、10μm以下であり、
前記第1固化液の噴霧打力は、1g/cm2以下である、リチウムイオン二次電池の製造装置。 - 請求項8記載のリチウムイオン二次電池の製造装置を用いて形成された、リチウムイオン二次電池。
- 請求項11記載のリチウムイオン二次電池において、
前記集電箔上の前記電極材スラリを乾燥させて形成した電極層と、
前記電極材スラリ上の前記絶縁材スラリを乾燥させて形成した絶縁層と、
前記電極層と前記絶縁層との界面近傍に形成された、前記電極層と前記絶縁層との混合層と、
を有し、
前記混合層の厚さは、前記絶縁層の厚さの20%以下である、リチウムイオン二次電池。 - 請求項11記載のリチウムイオン二次電池において、
前記集電箔と、
前記集電箔上の前記電極材スラリを乾燥させて形成した電極層と、
前記電極材スラリ上の前記絶縁材スラリを乾燥させて形成した絶縁層と、
を有する電極板を、複数重ねた構造を有する、リチウムイオン二次電池。 - (a)集電箔の表面上に、第1の塗工部を用いて結着材を含む電極材スラリを塗布する工程、
(b)前記電極材スラリ上に、第2の塗工部を用いて、前記結着材を析出させる第1成分を含む絶縁材スラリを塗布する工程、
(c)前記(b)工程の後、前記結着材を析出させる第2成分を含む固化液を、前記電極材スラリに供給することで、前記電極材スラリを固化させる工程、
(d)前記(c)工程の後、前記電極材スラリおよび前記絶縁材スラリを乾燥させる工程、
を有する、リチウムイオン二次電池の製造方法。 - 請求項14記載のリチウムイオン二次電池の製造方法において、
前記第1成分および前記第2成分は、水またはアルコールを含有する、リチウムイオン二次電池の製造方法。 - 請求項15記載のリチウムイオン二次電池の製造方法において、
前記アルコールがメタノール、エタノール、プロパノール、ブタノール、ヘキサノール、ヘプタノールまたはオクタノールを含有する、リチウムイオン二次電池の製造方法。 - 請求項14記載のリチウムイオン二次電池の製造方法において、
前記(d)工程では、前記電極材スラリを乾燥させて電極層を形成し、前記電極材スラリ上の前記絶縁材スラリを乾燥させて絶縁層を形成し、
(e)前記集電箔、前記電極層および前記絶縁層を有する電極板を、複数重ねる工程をさらに有する、リチウムイオン二次電池の製造方法。 - 集電箔の表面に、結着材を含む電極材スラリを塗布する第1の塗工部と、
前記電極材スラリ上に、前記結着材を析出させる第1成分を含む絶縁材スラリを塗布する第2の塗工部と、
前記結着材を析出させる第2成分を含む固化液を、前記電極材スラリに供給することで、前記電極材スラリを固化させる固化部と、
前記電極材スラリおよび前記絶縁材スラリを乾燥させる乾燥室と、
前記集電箔を、前記第1の塗工部、前記第2の塗工部、前記固化部および前記乾燥室の順に搬送する搬送部と、
を有する、リチウムイオン二次電池の製造装置。 - 請求項18記載のリチウムイオン二次電池の製造装置において、
前記第1成分および前記第2成分は、水またはアルコールを含有する、リチウムイオン二次電池の製造装置。 - 請求項18記載のリチウムイオン二次電池の製造装置において、
前記アルコールがメタノール、エタノール、プロパノール、ブタノール、ヘキサノール、ヘプタノールまたはオクタノールを含有する、リチウムイオン二次電池の製造装置。
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US11223038B2 (en) * | 2017-07-03 | 2022-01-11 | Vehicle Energy Japan Inc. | Method for manufacturing secondary battery |
JP6988911B2 (ja) * | 2017-11-24 | 2022-01-05 | 日本電気株式会社 | 二次電池用電極の製造方法および二次電池の製造方法 |
JP2022041420A (ja) * | 2020-09-01 | 2022-03-11 | エムテックスマート株式会社 | 塗布方法、燃料電池の製造方法または燃料電池、2次電池の製造方法または2次電池、全固体電池の製造方法または全固体電池 |
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CN113013558B (zh) * | 2020-12-25 | 2023-04-25 | 连云港普利特电子科技有限公司 | 一种双极电池极耳及其生产方法 |
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