WO2021245745A1 - 電池及びその製造方法 - Google Patents

電池及びその製造方法 Download PDF

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Publication number
WO2021245745A1
WO2021245745A1 PCT/JP2020/021599 JP2020021599W WO2021245745A1 WO 2021245745 A1 WO2021245745 A1 WO 2021245745A1 JP 2020021599 W JP2020021599 W JP 2020021599W WO 2021245745 A1 WO2021245745 A1 WO 2021245745A1
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Prior art keywords
thin film
negative electrode
battery
conductive thin
separator
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English (en)
French (fr)
Japanese (ja)
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浩 井本
健 緒方
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Terawatt Technology KK
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Terawatt Technology KK
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Priority to JP2022529145A priority Critical patent/JP7359491B2/ja
Priority to PCT/JP2020/021599 priority patent/WO2021245745A1/ja
Publication of WO2021245745A1 publication Critical patent/WO2021245745A1/ja
Priority to US18/071,312 priority patent/US20230100360A1/en
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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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • 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 battery and a method for manufacturing the same.
  • a secondary battery that charges and discharges by moving metal ions between a positive electrode and a negative electrode is known to exhibit high voltage and high energy density, and is typically a lithium ion secondary battery. It has been known.
  • an active material capable of holding lithium is introduced into the positive electrode and the negative electrode, and charging / discharging is performed by exchanging lithium ions between the positive electrode active material and the negative electrode active material.
  • a lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode has been developed.
  • Patent Document 1 describes a high energy density, high power lithium metal anode having a volumetric energy density of greater than 1000 Wh / L and / or a mass energy density of greater than 350 Wh / kg when discharged at room temperature at a rate of at least 1 C. Secondary batteries are disclosed. Patent Document 1 discloses the use of an ultrathin lithium metal anode in order to realize such a lithium metal anode secondary battery.
  • Patent Document 2 in a lithium secondary battery including a positive electrode, a negative electrode, a separation film interposed between them, and an electrolyte, in the negative electrode, metal particles are formed on a negative electrode current collector, and the negative electrode is charged.
  • a lithium secondary battery that is moved from the positive electrode and forms a lithium metal on the negative electrode current collector in the negative electrode is disclosed.
  • Patent Document 2 provides a lithium secondary battery in which such a lithium secondary battery solves a problem caused by the reactivity of a lithium metal and a problem generated in the assembly process, and has improved performance and life. Discloses what can be done.
  • a typical secondary battery that charges and discharges by exchanging metal ions between a positive electrode active material and a negative electrode active material does not have sufficient energy density.
  • a lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode as described in the above patent document dendrites are likely to be formed on the surface of the negative electrode by repeating charging and discharging. Inactivated lithium, to which the potential from the negative electrode is not applied, is deposited, and the capacity is likely to decrease. As a result, the cycle characteristics are not sufficient.
  • a method of applying a large physical pressure to the battery to keep the interface between the negative electrode and the separator at a high pressure has been developed in order to suppress discrete growth at the time of lithium metal precipitation.
  • the application of such a high voltage requires a large mechanical mechanism, the weight and volume of the battery as a whole become large, and the energy density decreases.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a battery having excellent energy density and cycle characteristics at the initial stage of a cycle.
  • the battery according to an embodiment of the present invention is arranged between a positive electrode, a negative electrode having no negative electrode active material, a separator arranged between the positive electrode and the negative electrode, and between the separator and the negative electrode.
  • a conductive thin film is provided, and the film thickness of the conductive thin film is 1 ⁇ m or less.
  • the precipitated metal layer can be uniformly formed and dissolved. Become. Therefore, the formation of dendrites on the surface of the negative electrode is suppressed, which contributes to the improvement of cycle characteristics. Further, in the present invention, when the film thickness of the conductive thin film is 1 ⁇ m or less, the increase in the volume of the battery due to the presence of the conductive thin film is suppressed, and the energy density is not lowered.
  • the conductive thin film is formed on the separator.
  • the precipitated metal layer deposited on the surface of the negative electrode is formed in the region between the conductive thin film and the negative electrode. Therefore, the potential can be made uniform from both sides of the precipitated metal layer through the negative electrode and the conductive thin film, and the formation of dendrites is suppressed.
  • the conductive thin film is a thin film made of carbon, a thin film made of a metal or an alloy, or a laminated film thereof.
  • the metal constituting the precipitated metal layer is suppressed from being irreversibly incorporated into the conductive thin film, and the energy density is not lowered.
  • the film thickness is 1 ⁇ m or less, a uniform film thickness and a uniform conductive thin film can be formed, so that a conductive thin film effective for suppressing dendrite can be formed.
  • an electrolytic solution for immersing the separator and the conductive thin film. Since this electrolytic solution acts as a conductive path for metal ions serving as charge carriers, the internal resistance of the battery is reduced, which contributes to the improvement of energy density and cycle characteristics.
  • the battery is preferably a lithium secondary battery in which lithium metal is deposited on the surface of the negative electrode and the deposited lithium is dissolved to charge and discharge the battery.
  • the present invention exerts an effect of improving the energy density and cycle characteristics at the initial stage of a cycle, particularly in such a lithium secondary battery.
  • the method for manufacturing a battery according to an embodiment of the present invention includes a step of forming a conductive thin film of 1 ⁇ m or less on a separator, and the negative electrode, the separator, and the positive electrode so that the conductive thin film faces the negative electrode. It comprises a step of forming a laminated body by stacking them.
  • a conductive thin film having a uniform film thickness of 1 ⁇ m or less on the separator by forming a conductive thin film having a uniform film thickness of 1 ⁇ m or less on the separator, the formation of dendrites on the surface of the negative electrode is suppressed, and a battery contributing to the improvement of cycle characteristics is manufactured. can.
  • the film thickness of the conductive thin film is 1 ⁇ m or less, the volume of the battery is hardly increased, so that the energy density is not lowered. As a result, a battery having excellent energy density and cycle characteristics at the initial stage of the cycle can be manufactured.
  • a thin film made of carbon, a thin film made of metal or an alloy, or a laminated film thereof is formed.
  • the metal constituting the precipitated metal layer is suppressed from being irreversibly incorporated into the conductive thin film, and the energy density is not lowered.
  • the step of forming the laminated body there may be further a step of injecting an electrolytic solution into the laminated body. Since this electrolytic solution acts as a conductive path for metal ions serving as charge carriers, the internal resistance of the battery is reduced, and a battery having excellent energy density and cycle characteristics is manufactured.
  • the present embodiments will be described in detail with reference to the drawings as necessary.
  • the same elements are designated by the same reference numerals, and duplicate description will be omitted.
  • the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified.
  • the dimensional ratios in the drawings are not limited to the ratios shown.
  • FIG. 1 is a schematic diagram of a battery according to this embodiment.
  • the battery 1 according to the present embodiment includes a positive electrode 10, a negative electrode 30 having no negative electrode active material, a separator 20 arranged between the positive electrode 10 and the negative electrode 30, and a separator 20 and a negative electrode.
  • a conductive thin film 41 arranged between and 30 is provided.
  • the positive electrode 10 has a positive electrode current collector 11 and a positive electrode active material layer 12 formed on the positive electrode current collector 11.
  • the positive electrode current collector 11 is not particularly limited as long as it is a conductor that does not react with metal ions that are charge carriers in the battery.
  • the metal serving as a charge carrier is lithium, for example, aluminum is used as the positive electrode current collector.
  • the positive electrode active material layer 12 is a substance for holding metal ions on the positive electrode, and serves as a host material for metal ions.
  • the positive electrode active material layer 12 is provided from the viewpoint of increasing the stability and output voltage of the battery 1.
  • the positive electrode active material layer 12 contains a positive electrode active material, and the material of the positive electrode active material is not particularly limited, and examples thereof include metal oxides and metal phosphates.
  • the metal oxide is not particularly limited, and examples thereof include a cobalt oxide-based compound, a manganese oxide-based compound, and a nickel oxide-based compound.
  • the metal phosphate is not particularly limited, and examples thereof include iron phosphate compounds and cobalt phosphate compounds.
  • the positive electrode active material is referred to as, for example, lithium nickel cobalt aluminum oxide (NCA, LiNiCoAlO 2 ) or lithium nickel cobalt magnesium oxide (LiNiCoMnO 2, NCM).
  • NCM622, NCM523, NCM811, etc. lithium cobaltate (LCO, LiCoO 2 ), lithium iron phosphate (LFP, LiFePO 4 ), and the like.
  • LCO lithium cobaltate
  • LFP lithium iron phosphate
  • LiFePO 4 lithium iron phosphate
  • the positive electrode active material as described above one type may be used alone or two or more types may be used in combination.
  • the positive electrode active material layer 12 may contain a binder.
  • a binder for example, a fluorine-based binder, an aqueous-based binder, and an imide-based binder are used.
  • a binder include polyvinylidene fluoride (PvDF), a mixture of styrene-butadiene rubber and carboxymethyl cellulose (SBR-CMC), polyacrylic acid (PAA), lithium polyacrylate (Li-PAA), and polyimide. (PI), polyamide-imide (PAI), aramid and the like are used.
  • the positive electrode active material layer 12 may contain a conductive auxiliary agent.
  • the conductive auxiliary agent include carbon black, carbon nanofiber (VGCF), single-walled carbon nanotube (SWCNT), and multi-walled carbon nanotube (MWCNT).
  • the weight per unit area of the positive electrode active material layer 12 is, for example, 10-40 mg / cm 2 .
  • the thickness of the positive electrode active material layer 12 is, for example, 30 to 150 ⁇ m.
  • the density of the positive electrode active material layer 12 is, for example, 2.5 to 4.5 g / ml.
  • the area capacity of the positive electrode active material layer 12 is, for example, 1.0 to 10.0 mAh / cm 2 .
  • the negative electrode 30 does not have a negative electrode active material and is composed of a negative electrode current collector. It is difficult to increase the energy density of a battery having a negative electrode having a negative electrode active material due to the presence of the negative electrode active material. On the other hand, since the battery 1 of the present embodiment includes the negative electrode 30 having no negative electrode active material, such a problem does not occur. That is, the battery 1 of the present embodiment has a high energy density because the metal is deposited on the surface of the negative electrode 30 and the deposited metal is dissolved to perform charging and discharging.
  • the "negative electrode active material” means a substance for holding a metal corresponding to a metal ion as a charge carrier (hereinafter referred to as "carrier metal”) in the negative electrode in a battery, and is paraphrased as a host material of the carrier metal. You may.
  • the mechanism of such holding is not particularly limited, and examples thereof include intercalation, alloying, and occlusion of metal clusters.
  • the capacity of the layer of the "negative electrode active material” is usually set to be the same as the capacity of the positive electrode.
  • the negative electrode active material is not particularly limited as long as it has the above-mentioned holding mechanism, and examples thereof include carbon-based substances, metal oxides, and metals or alloys.
  • the carbon-based substance is not particularly limited, and examples thereof include graphene, graphite, hard carbon, mesoporous carbon, carbon nanotubes, and carbon nanohorns.
  • the metal oxide is not particularly limited, and examples thereof include titanium oxide-based compounds, tin oxide-based compounds, and cobalt oxide-based compounds.
  • the metal or alloy is not particularly limited as long as it can be alloyed with the carrier metal, and examples thereof include silicon, germanium, tin, lead, aluminum, gallium, and alloys containing these.
  • the negative electrode 30 is not particularly limited as long as it does not have a negative electrode active material and can be used as a current collector, but for example, Cu, Ni, Ti, Fe, and other metals that do not react with Li, and , These alloys, as well as those consisting of at least one selected from the group consisting of stainless steel (SUS).
  • SUS stainless steel
  • various conventionally known types of SUS can be used.
  • the negative electrode material as described above one type may be used alone or two or more types may be used in combination.
  • the “metal that does not react with Li” means a metal that does not react with lithium ions or lithium metal to alloy under the operating conditions of the battery 1.
  • the negative electrode 30 is preferably a lithium-free electrode. According to such an aspect, since it is not necessary to use a highly flammable lithium metal in the production, the battery 1 is further excellent in safety and productivity. From the same viewpoint and from the viewpoint of improving the stability of the negative electrode 30, the negative electrode 30 is more preferably selected from the group consisting of Cu, Ni, and alloys thereof, and stainless steel (SUS). It consists of one kind. From the same viewpoint, the negative electrode 30 is more preferably made of Cu, Ni, or an alloy made of these, and particularly preferably made of Cu or Ni.
  • the separator 20 is a member that separates the positive electrode 10 and the negative electrode 30 to prevent a short circuit, and secures the ionic conductivity of metal ions serving as charge carriers between the positive electrode 10 and the negative electrode 30, and is a member that does not react with metal ions. Consists of. Further, when an electrolytic solution is used, the separator 20 also plays a role of holding the electrolytic solution.
  • the separator base material 21 constituting the separator 20 is not limited as long as it plays the above role, but is composed of a porous material, for example, porous polyethylene (PE), polypropylene (PP), or a laminated structure thereof. ..
  • the separator 20 preferably has a separator base material 21 and a separator coating layer 22 that covers the surface of the separator base material 21.
  • the separator coating layer 22 covers both sides of the separator base material 21, but may cover only one side.
  • the separator coating layer 22 is a layer in which the separator base material 21 is vertically adjacent to each other (in FIG. 1, the conductive thin film 41 and the positive electrode active material layer 12) while ensuring ionic conductivity without reacting with metal ions serving as charge carriers. ) Is firmly adhered.
  • inorganic particles such as silica, alumina, titania, zirconia, magnesium oxide, and magnesium hydroxide may be added to the binder.
  • the conductive thin film 41 is provided to apply a potential to the precipitated metal layer on the surface of the negative electrode to suppress the formation of dendrites.
  • the conductive thin film 41 is interposed between the negative electrode 30 and the separator 20. In this embodiment, the conductive thin film 41 is formed on the separator 20.
  • the conductive thin film 41 is preferably composed of a thin film made of metal or an alloy, a thin film made of carbon, or a laminated film thereof.
  • the metals and alloying elements that form the conductive thin film are not limited. When an element that forms an alloy with lithium is used, a metal or alloy that does not form an alloy with lithium is once formed on the separator side, or a thin film that forms a base with the above-mentioned carbon thin film is formed on the separator side, and a metal that forms an alloy with lithium is formed on the thin film. Alternatively, it is preferable to form a thin film with an alloy. Examples of metals and alloys that do not form an alloy with lithium include Cu, Ni, Fe, Mn, Ti, Cr, and stainless steel. Examples of the metal and alloy forming an alloy with lithium include Si, Sn, Al, In, Zn, Ag, Bi, Pb, Sb, and alloys containing these elements.
  • Thin film made of carbon a characteristic that consist Sp 3 carbon atoms, diamond-like carbon
  • DLC diamond-like carbon
  • the thin film made of carbon may be laminated on the separator with the thin film made of metal or alloy, and may be further patterned in-plane.
  • the total film thickness of the conductive thin film is preferably 1 ⁇ m or less.
  • the total thickness of the conductive thin film is, for example, 0.9 ⁇ m, 0.8 ⁇ m, 0.7 ⁇ m, 0.6 ⁇ m, 0.5 ⁇ m, 0.4 ⁇ m, 0.3 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m (100 nm).
  • the film thickness is set to 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm, 5 nm, or between these.
  • the method for forming the thin film is not limited for the conductive thin film 41, but a CVD method, a PVD method, a vacuum vapor deposition method, sputtering, electrolytic plating, electrolytic plating, or the like is used.
  • This is not a preferable method because a part of the coating film is irreversibly incorporated into such a coating film and it is difficult to uniformly form the coating film on the separator surface with a thickness of 1 ⁇ m or less.
  • the carbonaceous particles and the coating film made of the binder component are clearly distinguished in that the conductive thin film 41 is made of only carbon without containing such a binder component.
  • a thin film made of carbon can achieve a low resistance and a uniform film thickness while reducing the film thickness as compared with a coating film (carbon coat layer) in which carbonaceous particles are dispersed in a binder component.
  • the battery 1 may have an electrolytic solution.
  • the electrolytic solution is immersed in the separator 20 and the conductive thin film 41.
  • This electrolytic solution is a solution having ionic conductivity made by dissolving an electrolyte in a solvent and acts as a conductive path for lithium ions. Therefore, by having the electrolytic solution, the internal resistance of the battery 1 can be reduced, and the energy density and the cycle characteristics can be improved.
  • a lithium salt is preferably used as the electrolyte.
  • the lithium salt is not particularly limited, but LiPF 6 , LiBF 4 , lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), LiClO 4 , lithium bisoxalate boronate (LiBOB). ), Lithium bis (pentafluoroethanesulfonyl) imide (LiBETI).
  • LiFSI is preferable as the lithium salt from the viewpoint of further improving the cycle characteristics of the battery 1.
  • the above lithium salts may be used alone or in combination of two or more.
  • the solvent is not particularly limited, but is, for example, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), diethyl carbonate (DEC), ⁇ -butyrolactone (GBL). ), 1,3-Dioxolane (DOL), and fluoroethylene carbonate (FEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DME 1,2-dimethoxyethane
  • DEC diethyl carbonate
  • GBL ⁇ -butyrolactone
  • DOL 1,3-Dioxolane
  • FEC fluoroethylene carbonate
  • “suppressing the formation of dendrite on the surface of the negative electrode” means that the precipitate of the carrier metal formed on the surface of the negative electrode by charging / discharging or repeating the battery becomes dendrite-like. Means to suppress. In other words, it means that the precipitate of the carrier metal formed on the surface of the negative electrode by charging / discharging or repeating the charging / discharging of the battery is induced to grow in a non-dendrite state.
  • the “non-dendritic shape” is not particularly limited, but is typically a plate shape, a valley shape, or a hill shape.
  • FIG. 2 is a schematic view of the battery charge / discharge cycle according to the present embodiment at one time point.
  • lithium metal is deposited on the negative electrode 30 to form a precipitated metal layer 50 during charging, and the precipitated metal layer 50 is dissolved from above the negative electrode 30 during discharging.
  • the precipitated metal layer 50 is formed between the negative electrode 30 and the separator 41.
  • the uniform precipitation and efficiency of the precipitated metal layer 50 can be applied. Dissolution is possible. Therefore, in the present embodiment, the growth of the precipitated metal layer 50 in the form of dendrites can be suppressed, and the remaining inactive precipitated metal layer 50 that is not dissolved can be suppressed, thus improving the cycle characteristics. Can be made to. Further, in the present embodiment, since the film thickness of the conductive thin film 41 is 1 ⁇ m or less, the increase in the volume of the battery due to the presence of the conductive thin film 41 is suppressed, and the energy density is not lowered. Further, the metal constituting the precipitated metal layer is suppressed from being irreversibly incorporated into the conductive thin film 41, and the energy density is not lowered.
  • the positive electrode 10 is manufactured, for example, as follows.
  • the above-mentioned positive electrode active material, binder, and, if necessary, a conductive auxiliary agent are mixed to obtain a positive electrode mixture.
  • the blending ratio of the binder and the positive electrode active material is, for example, 20:80 to 1:99.
  • the positive electrode mixture contains a conductive auxiliary agent, the content thereof is, for example, 0.1 to 5% by mass based on the weight of the entire mixture.
  • the obtained positive electrode mixture is applied to one side of a positive electrode current collector 11 made of, for example, a metal foil (for example, Al foil) of 5 ⁇ m or more and 1 mm or less, and press-molded to form a positive electrode active material layer 12.
  • the obtained molded body is punched to a predetermined size by punching to obtain a positive electrode 10 (FIG. 3).
  • a metal foil of 1 ⁇ m or more and 1 mm or less (for example, an electrolytic Cu foil) is washed with a solvent containing sulfamic acid, punched into a predetermined size, ultrasonically washed with ethanol, and then dried. To obtain a negative electrode 30.
  • a separator 20 having a conductive thin film 41 is formed before stacking with the positive electrode 10 and the negative electrode 30.
  • the separator 20 is prepared.
  • the above-mentioned binder solution is applied to one surface of the separator base material 21, dried to form the separator coating layer 22 on one surface, and then the binder solution is further applied to the other surface of the separator base material 21. Then, it is dried to form a separator coating layer 22 on the other surface.
  • These coating layers may be formed at the same time.
  • a conductive thin film 41 having a diameter of 1 ⁇ m or less is formed on the separator 20.
  • a thin film made of metal or an alloy, a thin film made of carbon, or a laminated film thereof is formed.
  • the method for producing the thin film is not limited, but a CVD method, a PVD method, a vacuum vapor deposition method, sputtering, electroless plating, electrolytic plating and the like are used. By using these methods, a conductive thin film 41 having a uniform film thickness of 1 ⁇ m or less is formed on the separator 20.
  • the positive electrode 10, the separator 20, and the negative electrode 30 obtained as described above are laminated in this order so that the conductive thin film 41 faces the negative electrode 30.
  • metal terminals for example, Al, Ni, etc.
  • metal terminals for example, Al, Ni, etc.
  • a conventionally known method may be used, and for example, ultrasonic welding may be used.
  • a battery is manufactured by injecting an electrolytic solution into the exterior body and sealing the exterior body (FIG. 1).
  • a conductive thin film 41 having a uniform film thickness of 1 ⁇ m or less can be formed on the separator 20. Therefore, since a uniform potential can be applied to the precipitated metal layer 50, it is possible to suppress the growth of the precipitated metal layer 50 in the form of dendrite, and the inactive precipitated metal layer 50 that is not dissolved remains. Since it can be suppressed, the cycle characteristics can be improved. Further, in the present embodiment, the conductive thin film 41 having a film thickness of 1 ⁇ m or less can be easily formed, the increase in the volume of the battery due to the presence of the conductive thin film 41 is suppressed, and the energy density is not lowered.
  • the metal constituting the precipitated metal layer is suppressed from being irreversibly incorporated into the conductive thin film 41, and the energy density is not lowered. As a result, a battery having excellent energy density and cycle characteristics at the initial stage of the cycle can be manufactured.
  • the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
  • the present invention can be modified in various ways as long as it does not deviate from the gist thereof. ..
  • Example 1 (Positive electrode) NCM622 (LiNi 0.6 Co 0.2 Mn 0.2 O 2 ) as a positive electrode active material, PVdF as a binder, a conductive auxiliary agent, and N-methyl-pyrrolidone (NMP) as a solvent are mixed to prepare a slurry to prepare a positive electrode. It was applied, dried and pressed on the aluminum foil which is the current collector 11.
  • a lithium-ion battery grade separator having a laminated structure of polypropylene (PP) / polyethylene (PE) / polypropylene (PP) having a total thickness of about 12 ⁇ m is used as a base material, and a thin film made of carbon having a thickness of 20 nm is used on the surface thereof. (C) was formed by sputtering.
  • a copper foil was used as the negative electrode. Further, as the electrolytic solution, an electrolytic solution in which 4M LiFSI was dissolved in DME (dimethoxyethane) was used.
  • a cell made of an aluminum laminate consisting of one positive electrode, one separator, and one negative electrode was prepared, and the electrolytic solution was injected and then sealed and used for cycle evaluation.
  • As the separator a conductive thin film was laminated facing the negative electrode side to create a cell.
  • Example 1 a battery having a structure corresponding to the present embodiment was manufactured.
  • Example 2 to 8 batteries were manufactured in the same manner as in Example 1 except that the type of the negative electrode, the type and the film thickness of the conductive thin film on the separator (Sep) were different from those of Example 1. In Examples 2 to 8, sputtering was used to form the thin film. In Example 3, a copper foil having a metal bismuth layer having an average thickness of 100 nm formed on the surface was used as the negative electrode.
  • Comparative Example 1 In Comparative Example 1, a battery was manufactured in the same manner as in Example 1 except that a conductive thin film was not formed.
  • a flat cell was clipped from both sides with metal plates, and a charge / discharge cycle was performed.
  • a charge / discharge cycle test was carried out in an environment with a temperature of 25 ° C. by charging 4.2VCC with a current equivalent to a current of 0.1C and discharging 3.0VCC with a current equivalent to a current of 0.1C. .. Table 1 shows the capacity retention rate of the battery after 30 cycles.
  • Example 1-8 an excellent capacity retention rate as compared with Comparative Example 1 can be obtained, and specifically, a capacity retention rate of 80% or more for 30 cycles can be realized. Can be done. Further, in Examples 1-8, the film thickness of the conductive thin film is 100 nm, the volume of the battery is hardly increased due to the presence of the conductive thin film, and a high energy density can be realized.
  • the battery of the present invention Since the battery of the present invention has a high energy density and excellent cycle characteristics, it has industrial applicability as a power storage device used for various purposes.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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