WO2011070712A1 - Lithium-ion battery and method for producing same - Google Patents

Lithium-ion battery and method for producing same Download PDF

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Publication number
WO2011070712A1
WO2011070712A1 PCT/JP2010/006477 JP2010006477W WO2011070712A1 WO 2011070712 A1 WO2011070712 A1 WO 2011070712A1 JP 2010006477 W JP2010006477 W JP 2010006477W WO 2011070712 A1 WO2011070712 A1 WO 2011070712A1
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positive electrode
conductive layer
electrode
electrically conductive
negative electrode
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PCT/JP2010/006477
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French (fr)
Japanese (ja)
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利光 野口
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株式会社日立製作所
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Priority to KR1020127014775A priority Critical patent/KR101375422B1/en
Publication of WO2011070712A1 publication Critical patent/WO2011070712A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • 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
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • 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
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary 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
    • 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 lithium ion secondary battery and a manufacturing method thereof.
  • Lithium ion secondary batteries are used as power sources for portable information devices such as notebook personal computers and mobile phones, portable acoustic devices, radios, and electric tools because of their high energy density. Lithium ion secondary batteries also have the advantages of high capacity and high output. For this reason, in recent years, it has also been used as a power source for power storage systems such as an electric vehicle, a hybrid electric vehicle using both an internal combustion engine and an electric motor (hereinafter, both are referred to as an electric vehicle), and an uninterruptible power supply.
  • an electric vehicle a hybrid electric vehicle using both an internal combustion engine and an electric motor
  • Such a lithium ion secondary battery includes a positive electrode using a positive electrode active material capable of releasing and storing lithium ions by charging and discharging, and a negative electrode using a negative electrode active material capable of storing and releasing lithium ions by charging and discharging. These are superposed through separators and are infiltrated into the electrolytic solution. More specifically, materials such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ) are used for the positive electrode, and lithium ions such as carbon materials are stored and released for the negative electrode. Lithium ion secondary batteries using each possible material are widely used.
  • the positive electrode active material as described above does not have sufficient electronic conductivity. Therefore, in the positive electrode, in general, the positive electrode active material contains conductive powder that is low-cost and stable in the battery, such as graphite and carbon black, as a conductive auxiliary agent, and a binder is further added and mixed. The positive electrode mixture produced in this way is used. On the other hand, the carbon material used as the negative electrode active material is in a state where lithium ions are completely released during battery assembly, that is, in a discharged state. In the negative electrode, a negative electrode mixture prepared by adding a binder for ensuring adhesion to the negative electrode active material and mixing them is used.
  • the electrode internal structure of a lithium ion secondary battery is a wound type or a laminated type in order to increase capacity and output. That is, a positive electrode and a negative electrode in which an active material is applied to a metal foil serving as a current collector are wound or stacked with a separator interposed therebetween, and the wound body or the stacked body is stored in a metal cylindrical or rectangular battery outer container. is doing.
  • the electrolytic solution is subsequently injected, and the lid is attached and sealed.
  • an aluminum laminate container is also used for the battery outer container.
  • the lithium ion secondary battery assembled by such a method is given a function as a battery by the first charge after the assembly.
  • an internal short circuit may occur.
  • the mixed metal foreign matter dissolves on the positive electrode and diffuses as ions, and when it reaches the negative electrode, the metal re-deposits. As deposition progresses and the metal grows toward the positive electrode, it becomes an electrical conduction path, and eventually an internal short circuit occurs between the negative electrode and the positive electrode.
  • the internal short circuit occurs, the charged electricity is consumed, the usable capacity is reduced, or even if an attempt is made to charge the battery, a current flows through the internal short circuit part, and charging does not proceed.
  • Patent Document 1 In order to sort out batteries that are contaminated with metal foreign matter, in Patent Document 1, after charging, the battery is separated from the charging circuit and allowed to stand, and the change in the open circuit voltage of the battery is measured. The product is defective.
  • Patent Documents 2 and 3 describe a method in which a metallic foreign material is dissolved and diffused electrochemically and is not deposited on the negative electrode.
  • Patent Document 4 describes a method in which a substance that traps impurities including cations is contained in a battery and is not deposited as a metal.
  • Patent Document 1 has a problem that it takes time until it can be determined as a defective product in the configuration of the conventional positive electrode, negative electrode, and separator.
  • Patent Documents 2 to 4 also take time from dissolution to diffusion. When the mass of the metal foreign matter is large, the diffusion becomes insufficient, and metal ions may reach the negative electrode and precipitate.
  • an object of the present invention is to provide a lithium ion secondary battery capable of detecting an internal short circuit due to the mixing of a metal foreign substance with higher sensitivity earlier than before and a manufacturing method thereof.
  • a lithium ion secondary battery of the present invention includes a battery outer container, a positive electrode, a negative electrode, an electrical insulating layer provided between the positive electrode and the negative electrode, and an electrolyte.
  • an electrically conductive layer is provided in an electrically insulating layer between the positive electrode and the negative electrode.
  • the present invention it is possible to provide a lithium ion secondary battery capable of detecting an internal short circuit due to the mixing of metal foreign matters at an early stage with high sensitivity and a method for manufacturing the same.
  • FIG. 1 shows a schematic cross-sectional view of the vicinity of the electrode of the lithium ion secondary battery of this example.
  • the battery according to this example includes a positive electrode 16 having a positive electrode side current collector 6 and a positive electrode side mixture layer 5, a negative electrode 15 having a negative electrode side current collector 1 and a negative electrode side mixture layer 2, and a positive electrode 16. And an electric insulating layer 3 provided between the negative electrode 15 and an electric conductive layer 4 provided in the electric insulating layer 3.
  • the positive electrode 16 is composed of lithium manganate, which is one of lithium transition metal composite oxides, as an active material, carbon powder as a conductive additive, and polyvinylidene fluoride (hereinafter abbreviated as PVDF) as a binder.
  • the slurry dispersed and kneaded (hereinafter abbreviated as NMP) was applied to the positive electrode side current collector 6 made of Al to form a positive electrode side mixture layer 5, and dried to prepare.
  • the negative electrode 15 is a carbon powder that can occlude and release lithium ions as an active material, and a slurry obtained by dispersing and kneading PVDF in NMP as a binder is applied to the negative electrode side current collector 1 made of Cu to apply a negative electrode side mixture layer 2 and dried.
  • the electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows. Among those used as separators for lithium ion secondary batteries, a microporous polypropylene sheet and a polyethylene sheet each having a thickness of 18 ⁇ m were prepared. These become the electrical insulating layer 3.
  • a Cu layer having a thickness of about 0.5 ⁇ m was formed on one side of the polypropylene sheet using an ion beam sputtering apparatus to form an electrically conductive layer having a through hole ((1) and (2) in FIG. 3). On this Cu layer, another polyethylene sheet was laminated and thermocompression bonded ((3) and (4) in FIG. 3). As shown in (4) of FIG. 3, a sheet having a three-layer structure of polypropylene / Cu / polyethylene was thereby obtained.
  • this is referred to as a separator (A).
  • the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to permeate an electrolyte (not shown) and maintain ionic conductivity.
  • the through hole 7 penetrates from the positive electrode 16 to the negative electrode 15.
  • the average pore diameter of the through-holes 7 is preferably 0.05 to 5 ⁇ m from the viewpoint of electrolyte permeability, separation between the positive electrode 16 and the negative electrode 15 and prevention of passage of the peeled electrode mixture particles.
  • the thickness of the electrical insulating layer is 18 ⁇ m, the smaller the distance between the positive electrode 16 and the electrical conductive layer 4, the earlier it can detect the contamination of metallic foreign matter with high sensitivity.
  • the thickness may be further reduced as long as the property is maintained.
  • the ion beam sputtering apparatus is used for forming the electrically conductive layer 4
  • an RF sputtering apparatus, a magnetron sputtering apparatus, or a vacuum evaporation apparatus may be used. Since the underlying polypropylene sheet has through-holes 7, when a Cu layer having a thickness of about 0.05 to 20 ⁇ m is formed thereon, the through-holes 7 are maintained, electrical conductivity is also exhibited, and the through-holes 7 are provided. It becomes an electrically conductive layer.
  • Cu is used as an example for the electrically conductive layer, but other materials than Cu can be used as long as they have electrical conductivity, do not form an alloy with Li, and do not dissolve in the electrolyte.
  • conductive metal oxides such as indium tin oxide (ITO) and MnO 2 can be used.
  • ITO indium tin oxide
  • MnO 2 metal oxides, alloys, and conductive polymers can be used.
  • polypropylene sheet and the polyethylene sheet In addition to the polypropylene sheet and the polyethylene sheet, other polyolefin resin, polyester resin, polyimide resin, and fluororesin sheet having through holes may be used.
  • a laminated sheet in which polypropylene and polyethylene having through holes are laminated together may be used.
  • a Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (A). Subsequently, the positive electrode 16, the separator (A), the negative electrode 15, and the separator (A) were sequentially stacked to produce an electrode laminate 14.
  • the manufactured electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode laminate 14 and the terminals 8, 9, 14 attached to the battery outer casing 12 by lead wires. .
  • the positive electrode of the electrode laminate 14 was connected to the positive electrode terminal 8
  • the negative electrode of the electrode laminate 14 was connected to the negative electrode terminal 13
  • the electric conduction layer 4 was connected to the terminal 10 connected to the electric conduction layer. Thereafter, an electrolyte was injected.
  • LiPF 6 lithium hexafluorophosphate
  • DMC dimethyl carbonate
  • a battery lid (not shown) was attached to the battery outer container 12 and sealed with thermocompression bonding and an adhesive, and the batteries shown in FIGS. 5 and 6 were assembled.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • a battery voltage of ⁇ 4.2 V (referenced to the positive electrode) is applied to the electric conduction layer 4 through the terminal 10 connected to the electric conduction layer, and the potential difference between the electric conduction layer 4 and the positive electrode 16 is applied. And the current was measured.
  • a voltage different from that of the negative electrode 15 may be applied to the electrically conductive layer 4.
  • a lower voltage for example, ⁇ 4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
  • a battery voltage of ⁇ 4.2 V (referenced to the positive electrode) same as that of the negative electrode 15 is applied to the electric conduction layer. The potential difference and current may be measured.
  • Example 2 Since the electrical conductive layer 4 is not particularly used after shipment of the lithium ion secondary battery, the terminal 10 connected to the electrical conductive layer is hidden by a member or connected to the electrical conductive layer before shipment after inspection. The terminal 10 and the lead wire may be removed. (Example 2) The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
  • the electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows.
  • the separators used for lithium ion secondary batteries two microporous polyethylene sheets having a thickness of 18 ⁇ m were prepared. These become the electrical insulating layer 3.
  • the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity.
  • the average pore diameter of the through holes is preferably 0.05 to 5 ⁇ m from the viewpoint of electrolyte permeability, separation between the positive electrode and the negative electrode, and prevention of passage of the peeled electrode mixture particles.
  • the thickness of the electrical insulating layer is 18 ⁇ m, the smaller the distance between the positive electrode 16 and the electrical conductive layer 4, the earlier it can detect the contamination of metallic foreign matter with high sensitivity.
  • the thickness may be further reduced as long as the property is maintained.
  • a Cu film may be formed by electroplating using the Cu film as a seed layer after the Cu film is formed by the electroless plating method. Or after attaching Cu film by dry film-forming method like Example 1, you may form Cu film or Ni film by electroplating method using it as a seed layer.
  • the underlying polyethylene sheet has through-holes, when a Cu layer having a thickness of about 0.05 to 20 ⁇ m is formed on the polyethylene sheet, the through-holes are maintained and also exhibit electrical conductivity, and the electrically conductive layer having through-holes 4
  • Cu is used as an example for the electrically conductive layer, but other materials than Cu can be used as long as they have electrical conductivity, do not form an alloy with Li, and do not dissolve in the electrolyte.
  • Ni is used. You can also.
  • a polyethylene sheet not only a polyethylene sheet but also a sheet of polypropylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used.
  • a polyimide resin surface modification with an aqueous alkali hydroxide solution, ultraviolet light, plasma, or the like is necessary as a pretreatment for electroless plating.
  • a fluororesin surface modification using metallic sodium-naphthalene is necessary as a pretreatment for electroless plating.
  • a laminated sheet in which polyethylene and polypropylene having through holes are laminated together may be used.
  • a Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (B). Subsequently, the positive electrode, the separator (B), the negative electrode, and the separator (B) were sequentially stacked and wound up, and the electrode winding body 11 was produced.
  • the electrode winding body 11 was housed in a Ni-plated Fe battery outer container, and electrical connection was established between the electrode winding body and the battery outer container. Thereafter, an electrolyte was injected.
  • the electrolyte a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
  • the battery lid was attached to the battery outer container and sealed by a caulking method, and the batteries shown in FIGS. 7 and 8 were assembled.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • a battery voltage of ⁇ 4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
  • a voltage different from that of the negative electrode may be applied to the electrically conductive layer.
  • a lower voltage for example, ⁇ 4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
  • Example 3 After charging is completed and the positive electrode and negative electrode are disconnected from the charge / discharge circuit, the same battery voltage of ⁇ 4.2 V (referenced to the positive electrode) as that of the negative electrode is applied to the conductive layer, and the potential difference between the conductive layer and the positive electrode And the current may be measured.
  • Example 3 The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
  • the electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode and the negative electrode were prepared as follows.
  • the separators used for lithium ion secondary batteries two microporous polyethylene sheets having a thickness of 18 ⁇ m were prepared. These become the electrical insulating layer 4.
  • the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity.
  • the average pore diameter of the through-holes 7 is preferably 0.05 to 5 ⁇ m from the viewpoint of electrolyte permeability, isolation between the positive electrode 16 and the negative electrode 15 and prevention of passage of the separated electrode mixture 2 and 5 particles.
  • the thickness of the electrical insulating layer 3 is set to 18 ⁇ m.
  • the electrically conductive layer is formed by applying a slurry containing carbon powder
  • a solution in which a conductive polymer such as polypyrrole, polythiophene, or polyaniline is dissolved in an organic solvent may be applied.
  • the underlying polyethylene sheet has through-holes, and carbon powder is coated on it, so when a carbon film with a thickness of about 0.05 to 20 ⁇ m is formed on it, the through-holes are maintained and the electrical conductivity is also reduced. It is expressed and becomes an electrically conductive layer having a through hole.
  • polyethylene sheet not only a polyethylene sheet but also a sheet of polypropylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used.
  • a laminated sheet in which polyethylene and polypropylene having through holes are laminated together may be used.
  • a Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (C). Subsequently, the positive electrode 16, the separator (C), the negative electrode 15, and the separator (C) were sequentially stacked to produce an electrode laminate 14.
  • the electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode stack and the battery outer casing. Thereafter, an electrolyte was injected.
  • an electrolyte a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
  • the battery lid was attached to the battery outer container, sealed with thermocompression bonding and an adhesive, and the battery shown in FIGS. 5 and 6 was assembled.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • a voltage different from that of the negative electrode 15 may be applied to the electrically conductive layer 4.
  • a lower voltage for example, ⁇ 4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
  • Example 4 The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
  • the electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows. Among those used as separators for lithium ion secondary batteries, one microporous polyethylene sheet having a thickness of 18 ⁇ m was prepared. This becomes an electrically insulating layer. On one side of this polyethylene sheet, a Cu layer having a thickness of about 0.5 ⁇ m was formed using an ion beam sputtering apparatus to form an electrically conductive layer having through holes ((1) and (2) in FIG. 3).
  • the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity.
  • the average pore diameter of the through holes is preferably 0.05 to 5 ⁇ m from the viewpoint of electrolyte permeability, separation between the positive electrode and the negative electrode, and prevention of passage of the peeled electrode mixture particles.
  • the thickness of the electrical insulating layer is 18 ⁇ m, the smaller the distance between the positive electrode 16 and the electrical insulating layer 3, the earlier it can detect the contamination of metallic foreign matter with high sensitivity.
  • the thickness may be further reduced as long as the property is maintained.
  • the ion beam sputtering apparatus is used for forming the electrically conductive layer 4
  • an RF sputtering apparatus, a magnetron sputtering apparatus, or a vacuum evaporation apparatus may be used. Since the underlying polypropylene sheet has through-holes, when a Cu layer having a thickness of about 0.05 to 20 ⁇ m is formed thereon, the through-holes are maintained and electrical conductivity is also exhibited, and the electrically conductive layer having through-holes 4
  • Cu is used for the electrically conductive layer 4, but other materials than Cu can be used as long as they are electrically conductive, do not form an alloy with Li, and do not dissolve in the electrolyte.
  • Conductive metal oxides such as carbon, indium tin oxide (ITO) and MnO 2 can also be used.
  • the underlying electrically conductive layer 4 has through-holes, when a solution in which PVDF is dispersed and dissolved in about 1 to 20 ⁇ m is applied to the underlying conductive layer 4, the through-holes are maintained and electrical insulation is also exhibited. An electrically insulating layer having a through hole is obtained.
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • PVA polyvinyl alcohol
  • CMC carboxymethylcellulose
  • a sheet of polyethylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used. Furthermore, you may use the lamination sheet which laminated
  • a Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (D). Subsequently, the positive electrode 16, the separator (D), the negative electrode 15, and the separator (D) were sequentially stacked to produce an electrode laminate 14.
  • the electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode stack and the battery outer casing. Thereafter, an electrolyte was injected.
  • an electrolyte a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
  • the battery lid was attached to the battery outer container and sealed with thermocompression bonding and an adhesive, and the batteries shown in FIGS. 5 and 6 were assembled.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • a battery voltage of ⁇ 4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
  • a voltage different from that of the negative electrode may be applied to the electrically conductive layer.
  • a lower voltage for example, ⁇ 4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
  • Example 1 A battery was assembled using a positive electrode, a negative electrode, and an electrolytic solution having the same specifications as those of Examples 1 to 4 except that the electrically conductive layer was not formed on the separator.
  • separators used as separators for lithium ion secondary batteries a porous polyethylene sheet having a thickness of 35 ⁇ m was used.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charge current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • the first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C.
  • 1C is a current value for charging the battery capacity in one hour.
  • a battery voltage of ⁇ 4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
  • the absolute value of the potential difference between the electrically conductive layer and the positive electrode becomes smaller than 4.2V, and at the same time, a short circuit current is observed.
  • the short circuit current varies depending on the applied voltage and the electrical resistance of the short circuit part. A battery in which such a change in potential difference and a short-circuit current were observed to be larger than the behavior of a non-defective battery in which no metal foreign matter was mixed and no internal short-circuit occurred was judged to be an internal short-circuit and was selected as a defective product.
  • a voltage different from that of the negative electrode may be applied to the electrically conductive layer.
  • a lower voltage for example, ⁇ 4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
  • the same battery voltage of ⁇ 4.2 V (referenced to the positive electrode) as that of the negative electrode is applied to the conductive layer, and the potential difference between the conductive layer and the positive electrode And the current may be measured.
  • the battery of the present invention caused an internal short circuit as early as 1/12 to 1/2 the time of the conventional battery.
  • an internal short circuit due to a metal foreign object could be detected earlier than before. Moreover, even if it is mixed in the past, the present invention can detect an internal short circuit caused by a small metal foreign object that is overlooked because it does not cause an internal short circuit.
  • Negative electrode side current collector 2 Negative electrode side mixture layer 3: Electrical insulating layer 4: Electrical conduction layer 5: Positive electrode side mixture layer 6: Positive electrode side current collector 7: Through hole 8: Terminal connected to positive electrode 9: Body of the battery outer container connected to the negative electrode 10: Terminal connected to the electrically conductive layer 11: Electrode winding body 12: Aluminum laminated battery outer container 13: Terminal connected to the negative electrode 14: Electrode laminate 15: Negative electrode 16: Positive electrode

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Abstract

Provided is a lithium-ion battery wherein internal short-circuits that are caused by inclusion of metallic foreign matter can be detected early with high sensitivity. Also provided is a method for producing the same. The lithium-ion battery, which is provided with a positive electrode (16), a negative electrode (15), and an electrolyte, is further provided with an electric insulating layer (3) which is between the positive electrode and the negative electrode and comprises an electroconductive layer (4). By applying a voltage between the positive electrode (16) and the electroconductive layer (4), and measuring a current and a potential difference between the positive electrode (16) and the electroconductive layer (4), the possibility of the occurrence of internal short-circuits in the lithium-ion battery can be detected early with high sensitivity since there is an earlier occurrence of a short-circuit between the positive electrode and the electroconductive layer than between the positive electrode and the negative electrode.

Description

リチウムイオン電池およびその製造方法Lithium ion battery and manufacturing method thereof
　本発明はリチウムイオン二次電池およびその製造方法に関する。 The present invention relates to a lithium ion secondary battery and a manufacturing method thereof.
　リチウムイオン二次電池は、高エネルギー密度の特長から、ノート型パーソナルコンピュータ、携帯電話などの携帯用情報機器、携帯型音響機器、無線機、電動工具などの電源に利用されている。また、リチウムイオン二次電池は、高容量、高出力という利点も有している。このため、近年、電気自動車や内燃機関と電気モータとを併用したハイブリッド電気自動車（以下、両者を電気自動車という。）、無停電電源など電力貯蔵システムの電源としても使用されるに至っている。 Lithium ion secondary batteries are used as power sources for portable information devices such as notebook personal computers and mobile phones, portable acoustic devices, radios, and electric tools because of their high energy density. Lithium ion secondary batteries also have the advantages of high capacity and high output. For this reason, in recent years, it has also been used as a power source for power storage systems such as an electric vehicle, a hybrid electric vehicle using both an internal combustion engine and an electric motor (hereinafter, both are referred to as an electric vehicle), and an uninterruptible power supply.
　かかるリチウムイオン二次電池は、充放電によりリチウムイオンの放出・吸蔵が可能な正極活物質を用いた正極と、充放電によりリチウムイオンの吸蔵・放出が可能な負極活物質を用いた負極とを、セパレータを介して重ね合わせ、それらを電解液に浸潤させている。より詳細には、正極にコバルト酸リチウム（LiCoO2）、ニッケル酸リチウム（LiNiO2）、マンガン酸リチウム（LiMn2O4）等の材料を、負極に炭素材料等のリチウムイオンの吸蔵・放出が可能な材料を、それぞれ用いたリチウムイオン二次電池が広く用いられている。 Such a lithium ion secondary battery includes a positive electrode using a positive electrode active material capable of releasing and storing lithium ions by charging and discharging, and a negative electrode using a negative electrode active material capable of storing and releasing lithium ions by charging and discharging. These are superposed through separators and are infiltrated into the electrolytic solution. More specifically, materials such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ) are used for the positive electrode, and lithium ions such as carbon materials are stored and released for the negative electrode. Lithium ion secondary batteries using each possible material are widely used.
　上記のような正極活物質には十分な電子伝導性がない。そこで、正極では、一般に、正極活物質に、導電助剤として黒鉛やカーボンブラック等の低コストかつ電池内で安定な導電性粉末を含有させ、更に結着剤（バインダ）を加え、それらを混合して作製した正極合剤が用いられる。一方、負極活物質として用いられる炭素材は、電池組立時にリチウムイオンがいわば放出しきった状態、すなわち放電状態である。負極では、負極活物質に、密着性確保のための結着剤を加え、それらを混合して作製した負極合剤が用いられる。 The positive electrode active material as described above does not have sufficient electronic conductivity. Therefore, in the positive electrode, in general, the positive electrode active material contains conductive powder that is low-cost and stable in the battery, such as graphite and carbon black, as a conductive auxiliary agent, and a binder is further added and mixed. The positive electrode mixture produced in this way is used. On the other hand, the carbon material used as the negative electrode active material is in a state where lithium ions are completely released during battery assembly, that is, in a discharged state. In the negative electrode, a negative electrode mixture prepared by adding a binder for ensuring adhesion to the negative electrode active material and mixing them is used.
　通常、リチウムイオン二次電池の電極内部構造は、容量と出力を上げるために、捲回式または積層式となっている。すなわち、集電体となる金属箔に活物質を塗布した正極及び負極がセパレータを挟んで捲回または積層され、この捲回体または積層体を金属製の円筒または角型の電池外装容器に収納している。 Usually, the electrode internal structure of a lithium ion secondary battery is a wound type or a laminated type in order to increase capacity and output. That is, a positive electrode and a negative electrode in which an active material is applied to a metal foil serving as a current collector are wound or stacked with a separator interposed therebetween, and the wound body or the stacked body is stored in a metal cylindrical or rectangular battery outer container. is doing.
　捲回体または積層体を電池外装容器に収納した後、続いて電解液を注液し、蓋を付けて封口している。電池外装容器には金属製容器以外に、アルミニウムラミネート容器も用いられている。かかる方法で組立てられたリチウムイオン二次電池は、組立後の最初の充電によって、電池としての機能が付与される。 After the wound body or laminate is stored in the battery outer case, the electrolytic solution is subsequently injected, and the lid is attached and sealed. In addition to the metal container, an aluminum laminate container is also used for the battery outer container. The lithium ion secondary battery assembled by such a method is given a function as a battery by the first charge after the assembly.
　上述した電池の原材料および製造工程において、電池内に金属異物が混入すると内部短絡が起こる可能性がある。混入した金属異物が正極上で溶解し、イオンとなって拡散し、負極上に到達すると金属が再析出する。析出が進み、正極に向かって金属が成長すると、それが電気的な導通経路となり、やがて負極と正極の間が内部短絡する。内部短絡すると、充電した電気が消費されてしまい、使える容量が減少したり、充電しようとしても内部短絡部に電流が流れてしまい、充電が進まないなど、正常な電池として機能しなくなる。　 In the battery raw material and manufacturing process described above, if a metal foreign object enters the battery, an internal short circuit may occur. The mixed metal foreign matter dissolves on the positive electrode and diffuses as ions, and when it reaches the negative electrode, the metal re-deposits. As deposition progresses and the metal grows toward the positive electrode, it becomes an electrical conduction path, and eventually an internal short circuit occurs between the negative electrode and the positive electrode. When the internal short circuit occurs, the charged electricity is consumed, the usable capacity is reduced, or even if an attempt is made to charge the battery, a current flows through the internal short circuit part, and charging does not proceed. *
　金属異物が混入した電池を選別するために、特許文献１では、充電後、電池を充電回路から切り離して放置し、電池の開回路電圧の変化を測定し、内部短絡によって開回路電圧が著しく低下したものを不良品としている。 In order to sort out batteries that are contaminated with metal foreign matter, in Patent Document 1, after charging, the battery is separated from the charging circuit and allowed to stand, and the change in the open circuit voltage of the battery is measured. The product is defective.
　さらに、このような内部短絡を抑制する方法として、次の方法が提案されている。特許文献２および3には、電気化学的に金属異物を溶解し拡散させて、負極上では析出させない方法が記載されている。また、特許文献４には、陽イオンを含む不純物を捕捉する物質を電池内に含有させ、金属として析出させない方法が記載されている。 Furthermore, the following method has been proposed as a method for suppressing such an internal short circuit. Patent Documents 2 and 3 describe a method in which a metallic foreign material is dissolved and diffused electrochemically and is not deposited on the negative electrode. Patent Document 4 describes a method in which a substance that traps impurities including cations is contained in a battery and is not deposited as a metal.
特開2003-36887号公報Japanese Patent Laid-Open No. 2003-36887 特開2005-243537号公報JP 2005-243537 特開2007-26752号公報JP 2007-26752 JP 特開2000-77103号公報JP 2000-77103 A
　特許文献１に記載の方法では、従来の正極と負極，セパレータの構成では，不良品と判定できるまでに時間がかかるという問題がある。 The method described in Patent Document 1 has a problem that it takes time until it can be determined as a defective product in the configuration of the conventional positive electrode, negative electrode, and separator.
　また、特許文献２乃至４に記載の方法も、溶解から拡散までに時間がかかる。金属異物の質量が大きい場合には拡散が不十分となり、負極に金属イオンが到達して析出する恐れがある。 In addition, the methods described in Patent Documents 2 to 4 also take time from dissolution to diffusion. When the mass of the metal foreign matter is large, the diffusion becomes insufficient, and metal ions may reach the negative electrode and precipitate.
　そこで、本発明は、金属異物の混入による内部短絡を従来よりも早期に、高感度で検出できるリチウムイオン二次電池およびその製造方法を提供することを課題とする。 Therefore, an object of the present invention is to provide a lithium ion secondary battery capable of detecting an internal short circuit due to the mixing of a metal foreign substance with higher sensitivity earlier than before and a manufacturing method thereof.
　上記課題を解決するために、本発明のリチウムイオン二次電池は、電池外装容器と、正極と、負極と、前記正極と前記負極との間に設けられた電気絶縁層と、電解質とを備えるリチウムイオン電池において、前記正極と負極との間の電気絶縁層中に、電気伝導層を備えることを特徴とする。 In order to solve the above-described problems, a lithium ion secondary battery of the present invention includes a battery outer container, a positive electrode, a negative electrode, an electrical insulating layer provided between the positive electrode and the negative electrode, and an electrolyte. In the lithium ion battery, an electrically conductive layer is provided in an electrically insulating layer between the positive electrode and the negative electrode.
　本発明によれば、金属異物の混入による内部短絡を早期に、高感度で検出できるリチウムイオン二次電池およびその製造方法を提供することができる。 According to the present invention, it is possible to provide a lithium ion secondary battery capable of detecting an internal short circuit due to the mixing of metal foreign matters at an early stage with high sensitivity and a method for manufacturing the same.
本発明のリチウムイオン二次電池の電極付近の断面概略図である。It is the cross-sectional schematic diagram of the electrode vicinity of the lithium ion secondary battery of this invention. 従来のリチウムイオン二次電池の電極付近の断面概略図である。It is the cross-sectional schematic diagram of the electrode vicinity of the conventional lithium ion secondary battery. 貫通孔を有する電気伝導層および電気絶縁層の形成過程の断面概略図である。It is the cross-sectional schematic of the formation process of the electrically conductive layer and electrical insulating layer which have a through-hole. 貫通孔を有する電気伝導層および電気絶縁層の断面概略図および拡大図である。It is the cross-sectional schematic and enlarged view of the electrically conductive layer and electrical insulating layer which have a through-hole. 本発明の構造を有する電極積層型リチウムイオン二次電池の上面外観概略図である。It is the upper surface outline schematic diagram of the electrode lamination type lithium ion secondary battery which has the structure of the present invention. 本発明の構造を有する電極積層型リチウムイオン二次電池の断面概略図である。1 is a schematic cross-sectional view of an electrode laminate type lithium ion secondary battery having the structure of the present invention. 本発明の構造を有する電極捲回体型リチウムイオン二次電池の外観概略図である。1 is a schematic external view of an electrode winding type lithium ion secondary battery having a structure of the present invention. 本発明の構造を有する電極捲回体型リチウムイオン二次電池の断面概略図である。1 is a schematic cross-sectional view of an electrode wound body type lithium ion secondary battery having the structure of the present invention.
　以下、本発明の実施形態について、図面を参照しながら説明する。ただし、本発明は以下の実施例に限定されるものではない。
（実施例１）
　図１に本実施例のリチウムイオン二次電池の電極付近の断面概略図を示す。本実施例にかかる電池は、正極側集電体６と正極側合剤層５とを有する正極１６と、負極側集電体１と負極側合剤層２とを有する負極１５と、正極１６と負極１５との間に設けられた電気絶縁層３と、電気絶縁層３中に設けられた電気伝導層４とを備える。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.
Example 1
FIG. 1 shows a schematic cross-sectional view of the vicinity of the electrode of the lithium ion secondary battery of this example. The battery according to this example includes a positive electrode 16 having a positive electrode side current collector 6 and a positive electrode side mixture layer 5, a negative electrode 15 having a negative electrode side current collector 1 and a negative electrode side mixture layer 2, and a positive electrode 16. And an electric insulating layer 3 provided between the negative electrode 15 and an electric conductive layer 4 provided in the electric insulating layer 3.
　正極１６は、活物質としてリチウム遷移金属複合酸化物の１つであるマンガン酸リチウム、導電助剤として炭素粉末、結着剤としてポリフッ化ビニリデン（以下PVDFと略す）を1-メチル-2-ピロリドン（以下NMPと略す）に分散、混練したスラリーをAl製の正極側集電体6に塗工して正極側合剤層5とし、乾燥させて作製した。 The positive electrode 16 is composed of lithium manganate, which is one of lithium transition metal composite oxides, as an active material, carbon powder as a conductive additive, and polyvinylidene fluoride (hereinafter abbreviated as PVDF) as a binder. The slurry dispersed and kneaded (hereinafter abbreviated as NMP) was applied to the positive electrode side current collector 6 made of Al to form a positive electrode side mixture layer 5, and dried to prepare.
　負極１５は、活物質としてリチウムイオンを吸蔵、放出できる炭素粉末、結着剤としてPVDFをNMPに分散、混練したスラリーをCu製の負極側集電体1に塗工して負極側合剤層2とし、乾燥させて作製した。 The negative electrode 15 is a carbon powder that can occlude and release lithium ions as an active material, and a slurry obtained by dispersing and kneading PVDF in NMP as a binder is applied to the negative electrode side current collector 1 made of Cu to apply a negative electrode side mixture layer 2 and dried.
　正極１６と負極１５との間の貫通孔を有する電気伝導層4および電気絶縁層3は次のように作製した。リチウムイオン二次電池用のセパレータとして用いられているものの中で、厚さ18μｍの微多孔質ポリプロピレンシートおよびポリエチレンシートをそれぞれ1枚ずつ用意した。これらは電気絶縁層３となる。そのうちのポリプロピレンシートの片面上に、イオンビームスパッタリング装置を用いて厚さ約0.5μmのCu層を形成して貫通孔を有する電気伝導層とした（図３の(1)、(2)）。このCu層の上に、もう1枚のポリエチレンシートを重ねて熱圧着した（図３の(3)、(4)）。図３の(4)に示すように、これにより、ポリプロピレン/Cu/ポリエチレンの3層構造のシートができた。これを以下ではセパレータ（A）と呼ぶことにする。 The electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows. Among those used as separators for lithium ion secondary batteries, a microporous polypropylene sheet and a polyethylene sheet each having a thickness of 18 μm were prepared. These become the electrical insulating layer 3. A Cu layer having a thickness of about 0.5 μm was formed on one side of the polypropylene sheet using an ion beam sputtering apparatus to form an electrically conductive layer having a through hole ((1) and (2) in FIG. 3). On this Cu layer, another polyethylene sheet was laminated and thermocompression bonded ((3) and (4) in FIG. 3). As shown in (4) of FIG. 3, a sheet having a three-layer structure of polypropylene / Cu / polyethylene was thereby obtained. Hereinafter, this is referred to as a separator (A).
　この電気伝導層４および電気絶縁層３は、図４に示すように、電解質（図示せず）が浸透し、イオン伝導性を保つために、貫通孔7を持つ微多孔質である必要がある。貫通孔７は、正極１６から負極１５まで貫通する。貫通孔７の平均孔径は電解質の浸透性と、正極１６と負極１５との隔離、剥離した電極合剤の粒子の通過を阻止する観点から0.05～5μmが望ましい。電池の組立工程において、電解質を注入すると、貫通孔7の中は電解質で満たされ、正極と負極との間を電解質中のイオンが移動できるようになる。 As shown in FIG. 4, the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to permeate an electrolyte (not shown) and maintain ionic conductivity. . The through hole 7 penetrates from the positive electrode 16 to the negative electrode 15. The average pore diameter of the through-holes 7 is preferably 0.05 to 5 μm from the viewpoint of electrolyte permeability, separation between the positive electrode 16 and the negative electrode 15 and prevention of passage of the peeled electrode mixture particles. When an electrolyte is injected in the battery assembly process, the through hole 7 is filled with the electrolyte, and ions in the electrolyte can move between the positive electrode and the negative electrode.
　ここでは、電気絶縁層の厚さを18μmとしたが、正極１６と電気伝導層４との距離が小さいほど、早期に、高感度で金属異物の混入を検出できるため、機械的強度と電気絶縁性が保たれる範囲でさらに薄くしてもよい。 Here, although the thickness of the electrical insulating layer is 18 μm, the smaller the distance between the positive electrode 16 and the electrical conductive layer 4, the earlier it can detect the contamination of metallic foreign matter with high sensitivity. The thickness may be further reduced as long as the property is maintained.
　また、ここでは、電気伝導層４の形成にイオンビームスパッタリング装置を用いたが、RFスパッタリング装置、マグネトロンスパッタリング装置または真空蒸着装置を用いてもよい。下地のポリプロピレンシートは貫通孔７を有しているため、その上に厚さ約0.05～20μmのCu層を形成すると、貫通孔７は維持され、電気伝導性も発現し、貫通孔７を有する電気伝導層となる。 Here, although the ion beam sputtering apparatus is used for forming the electrically conductive layer 4, an RF sputtering apparatus, a magnetron sputtering apparatus, or a vacuum evaporation apparatus may be used. Since the underlying polypropylene sheet has through-holes 7, when a Cu layer having a thickness of about 0.05 to 20 μm is formed thereon, the through-holes 7 are maintained, electrical conductivity is also exhibited, and the through-holes 7 are provided. It becomes an electrically conductive layer.
　電気伝導層には一例としてCuを用いたが、電気伝導性を有し、Liと合金を作らず、電解質に溶解しない物質であれば、Cu以外のものを用いることもでき、例えばNiやカーボン、インジウム・スズ酸化物（ITO）やMnO2のような導電性金属酸化物を用いることもできる。他に、金属、合金、導電性高分子も使用可能である。 Cu is used as an example for the electrically conductive layer, but other materials than Cu can be used as long as they have electrical conductivity, do not form an alloy with Li, and do not dissolve in the electrolyte. Also, conductive metal oxides such as indium tin oxide (ITO) and MnO 2 can be used. In addition, metals, alloys, and conductive polymers can be used.
　また、ポリプロピレンシートおよびポリエチレンシートだけでなく、貫通孔を有するその他のポリオレフィン樹脂，ポリエステル樹脂、ポリイミド樹脂、フッ素樹脂のシートを用いてもよい。 In addition to the polypropylene sheet and the polyethylene sheet, other polyolefin resin, polyester resin, polyimide resin, and fluororesin sheet having through holes may be used.
　さらに、貫通孔を有するポリプロピレンとポリエチレンとを互いに積層した積層シートを用いてもよい。 Furthermore, a laminated sheet in which polypropylene and polyethylene having through holes are laminated together may be used.
　セパレータ（A）の端部には電気的接続を取るためのリード線になるCu箔を圧接して取り付けた。続いて、上記の正極１６、セパレータ（A）、負極１５、セパレータ（A)を順次積み重ねて、電極積層体14を作製した。 A Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (A). Subsequently, the positive electrode 16, the separator (A), the negative electrode 15, and the separator (A) were sequentially stacked to produce an electrode laminate 14.
　次に、電極積層体１４を内蔵するリチウムイオン二次電池を図５及び図６に示す。製造した電極積層体14をアルミラミネート型の電池外装容器12に収納し、リード線により電極積層体１４と電池外装容器１２に付属した端子８、９、１４との間の電気的接続を取った。電極積層体１４の正極は正極端子８に接続され、電極積層体１４の負極は負極端子１３に接続され、電気伝導層４は電気伝導層に接続された端子１０に接続した。その後、電解質を注入した。電解質にはエチレンカーボネート（以下ECと称す）とジメチルカーボネート（以下DMCと称す）の混合溶液に六フッ化リン酸リチウム（LiPF6）を溶解した液を使用した。 Next, a lithium ion secondary battery incorporating the electrode laminate 14 is shown in FIGS. The manufactured electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode laminate 14 and the terminals 8, 9, 14 attached to the battery outer casing 12 by lead wires. . The positive electrode of the electrode laminate 14 was connected to the positive electrode terminal 8, the negative electrode of the electrode laminate 14 was connected to the negative electrode terminal 13, and the electric conduction layer 4 was connected to the terminal 10 connected to the electric conduction layer. Thereafter, an electrolyte was injected. As the electrolyte, a solution in which lithium hexafluorophosphate (LiPF 6 ) was dissolved in a mixed solution of ethylene carbonate (hereinafter referred to as EC) and dimethyl carbonate (hereinafter referred to as DMC) was used.
　続いて電池蓋（図示せず）を電池外装容器１２に取り付け、熱圧着および接着剤によって密閉し、図5および図6に示す電池を組み立てた。 Subsequently, a battery lid (not shown) was attached to the battery outer container 12 and sealed with thermocompression bonding and an adhesive, and the batteries shown in FIGS. 5 and 6 were assembled.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
　充電中、電気伝導層に接続された端子１０を介して電気伝導層４に負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層４と正極１６との間の電位差と電流を測定した。 During charging, a battery voltage of −4.2 V (referenced to the positive electrode) is applied to the electric conduction layer 4 through the terminal 10 connected to the electric conduction layer, and the potential difference between the electric conduction layer 4 and the positive electrode 16 is applied. And the current was measured.
　なお、電気伝導層４には負極１５とは異なる電圧を印加してもよい。溶解と析出を促進するために、電解質が分解しない範囲で、より低い電圧、例えば-4.5V（正極を基準）を電気伝導層に印加してもよい。負極１５と同じとした場合には、充電時に負極１５につなぐ回路と同じものを用いることができ、制御のための回路が簡略になる。 A voltage different from that of the negative electrode 15 may be applied to the electrically conductive layer 4. In order to promote dissolution and precipitation, a lower voltage, for example, −4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose. When the same as the negative electrode 15, the same circuit as that connected to the negative electrode 15 during charging can be used, and the control circuit is simplified.
　あるいは充電が完了し正極１６と負極１５を充放電回路から切り離した後、電気伝導層には負極１５と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極１６との間の電位差と電流を測定してもよい。 Alternatively, after charging is completed and the positive electrode 16 and the negative electrode 15 are disconnected from the charging / discharging circuit, a battery voltage of −4.2 V (referenced to the positive electrode) same as that of the negative electrode 15 is applied to the electric conduction layer. The potential difference and current may be measured.
　なお、リチウムイオン二次電池の出荷後は、電気導電層４は特に使用しないので、検査後出荷前に、電気伝導層に接続された端子１０を部材で隠したり、電気伝導層に接続された端子１０とリード線を除去したりしてもよい。
（実施例２）
　正極１６および負極１５は実施例１と同様の方法で作製した。 Since the electrical conductive layer 4 is not particularly used after shipment of the lithium ion secondary battery, the terminal 10 connected to the electrical conductive layer is hidden by a member or connected to the electrical conductive layer before shipment after inspection. The terminal 10 and the lead wire may be removed.
(Example 2)
The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
　正極１６と負極１５との間の貫通孔を有する電気伝導層4および電気絶縁層3は次のように作製した。リチウムイオン二次電池用のセパレータとして用いられているものの中で、厚さ18μmの微多孔質ポリエチレンシートを２枚用意した。これらは電気絶縁層３となる。 The electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows. Among the separators used for lithium ion secondary batteries, two microporous polyethylene sheets having a thickness of 18 μm were prepared. These become the electrical insulating layer 3.
　そのうちの1枚の片面上に、アルカリ性過マンガン酸カリウム溶液を接触させ、ポリエチレンシート表面をマイクロエッチングした。
続いてマイクロエッチングした表面にパラジウムを吸着させ、無電解めっきのために触媒化した。その後、無電解Cuめっき法を用いて、厚さ約0.5μmのCu膜を形成して電気伝導層とした（図３の(1)、(2)）。 An alkaline potassium permanganate solution was brought into contact with one surface of one of them, and the polyethylene sheet surface was microetched.
Subsequently, palladium was adsorbed on the micro-etched surface and catalyzed for electroless plating. Thereafter, using an electroless Cu plating method, a Cu film having a thickness of about 0.5 μm was formed to form an electrically conductive layer ((1) and (2) in FIG. 3).
　このCu層の上に、もう1枚のポリエチレンシートを重ねて熱圧着した（図３の(3)、(4)）。図３の(4)に示すように、これにより、ポリエチレン/Cu/ポリエチレンの3層構造のシートができた。これを以下ではセパレータ（B）と呼ぶことにする。 ¡Another polyethylene sheet was stacked on this Cu layer and thermocompression bonded ((3) and (4) in Fig. 3). As shown in FIG. 3 (4), a sheet having a three-layer structure of polyethylene / Cu / polyethylene was thus obtained. Hereinafter, this is referred to as a separator (B).
　この電気伝導層４および電気絶縁層３は、図４に示すように、電解質が浸透し、イオン伝導性を保つために、貫通孔7を持つ微多孔質である必要がある。貫通孔の平均孔径は電解質の浸透性と、正極と負極との隔離、剥離した電極合剤の粒子の通過を阻止する観点から0.05～5μmが望ましい。電池の組立工程において、電解質を注入すると、貫通孔7の中は電解質で満たされ、正極と負極との間を電解質中のイオンが移動できるようになる。 As shown in FIG. 4, the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity. The average pore diameter of the through holes is preferably 0.05 to 5 μm from the viewpoint of electrolyte permeability, separation between the positive electrode and the negative electrode, and prevention of passage of the peeled electrode mixture particles. When an electrolyte is injected in the battery assembly process, the through hole 7 is filled with the electrolyte, and ions in the electrolyte can move between the positive electrode and the negative electrode.
　ここでは、電気絶縁層の厚さを18μmとしたが、正極１６と電気伝導層４との距離が小さいほど、早期に、高感度で金属異物の混入を検出できるため、機械的強度と電気絶縁性が保たれる範囲でさらに薄くしてもよい。 Here, although the thickness of the electrical insulating layer is 18 μm, the smaller the distance between the positive electrode 16 and the electrical conductive layer 4, the earlier it can detect the contamination of metallic foreign matter with high sensitivity. The thickness may be further reduced as long as the property is maintained.
　また、ここでは、無電解めっき法のみを用いたが、無電解めっき法でCu膜を付けた後、それをシード層として電気めっき法でCu膜またはNi膜を形成してもよい。あるいは実施例１のようにドライ成膜法でCu膜を付けた後、それをシード層として電気めっき法でCu膜またはNi膜を形成してもよい。 Although only the electroless plating method is used here, a Cu film may be formed by electroplating using the Cu film as a seed layer after the Cu film is formed by the electroless plating method. Or after attaching Cu film by dry film-forming method like Example 1, you may form Cu film or Ni film by electroplating method using it as a seed layer.
　下地のポリエチレンシートは貫通孔を有しているため、その上に厚さ約0.05～20μmのCu層を形成すると、貫通孔は維持され、電気伝導性も発現し、貫通孔を有する電気伝導層４となる。 Since the underlying polyethylene sheet has through-holes, when a Cu layer having a thickness of about 0.05 to 20 μm is formed on the polyethylene sheet, the through-holes are maintained and also exhibit electrical conductivity, and the electrically conductive layer having through-holes 4
　電気伝導層には一例としてCuを用いたが、電気伝導性を有し、Liと合金を作らず、電解質に溶解しない物質であれば、Cu以外のものを用いることもでき、例えばNiを用いることもできる。 Cu is used as an example for the electrically conductive layer, but other materials than Cu can be used as long as they have electrical conductivity, do not form an alloy with Li, and do not dissolve in the electrolyte. For example, Ni is used. You can also.
　また、ポリエチレンシートだけでなく、貫通孔を有するポリプロピレン樹脂、ポリエステル樹脂、ポリイミド樹脂、フッ素樹脂のシートを用いてもよい。
ただし、ポリイミド樹脂の場合は、無電解めっきの前処理として、水酸化アルカリ水溶液または紫外線、プラズマなどによる表面改質が必要である。
フッ素樹脂の場合は、無電解めっきの前処理として、金属ナトリウム-ナフタレンを用いた表面改質が必要である。 Further, not only a polyethylene sheet but also a sheet of polypropylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used.
However, in the case of a polyimide resin, surface modification with an aqueous alkali hydroxide solution, ultraviolet light, plasma, or the like is necessary as a pretreatment for electroless plating.
In the case of a fluororesin, surface modification using metallic sodium-naphthalene is necessary as a pretreatment for electroless plating.
　さらに、貫通孔を有するポリエチレンとポリプロピレンとを互いに積層した積層シートを用いてもよい。 Furthermore, a laminated sheet in which polyethylene and polypropylene having through holes are laminated together may be used.
　セパレータ（B）の端部には電気的接続を取るためのリード線になるCu箔を圧接して取り付けた。続いて、上記の正極、セパレータ（B）、負極、セパレータ（B)を順次積み重ねて巻き取り、電極捲回体11を作製した。 A Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (B). Subsequently, the positive electrode, the separator (B), the negative electrode, and the separator (B) were sequentially stacked and wound up, and the electrode winding body 11 was produced.
　次に電極捲回体11を、NiめっきしたFe製電池外装容器に収納し、電極捲回体と電池外装容器との間の電気的接続を取った。その後、電解質を注入した。電解質にはEC、DMCの混合溶液にLiPF6を溶解した液を使用した。 Next, the electrode winding body 11 was housed in a Ni-plated Fe battery outer container, and electrical connection was established between the electrode winding body and the battery outer container. Thereafter, an electrolyte was injected. As the electrolyte, a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
　続いて電池蓋を電池外装容器に取り付け、かしめ加工法によって密閉し、図7および8に示す電池を組み立た。 Subsequently, the battery lid was attached to the battery outer container and sealed by a caulking method, and the batteries shown in FIGS. 7 and 8 were assembled.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
　充電中、電気伝導層に負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定した。 During charging, a battery voltage of −4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
　なお、電気伝導層には負極とは異なる電圧を印加してもよい。溶解と析出を促進するために、電解質が分解しない範囲で、より低い電圧、例えば-4.5V（正極を基準）を電気伝導層に印加してもよい。 Note that a voltage different from that of the negative electrode may be applied to the electrically conductive layer. In order to promote dissolution and precipitation, a lower voltage, for example, −4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
　あるいは充電が完了し正極と負極を充放電回路から切り離した後、電気伝導層には負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定してもよい。
（実施例３）
　正極１６および負極１５は実施例１と同様の方法で作製した。 Alternatively, after charging is completed and the positive electrode and negative electrode are disconnected from the charge / discharge circuit, the same battery voltage of −4.2 V (referenced to the positive electrode) as that of the negative electrode is applied to the conductive layer, and the potential difference between the conductive layer and the positive electrode And the current may be measured.
(Example 3)
The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
　正極と負極との間の貫通孔を有する電気伝導層4および電気絶縁層3は次のように作製した。リチウムイオン二次電池用のセパレータとして用いられているものの中で、厚さ18μmの微多孔質ポリエチレンシートを２枚用意した。これらは電気絶縁層４となる。 The electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode and the negative electrode were prepared as follows. Among the separators used for lithium ion secondary batteries, two microporous polyethylene sheets having a thickness of 18 μm were prepared. These become the electrical insulating layer 4.
　そのうちの1枚の片面上に、カーボン粉末とPVDFをNMPに分散溶解させたスラリーを塗布し、60～100℃で減圧乾燥させ、厚さ約1μmのカーボン膜を形成して電気伝導層とした電気伝導層とした（図３の(1)、(2)）。このカーボン層の上に、もう1枚のポリエチレンシートを重ねて熱圧着した（図３の(3)、(4)）。図３の(4)に示すように、これにより、ポリエチレン/カーボン/ポリエチレンの3層構造のシートができた。これを以下ではセパレータ（C）と呼ぶことにする。 On one of them, a slurry in which carbon powder and PVDF are dispersed and dissolved in NMP is applied and dried under reduced pressure at 60 to 100 ° C. to form a carbon film having a thickness of about 1 μm as an electrically conductive layer. An electrically conductive layer was formed ((1) and (2) in FIG. 3). On this carbon layer, another polyethylene sheet was stacked and thermocompression bonded ((3) and (4) in FIG. 3). As shown in FIG. 3 (4), a sheet having a three-layer structure of polyethylene / carbon / polyethylene was thus obtained. Hereinafter, this is referred to as a separator (C).
　この電気伝導層４および電気絶縁層３は、図４に示すように、電解質が浸透し、イオン伝導性を保つために、貫通孔7を持つ微多孔質である必要がある。貫通孔７の平均孔径は電解質の浸透性と、正極１６と負極１５との隔離、剥離した電極合剤２、５の粒子の通過を阻止する観点から0.05～5μmが望ましい。電池の組立工程において、電解質を注入すると、貫通孔7の中は電解質で満たされ、正極１６と負極１５との間を電解質中のイオンが移動できるようになる。 As shown in FIG. 4, the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity. The average pore diameter of the through-holes 7 is preferably 0.05 to 5 μm from the viewpoint of electrolyte permeability, isolation between the positive electrode 16 and the negative electrode 15 and prevention of passage of the separated electrode mixture 2 and 5 particles. When the electrolyte is injected in the battery assembly process, the through hole 7 is filled with the electrolyte, and ions in the electrolyte can move between the positive electrode 16 and the negative electrode 15.
　ここでは、電気絶縁層３の厚さを18μmとしたが、正極１６と電気伝導層４との距離が小さいほど、早期に、高感度で金属異物の混入を検出できるため、機械的強度と電気絶縁性が保たれる範囲でさらに薄くしてもよい。 Here, the thickness of the electrical insulating layer 3 is set to 18 μm. However, the smaller the distance between the positive electrode 16 and the electrical conductive layer 4 is, the earlier it can detect the contamination of metallic foreign matter with high sensitivity. You may make it still thinner as long as insulation is maintained.
　ここでは、カーボン粉末を含むスラリーを塗布して電気伝導層を形成したが、ポリピロール、ポリチオフェン、ポリアニリンのような導電性高分子を有機溶剤に溶解させた溶液を塗布してもよい。 Here, although the electrically conductive layer is formed by applying a slurry containing carbon powder, a solution in which a conductive polymer such as polypyrrole, polythiophene, or polyaniline is dissolved in an organic solvent may be applied.
　下地のポリエチレンシートは貫通孔を有しており、そこにカーボン粉末を塗布しているため、その上に厚さ約0.05～20μmのカーボン膜を形成すると、貫通孔は維持され、電気伝導性も発現し、貫通孔を有する電気伝導層となる。 The underlying polyethylene sheet has through-holes, and carbon powder is coated on it, so when a carbon film with a thickness of about 0.05 to 20 μm is formed on it, the through-holes are maintained and the electrical conductivity is also reduced. It is expressed and becomes an electrically conductive layer having a through hole.
　また、ポリエチレンシートだけでなく、貫通孔を有するポリプロピレン樹脂、ポリエステル樹脂、ポリイミド樹脂、フッ素樹脂のシートを用いてもよい。 Further, not only a polyethylene sheet but also a sheet of polypropylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used.
　さらに、貫通孔を有するポリエチレンとポリプロピレンとを互いに積層した積層シートを用いてもよい。 Furthermore, a laminated sheet in which polyethylene and polypropylene having through holes are laminated together may be used.
　セパレータ（C）の端部には電気的接続を取るためのリード線になるCu箔を圧接して取り付けた。続いて、上記の正極１６、セパレータ（C）、負極１５、セパレータ（C)を順次積み重ねて電極積層体14を作製した。 A Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (C). Subsequently, the positive electrode 16, the separator (C), the negative electrode 15, and the separator (C) were sequentially stacked to produce an electrode laminate 14.
　次に電極積層体14をアルミラミネート型の電池外装容器12に収納し、電極積層体と電池外装容器との間の電気的接続を取った。その後、電解質を注入した。電解質にはEC、DMCの混合溶液にLiPF6を溶解した液を使用した。 Next, the electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode stack and the battery outer casing. Thereafter, an electrolyte was injected. As the electrolyte, a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
　続いて電池蓋を電池外装容器に取り付け、熱圧着および接着剤によって密閉し、図5および6に示す電池を組み立てた。 Subsequently, the battery lid was attached to the battery outer container, sealed with thermocompression bonding and an adhesive, and the battery shown in FIGS. 5 and 6 was assembled.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
　充電中、電気伝導層４に負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層４と正極１６との間の電位差と電流を測定した。 During charging, a battery voltage of −4.2 V (referenced to the positive electrode) same as that of the negative electrode was applied to the electrically conductive layer 4, and the potential difference and current between the electrically conductive layer 4 and the positive electrode 16 were measured.
　なお、電気伝導層４には負極１５とは異なる電圧を印加してもよい。溶解と析出を促進するために、電解質が分解しない範囲で、より低い電圧、例えば-4.5V（正極を基準）を電気伝導層に印加してもよい。 A voltage different from that of the negative electrode 15 may be applied to the electrically conductive layer 4. In order to promote dissolution and precipitation, a lower voltage, for example, −4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
　あるいは充電が完了し正極１６と負極１５を充放電回路から切り離した後、電気伝導層には負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層４と正極１６との間の電位差と電流を測定してもよい。
（実施例４）
　正極１６および負極１５は実施例１と同様の方法で作製した。 Alternatively, after charging is completed and the positive electrode 16 and the negative electrode 15 are disconnected from the charge / discharge circuit, a battery voltage of −4.2 V (referenced to the positive electrode) is applied to the electrically conductive layer, and the electrically conductive layer 4 and the positive electrode 16 The potential difference and current may be measured.
Example 4
The positive electrode 16 and the negative electrode 15 were produced in the same manner as in Example 1.
　正極１６と負極１５との間の貫通孔を有する電気伝導層4および電気絶縁層3は次のように作製した。リチウムイオン二次電池用のセパレータとして用いられているものの中で、厚さ18μmの微多孔質ポリエチレンシートを1枚用意した。これは電気絶縁層となる。このポリエチレンシートの片面上に、イオンビームスパッタリング装置を用いて厚さ約0.5μmのCu層を形成して貫通孔を有する電気伝導層とした（図３の(1)、(2)）。 The electric conductive layer 4 and the electric insulating layer 3 having a through hole between the positive electrode 16 and the negative electrode 15 were produced as follows. Among those used as separators for lithium ion secondary batteries, one microporous polyethylene sheet having a thickness of 18 μm was prepared. This becomes an electrically insulating layer. On one side of this polyethylene sheet, a Cu layer having a thickness of about 0.5 μm was formed using an ion beam sputtering apparatus to form an electrically conductive layer having through holes ((1) and (2) in FIG. 3).
　このCu層の上に、PVDFをNMPに分散溶解させた溶液を塗布し、60～100℃で減圧乾燥し、約20μmの電気絶縁層を形成した（図３の(3)、(4)）。図３の(4)に示すように、これにより、PVDF/Cu/ポリエチレンの3層構造のシートができた。これを以下ではセパレータ（D）と呼ぶことにする。 On this Cu layer, a solution in which PVDF was dispersed and dissolved in NMP was applied and dried under reduced pressure at 60 to 100 ° C. to form an electrically insulating layer of about 20 μm ((3) and (4) in FIG. 3). . As shown in (4) of FIG. 3, a sheet having a three-layer structure of PVDF / Cu / polyethylene was thereby obtained. Hereinafter, this is referred to as a separator (D).
　この電気伝導層４および電気絶縁層３は、図４に示すように、電解質が浸透し、イオン伝導性を保つために、貫通孔7を持つ微多孔質である必要がある。貫通孔の平均孔径は電解質の浸透性と、正極と負極との隔離、剥離した電極合剤の粒子の通過を阻止する観点から0.05～5μmが望ましい。電池の組立工程において、電解質を注入すると、貫通孔7の中は電解質で満たされ、正極１６と負極１５との間を電解質中のイオンが移動できるようになる。 As shown in FIG. 4, the electric conductive layer 4 and the electric insulating layer 3 need to be microporous having through-holes 7 in order to allow the electrolyte to permeate and maintain ionic conductivity. The average pore diameter of the through holes is preferably 0.05 to 5 μm from the viewpoint of electrolyte permeability, separation between the positive electrode and the negative electrode, and prevention of passage of the peeled electrode mixture particles. When the electrolyte is injected in the battery assembly process, the through hole 7 is filled with the electrolyte, and ions in the electrolyte can move between the positive electrode 16 and the negative electrode 15.
　ここでは、電気絶縁層の厚さを18μmとしたが、正極１６と電気絶縁層３との距離が小さいほど、早期に、高感度で金属異物の混入を検出できるため、機械的強度と電気絶縁性が保たれる範囲でさらに薄くしてもよい。 Here, although the thickness of the electrical insulating layer is 18 μm, the smaller the distance between the positive electrode 16 and the electrical insulating layer 3, the earlier it can detect the contamination of metallic foreign matter with high sensitivity. The thickness may be further reduced as long as the property is maintained.
　また、ここでは、電気伝導層４の形成にイオンビームスパッタリング装置を用いたが、RFスパッタリング装置、マグネトロンスパッタリング装置または真空蒸着装置を用いてもよい。下地のポリプロピレンシートは貫通孔を有しているため、その上に厚さ約0.05～20μmのCu層を形成すると、貫通孔は維持され、電気伝導性も発現し、貫通孔を有する電気伝導層４となる。 Here, although the ion beam sputtering apparatus is used for forming the electrically conductive layer 4, an RF sputtering apparatus, a magnetron sputtering apparatus, or a vacuum evaporation apparatus may be used. Since the underlying polypropylene sheet has through-holes, when a Cu layer having a thickness of about 0.05 to 20 μm is formed thereon, the through-holes are maintained and electrical conductivity is also exhibited, and the electrically conductive layer having through-holes 4
　電気伝導層４には一例としてCuを用いたが、電気伝導性を有し、Liと合金を作らず、電解質に溶解しない物質であれば、Cu以外のものを用いることもでき、例えばNiやカーボン、インジウム・スズ酸化物（ITO）やMnO2のような導電性金属酸化物を用いることもできる。 As an example, Cu is used for the electrically conductive layer 4, but other materials than Cu can be used as long as they are electrically conductive, do not form an alloy with Li, and do not dissolve in the electrolyte. Conductive metal oxides such as carbon, indium tin oxide (ITO) and MnO 2 can also be used.
　下地の電気伝導層４は貫通孔を有しているため、その上に約1～20μmにPVDFをNMPに分散溶解させた溶液を塗布すると、 貫通孔は維持され、電気絶縁性も発現し、貫通孔を有する電気絶縁層となる。 Since the underlying electrically conductive layer 4 has through-holes, when a solution in which PVDF is dispersed and dissolved in about 1 to 20 μm is applied to the underlying conductive layer 4, the through-holes are maintained and electrical insulation is also exhibited. An electrically insulating layer having a through hole is obtained.
　Cu層の上に形成する電気絶縁層３としては、PVDFのほかに、ポリテトラフルオロエチレン（PTFE）、スチレン－ブタジエンゴム（SBR）、ポリビニルアルコール（PVA）、カルボキシメチルセルロース（CMC）を用いてもよい。多孔質を保つためにアルミナまたはシリカのような無機物粒子を混合させてもよい。 In addition to PVDF, polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), and carboxymethylcellulose (CMC) may be used as the electrical insulating layer 3 formed on the Cu layer. Good. In order to maintain the porosity, inorganic particles such as alumina or silica may be mixed.
　また、ポリプロピレンシートだけでなく、貫通孔を有するポリエチレン樹脂、ポリエステル樹脂、ポリイミド樹脂、フッ素樹脂のシートを用いてもよい。
さらに、貫通孔を有するポリプロピレンとポリエチレンとを互いに積層した積層シートを用いてもよい。 In addition to a polypropylene sheet, a sheet of polyethylene resin, polyester resin, polyimide resin, or fluororesin having through holes may be used.
Furthermore, you may use the lamination sheet which laminated | stacked the polypropylene and polyethylene which have a through-hole mutually.
　セパレータ（D）の端部には電気的接続を取るためのリード線になるCu箔を圧接して取り付けた。続いて、上記の正極１６、セパレータ（D）、負極１５、セパレータ（D)を順次積み重ねて、電極積層体14を作製した。 A Cu foil serving as a lead wire for electrical connection was pressed and attached to the end of the separator (D). Subsequently, the positive electrode 16, the separator (D), the negative electrode 15, and the separator (D) were sequentially stacked to produce an electrode laminate 14.
　次に電極積層体14をアルミラミネート型の電池外装容器12に収納し、電極積層体と電池外装容器との間の電気的接続を取った。その後、電解質を注入した。電解質にはEC、DMCの混合溶液にLiPF6を溶解した液を使用した。
続いて電池蓋を電池外装容器に取り付け、熱圧着および接着剤によって密閉し、図5および6に示す電池を組み立てた。 Next, the electrode laminate 14 was housed in an aluminum laminate type battery outer casing 12, and electrical connection was established between the electrode stack and the battery outer casing. Thereafter, an electrolyte was injected. As the electrolyte, a solution obtained by dissolving LiPF 6 in a mixed solution of EC and DMC was used.
Subsequently, the battery lid was attached to the battery outer container and sealed with thermocompression bonding and an adhesive, and the batteries shown in FIGS. 5 and 6 were assembled.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
　充電中、電気伝導層に負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定した。 During charging, a battery voltage of −4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
　なお、電気伝導層には負極とは異なる電圧を印加してもよい。溶解と析出を促進するために、電解質が分解しない範囲で、より低い電圧、例えば-4.5V（正極を基準）を電気伝導層に印加してもよい。 Note that a voltage different from that of the negative electrode may be applied to the electrically conductive layer. In order to promote dissolution and precipitation, a lower voltage, for example, −4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
　あるいは充電が完了し正極と負極を充放電回路から切り離した後、電気伝導層には負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定してもよい。
（比較例１）
　セパレータに電気伝導層を形成しない点のほかは、実施例１乃至４と同一仕様の正極、負極、電解液を用いて電池を組み立てた。
セパレータはリチウムイオン二次電池用のセパレータとして用いられているものの中で、厚さ35μmの多孔質ポリエチレンシートを用いた。 Alternatively, after charging is completed and the positive electrode and negative electrode are disconnected from the charge / discharge circuit, the same battery voltage of −4.2 V (referenced to the positive electrode) as that of the negative electrode is applied to the conductive layer, and the potential difference between the conductive layer and the positive electrode And the current may be measured.
(Comparative Example 1)
A battery was assembled using a positive electrode, a negative electrode, and an electrolytic solution having the same specifications as those of Examples 1 to 4 except that the electrically conductive layer was not formed on the separator.
Among separators used as separators for lithium ion secondary batteries, a porous polyethylene sheet having a thickness of 35 μm was used.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。
（評価例）
　本発明の効果を確認するために、実施例１乃至４および比較例１の電池に、電極作製過程で、平均粒径80μm前後および30μm前後の金属異物（Fe）を正極中および正極表面上に1～10個混入させた。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charge current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
(Evaluation example)
In order to confirm the effect of the present invention, in the batteries of Examples 1 to 4 and Comparative Example 1, metallic foreign matters (Fe) having an average particle size of about 80 μm and about 30 μm were placed in the positive electrode and on the positive electrode surface during the electrode preparation process. 1-10 were mixed.
　組み立て完了後の最初の充電は定電圧4.2V、充電電流１C相当の電流値で実施した。ただし、1Cは電池容量を1時間で充電する電流値である。 The first charge after the assembly was completed was performed at a constant voltage of 4.2V and a current value equivalent to a charging current of 1C. However, 1C is a current value for charging the battery capacity in one hour.
　充電中、電気伝導層に負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定した。　
　内部短絡が起きると、電気伝導層と正極との間の電位差の絶対値が4.2Vよりも小さくなり、同時に短絡電流が観測される。短絡電流は印加した電圧と、短絡部の電気抵抗によって変わる。このような電位差の変化と短絡電流が、金属異物の混入がなく内部短絡が起こらない良品の電池の挙動と比べて大きく観測された電池は内部短絡発生と判断し、不良品として選別した。 During charging, a battery voltage of −4.2 V (referenced to the positive electrode) was applied to the electrically conductive layer, and the potential difference and current between the electrically conductive layer and the positive electrode were measured.
When an internal short circuit occurs, the absolute value of the potential difference between the electrically conductive layer and the positive electrode becomes smaller than 4.2V, and at the same time, a short circuit current is observed. The short circuit current varies depending on the applied voltage and the electrical resistance of the short circuit part. A battery in which such a change in potential difference and a short-circuit current were observed to be larger than the behavior of a non-defective battery in which no metal foreign matter was mixed and no internal short-circuit occurred was judged to be an internal short-circuit and was selected as a defective product.
　なお、電気伝導層には負極とは異なる電圧を印加してもよい。溶解と析出を促進するために、電解質が分解しない範囲で、より低い電圧、例えば-4.5V（正極を基準）を電気伝導層に印加してもよい。 Note that a voltage different from that of the negative electrode may be applied to the electrically conductive layer. In order to promote dissolution and precipitation, a lower voltage, for example, −4.5 V (referenced to the positive electrode) may be applied to the electrically conductive layer as long as the electrolyte does not decompose.
　あるいは充電が完了し正極と負極を充放電回路から切り離した後、電気伝導層には負極と同じ-4.2V（正極を基準）の電池電圧を印加し、電気伝導層と正極との間の電位差と電流を測定してもよい。 Alternatively, after charging is completed and the positive electrode and negative electrode are disconnected from the charge / discharge circuit, the same battery voltage of −4.2 V (referenced to the positive electrode) as that of the negative electrode is applied to the conductive layer, and the potential difference between the conductive layer and the positive electrode And the current may be measured.
　この結果を表１に示す。ここでは、本発明の電気伝導層と正極との間で起きた短絡を内部短絡と表現している。 The results are shown in Table 1. Here, a short circuit occurring between the electrically conductive layer of the present invention and the positive electrode is expressed as an internal short circuit.
Figure JPOXMLDOC01-appb-T000001
　平均粒径80μmの金属異物の場合、本発明の電池では，従来の電池の場合の1/12～1/2の時間内という早期に内部短絡が起きた。
Figure JPOXMLDOC01-appb-T000001
In the case of metallic foreign matter having an average particle size of 80 μm, the battery of the present invention caused an internal short circuit as early as 1/12 to 1/2 the time of the conventional battery.
　また、平均粒径30μmの金属異物の場合、従来の電池では、内部短絡が起こらなかったが、本発明の電池では内部短絡が発生した。 Further, in the case of a metal foreign matter having an average particle diameter of 30 μm, an internal short circuit did not occur in the conventional battery, but an internal short circuit occurred in the battery of the present invention.
　つまり、本発明によれば、金属異物による内部短絡を従来よりも早期に検出できた。また従来は混入していても内部短絡しないために見逃していた小さな金属異物による内部短絡を本発明では検出できた。 That is, according to the present invention, an internal short circuit due to a metal foreign object could be detected earlier than before. Moreover, even if it is mixed in the past, the present invention can detect an internal short circuit caused by a small metal foreign object that is overlooked because it does not cause an internal short circuit.
   1：負極側集電体
   2：負極側合剤層
   3：電気絶縁層
   4：電気伝導層
   5：正極側合剤層
   6：正極側集電体
   7：貫通孔
   8：正極に接続された端子
   9：負極に接続された電池外装容器の胴体
  10：電気伝導層に接続された端子
  11：電極捲回体
  12：アルミラミネート型の電池外装容器
  13：負極に接続された端子
  14：電極積層体
  15：負極
  16：正極 1: Negative electrode side current collector 2: Negative electrode side mixture layer 3: Electrical insulating layer 4: Electrical conduction layer 5: Positive electrode side mixture layer 6: Positive electrode side current collector 7: Through hole 8: Terminal connected to positive electrode 9: Body of the battery outer container connected to the negative electrode 10: Terminal connected to the electrically conductive layer 11: Electrode winding body 12: Aluminum laminated battery outer container 13: Terminal connected to the negative electrode 14: Electrode laminate 15: Negative electrode 16: Positive electrode

Claims (10)

  1. 　電池外装容器と、
    　正極と、
    　負極と、
    　前記正極と前記負極との間に設けられた電気絶縁層と、
    　電解質とを備えるリチウムイオン電池において、
    　前記正極と負極との間の電気絶縁層中に、電気伝導層を備えることを特徴とするリチウムイオン電池。     A battery case,
    A positive electrode;
    A negative electrode,
    An electrical insulating layer provided between the positive electrode and the negative electrode;
    In a lithium ion battery comprising an electrolyte,
    A lithium ion battery comprising an electrically conductive layer in an electrically insulating layer between the positive electrode and the negative electrode.
  2. 　請求項１において、
    　前記電気絶縁層及び前記電気伝導層は、前記電解質が充填され、前記正極から前記負極まで貫通する貫通孔を備えたことを特徴とするリチウムイオン電池。     In claim 1,
    The lithium ion battery, wherein the electrically insulating layer and the electrically conductive layer are filled with the electrolyte and have through holes penetrating from the positive electrode to the negative electrode.
  3. 　請求項１において、
    　前記電気伝導層は、負極と電気的に接続されていることを特徴とするリチウムイオン電池。     In claim 1,
    The lithium ion battery, wherein the electrically conductive layer is electrically connected to a negative electrode.
  4. 　請求項１において、
    　前記電気伝導層は、正極および負極とは電気的に独立して、電気的接続のためのリード線と、前記電池外装容器との電気的接点を有していることを特徴とするリチウムイオン電池。     In claim 1,
    The lithium ion battery, wherein the electrically conductive layer is electrically independent of a positive electrode and a negative electrode, and has an electrical contact between a lead wire for electrical connection and the battery outer casing. .
  5. 　請求項１において、
    　前記電気伝導層は、金属、合金、カーボン、導電性金属酸化物、導電性高分子のうちの少なくとも１つからなることを特徴とするリチウムイオン電池。     In claim 1,
    The lithium ion battery is characterized in that the electrically conductive layer is made of at least one of metal, alloy, carbon, conductive metal oxide, and conductive polymer.
  6. 　請求項１において、
    　前記電気絶縁層は、ポリプロピレンシート、ポリエチレンシート、ポリオレフィン樹脂、ポリエステル樹脂、フッ素樹脂、ポリイミド樹脂のうち少なくとも１つからなることを特徴とするリチウムイオン電池。     In claim 1,
    The lithium ion battery is characterized in that the electrical insulating layer is made of at least one of a polypropylene sheet, a polyethylene sheet, a polyolefin resin, a polyester resin, a fluororesin, and a polyimide resin.
  7. [規則91に基づく訂正 07.01.2011]　
    　電池外装容器と、
    　正極と、
    　負極と、
    　前記正極と前記負極との間に設けられた電気絶縁層と、
    　電解質を備えるリチウムイオン電池の製造方法において、
    　正極と負極の間に、内部に電気伝導層を有する電気絶縁層を形成して電極捲回体または電極積層体を形成する工程と、
    　前記電極捲回体または電極積層体に電解質を充填する工程と、
    　前記電解質充填後に充電を行なう工程と，
    　前記正極と前記電気伝導層との間に電圧を印加する工程を含む
    　ことを特徴とするリチウムイオン電池の製造方法。     [Correction 07.01.2011 based on Rule 91]
    A battery case,
    A positive electrode;
    A negative electrode,
    An electrical insulating layer provided between the positive electrode and the negative electrode;
    In a method for producing a lithium ion battery comprising an electrolyte,
    Forming an electrode winding body or an electrode laminate by forming an electrically insulating layer having an electrically conductive layer inside between the positive electrode and the negative electrode;
    Filling the electrode winding body or electrode laminate with an electrolyte; and
    Charging after the electrolyte is filled;
    The manufacturing method of the lithium ion battery characterized by including the process of applying a voltage between the said positive electrode and the said electrically conductive layer.
  8. 　請求項７において、
    　前記充電を行なう工程では、前記正極と前記電気伝導層との間に電圧を印加し，前記正極と前記電気伝導層との間の電位差および電流を測定しながら前記充電を行なうことを特徴とするリチウムイオン電池の製造方法。     In claim 7,
    In the charging step, a voltage is applied between the positive electrode and the electrically conductive layer, and the charging is performed while measuring a potential difference and a current between the positive electrode and the electrically conductive layer. A method for producing a lithium ion battery.
  9. 　請求項８において、
    　前記充電を行なう工程では、前記電気伝導層に、前記正極よりも低い電極電位を印加することを特徴とするリチウムイオン電池の製造方法。     In claim 8,
    In the charging step, an electrode potential lower than that of the positive electrode is applied to the electrically conductive layer.
  10. 　請求項７において、
    　前記充電を行なう工程の後に、前記正極と前記電気伝導層との間に電圧を印加し，前記正極と前記電気伝導層との間の電位差および電流の測定を行なうことを特徴とするリチウムイオン電池の製造方法。     In claim 7,
    After the step of performing charging, a voltage is applied between the positive electrode and the electrically conductive layer to measure a potential difference and current between the positive electrode and the electrically conductive layer. Manufacturing method.
PCT/JP2010/006477 2009-12-11 2010-11-04 Lithium-ion battery and method for producing same WO2011070712A1 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016091567A1 (en) * 2014-12-10 2016-06-16 Bayerische Motoren Werke Aktiengesellschaft Lithium ion cell
CN105940525A (en) * 2014-01-30 2016-09-14 帝人株式会社 Separator for nonaqueous secondary batteries, and nonaqueous secondary battery
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US9954213B2 (en) 2011-07-11 2018-04-24 California Institute Of Technology Electrochemical systems with at least one electronically and ionically conductive layer
EP3327822A1 (en) * 2016-11-29 2018-05-30 Lithium Energy and Power GmbH & Co. KG Battery cell
US9991492B2 (en) 2013-11-18 2018-06-05 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
US10158110B2 (en) 2011-07-11 2018-12-18 California Institute Of Technology Separators for electrochemical systems
US10236493B2 (en) 2014-07-02 2019-03-19 Pellion Technologies, Inc. Multi-electrode electrochemical cell and method of making the same
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* Cited by examiner, † Cited by third party
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08180853A (en) * 1994-12-21 1996-07-12 Mitsubishi Cable Ind Ltd Separator and lithium secondary battery
WO2001063687A1 (en) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Nonaqueous electrolyte secondary cell
JP2006269358A (en) * 2005-03-25 2006-10-05 Mitsubishi Chemicals Corp Porous separator for nonaqueous electrolyte secondary cell and nonaqueous electrolyte secondary cell using above

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08180853A (en) * 1994-12-21 1996-07-12 Mitsubishi Cable Ind Ltd Separator and lithium secondary battery
WO2001063687A1 (en) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Nonaqueous electrolyte secondary cell
JP2006269358A (en) * 2005-03-25 2006-10-05 Mitsubishi Chemicals Corp Porous separator for nonaqueous electrolyte secondary cell and nonaqueous electrolyte secondary cell using above

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US10608234B2 (en) 2014-07-02 2020-03-31 Viking Power Systems Pte. Ltd. Multi-electrode electrochemical cell and method of making the same
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JP2011124104A (en) 2011-06-23

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