WO2011070712A1 - Batterie lithium-ion et son procédé de fabrication - Google Patents

Batterie lithium-ion et son procédé de fabrication Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
conductive layer
electrode
electrically conductive
negative electrode
Prior art date
Application number
PCT/JP2010/006477
Other languages
English (en)
Japanese (ja)
Inventor
利光 野口
Original Assignee
株式会社日立製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Priority to KR1020127014775A priority Critical patent/KR101375422B1/ko
Publication of WO2011070712A1 publication Critical patent/WO2011070712A1/fr

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne une batterie lithium-ion dans laquelle des courts-circuits internes qui sont provoqués par inclusion d'un corps étranger métallique peuvent être détectés de manière anticipée avec une sensibilité élevée. La présente invention concerne également un procédé de fabrication de ladite batterie. La batterie lithium-ion, qui est munie d'une électrode positive (16), d'une électrode négative (15) et d'un électrolyte, est en outre munie d'une couche d'isolation électrique (3) qui est située entre l'électrode positive et l'électrode négative et comprend une couche électroconductrice (4). En appliquant une tension entre l'électrode positive (16) et la couche électroconductrice (4) et en mesurant un courant et une différence de potentiel entre l'électrode positive (16) et la couche électroconductrice (4), la possibilité d'occurrence de courts-circuits internes dans la batterie lithium-ion peut être détectée de manière anticipée avec une sensibilité élevée puisqu'il existe une occurrence précédente de court-circuit entre l'électrode positive et la couche électroconductrice qu'entre l'électrode positive et l'électrode négative.
PCT/JP2010/006477 2009-12-11 2010-11-04 Batterie lithium-ion et son procédé de fabrication WO2011070712A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020127014775A KR101375422B1 (ko) 2009-12-11 2010-11-04 리튬 이온 전지 및 그의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009281122A JP5452202B2 (ja) 2009-12-11 2009-12-11 リチウムイオン電池およびその製造方法
JP2009-281122 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011070712A1 true WO2011070712A1 (fr) 2011-06-16

Family

ID=44145279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/006477 WO2011070712A1 (fr) 2009-12-11 2010-11-04 Batterie lithium-ion et son procédé de fabrication

Country Status (3)

Country Link
JP (1) JP5452202B2 (fr)
KR (1) KR101375422B1 (fr)
WO (1) WO2011070712A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016091567A1 (fr) * 2014-12-10 2016-06-16 Bayerische Motoren Werke Aktiengesellschaft Élément lithium-ions
CN105940525A (zh) * 2014-01-30 2016-09-14 帝人株式会社 非水系二次电池用隔膜及非水系二次电池
EP3093905A1 (fr) * 2015-05-15 2016-11-16 Robert Bosch GmbH Élément de batterie et procédé de commande d'un flux ionique dans un élément de batterie
US9954213B2 (en) 2011-07-11 2018-04-24 California Institute Of Technology Electrochemical systems with at least one electronically and ionically conductive layer
EP3327822A1 (fr) * 2016-11-29 2018-05-30 Lithium Energy and Power GmbH & Co. KG Batterie
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
US10714724B2 (en) 2013-11-18 2020-07-14 California Institute Of Technology Membranes for electrochemical cells
US11271214B2 (en) 2015-12-02 2022-03-08 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells
WO2022052119A1 (fr) * 2020-09-14 2022-03-17 宁德新能源科技有限公司 Électrolyte solide composite, batterie, et dispositif électronique

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10476114B2 (en) * 2013-05-03 2019-11-12 The Board Of Trustees Of The Leland Stanford Junior University Rechargeable battery safety by multifunctional separators and electrodes
US20150004450A1 (en) * 2013-06-28 2015-01-01 Naoki Matsumura Detection Mechanism
JP6558906B2 (ja) * 2015-02-06 2019-08-14 株式会社日本触媒 セパレータ及びそれを含んで構成される電池
DE102017215962A1 (de) 2017-09-11 2019-03-14 Robert Bosch Gmbh Verfahren zur Herstellung einer Elektrodeneinheit für eine Batteriezelle und Batteriezelle
EP3499532B1 (fr) * 2017-12-15 2022-12-07 Hitachi Energy Switzerland AG Supercondensateur
WO2023276964A1 (fr) * 2021-06-28 2023-01-05 日東電工株式会社 Stratifié pour batterie, et procédé de fabrication de celui-ci
CN117561640A (zh) * 2021-06-28 2024-02-13 日东电工株式会社 非水系电解质二次电池用隔膜及非水系电解质二次电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08180853A (ja) * 1994-12-21 1996-07-12 Mitsubishi Cable Ind Ltd セパレータ及びＬｉ二次電池
WO2001063687A1 (fr) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Element secondaire a electrolyte non-aqueux
JP2006269358A (ja) * 2005-03-25 2006-10-05 Mitsubishi Chemicals Corp 非水系電解液二次電池用多孔質セパレータおよびそれを用いた非水系電解液二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08180853A (ja) * 1994-12-21 1996-07-12 Mitsubishi Cable Ind Ltd セパレータ及びＬｉ二次電池
WO2001063687A1 (fr) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Element secondaire a electrolyte non-aqueux
JP2006269358A (ja) * 2005-03-25 2006-10-05 Mitsubishi Chemicals Corp 非水系電解液二次電池用多孔質セパレータおよびそれを用いた非水系電解液二次電池

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10693117B2 (en) 2011-07-11 2020-06-23 California Institute Of Technology Electrochemical systems with ionically conductive and electronically insulating separator
US11527802B2 (en) 2011-07-11 2022-12-13 California Institute Of Technology Electrochemical systems with ionically conductive and electronically insulating separator
US9954213B2 (en) 2011-07-11 2018-04-24 California Institute Of Technology Electrochemical systems with at least one electronically and ionically conductive layer
US10158110B2 (en) 2011-07-11 2018-12-18 California Institute Of Technology Separators for electrochemical systems
US11177537B2 (en) 2013-11-18 2021-11-16 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
US10714724B2 (en) 2013-11-18 2020-07-14 California Institute Of Technology Membranes for electrochemical cells
US9991492B2 (en) 2013-11-18 2018-06-05 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
CN105940525A (zh) * 2014-01-30 2016-09-14 帝人株式会社 非水系二次电池用隔膜及非水系二次电池
US10608235B2 (en) 2014-07-02 2020-03-31 Viking Power Systems Pte. Ltd. Multi-electrode electrochemical cell and method of making the same
US10236493B2 (en) 2014-07-02 2019-03-19 Pellion Technologies, Inc. Multi-electrode electrochemical cell and method of making the same
US10608234B2 (en) 2014-07-02 2020-03-31 Viking Power Systems Pte. Ltd. Multi-electrode electrochemical cell and method of making the same
WO2016091567A1 (fr) * 2014-12-10 2016-06-16 Bayerische Motoren Werke Aktiengesellschaft Élément lithium-ions
US10199622B2 (en) 2015-05-15 2019-02-05 Robert Bosch Gmbh Battery cell and method for controlling ion flow within the battery cell
CN106159168B (zh) * 2015-05-15 2021-03-23 锂能源和电力有限责任两合公司 电池单池和用于对电池单池内的离子流进行控制的方法
CN106159168A (zh) * 2015-05-15 2016-11-23 锂能源和电力有限责任两合公司 电池单池和用于对电池单池内的离子流进行控制的方法
EP3093905A1 (fr) * 2015-05-15 2016-11-16 Robert Bosch GmbH Élément de batterie et procédé de commande d'un flux ionique dans un élément de batterie
US11271214B2 (en) 2015-12-02 2022-03-08 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells
US11894562B2 (en) 2015-12-02 2024-02-06 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells
EP3327822A1 (fr) * 2016-11-29 2018-05-30 Lithium Energy and Power GmbH & Co. KG Batterie
WO2022052119A1 (fr) * 2020-09-14 2022-03-17 宁德新能源科技有限公司 Électrolyte solide composite, batterie, et dispositif électronique

Also Published As

Publication number Publication date
KR101375422B1 (ko) 2014-03-17
JP2011124104A (ja) 2011-06-23
KR20120091328A (ko) 2012-08-17
JP5452202B2 (ja) 2014-03-26

Similar Documents

Publication Publication Date Title
JP5452202B2 (ja) リチウムイオン電池およびその製造方法
JP4927064B2 (ja) 二次電池
JP5397711B2 (ja) 電池用電極の製造方法
EP2731169B1 (fr) Batterie secondaire
EP2814082B1 (fr) Cellules électrochimiques avec des séparateurs de contenant du verre
JP2021513190A (ja) 電気化学素子用セパレータ及びそれを含む電気化学素子
WO2007060910A1 (fr) Materiau exterieur pour un dispositif electrochimique et dispositif electrochimique comprenant un tel materiau exterieur
JP2007059230A (ja) 非水電解液二次電池及びこれを用いた電池パック
JP5590381B2 (ja) リチウムイオン二次電池
KR20130105362A (ko) 전기 디바이스용 정극 및 이것을 사용한 전기 디바이스
JP2010225539A (ja) リチウムイオン二次電池用電極及びリチウムイオン二次電池
JP2012043629A (ja) 非水系電解液二次電池用セパレータ及び非水系電解液二次電池
JP2014107061A (ja) 非水電解質電池
JP2010102868A (ja) リチウム二次電池
CN110402506B (zh) 锂离子二次电池
JP4952314B2 (ja) 非水系二次電池用セパレータおよびこれを備えた非水系二次電池
CN110416630B (zh) 全固体电池
US20140315084A1 (en) Method and apparatus for energy storage
KR20160027364A (ko) 이차전지용 전극조립체
CN111386616A (zh) 制造二次电池用电极的方法和制造二次电池的方法
JP2011018594A (ja) 電池用電極の製造方法
TW202019003A (zh) 電化學裝置用之隔板、彼之製造方法及包含彼之電化學裝置
JP3648540B2 (ja) 非水電解質二次電池
JP2010003614A (ja) 電極用集電体の製造方法
JP6846570B2 (ja) 非水電解質二次電池及び非水電解質二次電池の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10835643

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20127014775

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10835643

Country of ref document: EP

Kind code of ref document: A1