WO2015049778A1 - Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion - Google Patents

Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion Download PDF

Info

Publication number
WO2015049778A1
WO2015049778A1 PCT/JP2013/077028 JP2013077028W WO2015049778A1 WO 2015049778 A1 WO2015049778 A1 WO 2015049778A1 JP 2013077028 W JP2013077028 W JP 2013077028W WO 2015049778 A1 WO2015049778 A1 WO 2015049778A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
ion secondary
positive electrode
lithium ion
secondary battery
Prior art date
Application number
PCT/JP2013/077028
Other languages
English (en)
Japanese (ja)
Inventor
貴嗣 上城
安藤　慎輔
篤彦 大沼
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 PCT/JP2013/077028 priority Critical patent/WO2015049778A1/fr
Publication of WO2015049778A1 publication Critical patent/WO2015049778A1/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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/12—Testing dielectric strength or breakdown voltage ; Testing or monitoring effectiveness or level of insulation, e.g. of a cable or of an apparatus, for example using partial discharge measurements; Electrostatic testing
    • G01R31/18—Subjecting similar articles in turn to test, e.g. go/no-go tests in mass production
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5005—Auxiliary electrodes
    • 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
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H01M2010/4271—Battery management systems including electronic circuits, e.g. control of current or voltage to keep battery in healthy state, cell balancing
    • 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, a lithium ion secondary battery system, a potential detection method for a lithium ion secondary battery, and a control method for a lithium ion secondary battery.
  • An object of this invention is to detect the electric potential of each of a positive electrode and a negative electrode accurately.
  • a lithium ion secondary battery having a positive electrode, a negative electrode, a positive electrode reference electrode, and a negative electrode reference electrode, the positive electrode reference electrode including a positive electrode active material for a reference electrode used for a positive electrode of a lithium battery or a lithium ion secondary battery, and a negative electrode
  • a reference electrode is a lithium ion secondary battery containing the negative electrode active material for reference electrodes used for the negative electrode of a lithium battery or a lithium ion secondary battery.
  • the potentials of the positive electrode and the negative electrode can be detected with high accuracy. Problems, configurations, and effects other than those described above will become apparent from the following description of the embodiments.
  • FIG. 1 is a schematic diagram showing the configuration of a lithium ion secondary battery in one embodiment of the present invention.
  • an electrode group including a positive electrode 101, a separator 103, a negative electrode 102, a positive electrode reference electrode 104, and a negative electrode reference electrode 105 are installed and configured in a battery case 106.
  • the electrode group has a configuration in which the positive electrode 101, the separator 103, the negative electrode 102, and the separator 103 are alternately stacked and wound, or the positive electrode 101, the separator 103, the negative electrode 102, and the separator 103 are alternately stacked.
  • the shape of the battery includes a cylindrical shape, a flat oval shape, and a square shape when the electrode group is wound, and a rectangular shape and a laminate shape when the electrode group is wound. The shape may be selected.
  • the positive electrode 101, the negative electrode 102, the positive electrode reference electrode 104, and the negative electrode reference electrode 105 are disposed away from each other through the electrolytic solution.
  • the electrolytic solution for example, a non-aqueous solution in which 1 mol / l of lithium hexafluorophosphate as a lithium salt is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate having a volume ratio of 1: 1 is injected.
  • the positive electrode reference electrode 104 is disposed in the vicinity of the positive electrode 101, and the negative electrode reference electrode 105 is disposed in the vicinity of the negative electrode 102.
  • the location of the positive electrode reference electrode 104 and the negative electrode reference electrode 105 is not limited, but the electrode potential changes when the concentration of the electrolyte solution around the electrode is different. Therefore, the potentials VP and VN of the positive electrode 101 and the negative electrode 102 are accurately detected. It is difficult. Therefore, it is desirable that the positive electrode reference electrode 104 is disposed in the vicinity of the positive electrode 101 and the negative electrode reference electrode 105 is disposed in the vicinity of the negative electrode 102 so as not to be affected by the electrolyte concentration.
  • FIG. 2 shows a specific example of the installation location of the positive electrode reference electrode 104 and the negative electrode reference electrode 105.
  • FIG. 2 is a schematic arrangement view of electrodes of a lithium ion secondary battery.
  • the positive electrode 101 includes a positive electrode current collector foil and a positive electrode active material applied on the positive electrode current collector foil.
  • the positive electrode 101 takes a form in which a positive electrode active material is applied to a positive electrode current collector foil such as aluminum, and the positive electrode reference electrode 104 is applied to the positive electrode active material on the positive electrode current collector foil in the vicinity of the applied positive electrode active material. Place it on the part that is not.
  • the applied positive electrode active material and the positive electrode reference electrode 104 are arranged adjacent to each other on the same plane.
  • the negative electrode 102 includes a negative electrode current collector foil and a negative electrode active material coated on the negative electrode current collector foil.
  • the negative electrode 102 takes a form in which a negative electrode active material is applied to a negative electrode current collector foil such as copper, and the negative electrode reference electrode 105 is applied to the negative electrode active material on the negative electrode current collector foil in the vicinity of the applied negative electrode active material. Place it on the part that is not.
  • the applied negative electrode active material and the negative electrode reference electrode 105 are arranged adjacent to each other on the same plane. As shown in FIG. 2, the combination of the positive electrode 101 and the positive electrode reference electrode 104, the separator 103, and the combination of the negative electrode 102 and the negative electrode reference electrode 105 are stacked in this order.
  • the positive electrode reference electrode 104 and the negative electrode reference electrode 105 are covered with a polyolefin-based resin sheet that is used for the separator 103, and the positive electrode 101 and the positive electrode reference electrode 104, and the negative electrode 102 and the negative electrode reference electrode 105. Does not have electrical conductivity. As shown in FIG. 2, by disposing the positive electrode reference electrode 104 and the negative electrode reference electrode 105, it is not necessary to incorporate the separator 103, so that the electrode as shown in FIG.
  • the positive electrode reference electrode 104 and the negative electrode reference electrode 105 may be incorporated in the separator 103 as shown in FIG.
  • the positive electrode 101 and the negative electrode 102 are stacked facing each other through the separator 103, and the positive electrode reference electrode 104 and the negative electrode reference electrode 105 are incorporated into the separator 103 having a two-layer and three-layer structure.
  • the positive electrode 101, the negative electrode 102, the positive electrode reference electrode 104, and the negative electrode reference electrode 105 do not have electrical conductivity with each other.
  • FIG. 2 by disposing the positive electrode reference electrode 104 and the negative electrode reference electrode 105, the use area of the positive electrode 101 and the negative electrode 102 can be increased, and the battery capacity per unit volume can be increased.
  • the positive electrode 101 includes a positive electrode active material made of a lithium-containing oxide that can reversibly insert and desorb lithium ions.
  • the positive electrode active material include layered transition metal oxides with or without substitution elements, lithium transition metal phosphates, and spinel type transition metal oxides.
  • the layered transition metal oxide lithium nickelate LiNiO 2 or lithium cobaltate LiCoO 2
  • the transition metal lithium phosphate iron lithium LiFePO 4 manganese manganese phosphate LiMnPO 4
  • spinel type transition metal oxide examples thereof include lithium manganate LiMn 2 O 4 .
  • One kind or two or more kinds of the above materials may be contained as the positive electrode active material.
  • lithium ions are desorbed in the charging process, and lithium ions desorbed from the negative electrode active material in the negative electrode 102 are inserted in the discharging process.
  • the negative electrode 102 is, for example, a carbon material that can reversibly insert and desorb lithium ions, silicon-based material Si, SiO, lithium titanate with or without a substitution element, lithium vanadium composite oxide, lithium and metal, for example, , A negative electrode active material made of an alloy with tin, aluminum, antimony or the like.
  • a carbon material as a raw material, natural graphite, a composite carbonaceous material obtained by forming a film on natural graphite by a dry CVD method or a wet spray method, a resin material such as epoxy or phenol, or a pitch-based material obtained from petroleum or coal Examples thereof include artificial graphite and non-graphitizable carbon material produced by firing.
  • the above materials may be contained singly or in combination of two or more as the negative electrode active material.
  • the negative electrode active material in the negative electrode 102 undergoes insertion / extraction reaction or conversion reaction of lithium ions in the charge / discharge process.
  • a polypropylene separator is used as the separator 103 used between the positive electrode 101 and the negative electrode 102.
  • a microporous film or non-woven fabric made of polyolefin such as polyethylene can be used.
  • the positive electrode terminal 107 and the negative electrode terminal 109 are energized with the positive electrode 101 and the negative electrode 102, respectively, and the lithium ion secondary battery 120 is charged and discharged by an external circuit via the positive electrode terminal 107 and the negative electrode terminal 109.
  • the positive electrode reference electrode 104 and the negative electrode reference electrode 105 are electrically connected to the positive electrode reference electrode terminal 108 and the negative electrode reference electrode terminal 110, respectively.
  • the positive electrode reference electrode 104 is made of a material including the positive electrode active material used for the positive electrode of the lithium ion secondary battery described above or the positive electrode active material used for the positive electrode of the lithium battery.
  • the potential difference between the positive electrode 101 and the positive electrode reference electrode 104 is small, and the maximum range of the voltmeter for measuring the potential difference can be reduced, so that the positive electrode potential can be detected with high accuracy.
  • the small potential difference means that the potential difference between the positive electrode 101 and the positive electrode reference electrode 104 is 2 V or less, preferably 1.5 V, and more preferably 1 V or less.
  • Examples of the positive electrode active material for the reference electrode used for the positive electrode of the lithium battery include graphite fluoride, thionyl chloride, lithium copper oxide, manganese dioxide and the like. Of these, thionyl chloride and manganese dioxide are preferable because of their relatively high potential.
  • lithium transition metal lithium with or without a substitution element LiMPO 4 (M is a transition metal and is at least one of iron, manganese, and vanadium)
  • the material is selected from a group of materials having a flat and stable charge / discharge potential of about 3 V to about 6 V with respect to (Li + ).
  • lithium transition metal lithium having a wide, flat and stable charge / discharge potential region is desirable from the viewpoint of potential stability.
  • the positive electrode reference electrode 104 may contain one or more of the above materials. When two or more kinds of the above materials are included in the positive electrode reference electrode 104, a plurality of potential stable regions exist, and each region becomes narrower with respect to 1 mol of the active material. Therefore, in consideration of potential stability, it is desirable to use the above-mentioned material alone as the positive electrode reference electrode 104.
  • the negative electrode reference electrode 105 is made of a material including the negative electrode active material used for the negative electrode of the lithium ion secondary battery described above and the negative electrode active material used for the negative electrode of the lithium battery. That is, the negative electrode reference electrode 105 includes a negative electrode active material for a reference electrode used for a positive electrode of a lithium battery.
  • the potential difference between the negative electrode 102 and the negative electrode reference electrode 105 is small, and the maximum range of the voltmeter for measuring the potential difference can be reduced, so that the negative electrode potential can be detected with high accuracy.
  • the small potential difference means that the potential difference between the negative electrode 102 and the negative electrode reference electrode 105 is 2 V or less, desirably 1.5 V, and more desirably 1 V or less.
  • the negative electrode material has a region in which Li insertion / extraction occurs as a two-phase coexistence reaction, such as lithium titanate, lithium vanadium composite oxide, graphite, and the like, and about 0 V with respect to the reference potential (Li / Li + ). It is desirable to select from a group of materials having a flat and stable charge / discharge potential of ⁇ 3V or lithium metal. Among them, lithium titanate having a wide, flat and stable charge / discharge potential region is desirable from the viewpoint of potential stability. Further, in order not to change the potential of the negative electrode reference electrode 105, it is desirable to insert Li into the negative electrode reference electrode 105 containing the above-described material excluding lithium metal up to a region where the two-phase coexistence reaction occurs.
  • the negative electrode reference electrode 105 one or more of the above materials may be contained.
  • the negative electrode 105 includes two or more of the above materials, there are a plurality of potential stable regions, and each region becomes narrower than 1 mol of the active material. Therefore, in consideration of potential stability, it is desirable to use the above-mentioned materials alone as the negative electrode reference electrode 105.
  • ⁇ Voltmeter 130> Outside the lithium ion secondary battery 120, the positive electrode terminal 107, the positive electrode reference electrode terminal 108, the negative electrode terminal 109, the negative electrode reference electrode terminal 110 and the voltmeter 130 are connected to detect a potential difference, thereby charging or discharging or resting.
  • the potentials VP and VN of the positive electrode 101 and the negative electrode 102 can be detected.
  • a potential difference ⁇ VP1 is detected by connecting the positive electrode terminal 107 and the positive electrode reference electrode terminal 108 to the voltmeter 130, and a potential difference ⁇ VN1 is detected by connecting the negative electrode terminal 109 and the negative electrode reference electrode terminal 110 to the voltmeter 130. Is done.
  • the potential difference ⁇ VP2 is detected by connecting the positive electrode terminal 107 and the negative electrode reference electrode terminal 110 to the voltmeter 130
  • the potential difference ⁇ VN2 is detected by connecting the negative electrode terminal 109 and the positive electrode reference electrode terminal 108 to the voltmeter 130. Is detected.
  • the potentials of the positive electrode 101 and the negative electrode 102 VP and VN can be detected.
  • the potential difference ⁇ VR between the reference electrodes can be detected based on the potential difference between the positive electrode reference electrode 108 and the negative electrode reference electrode 110.
  • the potential of ⁇ VP1 and the positive electrode reference electrode 104 is used from the positive electrode reference electrode 104 and the negative electrode reference electrode 105 measured in advance as the detected ⁇ VP1 and ⁇ VP2 for the following reason. It is desirable to detect the potential VP of the positive electrode 101.
  • the voltmeter 130 has a device-specific error.
  • the accuracy of the voltmeter 130 is expressed in the range of the class accuracy 0.05 to 3.5 (class), and the accuracy varies depending on the equipment. Since the error caused by the voltmeter 130 is determined by a percentage of the class accuracy with respect to the maximum range, the potential VP of the positive electrode 101 can be detected more accurately as the maximum range is smaller.
  • the potential VRP of the positive electrode reference electrode 104 has a range of about 3V to about 6V
  • the potential VRN of the negative electrode reference electrode 105 has a range of about 0V to about 3V
  • the potential VP of the positive electrode 101 has a range of about 3V to about 6V.
  • ⁇ VP1 has a smaller value than ⁇ VP2 and the maximum range can be set small, so that the potential VP of the positive electrode 101 can be detected with high accuracy.
  • class accuracy the smaller the value, the higher the accuracy of the potential difference that is automatically detected, which is desirable.
  • the lithium salt is not particularly limited, but for inorganic lithium salts, LiPF 6 , LiBF 4 , LiClO 4 , LiI, LiCl, LiBr, etc., and for organic lithium salts, LiB [OCOCF 3 ] 4 , LiB [OCOCF 2 CF 3 ] 4 , LiPF 4 (CF 3 ) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 CF 3 ) 2 or the like can be used.
  • an aprotic organic solvent such as ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate, or a solvent of two or more mixed organic compounds is used.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • propylene carbonate or a solvent of two or more mixed organic compounds.
  • Lithium ion secondary batteries have good discharge characteristics during charge / discharge cycles, low temperature and high current discharge characteristics, long-term storage, and long-term high-temperature storage characteristics. Therefore, there is a demand for an organic electrolyte that satisfies these requirements. In order to satisfy the above various requirements, it is difficult to use a solvent composed of only one kind of compound, and it is necessary to mix two or more kinds of compounds and use them as a solvent.
  • the degree of dissociation of the lithium salt is improved and ion conductivity is improved.
  • ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like dimethyl carbonate (DMC) , Ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), and the like.
  • Solid electrolyte When using a solid polymer electrolyte (polymer electrolyte) in addition to the electrolyte as the electrolyte, ion-conducting polymers such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyhexafluoropropylene, and polyethylene oxide are used as the electrolyte. Can be used. When these solid polymer electrolytes are used, there is an advantage that the separator 103 can be omitted.
  • the lithium ion secondary battery system 200 indicates an assembled battery in which a plurality of lithium ion secondary batteries including the lithium ion secondary battery 120 are connected in series or in parallel.
  • the lithium ion secondary battery system 200 indicates an assembled battery in which a plurality of lithium ion secondary batteries including the lithium ion secondary battery 120 are connected in series or in parallel.
  • a system in which a plurality of lithium ion secondary batteries including a lithium ion secondary battery 120 are connected in series will be described.
  • FIG. 4 is a circuit diagram of a lithium ion secondary battery system having a lithium ion secondary battery 120 showing a configuration in an embodiment of the present invention, and shows a basic configuration of a charge / discharge control system of the lithium ion secondary battery 120. It is a block diagram.
  • the lithium ion secondary battery 120 in FIG. 4 includes a receiver 140 that intercepts ⁇ VP1, ⁇ VP2, ⁇ VN1, ⁇ VN2, and ⁇ VR detected by connecting a plurality of lithium ion secondary batteries 120 and a voltmeter 130, and electronic control.
  • the power supply circuit 143 which is a power source of the unit 142 and the electronic control unit 142 is included.
  • the electronic control unit 142 includes ⁇ VP1, ⁇ VP2, ⁇ VN1, ⁇ VN2, and ⁇ VR transferred from the receiver 140, and the potential VRP with respect to the reference potential (Li / Li + ) of the positive electrode reference electrode 104 and the negative electrode reference electrode 105, which are measured in advance.
  • the VRN is used to calculate the potentials VP and VN of the positive electrode 101 and the negative electrode 102 to determine whether the electrode state satisfies the set condition, the FlashRom 141 that stores the received electrode information, and the determination unit 144.
  • the control unit 145 controls the amount of current supplied to the lithium ion secondary battery 120 according to the signal transmitted by.
  • FIG. 5 is a flowchart for explaining a control structure related to suppression of deterioration of the lithium ion secondary battery 120 in the lithium ion secondary battery system according to the embodiment of the present invention shown in FIG.
  • the process shown in this control flowchart is called from the main routine and executed at regular intervals.
  • the principle of the lithium ion secondary battery 120 is that charge / discharge reaction proceeds when lithium ions in the electrolyte are inserted into and desorbed from the electrode active material.
  • the voltage of the positive electrode 101 reaches a certain level or more
  • lithium in the positive electrode active material is excessively desorbed, the crystal structure becomes unstable and deteriorates, and the battery performance decreases. there is a possibility.
  • the voltage is 0 V or less in the negative electrode 102, there is a risk that the lithium metal is dendrite deposited and the battery is short-circuited.
  • the voltage is lower than a certain voltage, side reactions are promoted and the crystal structure is collapsed, which may reduce the battery life.
  • the crystal structure In the discharging process of the lithium ion secondary battery 120, when the voltage of the positive electrode 101 becomes a certain voltage or lower, the crystal structure may be irreversibly transferred, and the battery performance may be deteriorated. In addition, depending on the material used for the negative electrode 102, lithium may be excessively desorbed, the crystal structure may become unstable, causing deterioration, and battery performance may be reduced.
  • the potentials VP and VN of the positive electrode 101 and the negative electrode 102 with respect to the calculated reference potential (Li / Li + ) are determined, and the charge amount to the lithium ion secondary battery 120 is suppressed.
  • the maximum potential A1 of the positive electrode 101 that can prevent the crystal structure of the positive electrode 101 from being collapsed is defined in advance, and calculated from ⁇ VP1 and the potential VRP of the positive electrode reference electrode 104.
  • the potential VP of the positive electrode 101 becomes equal to or higher than the specified value A1
  • the charge amount of the lithium ion secondary battery 120 is suppressed so that the potential VP of the positive electrode 101 becomes smaller than the specified value A1.
  • a potential at which a side reaction obtained by measurement is rapidly accelerated or a potential B1 at which the crystal structure of the negative electrode material collapses is defined, and is calculated from ⁇ VN1 and the potential VRN of the negative electrode reference electrode 105.
  • the potential VN of the negative electrode 102 becomes equal to or less than the specified value B1
  • the charge amount of the lithium ion secondary battery 120 is suppressed so that the potential VN of the negative electrode 102 becomes larger than the specified value B1.
  • the minimum potential A2 of the positive electrode 101 that can prevent the irreversible transition of the crystal structure of the positive electrode 101 during discharge of the lithium ion secondary battery 120 is defined in advance, and the positive electrode calculated from ⁇ VP1 and the potential VRP of the positive electrode reference electrode 104 When the potential VP of 101 becomes equal to or less than the specified value A2, the discharge amount of the lithium ion secondary battery 120 is suppressed so that the potential VP of the positive electrode 101 becomes larger than the specified value A2.
  • a potential at which a side reaction obtained by measurement is rapidly accelerated or a maximum potential B2 at which the crystal structure of the negative electrode material becomes unstable is defined, and ⁇ VN1 and the negative electrode reference electrode 105
  • the potential VN of the negative electrode 102 calculated from the potential VRN becomes equal to or higher than the specified value B2
  • the discharge amount of the lithium ion secondary battery 120 is suppressed so that the potential VN of the negative electrode 102 becomes smaller than the specified value B2.
  • ⁇ VP1, ⁇ VP2, ⁇ VN1, ⁇ VN2, and ⁇ VR detected from the lithium ion secondary battery 120 are output to the electronic control unit 142 via the receiver 140.
  • a command is issued from the determination unit 144 in the electronic control unit 142 to the control unit 145, and the lithium ion secondary The amount of charge to the battery 120 is controlled.
  • Step S1 the determination unit 144 determines whether or not the lithium ion secondary battery 120 is being charged. If it is determined that the battery is not being charged (NO in step S1), the process proceeds to step S6. If it is determined in step S1 that lithium ion secondary battery 120 is being charged (YES in step S1), the process proceeds to step S2.
  • Step S2> The determination unit 144 calculates the potentials VP and VN of the positive electrode 101 and the negative electrode 102 using ⁇ VP1, ⁇ VP2, ⁇ VN1, ⁇ VN2, and ⁇ VR and the potentials VRP and VRN of the positive electrode reference electrode 104 and the negative electrode reference electrode 105 that are measured in advance. To do. When the calculation is completed, the process proceeds to step 3.
  • Step S3> the determination unit 144 determines whether or not the potential VP of the positive electrode 101 is smaller than the specified value A1, and whether or not the potential VN of the negative electrode 102 is larger than the specified value B1. If it is determined that neither or one of the conditions is not satisfied (NO in step S3), the process proceeds to step S4. If it is determined in step S3 that both conditions are satisfied (YES in step S3), the process proceeds to step S5.
  • Step S4> The determination unit 144 issues a command to the control unit 145 for the purpose of preventing the degradation of the battery performance due to the collapse of the crystal structure of the positive electrode 101 and the side reaction at the negative electrode 102 or the collapse of the crystal structure.
  • the amount of current to the ion secondary battery 120 is controlled.
  • Step S5> The process returns to the start, and the process starts again from step S1.
  • Step S6> In the determination unit 144, it is determined whether or not the lithium ion secondary battery 120 is being discharged. If it is determined that the battery is not discharged, that is, if it is determined that the battery is not in operation (NO in step S6), the process proceeds to step S5. If it is determined in step S6 that lithium ion secondary battery 120 is being discharged (YES in step S6), the process proceeds to step S7.
  • the potentials VP and VN are calculated.
  • Step S8> The determination unit 144 determines whether the potential VP of the positive electrode 101 is greater than the specified value A2, and whether the potential VN of the negative electrode 102 is smaller than the specified value B2. If it is determined that neither or one of the conditions is not satisfied (NO in step S8), the process proceeds to step S4. If it is determined in step S8 that both conditions are satisfied (YES in step S8), the process proceeds to step S5.
  • the potential difference ⁇ VR between the positive electrode reference electrode 104 and the negative electrode reference electrode 105 is an abnormal value, that is, an unstable value rather than a stable potential
  • ⁇ VP1 is an abnormal value, that is, ⁇ VP1 suddenly changes
  • the value of ⁇ VP2 is used.
  • the potential VP of the positive electrode 101 is calculated.
  • ⁇ VN1 is an abnormal value, that is, when ⁇ VN1 suddenly changes, the value of ⁇ VN2 is set.
  • the potential VN of the negative electrode 102 is calculated.
  • the potential difference ⁇ VR is used for confirming whether the positive electrode reference electrode 104 and the negative electrode reference electrode 105 hold a normal potential.
  • the potential VP of the positive electrode 101 is calculated from the potential difference between the positive electrode 101 and the positive electrode reference electrode 104 according to the present invention
  • the potential VN of the negative electrode 102 is calculated from the potential difference between the negative electrode 102 and the negative electrode reference electrode 105.
  • the effect of obtaining the values of the potentials VP and VN of the 101 and the negative electrode 102 is shown in the following examples.
  • reference electrode 1-1 Preparation of reference electrode A Lithium titanate 90 wt. % And polyvinylidene fluoride (PVDF) 10 wt. N-methyl-2-pyrrolidone was added to the% mixture and mixed to prepare reference electrode slurry A. The slurry A was applied to a platinum wire and vacuum-dried at 120 ° C. for 2 hours to obtain a reference electrode A to be the negative electrode reference electrode 105.
  • PVDF polyvinylidene fluoride
  • the reference electrode A In order to fill the reference electrode A with Li, the reference electrode A, separator, and Li metal were laminated in this order in the glove box, and after fixing these, hexafluoride was added to a mixed solvent of 1: 1 ethylene carbonate and diethyl carbonate. It was immersed in an electrolytic solution A in which 1 mol / l of lithium phosphate was dissolved, and a current was passed between the reference electrode A and the Li metal.
  • Li 4 Ti 5 O 12 is the standard (0%) and lithium is filled and the composition becomes Li 7 Ti 5 O 12 is defined as 100%
  • the potential of the reference electrode A filled with Li 50% Was 1.563 V (vsLi / Li + ).
  • the Li loading was 20-80%, the potential was almost unchanged.
  • Reference Electrode B LiFePO 4 90 wt. % And polyvinylidene fluoride (PVDF) 10 wt. N-methyl-2-pyrrolidone was added to and mixed with the% mixture to prepare a reference electrode slurry B.
  • the slurry B was applied to a platinum wire and vacuum dried at 120 ° C. for 2 hours to obtain a reference electrode B to be the positive electrode reference electrode 104.
  • the reference electrode B In order to fill the reference electrode B with Li, the reference electrode B, the separator, and the Li metal are stacked in this order in the glove box, and after fixing these, the electrode is immersed in the electrolytic solution A, and between the reference electrode B and the Li metal. A current was passed through.
  • Li 0 FePO 4 is the standard (0%) and lithium is filled and the composition becomes Li 1 FePO 4 is defined as 100%
  • the potential of the reference electrode B filled with 50% Li is 3.430V. (VsLi / Li + ).
  • the Li loading was 20-80%, the potential was almost unchanged.
  • Negative Electrode As a negative electrode active material, non-graphitizable carbon, N-methyl-2-pyrrolidone, PVDF 10 wt. % was added to prepare negative electrode slurry A.
  • This negative electrode slurry A was applied to a negative electrode foil which is a copper foil having a thickness of 10 ⁇ m, dried and then pressed and cut to obtain a negative electrode A.
  • the potential of the positive electrode and the negative electrode was measured.
  • the circuit of FIG. 1 was assembled to evaluate the positive electrode potential and the negative electrode potential.
  • the potential of the reference electrode A was calculated at 1.563V
  • the potential of the reference electrode B was calculated at 3.430V.
  • the circuit of FIG. 1 was assembled and the negative electrode potential was evaluated. Table 1 shows the positive electrode negative electrode potential obtained.
  • the voltmeter a high precision voltmeter with an error of 0.1% and a low precision voltmeter with an error of 2% were used.
  • Example 1 (2) the stacking order when the lithium ion secondary battery containing the reference electrode is manufactured is stacked in the order of separator, negative electrode A, separator, reference electrode A, separator, reference electrode B, separator positive electrode A, and separator. Except for the above, a lithium ion secondary battery B containing a reference electrode was produced in the same manner as in Example 1.
  • Example 1 (2) the reference electrode A and the reference electrode B when the reference electrode-containing lithium ion secondary battery was manufactured were changed to the reference electrode A to prepare a reference electrode-containing lithium ion secondary battery C.
  • Example 1 (2) the reference electrode A and the reference electrode B when the reference electrode-containing lithium ion secondary battery was manufactured were changed to the reference electrode B, and a reference electrode-containing lithium ion secondary battery C was manufactured.
  • Example 1 (2) a reference electrode-containing lithium ion secondary battery D was prepared by changing the reference electrode A and the reference electrode B to Li metal when the reference electrode-containing lithium ion secondary battery was manufactured.
  • the positive electrode potential VP is calculated based on the potential difference between the positive electrode 101 and the positive electrode reference electrode 104
  • the negative electrode potential VN is calculated based on the potential difference between the negative electrode 102 and the negative electrode reference electrode 105.
  • the value of the potential VN of the negative electrode can be obtained.
  • a battery system that suppresses the charge / discharge amount to the lithium ion secondary battery 120 using the calculated positive potential VP and negative potential VN is provided. it can.
  • the lithium-ion secondary battery of the present invention and the battery system having the secondary battery temporarily store the in-vehicle power storage system used in plug-in hybrid vehicles and electric vehicles, and the power generated by power generation. Therefore, it can be applied to a stationary power storage system.
  • Negative electrode reference electrode terminal 120 Lithium ion secondary battery 130 Voltmeter 140 Receiver 141 FlashRom 142 Electronic Control Unit 143 Determination Unit 144 Control Unit 200 Lithium Ion Secondary Battery System

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)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie rechargeable au lithium-ion grâce à laquelle il est possible de détecter avec précision des potentiels d'une électrode positive et d'une électrode négative. La batterie rechargeable au lithium-ion (120) selon la présente invention comporte une électrode positive (101), une électrode négative (102), une électrode de référence d'électrode positive (104), et une électrode de référence d'électrode négative (105). L'électrode de référence d'électrode positive comprend un matériau actif d'électrode positive d'électrode de référence utilisé dans l'électrode positive d'une batterie au lithium ou d'une batterie rechargeable au lithium-ion, l'électrode de référence d'électrode négative comprend un matériau actif d'électrode négative d'électrode de référence utilisé dans l'électrode négative d'une batterie au lithium ou d'une batterie rechargeable au lithium-ion, le matériau actif d'électrode positive d'électrode de référence est, par exemple, phosphate-fer-lithium de type olivine, et le matériau actif d'électrode négative d'électrode de référence est, par exemple, oxyde de titane-lithium.
PCT/JP2013/077028 2013-10-04 2013-10-04 Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion WO2015049778A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/077028 WO2015049778A1 (fr) 2013-10-04 2013-10-04 Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/077028 WO2015049778A1 (fr) 2013-10-04 2013-10-04 Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion

Publications (1)

Publication Number Publication Date
WO2015049778A1 true WO2015049778A1 (fr) 2015-04-09

Family

ID=52778387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/077028 WO2015049778A1 (fr) 2013-10-04 2013-10-04 Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion

Country Status (1)

Country Link
WO (1) WO2015049778A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016035309A1 (fr) * 2014-09-03 2016-03-10 株式会社Ｇｓユアサ Élément de stockage d'énergie
JP2017533545A (ja) * 2015-01-19 2017-11-09 ローベルト ボッシュ ゲゼルシャフト ミット ベシュレンクテル ハフツング ガルバニ要素のための巻回電極体及びその製造方法
CN108039514A (zh) * 2017-11-17 2018-05-15 清华大学 一种带有参比电极的锂离子电池的电镀制备方法
JP2018519647A (ja) * 2015-08-24 2018-07-19 エルジー・ケム・リミテッド 相対電極電位の測定のための基準電極を含む電池セルの製造方法およびこれによって製造された電池セル
JP2019050168A (ja) * 2017-09-12 2019-03-28 日立化成株式会社 二次電池および電源システム
CN112034020A (zh) * 2020-08-19 2020-12-04 国联汽车动力电池研究院有限责任公司 一种测定锂离子电池负极预嵌锂量的方法和装置
CN112526357A (zh) * 2020-11-25 2021-03-19 上海空间电源研究所 一种锂离子电池功率匹配性评价方法
CN113422115A (zh) * 2021-07-02 2021-09-21 广州小鹏汽车科技有限公司 锂离子电芯、锂离子电芯制备方法及析锂检测方法
CN113711407A (zh) * 2020-01-02 2021-11-26 株式会社Lg新能源 用于评估电极性能的电极组件和电极性能评估方法
FR3141563A1 (fr) * 2022-10-27 2024-05-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Préparation d’un matériau actif pour électrode de référence
FR3141562A1 (fr) * 2022-10-27 2024-05-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Préparation d’une électrode de référence à partir d’un matériau électro-actif à un état de charge intermédiaire

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005019116A (ja) * 2003-06-25 2005-01-20 Kri Inc 電気化学セル
JP2008276972A (ja) * 2007-04-25 2008-11-13 Toyota Motor Corp リチウム二次電池の制御装置、電動機駆動装置、リチウム二次電池の制御方法、およびリチウム二次電池の制御方法をコンピュータに実行させるためのプログラムを記録したコンピュータ読取可能な記録媒体
JP2010086873A (ja) * 2008-10-01 2010-04-15 Nissan Motor Co Ltd 電池、電池の電極電位を推定するための方法および装置
JP2010161001A (ja) * 2009-01-09 2010-07-22 Kri Inc 電気化学セル
JP2012033365A (ja) * 2010-07-30 2012-02-16 National Institute Of Advanced Industrial & Technology 参照電極、その製造方法、および電気化学セル
JP2013020915A (ja) * 2011-07-14 2013-01-31 Toyota Motor Corp 固体電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005019116A (ja) * 2003-06-25 2005-01-20 Kri Inc 電気化学セル
JP2008276972A (ja) * 2007-04-25 2008-11-13 Toyota Motor Corp リチウム二次電池の制御装置、電動機駆動装置、リチウム二次電池の制御方法、およびリチウム二次電池の制御方法をコンピュータに実行させるためのプログラムを記録したコンピュータ読取可能な記録媒体
JP2010086873A (ja) * 2008-10-01 2010-04-15 Nissan Motor Co Ltd 電池、電池の電極電位を推定するための方法および装置
JP2010161001A (ja) * 2009-01-09 2010-07-22 Kri Inc 電気化学セル
JP2012033365A (ja) * 2010-07-30 2012-02-16 National Institute Of Advanced Industrial & Technology 参照電極、その製造方法、および電気化学セル
JP2013020915A (ja) * 2011-07-14 2013-01-31 Toyota Motor Corp 固体電池

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016035309A1 (fr) * 2014-09-03 2016-03-10 株式会社Ｇｓユアサ Élément de stockage d'énergie
JP2017533545A (ja) * 2015-01-19 2017-11-09 ローベルト ボッシュ ゲゼルシャフト ミット ベシュレンクテル ハフツング ガルバニ要素のための巻回電極体及びその製造方法
US10141609B2 (en) 2015-01-19 2018-11-27 Robert Bosch Gmbh Electrode coil for a galvanic element, and method for producing same
JP2018519647A (ja) * 2015-08-24 2018-07-19 エルジー・ケム・リミテッド 相対電極電位の測定のための基準電極を含む電池セルの製造方法およびこれによって製造された電池セル
JP7017349B2 (ja) 2017-09-12 2022-02-08 昭和電工マテリアルズ株式会社 二次電池および電源システム
JP2019050168A (ja) * 2017-09-12 2019-03-28 日立化成株式会社 二次電池および電源システム
CN108039514A (zh) * 2017-11-17 2018-05-15 清华大学 一种带有参比电极的锂离子电池的电镀制备方法
CN113711407B (zh) * 2020-01-02 2024-01-26 株式会社Lg新能源 用于评估电极性能的电极组件和用于评估电极性能的方法
CN113711407A (zh) * 2020-01-02 2021-11-26 株式会社Lg新能源 用于评估电极性能的电极组件和电极性能评估方法
CN112034020A (zh) * 2020-08-19 2020-12-04 国联汽车动力电池研究院有限责任公司 一种测定锂离子电池负极预嵌锂量的方法和装置
CN112526357A (zh) * 2020-11-25 2021-03-19 上海空间电源研究所 一种锂离子电池功率匹配性评价方法
CN113422115A (zh) * 2021-07-02 2021-09-21 广州小鹏汽车科技有限公司 锂离子电芯、锂离子电芯制备方法及析锂检测方法
CN113422115B (zh) * 2021-07-02 2023-08-25 广州小鹏汽车科技有限公司 锂离子电芯、锂离子电芯制备方法及析锂检测方法
FR3141563A1 (fr) * 2022-10-27 2024-05-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Préparation d’un matériau actif pour électrode de référence
FR3141562A1 (fr) * 2022-10-27 2024-05-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Préparation d’une électrode de référence à partir d’un matériau électro-actif à un état de charge intermédiaire
EP4365975A1 (fr) * 2022-10-27 2024-05-08 Commissariat à l'énergie atomique et aux énergies alternatives Préparation d'un matériau actif pour électrode de référence
EP4365985A1 (fr) * 2022-10-27 2024-05-08 Commissariat à l'énergie atomique et aux énergies alternatives Préparation d'une électrode de référence à partir d'un matériau électro-actif à un état de charge intermédiaire

Similar Documents

Publication Publication Date Title
WO2015049778A1 (fr) Batterie rechargeable au lithium-ion, système à batterie rechargeable au lithium-ion, procédé pour détecter un potentiel dans une batterie rechargeable au lithium-ion, et procédé pour commander une batterie rechargeable au lithium-ion
US9761876B2 (en) Energy storage device and energy storage unit
EP2854203B1 (fr) Batterie
JP6047881B2 (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
JP6047871B2 (ja) 組電池、それを用いた蓄電装置
JP6056125B2 (ja) 組電池及び蓄電装置
US20180131202A1 (en) Power storage device
KR20140118809A (ko) 프리 도핑제, 이것을 이용한 축전 디바이스 및 그 제조 방법
JP2013178935A (ja) リチウムイオン二次電池及びそれを用いた組電池並びに蓄電装置
KR20160134808A (ko) 비수 전해액 이차 전지
JP2019160734A (ja) 組電池、電池パック、車両、及び、定置用電源
US9991563B2 (en) Energy storage device and energy storage apparatus
WO2015040684A1 (fr) Électrode de référence à fonction de thermomètre, accumulateur lithium-ion incluant l'électrode de référence à fonction de thermomètre, système d'accumulateurs lithium-ion incluant l'électrode de référence à fonction de thermomètre, et procédé de commande d'accumulateur lithium-ion
KR20170070095A (ko) 리튬 이온 이차 전지
JP5857839B2 (ja) 蓄電素子、蓄電素子の製造方法及び非水電解液
KR20160133828A (ko) 음극, 이의 제조방법 및 이를 포함하는 리튬 이차전지
JP2013211157A (ja) 組電池、それを用いた蓄電装置、並びに寿命判定方法
JP2013197052A (ja) リチウムイオン蓄電デバイス
JP2015187949A (ja) リチウムイオン二次電池
JP5748972B2 (ja) 非水電解液二次電池パック
WO2015040685A1 (fr) Séparateur pour batterie secondaire au lithium-ion, batterie secondaire au lithium-ion mettant en œuvre celui-ci, et module de batterie secondaire au lithium-ion
US20180241041A1 (en) Lithium ion secondary battery
JP6589386B2 (ja) 蓄電素子
JP2013197051A (ja) リチウムイオン蓄電デバイス
JP2013178936A (ja) リチウムイオン二次電池及びそれを用いた組電池並びに蓄電装置

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: 13895033

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13895033

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP