WO2015005294A1 - Dispositif de stockage d'électricité - Google Patents

Dispositif de stockage d'électricité Download PDF

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Publication number
WO2015005294A1
WO2015005294A1 PCT/JP2014/068090 JP2014068090W WO2015005294A1 WO 2015005294 A1 WO2015005294 A1 WO 2015005294A1 JP 2014068090 W JP2014068090 W JP 2014068090W WO 2015005294 A1 WO2015005294 A1 WO 2015005294A1
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Prior art keywords
negative electrode
storage device
capacity
active material
electrode
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PCT/JP2014/068090
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English (en)
Japanese (ja)
Inventor
照明 手塚
信雄 安東
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Ｊｍエナジー株式会社
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Priority to JP2015526330A priority Critical patent/JP6487841B2/ja
Publication of WO2015005294A1 publication Critical patent/WO2015005294A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 an electricity storage device having high energy density, high output, and durability.
  • an electricity storage device called a hybrid capacitor, which combines the electricity storage principles of a lithium ion secondary battery and an electric double layer capacitor, has attracted attention.
  • a hybrid capacitor a carbon material capable of inserting and extracting lithium ions is previously occluded and supported (hereinafter also referred to as dope) by a chemical method or an electrochemical method to lower the negative electrode potential. Therefore, an electricity storage device that can obtain a high energy density has been proposed (see, for example, Patent Document 1).
  • the cell capacity when discharging from a fully charged state to half the voltage is a [mAh]
  • the capacity when the charged negative electrode is discharged to 1.5 V [Li / Li + ] is the complete negative electrode capacity b [ mAh]
  • the ratio of the positive electrode active material and the negative electrode active material is regulated so as to satisfy 0.05 ⁇ a / b ⁇ 0.3
  • an organic electrolyte capacitor with a high output (for example, patent document) 2) is also proposed.
  • the present invention has been made based on the above circumstances, and an object thereof is to provide a power storage device having high energy density, high output, and durability.
  • the capacity when the battery is discharged from 0.75 hours to 1.25 hours from the fully charged state of the storage device to half the full charge voltage is defined as the cell capacity a (mAh).
  • the capacity when the negative electrode was discharged until the negative electrode potential became 1.5 V was defined as the complete negative electrode capacity b (mAh), and the negative electrode was charged with constant current-constant voltage at 0 V for 12 hours.
  • CCCV charge When the total negative electrode charge capacity c (mAh) is assumed, the capacity is 0.35 ⁇ a / b ⁇ 0.95, 0.55 ⁇ b / c ⁇ 1.00, 0.35 ⁇ a / c ⁇ 0.55 is satisfied, the electrode density of the positive electrode active material layer is 0.54 g / cm 3 to 0.7 g / cm 3 , and the electrode weight per unit area of the positive electrode active material layer is 70 g / m 2 to An electricity storage device, which is 110 g / m 2 .
  • the electricity storage device of the present invention for example, a lithium ion capacitor, a lithium ion secondary battery, high durability is obtained without deterioration even when the load on the negative electrode is increased, high energy density is obtained, and high output Characteristics are obtained.
  • the electricity storage device of the present invention basically has an electrode unit in which the positive electrode and the negative electrode are alternately stacked or wound via a separator in the outer container.
  • the outer container a cylindrical shape, a rectangular shape, a laminate shape, or the like can be appropriately used, and is not particularly limited.
  • positive electrode means the electrode on the side where current flows out during discharging and current flows in during charging
  • negative electrode refers to current flowing in during discharging. It means the pole on the side where current flows out during charging.
  • “dope” means occlusion, adsorption or insertion, and refers to a phenomenon in which at least one of lithium ions and anions enters the positive electrode active material, or a phenomenon in which lithium ions enter the negative electrode active material.
  • “de-doping” means desorption and release, and refers to a phenomenon in which lithium ions or anions are desorbed from the positive electrode active material, or a phenomenon in which lithium ions are desorbed from the negative electrode active material.
  • the negative electrode and the positive electrode is previously doped with lithium ions. More preferably, the negative electrode is pre-doped with lithium ions.
  • the negative electrode is pre-doped with lithium ions.
  • a method of pre-doping lithium ions into at least one of the negative electrode and the positive electrode for example, metallic lithium or the like is disposed in the electricity storage device as a lithium electrode, and the lithium is contacted by electrochemical contact between at least one of the negative electrode and the positive electrode and the lithium electrode.
  • a method of doping ions is used.
  • lithium ions can be uniformly doped into at least one of the negative electrode and the positive electrode also by locally arranging the lithium electrode in the cell and bringing it into electrochemical contact.
  • the electricity storage device of the present invention includes, for example, a positive electrode in which a positive electrode active material layer is formed on a positive electrode current collector having holes penetrating the front and back surfaces, a first separator, and a negative electrode current collector having holes penetrating the front and back surfaces.
  • a negative electrode on which a negative electrode active material layer is formed, and a second separator are wound or laminated in this order, and at least one lithium electrode is disposed in an excess portion of the first separator so as not to contact the positive electrode, A lithium electrode is short-circuited to constitute an electrode unit.
  • the electrolyte is filled to start doping of lithium ions from the lithium electrode, and the negative electrode active material layer is doped with lithium ions be able to.
  • an electrical storage device is comprised.
  • the electricity storage device of the present invention include a lithium ion capacitor and a lithium ion secondary battery.
  • a lithium ion capacitor is preferable.
  • the lithium ion capacitor means an electricity storage device containing lithium ions in which the positive electrode is a polarizable electrode and the negative electrode is a non-polarizable electrode.
  • a positive electrode material of a lithium ion capacitor a material having a large specific surface area such as activated carbon or polyacene is preferably used, and as a negative electrode material, the surface of core particles made of graphite, non-graphitizable carbon, or natural graphite is derived from tar or pitch.
  • a carbonaceous material such as a polyacene organic semiconductor (PAS) having a polyacene skeleton structure of 05, a metal oxide such as lithium titanate, a metal alloy such as silicon or tin is preferably used.
  • the negative electrode is preferably a negative electrode doped with lithium ions in advance.
  • a lithium ion capacitor in which the negative electrode is a negative electrode doped with lithium ions in advance is preferable because the use of the electricity storage device can be started from the charging operation.
  • the lithium ion capacitor of the present invention preferably has an energy density of 31.5 Wh / L or more, and more preferably 33 Wh / L or more.
  • the lithium ion secondary battery means an electricity storage device containing lithium ions in which the positive electrode and the negative electrode are non-polarizable electrodes.
  • the positive electrode material of the lithium ion secondary battery transition metal composite oxides such as lithium cobaltate and lithium iron phosphate are preferably used.
  • the negative electrode material carbonaceous materials such as graphite and non-graphitizable carbon, metal oxides such as lithium titanate, metal alloys such as silicon and tin are preferably used.
  • the capacity when discharging from the fully charged state of the electricity storage device to half the full charge voltage over 0.75 hours to 1.25 hours is defined as a cell capacity a (mAh)
  • the capacity when the negative electrode in a fully charged state of the electricity storage device was discharged until the negative electrode potential reached 1.5 V (Li / Li + ) was defined as the complete negative electrode capacity b (mAh), and the negative electrode was kept at 0 V for 12 hours.
  • the total negative charge capacity c (mAh) is constant current-constant voltage charge (CCCV charge) over 0.35 ⁇ a / b ⁇ 0.95, 0.55 ⁇ b / c ⁇ 1.
  • the electrode density of the positive electrode active material layer is 0.54 g / cm 3 to 0.7 g / cm 3
  • the electrode weight per unit area of the positive electrode active material layer having a characteristic that but a 70g / m 2 ⁇ 110g / m 2 .
  • the state of full charge of the electricity storage device means a state of charge arbitrarily set within the range of the maximum voltage that can be used over a long period of time without causing problems such as gas generation and resistance increase.
  • the fully charged voltage of the electricity storage device depends on the type of the electricity storage device, the material configuration of the positive and negative electrodes, and the electrolyte composition. In a lithium ion capacitor, the full charge voltage is about 3.6V to 4.0V, and in the lithium ion secondary battery, the full charge voltage is about 4.1V to 4.5V.
  • the potential of the negative electrode is preferably 0.2 V (Li / Li + ) or less, and 0.1 V (Li / Li + ) or less when fully charged. Is more preferable. Application of a voltage higher than the fully charged voltage is not preferable because it causes deterioration of the electricity storage device.
  • the cell capacity a varies depending on the cell size, but can be controlled by adjusting the mass of the positive electrode active material relative to the mass of the negative electrode active material when a positive electrode active material and a negative electrode active material having a predetermined capacity are used. Specifically, for example, when the basis weight of the negative electrode active material layer constituting the negative electrode is constant, the cell capacity a can be increased as the basis weight of the positive electrode active material layer is increased.
  • the cell capacity a is a current value (hereinafter referred to as a “current value ⁇ ”) at which the discharge time is 0.75 hours to 1.25 hours when discharging from a fully charged state to half the full charged voltage. ) Measured by discharging. Specifically, first, the power storage device is charged at a constant current having a current value ⁇ until the cell voltage reaches a set voltage related to full charge, and then a constant current-constant voltage charge in which the constant voltage of the set voltage is applied. (CCCV charge) is performed for 30 minutes until the battery is fully charged. Next, the battery is discharged from this state at a constant current of a current value ⁇ until it becomes half the set voltage. By repeating this charge / discharge five times, the storage device is brought into a steady state, and the capacity measured when the battery is discharged for the fifth time is defined as the cell capacity a.
  • a current value ⁇ a current value at which the discharge time is 0.75 hours to 1.25 hours when discharging from a fully charged state to
  • a constant voltage of 3.8 V is charged after charging the cell voltage to 3.8 V with a constant current of 200 mA (current value ⁇ ).
  • a constant current-constant voltage charge (CCCV charge) is applied for 30 minutes to achieve a fully charged state, and then the battery is discharged from this state at a constant current of 200 mA (current value ⁇ ) until the cell voltage reaches 1.9V.
  • the time required for the discharge at this time is about 1 hour. If the discharge is performed at a constant current of 2000 mA, the discharge time is 6 minutes or less and greatly falls below 0.75 hours depending on the internal resistance of the cell.
  • 0.75 hours to 1.25 hours defined in the present invention does not mean what value can be taken, and a current value that can be discharged to half the voltage in about 1 hour is derived and discharged. It specifies the approximate time to be performed. Specifically, it is preferable to set a current value that can be discharged in a range of 0.9 hours to 1.1 hours.
  • the complete negative electrode capacity b can be controlled by adjusting the amount of lithium ions doped in the negative electrode active material constituting the negative electrode when fully charged. Specifically, for example, as the thickness of the lithium electrode is increased, the complete negative electrode capacity b can be increased. Further, when the capacity of the positive electrode is increased, the complete negative electrode capacity b can be increased.
  • the complete negative electrode capacity b of the electricity storage device is the total of the negative electrode capacities obtained by the following measurements for each negative electrode in the fully charged electricity storage device.
  • the complete negative electrode capacity b is a constant current-constant voltage charge (CCCV charge) in which a power storage device is charged with a constant current having a current value ⁇ until the cell voltage reaches a set voltage, and then a constant voltage of a set voltage is applied. For 30 minutes until fully charged. Next, this fully charged power storage device is decomposed in an argon box so that the positive electrode and the negative electrode are not short-circuited, and the negative electrode is taken out.
  • CCCV charge constant current-constant voltage charge
  • the negative electrode is used as a working electrode, and the counter electrode and the reference electrode are made of a lithium metal plate. Each electrode plate is used to assemble a triode cell for measuring the negative electrode capacity, and this is discharged at a constant current of ⁇ until the negative electrode potential becomes 1.5 V, and the negative electrode capacity is measured.
  • the total negative electrode capacity b is obtained by multiplying the measured negative electrode capacity by the total number of negative electrodes.
  • the current value ⁇ is the same value as the current value ⁇ when there is only one negative electrode constituting the electricity storage device, and there are a plurality of negative electrodes constituting the electricity storage device, and each negative electrode has the same configuration. When it has, it becomes a value obtained by dividing the current value ⁇ by the number of negative electrodes.
  • a negative electrode other than the negative electrode located at the outermost part can be selected and taken out as a negative electrode for producing a three-electrode cell for measuring negative electrode capacity. Needed.
  • This negative electrode is used as the working electrode, and the counter electrode (both sides of the working electrode) And a three-electrode cell for measuring the negative electrode capacity using an electrode plate made of a lithium metal plate as a reference electrode, and the negative electrode at a constant current of 18.2 mA (current value ⁇ : 200 mA ⁇ 11 sheets).
  • the negative electrode capacity is measured by discharging until the potential reaches 1.5 V, and by multiplying this value by 11, the complete negative electrode capacity b can be obtained.
  • the ratio (a / b) of the cell capacity a to the complete negative electrode capacity b is 0.35 ⁇ a / b ⁇ 0.95. When a / b is less than 0.35, the energy density decreases.
  • a / b is larger than 0.95, lithium deposition is likely to occur during the cycle test, and the durability is deteriorated. Further, the capacity reduction due to lithium consumption is accelerated, and the characteristics are deteriorated.
  • a / b is preferably 0.36 ⁇ a / b ⁇ 0.93, and particularly preferably satisfies 0.45 ⁇ a / b ⁇ 0.7.
  • the negative electrode in the electricity storage device of the present invention has a total negative electrode charge capacity c (mAh) of 0.55 ⁇ b when the capacity when the negative electrode is charged with constant current-constant voltage (CCCV) at 0 V for 12 hours. It is necessary to satisfy /c ⁇ 1.00 and 0.35 ⁇ a / c ⁇ 0.55.
  • CCCV constant current-constant voltage
  • the ratio b / c of the complete negative electrode capacity b to the total negative electrode charge capacity c is in the above range, a high capacity retention rate is obtained for the power storage device, and high durability is obtained.
  • b / c is less than 0.55, lithium is insufficient and cycle durability is deteriorated.
  • the ratio a / c of the cell capacity a to the total negative electrode charge capacity c is less than 0.35, the energy density is lowered.
  • a / c is larger than 0.55, the capacity drop during the cycle test is increased and the durability is deteriorated. 0.36 ⁇ a / c ⁇ 0.54 is preferable, and 0.4 ⁇ a / c ⁇ 0.5 is particularly preferable.
  • the total negative electrode charge capacity c can be controlled by adjusting the type and mass of the negative electrode active material contained in the negative electrode. Specifically, for example, the total negative electrode charge capacity c can be increased as the mass ratio of the negative electrode active material in the negative electrode active material layer is increased. For example, when graphite, graphite-based composite particles, and polyacene organic semiconductor (PAS) are compared with the same weight as the negative electrode active material, the total negative electrode charge capacity c increases when PAS is used.
  • PAS polyacene organic semiconductor
  • the total negative electrode charging capacity c of the electricity storage device is the total of the respective negative electrode capacities obtained by the following measurements relating to the respective negative electrodes constituting the electricity storage device. Specifically, the total negative electrode charge capacity c is first charged by charging a negative electrode capacity measurement tripolar cell for measuring the complete negative electrode capacity b until the negative electrode potential becomes 0 V at a constant current of ⁇ . Then, constant current-constant voltage charging (CCCV charging) in which a constant voltage of 0 V is applied is performed for 12 hours, and the negative electrode capacity at this time is measured, whereby the total negative electrode charging capacity c is obtained.
  • CCCV charging constant current-constant voltage charging
  • the total negative electrode charge capacity c is equal to the negative electrode capacity measured in the three-electrode cell for measuring the negative electrode capacity. It is calculated
  • the positive electrode and the negative electrode are respectively provided with a positive electrode current collector and a negative electrode current collector that receive and distribute electricity.
  • a positive electrode current collector and a negative electrode current collector it is preferable to use a current collector in which through holes are formed.
  • the form and number of through holes in the positive electrode current collector and the negative electrode current collector are not particularly limited, and lithium ions and electrolysis supplied electrochemically from a lithium electrode arranged to face at least one of the positive electrode and the negative electrode It can set so that the lithium ion in a liquid can move between the front and back of an electrode, without interrupted
  • a porous current collector having through holes can be used.
  • the positive electrode current collector having a through hole for example, an expanded metal or a punching metal in which a through hole penetrating the back surface is formed by mechanical driving, laser processing using a CO 2 laser, a YAG laser, a UV laser, or the like is used.
  • a current collector in which a through hole penetrating the surface or a current collector in which a through hole is formed on the front and back surfaces by etching or electrolytic etching can be used.
  • the material of the positive electrode current collector aluminum, stainless steel or the like can be used, and aluminum is particularly preferable.
  • the thickness of the positive electrode current collector is not particularly limited, but it may be usually 1 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 40 ⁇ m, particularly preferably 10 ⁇ m to 40 ⁇ m.
  • the porosity (%) of the through holes of the positive electrode current collector is preferably 20% to 50%, more preferably 20% to 40%.
  • the porosity (%) of the positive electrode current collector can be obtained by the following formula (1).
  • Porosity (%) [1- (mass of positive electrode current collector / true specific gravity of positive electrode current collector) / (apparent volume of positive electrode current collector)] ⁇ 100 (1)
  • the positive electrode active material a material capable of reversibly doping and dedoping at least one kind of anion such as lithium ion and tetrafluoroborate is used, and examples thereof include activated carbon powder.
  • the specific surface area of the activated carbon is preferably 1900 m 2 / g to 3000 m 2 / g, and more preferably 1950 m 2 / g to 2800 m 2 / g.
  • the 50% volume cumulative diameter (D50) of the activated carbon is preferably 2 ⁇ m to 8 ⁇ m, particularly preferably 2 ⁇ m to 5 ⁇ m, from the viewpoint of the packing density of the activated carbon.
  • the energy density of the electricity storage device can be further improved.
  • the value of the 50% volume cumulative diameter (D50) is obtained by, for example, the microtrack method.
  • the positive electrode active material layer is formed by attaching the positive electrode active material to the positive electrode current collector by coating, printing, injection, spraying, vapor deposition, pressure bonding, or the like.
  • the thickness of the positive electrode active material layer is preferably 55 ⁇ m to 95 ⁇ m on one side, more preferably 60 ⁇ m to 90 ⁇ m, and particularly preferably 65 to 80 ⁇ m.
  • Electrode density of the positive electrode active material layer is 0.54 g / cm 3 to 0.7 g / cm 3 .
  • the electrode density of the positive electrode active material layer is less than 0.54 g / cm 3 .
  • the electrode density of the positive electrode active material layer is larger than 0.7 g / cm 3 , the pre-doping property is deteriorated and the cycle characteristics are deteriorated.
  • Electrode density of the positive electrode active material layer is preferably from 0.54g / cm 3 ⁇ 0.68g / cm 3, and even more preferably 0.6g / cm 3 ⁇ 0.68g / cm 3.
  • the electrode density of the positive electrode active material layer is usually determined by washing the positive electrode obtained by disassembling the electricity storage device with diethyl carbonate and vacuum drying at 100 ° C., then the mass of the positive electrode active material layer and the outer shape of the positive electrode active material It is determined by measuring the volume (apparent volume) and dividing the mass of the positive electrode active material layer by the outer volume of the positive electrode active material layer.
  • the “external volume of the positive electrode active material layer” is a volume calculated based on the measured values of the vertical dimension, the horizontal dimension, and the thickness dimension of the positive electrode active material layer.
  • a method of setting the electrode density within the above range a method of forming by a roll press or the like can be mentioned.
  • the electrode weight per unit area of the positive electrode active material layer is 70 g / m 2 to 110 g / m 2 .
  • the electrode weight per unit area of the positive electrode active material layer is preferably 75 g / m 2 to 110 g / m 2 .
  • the weight per unit area of the positive electrode active material layer was determined by washing the positive electrode obtained by disassembling the electricity storage device with diethyl carbonate and drying at 100 ° C., then punching the active material layer part into a predetermined area and measuring the mass. It is calculated by peeling the active material layer, measuring the mass of the current collector, and dividing the mass of the active material layer by the area.
  • the negative electrode current collector stainless steel, copper, nickel, or the like can be used.
  • the thickness of the negative electrode current collector is not particularly limited, but is usually 1 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 40 ⁇ m, and particularly preferably 10 ⁇ m to 30 ⁇ m.
  • the negative electrode current collector preferably has a hole penetrating the front and back surfaces, and the hole diameter of the through hole is, for example, 0.5 ⁇ m to 400 ⁇ m, preferably 0.5 ⁇ m to 350 ⁇ m, and preferably 1 ⁇ m. It is particularly preferred that the particle diameter is ⁇ 330 ⁇ m. Further, the porosity (%) of the through holes of the negative electrode current collector is preferably 20% to 70%, and more preferably 20% to 60%. Here, the porosity (%) of the negative electrode current collector can be obtained by the following formula (2).
  • Porosity (%) [1- (Mass of negative electrode current collector / true specific gravity of negative electrode current collector) / (apparent volume of negative electrode current collector)] ⁇ 100
  • Examples of the negative electrode current collector having a through hole include, for example, an expanded metal or a punching metal in which a through hole penetrating the back surface is formed by mechanical driving, laser processing using a CO 2 laser, a YAG laser, a UV laser, or the like.
  • a current collector in which a through-hole penetrating the back surface or a current collector in which a through-hole is formed on the front and back surfaces by etching can be used.
  • the negative electrode active material it is preferable to use graphite particles among materials that can be reversibly doped / dedoped with lithium ions.
  • graphite-based composite particles in which the surface of core particles made of graphite, non-graphitizable carbon, and natural graphite are coated with a graphitized substance derived from tar or pitch, and a heat-treated product of an aromatic condensation polymer.
  • PAS polyacene-based organic semiconductors
  • the aromatic condensation polymer refers to a condensate of an aromatic hydrocarbon compound and aldehydes.
  • the aromatic hydrocarbon compound include phenol, cresol, and xylenol
  • examples of the aldehyde include formaldehyde, acetaldehyde, and furfural.
  • the particle size is preferably graphite particles having a 50% volume cumulative diameter (D50) in the range of 1.0 ⁇ m to 10 ⁇ m from the viewpoint of improving the output, and graphite particles in the range of 2 ⁇ m to 5 ⁇ m. More preferred. Graphite-based particles having a 50% volume cumulative diameter (D50) of less than 1.0 ⁇ m are difficult to produce, and the durability may be reduced due to gas generation during charging. On the other hand, with graphite-based particles having a 50% volume cumulative diameter (D50) exceeding 10 ⁇ m, it is difficult to obtain an electricity storage device having a sufficiently low internal resistance.
  • D50 50% volume cumulative diameter
  • the negative electrode active material preferably has a specific surface area of 0.1 m 2 / g to 200 m 2 / g, more preferably 0.5 m 2 / g to 50 m 2 / g.
  • the specific surface area of the negative electrode active material is less than 0.1 m 2 / g, the resistance of the obtained electricity storage device is increased, while when the specific surface area of the negative electrode active material exceeds 200 m 2 / g, The irreversible capacity at the time of charging of the electricity storage device to be increased is high, and gas may be generated at the time of charging, which may reduce durability.
  • the 50% volume cumulative diameter (D50) of the graphite-based particles is a value determined by, for example, a microtrack method.
  • the negative electrode active material layer is formed by adhering the negative electrode active material to the negative electrode current collector by coating, printing, injection, spraying, vapor deposition, pressure bonding, or the like.
  • the preferable range of the thickness of the negative electrode active material layer varies depending on the balance with the mass of the positive electrode active material layer, but the thickness on one side may be 10 ⁇ m to 80 ⁇ m, preferably 10 ⁇ m to 65 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m.
  • each electrode positive electrode or negative electrode
  • each electrode includes each active material powder (positive electrode active material or negative electrode active material), a binder, and, if necessary, a conductive material, a thickener such as carboxymethyl cellulose (CMC),
  • CMC carboxymethyl cellulose
  • the slurry can be produced by mixing with water or an organic solvent and applying the resulting slurry to a current collector, or by forming the slurry into a sheet and sticking it to the current collector.
  • examples of the binder include a rubber-based binder such as SBR, a fluorine-containing resin obtained by seed polymerization of polytetrafluoroethylene, polyvinylidene fluoride, etc. with an acrylic resin, or an acrylic resin.
  • examples of the conductive material include acetylene black, ketjen black, graphite, and metal powder.
  • the amount of each of the binder and the conductive material to be added varies depending on the electric conductivity of the active material used, the shape of the electrode to be produced, etc., but both are usually preferably 2% by mass to 20% by mass with respect to the active material, In particular, 2% by mass to 10% by mass is more preferable.
  • a material having an air permeability measured by a method based on JISP8117 in the range of 1 sec to 200 sec can be used.
  • it can be appropriately selected from non-woven fabrics and microporous membranes composed of polyethylene, polypropylene, polyester, cellulose, polyolefin, cellulose / rayon, etc., and particularly polyethylene, polypropylene, cellulose / It is preferable to use a rayon nonwoven fabric.
  • the thickness of the separator is, for example, 5 ⁇ m to 20 ⁇ m, and preferably 5 ⁇ m to 15 ⁇ m. When the thickness of the separator is less than 5 ⁇ m, a short circuit is likely to occur. On the other hand, when it is larger than 20 ⁇ m, the resistance becomes high.
  • Electrode In the electricity storage device of the present invention, an aprotic organic solvent electrolyte solution of lithium salt is used as the electrolyte.
  • aprotic organic solvent of electrolyte examples include ethylene carbonate (hereinafter also referred to as “EC”), propylene carbonate (hereinafter also referred to as “PC”), cyclic carbonates such as butylene carbonate, and dimethyl carbonate. (Hereinafter also referred to as “DMC”), chain carbonates such as ethyl methyl carbonate (hereinafter also referred to as “EMC”), diethyl carbonate (hereinafter also referred to as “DEC”), and methylpropyl carbonate. You may use the mixed solvent which mixed 2 or more types of these.
  • the aprotic organic solvent constituting the electrolytic solution is an organic solvent other than cyclic carbonate and chain carbonate, for example, cyclic ester such as ⁇ -butyrolactone, cyclic sulfone such as sulfolane, cyclic ether such as dioxolane, propionic acid, etc. It may contain a chain carboxylic acid ester such as ethyl and a chain ether such as dimethoxyethane.
  • lithium salt of the electrolyte in the electrolytic solution examples include LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2, etc.
  • LiPF 6 is preferably used because of its high ion conductivity and low resistance.
  • the concentration of the lithium salt in the electrolytic solution is preferably 0.1 mol / L or more, more preferably 0.5 to 1.5 mol / L, because low internal resistance can be obtained.
  • the electricity storage device of the present invention has a capacity retention rate of 95% or more after 10,000 cycles of constant current charge / discharge at a time rate of 10 C in a voltage range of 3.8 V to 2.2 V. Furthermore, in the electricity storage device of the present invention, the rate of increase in the internal resistance after 10000 cycles of constant current charge / discharge at a time rate of 10 C in the voltage range of 3.8 V to 2.2 V is 3% or less.
  • the electricity storage device of the present invention satisfies 0.35 ⁇ a / b ⁇ 0.95, 0.55 ⁇ b / c ⁇ 1.00, 0.35 ⁇ a / c ⁇ 0.55, and the positive electrode
  • the electrode density of the active material layer is 0.54 g / cm 3 to 0.7 g / cm 3 and the electrode weight per unit area of the positive electrode active material layer satisfies 70 g / m 2 to 110 g / m 2 .
  • higher capacity can be obtained.
  • the maintenance rate can be maintained and the increase in internal resistance can be suppressed.
  • a wound-type, plate-like or sheet-like positive electrode and negative electrode in which a belt-like positive electrode and a negative electrode are wound through a separator are laminated in three or more layers via a separator.
  • a laminated type in which a unit having such a laminated structure is enclosed in an outer film or a rectangular outer can.
  • the structures of these power storage devices are known, for example, from Japanese Patent Application Laid-Open No. 2004-266091, and can have the same configuration as those power storage devices.
  • the electricity storage device of the present invention is not limited to a wound or stacked lithium ion capacitor, and can be suitably applied to a lithium ion secondary battery and other electricity storage devices.
  • Fabrication of positive electrode Conductive paint (Nippon Graphite Bunny Height T-602DEFK) is applied to both sides of a current collector material made of aluminum electrolytic etching foil having a pore diameter of 1 ⁇ m and a thickness of 30 ⁇ m.
  • the coating width was set to 100 mm
  • the coating thickness of both sides combined was set to 125 ⁇ m
  • both sides were coated, followed by drying under reduced pressure to form conductive layers on the front and back surfaces of the positive electrode current collector.
  • activated carbon particles having a 50% volume cumulative diameter (D50) value of 3 ⁇ m and a specific surface area of 2000 m 2 / g on the conductive layer formed on the front and back surfaces of the positive electrode current collector (Cataler Co., Ltd .: -CEP21K) (Positive electrode active material) 43 wt%, binder 1.5 wt% (manufactured by JSR: TRD201B), carboxylmethylcellulose sodium salt (Daicel 1120) 2 wt%, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) HS100)
  • a slurry containing 2.5 wt% and water 51 wt% was coated on both sides using a vertical die type double-side coating machine, then dried under reduced pressure and roll pressed to form an electrode on the conductive layer.
  • a positive electrode active material layer as a layer was formed.
  • the portion obtained by laminating the conductive layer and electrode layer of the positive electrode current collector thus obtained (hereinafter also referred to as “coating portion” for the positive electrode) is 60 mm ⁇ 80 mm, and no layers are formed.
  • the electrode layer is formed on both surfaces of the positive electrode current collector by cutting into a size of 60 mm ⁇ 95 mm so that the portion (hereinafter also referred to as “uncoated part” for the positive electrode) is 60 mm ⁇ 15 mm.
  • a positive electrode was produced.
  • Graphite-based composite particles having a pitch-coated surface (1) (Nippon Carbon Co., Ltd .: AGP30) (negative electrode active material) 40 wt%, SBR binder (JSR Co., Ltd .: TRD2001) 1 wt% and carboxymethyl cellulose sodium salt (Daicel) 1120)
  • a slurry containing 1.5 wt%, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd .: HS100) 2 wt%, and water 55.5 wt% was coated on both sides using a vertical die type double-side coating machine.
  • the portion where the electrode layer of the negative electrode current collector thus obtained (hereinafter also referred to as “coating portion” for the negative electrode) is 65 mm ⁇ 85 mm, and the portion where the electrode layer is not formed (hereinafter, A negative electrode having electrode layers formed on both sides of a negative electrode current collector was prepared by cutting into a size of 65 mm ⁇ 100 mm so that the negative electrode was also referred to as an “uncoated part”. .
  • a lithium ion supply member is prepared by cutting the foil-like lithium metal having a thickness of 46 ⁇ m so that the size of the foil-like lithium metal is 65 mm ⁇ 85 mm and pressing the copper foil on a copper foil having a thickness of 25 ⁇ m (manufactured by Nippon Foil Co., Ltd.). And this lithium ion supply member was arrange
  • a copper negative electrode power tab was stacked and welded. Thereby, a lithium ion capacitor element was obtained.
  • the positive electrode terminal and the negative electrode terminal of the electrode laminate unit project outward from the end portion of the other exterior film at the position serving as the housing portion on the other exterior film.
  • One exterior film was overlapped on this electrode laminate unit, and three sides (including two sides from which the positive electrode terminal and the negative electrode terminal protrude) at the outer peripheral edge of one exterior film and the other exterior film were heat-sealed.
  • an electrolytic solution containing LiPF 6 at a concentration of 1.2 mol / L using a mixed solvent of ethylene carbonate, propylene carbonate and diethyl carbonate (3: 1: 4 by volume, respectively) as an aprotic organic solvent is prepared.
  • the negative electrode was doped with lithium ions from a lithium foil (lithium ion supply member) by being left for 10 days.
  • a test laminate outer lithium ion capacitor (hereinafter referred to as cell 1) was produced. A total of four similar cells 1 were produced. The average cell capacity of the obtained cell 1 was 190 mAh.
  • a positive electrode obtained by disassembling one cell 1 is immersed in a container containing diethyl carbonate for 30 minutes for washing treatment, vacuum-dried at 100 ° C., and then placed in any place where an active material layer exists. Two pieces having a size of 2 cm 2 were cut out, the weight of one cut out positive electrode was measured with an electronic balance, and the thickness was measured with a micrometer. Next, only the current collector in the uncoated region where no active material layer was present was cut into the same size, the weight was measured with an electronic balance, and the thickness was measured with a micrometer. The weight of the positive electrode active material layer was calculated by subtracting the weight of the obtained current collector from the weight of the positive electrode.
  • the thickness of only the obtained current collector was subtracted from the thickness of the positive electrode to calculate the thickness of the positive electrode active material layer, and the external volume (apparent volume) of the positive electrode active material was calculated.
  • the positive electrode active material layer density was determined by dividing the mass of the positive electrode active material layer by the outer volume of the positive electrode active material layer.
  • the value obtained by multiplying the negative electrode capacity of 11 (the number of negative electrodes) by 11 (the number of negative electrodes) when discharging until Li + ) is defined as the complete negative electrode capacity b, and Table 1 shows the results based on the complete negative electrode capacity b.
  • (V) Cycle characteristic test [Capacity maintenance rate] The cell 1 is charged at a constant current of 1.9 A (time rate 10 C) until the cell voltage becomes 3.8 V, and then the cell voltage becomes 2.2 V at a constant current of 1.9 A. The cycle test was repeated 10,000 times for the charge / discharge cycle to discharge up to. The ratio of the capacity at the 10,000th cycle to the capacity at the first cycle in this cycle test is shown in Table 1 as a capacity retention rate. Table 1 shows “ ⁇ ” when the capacity maintenance ratio is 95% or more, “ ⁇ ” when 90% or more and less than 95%, and “x” when less than 90%.
  • the initial DC-IR is 10.35 m ⁇ or less, and the energy density is greater than 31.5 Wh / L, it is marked as ⁇ . Furthermore, when the capacity maintenance rate is 95% or more and the resistance increase rate is 3% or less, it is marked as ⁇ . When it is out of the above range, it is x.
  • the electrode density and basis weight of the positive electrode active material layer, a / b, b / c, and a / c are set as shown in Table 1, and the separator thickness is changed according to Table 1.
  • four S2-S13 and four C1-C10 were prepared in the same manner.
  • the cell capacity a, the complete negative electrode capacity b, the total negative electrode charge capacity c, the energy density and the DC-IR were measured in the same manner as in Example 1, and a cycle characteristic test was conducted to evaluate the characteristics. Went.
  • the current value was changed in accordance with the capacity of each cell so that the time rate was the same as that in Example 1. The results based on these results are shown in Table 1.
  • the positive electrode active material satisfying 0.35 ⁇ a / b ⁇ 0.95, 0.55 ⁇ b / c ⁇ 1.00, and 0.35 ⁇ a / c ⁇ 0.55 If the cell has a layer electrode density of 0.54 g / cm 3 to 0.7 g / cm 3 and a positive electrode active material layer electrode weight of 70 g / m 2 to 110 g / m 2 , a DC-IR In other words, it was possible to obtain an electric storage device having a low balance, that is, a large output, a high energy density, and a good balance of performance capable of suppressing a decrease in capacity and an increase in resistance after cycle testing.
  • the capacity drop during the cycle test became large and the characteristics deteriorated.
  • the C2 cell had an a / c of less than 0.35, so the energy density decreased.
  • the C3 cell had a b / c value exceeding 1.00, the capacity drop during the cycle test was large and the cell characteristics deteriorated.
  • the C4 cell had a b / c of less than 0.55, the capacity decreased and the resistance increased during the cycle test, and the characteristics deteriorated.
  • the initial DC-IR was high, the resistance increased during the cycle test, the capacity decreased, and the cell characteristics deteriorated.
  • the C6 cell has an electrode weight per unit area of the positive electrode active material layer of less than 70 g / cm 2 , the energy density was lowered.
  • the electrode density of the positive electrode active material layer was larger than 0.7 g / cm 3 , the initial DC-IR was high, the capacity decreased and the resistance increased during the cycle test, and the cell characteristics deteriorated.
  • the C8 cell had a lower energy density because the positive electrode active material layer had an electrode density of less than 0.54 g / cm 3 .
  • the capacity decreased and the resistance increased during the cycle test, and the cell characteristics deteriorated.
  • the a / b of the C10 cell was less than 0.35, the capacity decreased and the resistance increased during the cycle test, and the cell characteristics deteriorated.
  • the electricity storage device of the present invention can be used as a lithium ion capacitor, a lithium ion secondary battery, etc., with high energy density and high output characteristics without deterioration even when the capacity of the negative electrode is increased.
  • the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-146835 filed on July 12, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Cell Separators (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

　L'invention concerne un dispositif de stockage d'électricité caractérisé par une haute densité d'énergie, une faible résistance et une grande durabilité. Un dispositif de stockage d'électricité selon l'invention comporte: une unité d'électrodes dans laquelle une électrode positive sur laquelle est formée une couche de substance active d'électrode positive et un électrode négative sur laquelle est formée une couche de substance active d'électrode négative sont stratifiées en alternance avec interposition d'un séparateur, et un électrolyte constitué d'une solution électrolytique dans un solvant organique aprotique d'un sel de lithium. Les expressions 0,35 ≤ a/b ≤ 0,95, 0,55 ≤ b/c ≤ 1,00, et 0,35 ≤ a/c ≤ 0,55 sont vérifiées, où a est la capacité de la pile (mAh) lorsque le dispositif de stockage d'électricité est déchargé d'un état de charge complète à une tension valant la moitié de la tension de charge complète en 0,75 à 1,25 heure, b est la pleine capacité d'électrode négative (mAh) lorsque l'électrode négative dans l'état de charge complète est déchargée jusqu'à ce que le potentiel de l'électrode négative atteigne 1,5 V (Li/Li+), et c est la capacité totale de charge de l'électrode négative (mAh) lorsque l'électrode négative à 0V est soumise à une charge à courant constant et tension constante (CCCV) pendant 12 heures. La densité d'électrode de la couche de substance active d'électrode positive est de 0,54 à 0,7 g/cm3, et le poids d'électrode de la couche de substance active d'électrode positive est de 70 à 110 g/m2.
PCT/JP2014/068090 2013-07-12 2014-07-07 Dispositif de stockage d'électricité WO2015005294A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105896579A (zh) * 2016-04-26 2016-08-24 西南交通大学 考虑配网电压暂降导致电动汽车跳闸引发过电压的充电桩规划方法
JP2018056414A (ja) * 2016-09-30 2018-04-05 旭化成株式会社 非水系リチウム型蓄電素子
CN112042029A (zh) * 2018-04-19 2020-12-04 Jm能源株式会社 锂离子二次电池、锂离子电容器、以及它们的制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007116101A (ja) * 2005-09-26 2007-05-10 Nisshinbo Ind Inc 電気二重層キャパシタ
JP2008294314A (ja) * 2007-05-28 2008-12-04 Sanyo Electric Co Ltd キャパシタ
JP2009260187A (ja) * 2008-04-21 2009-11-05 Nissin Electric Co Ltd 蓄電デバイス
JP2010267878A (ja) * 2009-05-15 2010-11-25 Asahi Kasei Corp 非水系リチウム型蓄電素子

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100523536B1 (ko) * 2001-06-29 2005-10-25 후지 주고교 가부시키가이샤 유기 전해질 커패시터
JP4971729B2 (ja) * 2006-09-04 2012-07-11 富士重工業株式会社 リチウムイオンキャパシタ
JP2009224391A (ja) * 2008-03-13 2009-10-01 Japan Gore Tex Inc リチウムイオンキャパシタ用正極材およびリチウムイオンキャパシタ
WO2012063545A1 (fr) * 2010-11-10 2012-05-18 Ｊｍエナジー株式会社 Condensateur au lithium ion
JP5828633B2 (ja) * 2010-12-20 2015-12-09 Jsr株式会社 リチウムイオンキャパシタ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007116101A (ja) * 2005-09-26 2007-05-10 Nisshinbo Ind Inc 電気二重層キャパシタ
JP2008294314A (ja) * 2007-05-28 2008-12-04 Sanyo Electric Co Ltd キャパシタ
JP2009260187A (ja) * 2008-04-21 2009-11-05 Nissin Electric Co Ltd 蓄電デバイス
JP2010267878A (ja) * 2009-05-15 2010-11-25 Asahi Kasei Corp 非水系リチウム型蓄電素子

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105896579A (zh) * 2016-04-26 2016-08-24 西南交通大学 考虑配网电压暂降导致电动汽车跳闸引发过电压的充电桩规划方法
JP2018056414A (ja) * 2016-09-30 2018-04-05 旭化成株式会社 非水系リチウム型蓄電素子
CN112042029A (zh) * 2018-04-19 2020-12-04 Jm能源株式会社 锂离子二次电池、锂离子电容器、以及它们的制造方法

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