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WO2012002359A1 - Dispositif de stockage d'énergie et son procédé de production - Google Patents

Dispositif de stockage d'énergie et son procédé de production Download PDF

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Publication number
WO2012002359A1
WO2012002359A1 PCT/JP2011/064752 JP2011064752W WO2012002359A1 WO 2012002359 A1 WO2012002359 A1 WO 2012002359A1 JP 2011064752 W JP2011064752 W JP 2011064752W WO 2012002359 A1 WO2012002359 A1 WO 2012002359A1
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WIPO (PCT)
Prior art keywords
layer
positive electrode
electrode layer
negative electrode
separator
Prior art date
Application number
PCT/JP2011/064752
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English (en)
Japanese (ja)
Inventor
幸夫 得原
昌治 板谷
景司 堀川
恭丈 福田
学 澤田
伊藤　英治
宣弘 吉川
Original Assignee
株式会社村田製作所
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Application filed by 株式会社村田製作所 filed Critical 株式会社村田製作所
Priority to JP2012522631A priority Critical patent/JPWO2012002359A1/ja
Publication of WO2012002359A1 publication Critical patent/WO2012002359A1/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
    • H01G11/22—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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0468—Compression means for stacks of electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M6/42—Grouping of primary cells into batteries
    • H01M6/46—Grouping of primary cells into batteries of flat cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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 and a manufacturing method thereof.
  • a sheet-shaped current collector foil (aluminum foil or copper foil) wound in a roll shape is used as a die coater or comma.
  • a sheet-like electrode is produced by passing through a coater or the like and coating an active material (activated carbon, lithium composite oxide, carbon, etc.) on the current collector foil.
  • the sheet-like separator wound by roll shape is interposed between electrodes, and these electrodes and a separator are wound or a sheet
  • the laminated body is formed into a laminated body, and an aluminum tab or a nickel tab is welded so as to be electrically connected to the electrode by ultrasonic welding to form an external terminal electrode.
  • the element which consists of these electrode groups produced in this way is put in exterior bodies, such as an aluminum can or an aluminum laminate film, and after injecting electrolyte solution, it seals, and the electrical storage device is produced.
  • Patent Document 1 proposes a technique in which positive and negative electrodes are fixed to a separator interposed between them using an adhesive layer to integrate the electrode and the separator.
  • the electrode and the separator are integrated as described above, the electrode and the separator are completely in close contact with each other and there is no gap at all, and the permeation rate of the electrolytic solution is reduced.
  • Patent Document 2 it is proposed to form a groove on the surface of at least one electrode facing the separator.
  • the separator is a method in accordance with JIS P 8117, using a digital type Oken type air permeability tester (“EG01-5-1MR” manufactured by Asahi Seiko Co., Ltd.) and measuring the cylinder pressure at 0.25 MPa. When measured at a pressure of 0.05 MPa and a measured internal diameter of 30 mm, it means a layer having an air permeability of less than 1000 sec / 100 cc.
  • Patent Document 2 when a groove is formed on the surface of the electrode facing the separator, there is a problem that the amount of the active material is reduced and the energy density is lowered. Further, as disclosed in Patent Document 2, if the electrode and the separator are fixed by the adhesive layer, the element cannot be thinned due to the presence of the adhesive layer, and further, a process of providing the adhesive layer is necessary and complicated. There was a problem that there was.
  • the present invention relates to a power storage device that can prevent a change in the distance between electrodes and separation and displacement between the electrode and the separator, can reduce the thickness of the element, and can be manufactured at a low cost with a small number of man-hours.
  • the purpose is to provide.
  • an electricity storage device includes: A laminate in which a negative electrode layer is disposed between at least two positive electrode layers, and a separator layer is provided between the positive electrode layer and the negative electrode layer, or a positive electrode layer is disposed between at least two negative electrode layers, An electricity storage device comprising a laminate in which a separator layer is provided between each positive electrode layer, an electrolyte, and a package containing the laminate and the electrolyte, In the laminated body, the positive electrode layer and the negative electrode layer adjacent to each other are each directly bonded to the separator layer.
  • laminate means that layers are sequentially stacked and “winding” is included.
  • the distance between the positive electrode layer and the negative electrode layer changes, or the positive electrode layer Or a shift
  • the positive electrode layer and the separator layer are not peeled off, and the negative electrode layer and the separator layer are not peeled off. Since the gas is not trapped in the space formed by separation, an increase in resistance value can be prevented.
  • the positive electrode layer and the negative electrode layer are directly bonded to the separator layer without forming an adhesive layer, it is possible to prevent a decrease in the permeation rate of the electrolytic solution, and further, since there is no adhesive layer, it can be thinned. Since the step of forming the adhesive layer can be omitted, the manufacturing cost can be reduced. Furthermore, in the electricity storage device according to the present invention, the negative electrode layer is disposed between the positive electrode layers, and the positive electrode layer is disposed between the laminate or the negative electrode layer in which the separator layer is provided between the positive electrode layer and the negative electrode layer. Since the laminated body which is arrange
  • the stacked body includes a first end surface including an end surface of the positive electrode layer and an end surface of the separator layer, a second end surface including the end surface of the negative electrode layer and the end surface of the separator layer. And an external terminal electrode on each of the first end surface and the second end surface.
  • a plurality of positive electrode layers can be connected to the external terminal electrode at once, and a plurality of negative electrode layers can be connected to the external terminal electrode at the same time. Since there is no need to pull out the lead terminals from the lead terminals and connect the lead terminals to the external terminal electrodes, the process is simplified, and the electrical resistance can be reduced by the absence of the lead terminals.
  • the laminated body in which the external terminal electrodes are provided on the first end surface and the second end surface, respectively can be connected to the package electrode without passing through the lead wire when housed in a package, for example. Space saving and miniaturization are possible.
  • the said 1st end surface and the said 2nd end surface are each smooth.
  • the first end face and the second end face are smooth, for example, when an external force is applied to the end face in the manufacturing process, the end of the separator layer is chipped or between the positive or negative electrode layer and the separator layer. Separation can be prevented, and contact between the positive electrode layer and the negative electrode layer and a short circuit can be prevented.
  • the external terminal electrodes can be easily formed.
  • the electrode resistance can be further reduced, and the bonding strength of the external terminal electrode can be increased.
  • the gas is trapped in the space between the recess of the non-smooth end face and the external terminal electrode, and this gas expands when used at a high temperature, and the external terminal The electrode may be peeled off, but when the first end surface and the second end surface are smooth, the external terminal electrode is hardly peeled off.
  • each of the external terminal electrodes is bonded to the separator layer.
  • the bonding strength of the external terminal electrode to the laminate is further strengthened.
  • the electrode layer, the separator layer, and the external terminal electrode are integrated, it is possible to further prevent the change in the distance between the electrodes and the separation and deviation between the electrode and the separator.
  • the laminated body has a first end face on the first end face side including the end face of the positive electrode layer and the end face of the separator layer, and the end face of the negative electrode layer is covered with the separator layer on the first end face.
  • the end face of the positive electrode layer is covered with the separator layer on the second end face side including the end face of the negative electrode layer and the end face of the separator layer, and is reliably insulated from the formed external terminal electrode. It is preferable that the terminal is reliably insulated from the external terminal electrode. Thereby, when the external terminal electrode is directly installed on the laminate, it is possible to easily prevent short-circuiting between the end surfaces of the positive electrode layer and the negative electrode layer and the end surfaces of the different electrode layers.
  • the distance between the upper and lower negative electrode layers and between the positive electrode layers can be kept at a predetermined interval by the separator layer covering each end face of the positive electrode layer and the negative electrode layer to be insulated from the external terminal electrode. For this reason, when the external terminal electrode is directly installed on the end face of the laminate, it is possible to prevent the position of the separator layer covering each end face of the positive electrode layer or the negative electrode layer to be insulated from the external terminal electrode from moving and shifting. . As a result, it is possible to prevent the electrical conductivity from being cut due to tearing of the external terminal electrode provided on the end face, and it becomes easy to ensure continuous electrical conductivity over the entire external terminal electrode.
  • the separator layer includes insulator particles.
  • the separator layer contains the insulator particles, shrinkage of the separator layer and reduction of the porosity can be suppressed even when each layer is pressurized in the lamination process of the manufacturing process.
  • the said separator layer contains a thermoplastic resin.
  • the said insulator particle is an inorganic filler.
  • the inorganic filler has higher heat resistance and higher strength than, for example, the organic filler, it can be an electric storage device having heat resistance that can withstand surface mounting, and at the time of thermocompression bonding in the manufacturing process, etc. It is possible to suppress the deterioration of the separator layer and the decrease in the porosity in the heating process.
  • a method for manufacturing an electricity storage device includes: A laminate in which a negative electrode layer is disposed between at least two positive electrode layers, and a separator layer is provided between the positive electrode layer and the negative electrode layer, or a positive electrode layer is disposed between at least two negative electrode layers, A manufacturing method for manufacturing an electricity storage device comprising a laminate in which separator layers are provided between positive electrode layers, an electrolyte, and a package containing the laminate and the electrolyte, The positive electrode layer and the negative electrode layer are disposed so as to face each other with the separator layer interposed therebetween, and are adjacent to each other by integrating the positive electrode layer, the negative electrode layer, and the separator layer by pressure bonding or pressure bonding while heating or heating.
  • the electrical storage device in which the positive electrode layer and the negative electrode layer are bonded directly to the separator layer is manufactured.
  • the positive electrode layer and the negative electrode layer are arranged by pressing the positive electrode layer and the negative electrode layer so as to face each other through the separator layer, and press-bonding while pressing or heating or heating. Since the method includes directly bonding a layer to the separator layer, the positive electrode layer and the negative electrode layer can be bonded to the separator layer without forming an adhesive layer.
  • the positive electrode layer and the negative electrode layer are bonded to the separator layer, for example, even when gas is generated during charging / discharging, the electrode does not open, and the outer shape of the stacked body, particularly the stacked body. Since the shape of the end face is maintained without being deformed, the external terminal electrode formed on the end face can be prevented from peeling off.
  • the positive electrode layer and the negative electrode layer provided so as to correspond to each of the plurality of laminates are arranged so as to face each other with a separator layer interposed therebetween, and the positive electrode layer and the positive electrode layer are bonded by pressure bonding or heating or heating.
  • a device and a manufacturing method thereof can be provided.
  • FIG. 1 It is a perspective view showing a part of layered product 1 in an electrical storage device of an embodiment concerning the present invention by making a sectional view.
  • FIG. 1 It is sectional drawing of the electrical storage device of embodiment. It is sectional drawing which shows a part process of the manufacturing process in the Example of this invention, (1) Punches one block of a positive electrode assembly sheet
  • (4) is a view of the negative electrode / negative electrode integrated sheet bonded with two negative electrode aggregate sheets so that the negative electrode current collector layer 31a faces each other.
  • a cross section is shown. It is sectional drawing which shows the one part process of the manufacturing process in the Example of this invention, (5) is a figure of the process of bonding the positive electrode / positive electrode integrated sheet 20 and the negative electrode / negative electrode integrated sheet 30 alternately. Yes, (6) shows a cross section of a laminated assembly in which the positive electrode / positive electrode integrated sheet 20 and the negative electrode / negative electrode integrated sheet 30 are alternately stacked between the positive electrode integrated sheet 20a and the negative electrode integrated sheet 30a. Show. It is a graph which shows the frequency characteristic of the equivalent series capacity
  • the electrical storage device of embodiment which concerns on this invention is equipped with the laminated body 1 shown in FIG.
  • the stacked body 1 is configured by alternately arranging positive electrode layers 21 and negative electrode layers 31, and providing separator layers 11 between the positive electrode layers 21 and the negative electrode layers 31.
  • the positive electrode layer 21 and the negative electrode layer 31 are directly bonded to the separator layer 11 as described in detail later.
  • the positive electrode layer 21 includes a positive electrode current collector layer 21a and a positive electrode active material layer 21b formed on both surfaces thereof.
  • the negative electrode layer 31 includes a negative electrode current collector layer 31a and negative electrode active material layers formed on both surfaces thereof. And the material layer 31b.
  • One end face of the positive electrode current collector layer 21a is exposed, and one end face of the negative electrode current collector layer 31a is exposed on the other second end face 3.
  • a positive external terminal electrode 21t is formed on the first end surface 2 of the multilayer body 1 so as to be connected to one end surface of the positive electrode current collector layer 21a, and a negative electrode current collector is formed on the second end surface 3 of the multilayer body 1.
  • a negative external terminal electrode 31t is formed so as to be connected to one end surface of the electric conductor layer 31a.
  • the first end surface 2 on which the positive external terminal electrode 21t is formed and the second end surface 3 on which the negative external terminal electrode 31t is formed are respectively the end surface of the separator layer 11 and one end surface of the positive electrode current collector layer 21a or the negative electrode current collector. It is preferable that the body layer 31a is smooth so that one end surface of the body layer 31a is located on substantially the same plane.
  • the edge part of the separator layer 11 will be shown, for example. Chipping can be prevented, and contact between the positive electrode layer 21 and the negative electrode layer 31 and a short circuit can be prevented.
  • the laminate 1 configured as described above is disposed inside a package 50 into which an electrolytic solution has been injected.
  • the package 50 includes, for example, a base portion 50b made of a liquid crystal polymer that is a heat-resistant resin and a lid 50a.
  • a positive electrode package electrode 41 and a negative electrode package electrode 42 are separately provided on the base portion 50b. .
  • the positive external terminal electrode 21t of the stacked body 1 is connected to the positive electrode package electrode 41 of the base portion 50b, and the negative external terminal electrode 31t is connected to the negative electrode package electrode 42.
  • the positive electrode current collector layer 21a and the negative electrode current collector layer 31a are all drawn to the same thickness
  • the positive electrode active material layer 21b and the negative electrode active material layer 31b are all drawn to the same thickness.
  • the thickness of the positive electrode current collector layer 21a and the negative electrode current collector layer 31a located in the uppermost layer and the lowermost layer is appropriately reduced, for example, by reducing the thickness compared to other current collector layers. It is also possible to change the length.
  • Examples of the electricity storage device according to the present invention include a lithium ion secondary battery, a lithium ion capacitor, and an electric double layer capacitor.
  • the following materials can be used depending on the type of the electricity storage device.
  • Lithium ion secondary battery for example, an aluminum foil is used as the positive electrode current collector layer 21a, and a mixture layer containing a lithium composite oxide such as LiCoO 2 is provided as the positive electrode active material layer 21b on the aluminum foil.
  • An electrode is used as the positive electrode layer 21.
  • the negative electrode current collector layer 31a for example, a copper foil is used, and an electrode in which a mixture layer containing graphite is provided as the negative electrode active material layer 31b on the copper foil is used as the negative electrode layer 31.
  • a lithium ion secondary battery can be manufactured by using, as an electrolytic solution, 1 mol / l LiPF 6 dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate.
  • lithium ion capacitor for example, an aluminum foil is used as the positive electrode current collector layer 21 a, and an electrode in which a mixture layer containing activated carbon is provided on the aluminum foil as the positive electrode active material layer 21 b is used as the positive electrode layer 21.
  • the negative electrode current collector layer 31 a for example, a copper foil is used, and an electrode provided with a mixture layer containing graphite on the copper foil as the negative electrode active material layer 31 b is defined as the negative electrode layer 31.
  • Pre-dope with lithium ions by using those obtained by dissolving LiPF 6 in 1 mol / l in a mixed solvent of ethylene carbonate and diethyl carbonate as an electrolytic solution, it is possible to produce lithium ion capacitor.
  • an aluminum foil is used as the positive electrode current collector layer 21a, and an electrode in which a mixture layer containing a carbon material, for example, activated carbon, is provided on the aluminum foil as the positive electrode active material layer 21b.
  • an aluminum foil is used, and an electrode in which a mixture layer containing a carbon material, for example, activated carbon is provided on the aluminum foil is referred to as the negative electrode layer 31.
  • An electric double layer capacitor can be produced by using, as an electrolytic solution, 1 mol / l triethylmethylammonium tetrafluoroborate dissolved in propylene carbonate.
  • the positive electrode layer 21 and the negative electrode layer 31 are coated with an active material (activated carbon, lithium composite oxide, carbon, etc.) on the positive electrode current collector layer 21a and the negative electrode current collector layer 31a by a comma coater, a die coater, a gravure printing method, or the like. It is produced by processing. More preferably, it is produced by coating by a screen printing method. In screen printing, since the tension applied to the positive electrode current collector layer 21a and the negative electrode current collector layer 31a is low, a current collector with a thinner film thickness can be used.
  • active material activated carbon, lithium composite oxide, carbon, etc.
  • the separator layer 11 can be prepared by applying a slurry containing the components of the separator layer 11 on the positive electrode layer 21 and / or the negative electrode layer 31.
  • the separator layer slurry can be applied by a comma coater, a die coater, a gravure printing method, or the like, but is preferably prepared by a screen printing method.
  • the separator layer 11 is formed on the positive electrode layer 21 and / or the negative electrode layer 31 as described above, for example, the positive electrode layer 21 and the negative electrode layer 31 are opposed to each other via the separator layer 11, and the separator layer 11 is pressed.
  • the positive electrode layer 21 and the negative electrode layer 31 are joined. Moreover, it can crimp more firmly by heating at the time of crimping
  • the glass transition temperature of carboxymethyl cellulose is 45 ° C., and therefore it is preferable to heat at 45 ° C. or higher. If it does in this way, the positive electrode layer 21 and the negative electrode layer 31 can be more reliably joined to both surfaces of the separator layer 11 by plasticizing carboxymethylcellulose.
  • a thermoplastic resin, a thermosetting resin such as an epoxy resin, polyimide, polyamideimide, or polyamide can be used in addition to carboxymethylcellulose.
  • the polyamideimide include HR-11NN manufactured by Toyobo.
  • thermoplastic resin becomes soft when heated to the glass transition temperature or the melting point, so that the contact area with the electrode layer or separator layer to be joined increases by pressing while heating or heating, and strong bonding Is preferable.
  • polyvinylidene fluoride (hereinafter referred to as PVDF), which is a thermoplastic resin, has a stable slurry, excellent heat resistance and solvent resistance, and does not completely cover the active material due to point bonding. Reaction characteristics can be obtained.
  • thermosetting resin has high heat resistance, strong binding force, excellent chemical stability, and higher strength than the thermoplastic resin, the strength of the laminate is improved.
  • separator layer has a network structure of an organic compound, for example, compared to the case where the separator layer is formed by sintering inorganic particles, the laminate and the power storage device are resistant to bending and impact. High resistance.
  • a junction surface may be a main surface, an end surface or a side surface, or both.
  • the positive electrode layers 21 and the negative electrode layers 31 may be alternately laminated after the separator layers 11 are laminated, and in this way, the number of crimping steps can be reduced.
  • stacked the positive electrode layer 21 and the negative electrode layer 31 alternately via the separator layer 11 every time the positive electrode layer 21 and the negative electrode layer 31 are laminated
  • the main bonding may be performed by a laminated assembly in which a plurality of laminated bodies 1 are collectively formed, or may be performed for each laminated body after the laminated aggregate is separated into pieces.
  • the separator layer 11 preferably contains insulator particles.
  • the separator layer 11 includes the insulator particles, the shrinkage of the separator layer 11 or the burial of the pores can be suppressed even when each layer is pressed in the lamination process or the like, and the positive electrode layer 21 and the negative electrode layer can be more efficiently A good insulation state between 31 can be maintained.
  • the insulator particles to be contained in the separator layer 11 for example, organic particles such as polytetrafluoroethylene (PTFE), inorganic fillers such as silica and alumina, or a mixture thereof can be used. It is preferable to use an inorganic filler in order to obtain heat resistance that can withstand surface mounting and to hold holes more efficiently when the laminate 1 is thermocompression bonded. Furthermore, it is more preferable to use insulator particles that are irregular in the three-dimensional direction, such as crushed silica, because more voids are generated between the particles, an ion conduction path is secured, and the resistance of the electricity storage device can be reduced. .
  • PTFE polytetrafluoroethylene
  • the average particle diameter (D 50 ) of these insulator particles is not particularly limited, It is desirable that it is 2 ⁇ m or less. It is difficult to apply only one particle uniformly in a planar manner so that the particles do not overlap, and usually two to three or more particles are present in the thickness direction in the separator layer 11. For example, when three particles are present in the thickness direction in the separator layer 11, if the average particle diameter (D 50 ) is 2 ⁇ m or less, the thickness of the separator layer 11 can be 6 ⁇ m or less on average, and a smaller power storage device Can be supplied.
  • the separator layer 11 is produced by applying a slurry containing the components of the separator layer 11 on the positive electrode layer 21 and / or the negative electrode layer 31. What is the positive electrode layer 21 and the negative electrode layer 31? Separately, for example, it may be prepared and prepared by applying a slurry containing the component of the separator layer 11 on the base PET film.
  • a laminated assembly in which a plurality of laminated bodies 1 are integrated can be separated into pieces by cutting with a dicer cut or a guillotine cut. Accordingly, it is possible to manufacture a power storage device with high productivity more efficiently than manufacturing individual stacks one by one.
  • the end surface of the laminated body 1 after dividing into pieces is substantially smooth.
  • the end surface of the laminated body 1 is not smooth, for example, when the end surface of the separator layer 11 is recessed inside the end surfaces of the positive electrode layer 21 and the negative electrode layer 31, short-circuiting with the positive electrode layer 21 and the negative electrode layer 31 is performed. Further, delamination between the separator layer 11 and the separator layer 11 is likely to occur.
  • the separator layer 11 is easily cracked, and cracking occurs when stress is applied to the separator layer 11.
  • a short circuit between the positive electrode layer 21 and the negative electrode layer 31 tends to occur. That is, when the protruding separator layer 11 is cracked, the end of the positive electrode layer 21 or the negative electrode layer 31 becomes a fulcrum, and a crack that is recessed inward from the end surface of the positive electrode layer 21 or the negative electrode layer 31 may occur. Such a depressed crack tends to cause a short circuit between the positive electrode layer 21 and the negative electrode layer 31. In addition, delamination between the positive electrode layer 21 and the negative electrode layer 31 and the separator layer 11 easily occurs.
  • the end surface of the laminated body 1 is substantially smooth, it is difficult for a short circuit to occur even when stress is generated in the separator layer 11, the positive electrode layer 21, and the negative electrode layer 31. Further, delamination between the separator layer 11 and the positive electrode layer 21 and between the separator layer 11 and the negative electrode layer 31 are less likely to occur.
  • the end face is substantially smooth, it is easy to form the positive external terminal electrode 21t and the negative external terminal electrode 31t with good adhesion, and the electrical resistance can be reduced. Further, in addition to improving the bonding strength between the positive electrode external terminal electrode 21t and the negative electrode external terminal electrode 31t, in the laminate 1 in which the positive electrode layer 21 and the negative electrode layer 31 are bonded by the separator layer 11, When the gas is generated, the positive electrode layer 21 or the negative electrode layer 31 and the separator layer 11 are not opened, and the shape of the end face is maintained, so that the positive electrode external terminal electrode 21t and the negative electrode external terminal electrode 31t are prevented from being peeled off. it can.
  • the gas hardly remains between the positive electrode layer 21 or the negative electrode layer 31 and the separator layer 11, and the resistance value hardly increases.
  • gas is trapped in the space between the recess on the end face and the external terminal electrode, and this gas expands during high temperature use, and the external terminal electrode is likely to peel off from the end face.
  • the positive external terminal electrode 21t and the negative external terminal electrode 31t can be formed as follows.
  • the positive external terminal electrode 21t and the negative external terminal electrode 31t can be formed, for example, by depositing Al by sputtering.
  • the laminated body 1 is arrange
  • the terminal electrode 31t is electrically connected to the positive package electrode 41 and the negative package electrode 42, respectively.
  • the positive external terminal electrode 21t and the negative external terminal electrode 31t may be formed by applying a conductive adhesive directly to the side surface of the laminate 1 by dipping.
  • the positive electrode external terminal electrode 21t and the negative electrode external terminal electrode 31t may directly form a conductive film on the end surface of the laminate 1 by vapor deposition, sputtering, ion plating, thermal spraying, cold spraying, plating, or the like.
  • the conductive adhesive described above was applied onto the positive external terminal electrode 21t and the negative external terminal electrode 31t formed as the conductive film, and the positive external terminal electrode 21t and the negative external terminal electrode 31t were applied.
  • the laminated body 1 is disposed in the base portion 50b of the package so as to be connected to the positive electrode package electrode 41 and the negative electrode package electrode 42 by the conductive adhesive, and is heated and cured in the same manner as described above to be connected. That's fine.
  • an electrolytic solution is injected into the base portion 50b and sealed with the lid 50a, whereby the electricity storage device is completed.
  • an electrolytic solution when producing a lithium ion secondary battery as an electricity storage device, respectively, an electrolytic solution generally used in a lithium ion secondary battery can be used, and when producing a lithium ion capacitor, In general, an electrolytic solution used in a lithium ion capacitor can be used. When an electric double layer capacitor is manufactured, an electrolytic solution generally used in an electric double layer capacitor can be used.
  • an organic solvent generally selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, acetonitrile, or a mixture thereof, commonly used in power storage devices, LiPF 6 , LiBF 4 , LiTFSI, or other Li
  • an electrolytic solution in which a salt is dissolved or in the organic solvent tetramethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis
  • Examples thereof include an electrolytic solution in which (trifluoromethanesulfonyl) imide is dissolved.
  • an ionic liquid such as 1-ethyl-3-methylimidazolium tetrafluoroborate or 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide
  • Only ionic liquids substantially free of organic solvents can be used as the electrolyte.
  • an ionic liquid that does not substantially contain an organic solvent since the ionic liquid has a low vapor pressure up to a high temperature, expansion at a high temperature can be suppressed, and an electricity storage device with high heat resistance can be supplied.
  • 1-ethyl-3-methylimidazolium tetrafluoroborate has a smaller ionic radius of tetrafluoroborate, which is an anion, compared to 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide and the like. Therefore, an electricity storage device with lower resistance can be supplied.
  • an electric double layer capacitor was fabricated by the following process.
  • Step 1 (Preparation of current collector) An aluminum layer having a thickness of 0.5 ⁇ m was formed by vapor deposition on a base material PET film coated with wax as a release layer. On the surface of the aluminum layer formed by vapor deposition, an etching mask resist was applied by pattern printing and dried. The resist used was Ares SPR manufactured by Kansai Paint. Then, this film was immersed in 40 degreeC ferric chloride aqueous solution, and the aluminum layer was patterned.
  • this film was immersed in an organic solvent, the resist was peeled off, and then immersed in a mixed aqueous solution of sulfuric acid and hydrofluoric acid to remove the oxidized layer on the surface of the aluminum layer, thereby forming a positive electrode current collector layer 21a.
  • Process 2 (1) Preparation of slurry for active material layer 29.0 g of activated carbon (BET specific surface area 1668 m 2 / g, average pore diameter 1.83 nm, average particle diameter (D 50 ) 1.26 ⁇ m), carbon black (Tokai Carbon Co., Ltd.) 2.7 g of “Toka Black # 3855” manufactured by company, BET specific surface area 90 m 2 / g) is weighed and put into a 1000 ml pot, and further, PSZ grinding media with a diameter of 2.0 mm and 286 g of deionized water. Then, the mixture was dispersed by mixing at 150 rpm for 4 hours using a rolling ball mill.
  • activated carbon BET specific surface area 1668 m 2 / g, average pore diameter 1.83 nm, average particle diameter (D 50 ) 1.26 ⁇ m
  • carbon black Tokai Carbon Co., Ltd.
  • BET specific surface area 90 m 2 / g is weighed and put into a 1000
  • the positive electrode layer 21 composed of the positive electrode current collector layer 21a and the positive electrode active material layer 21b was formed.
  • the positive electrode active material layer 21 b is formed at a predetermined interval from the first end surface 2 so as not to be directly connected to the positive electrode external terminal electrode 21 t on the first end surface 2 of the multilayer body 1. . Since it comprises in this way, the slurry for active material layers is screen-printed so that when it cut
  • Process 3 (1) Preparation of slurry for separator layer Silica (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size (D 50 ) 0.7 ⁇ m in a 500 ml pot m) and 50 g of methyl ethyl ketone as a solvent were added. Further, PSZ grinding media having a diameter of 5 mm were put, and the mixture was dispersed by mixing at 150 rpm for 16 hours using a rolling ball mill. Thereafter, a binder solution of PVDF (Kureha L # 1120, molecular weight 280,000, 12 wt% solution) was added and mixed for 4 hours at 150 rpm using a rolling ball mill to prepare a separator layer slurry.
  • PVDF Kagaku Kogyo Co., Ltd., average particle size (D 50 ) 0.7 ⁇ m in a 500 ml pot m) and 50 g of methyl ethyl ketone as a solvent were added. Further, PS
  • separator layer slurry prepared by the above method was applied onto the positive electrode layer 21 and then heated at 120 ° C. for 30 minutes.
  • the separator layer 11 having a thickness of 3 ⁇ m was produced by drying.
  • a positive electrode assembly sheet in which a plurality of positive electrode layers 21 were formed on the separator layer 11 was formed on a base material PET film.
  • another positive electrode assembly sheet in which a plurality of positive electrode layers 21 were formed on the separator layer 11 was produced.
  • Process 4 Next, as shown in FIG. 3 (1), the block of the positive electrode assembly sheet was punched out and sucked and fixed to the suction plate 80, and the base PET film 100 was peeled off.
  • Process 5 Next, as shown in FIG. 3 (2), a punching block of the positive electrode assembly sheet sucked and fixed to the suction plate 80 to another punching block of the positive electrode assembly sheet from which the base PET film prepared in the same manner was peeled off. Were stacked so that the positive electrode current collector layers 21a face each other. The entire surface of the positive electrode assembly sheet arranged in an overlapping manner was pressed with a pressure plate (not shown) to join the positive electrode assembly sheets together. At this time, the temperature of the pressing plate was 150 ° C., the pressing pressure was 0.05 MPa, and the pressing time was 1 minute.
  • step 4 and step 5 the positive electrode / positive electrode integrated sheet 20 shown in FIG. 3 (3) in which the positive electrode layer 21 was embedded in the separator layer 11 was produced.
  • thermocompression bonding As shown in FIG. 4 (5), and a total of four sheets shown in FIG. 4 (6).
  • a laminated assembly formed by laminating the integrated sheets was prepared.
  • the temperature of the pressure plate was 150 ° C.
  • the pressure of the pressure was 0.05 MPa
  • the pressure time was 1 minute.
  • the positive electrode layer in which the positive electrode active material layer 21 b is formed only on one surface of the positive electrode current collector layer 21 a is embedded in the separator layer 11.
  • the negative electrode integrated sheet 30a formed by embedding the negative electrode layer in which the negative electrode active material layer 31b is formed only on one surface of the negative electrode current collector layer 31a in the separator layer 11 is provided as the uppermost layer. Provided in the lower layer. That is, in this example, when the laminated assembly is produced, the positive electrode / positive electrode integrated sheet 20 and the negative electrode / negative electrode integrated sheet 30 are alternately stacked on the negative electrode integrated sheet 30a, and finally the positive electrode is integrated.
  • the sheet 20a was bonded.
  • the positive electrode integrated sheet 20a is coated with a slurry containing a component of the separator layer on the base PET film and dried on the surface of the positive electrode aggregate sheet shown in FIG. 3 (1) where the positive electrode current collector 21a is formed. This was prepared by pasting together a 3 ⁇ m thick separator layer.
  • the negative electrode integrated sheet 30a was prepared by bonding a separator layer having a thickness of 3 ⁇ m to the surface of the negative electrode aggregate sheet on which the negative electrode current collector 31a was formed. As described above, in Example 1, a laminated assembly in which the positive electrode layer 21 and the negative electrode layer 31 were joined by the separator layer 11 was produced.
  • Step 6 The above laminated assembly is separated into pieces by a dicer along the cutting line D1 shown in FIG.
  • the laminated body 1 was produced.
  • the dimensions of the laminate 1 were a length of 4.7 mm and a width of 3.3 mm. 3 (1) to 3 (4) and FIGS. 4 (5) and 6 (6) referred to in the above description, the separator layer 11, the positive electrode layer 21, the negative electrode layer 31, and the like are drawn thick due to restrictions on drawing. However, the actual dimensions are not exactly enlarged or reduced. Also, in other drawings attached to the specification, the size or the positional relationship is appropriately modified or exaggerated so as to be easily constrained or understood.
  • Step 7 The positive external terminal electrode 21t and the negative external terminal electrode 31t were formed by Al sputtering.
  • Process 8 A conductive adhesive containing gold as conductive particles is applied to the first end surface 2 and the second end surface 2 by dipping, and the applied conductive adhesive is connected to the positive electrode package electrode 41 and the negative electrode package electrode 42, respectively.
  • the laminate 1 was placed on the base portion 50b of the package 50 and heated at 170 ° C. for 10 minutes to cure the conductive adhesive.
  • the positive external terminal electrode 21t and the negative external terminal electrode 31t are formed on the first end surface 2 and the second end surface 2, respectively, and the positive external terminal electrode 21t and the negative external terminal electrode 31t are respectively connected to the positive electrode package.
  • the electrode 41 and the negative electrode package electrode 42 were electrically connected.
  • Step 9 an electrolytic solution was injected into the package and sealed.
  • 1-ethyl-3-methylimidazolium tetrafluoroborate is injected as an electrolytic solution under reduced pressure, and a lid 50a made of a liquid crystal polymer is disposed on the upper surface of the base portion 50b of the package 50 in the same manner as the base portion 50b.
  • the base portion 50b and the lid 50a were welded by irradiating laser along the frame portion of the base portion 50b of the package 50.
  • FIG. 5 shows the frequency characteristics of the equivalent series capacitance of the electric double layer capacitor produced in this example.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Separators (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

L'invention porte sur un dispositif de stockage d'énergie qui permet de rendre plus minces des éléments, et qui peut être configuré à bas coût et avec peu d'heures-personnes. Le dispositif de stockage d'énergie comprend : un corps stratifié comprenant une couche d'électrode négative positionnée entre au moins deux couches d'électrode positive, et des couches de séparateur agencées entre les couches d'électrode positive et la couche d'électrode négative, ou un corps stratifié comprenant une couche d'électrode positive positionnée entre au moins deux couches d'électrode négative, et des couches de séparateur agencées entre les couches d'électrode négative et la couche d'électrode positive ; un électrolyte ; et un boîtier qui contient le corps stratifié et l'électrolyte. Dans le corps stratifié, des couches d'électrode positive et d'électrode négative adjacentes sont directement collées aux couches de séparateur respectives.
PCT/JP2011/064752 2010-06-28 2011-06-28 Dispositif de stockage d'énergie et son procédé de production WO2012002359A1 (fr)

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WO2022230901A1 (fr) * 2021-04-26 2022-11-03 株式会社村田製作所 Boîtier de batterie solide
US11830672B2 (en) 2016-11-23 2023-11-28 KYOCERA AVX Components Corporation Ultracapacitor for use in a solder reflow process

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WO2022230901A1 (fr) * 2021-04-26 2022-11-03 株式会社村田製作所 Boîtier de batterie solide
JP7639898B2 (ja) 2021-04-26 2025-03-05 株式会社村田製作所 固体電池パッケージ

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