WO2013002119A1 - Dispositif de stockage, et procédé de fabrication de celui-ci - Google Patents

Dispositif de stockage, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2013002119A1
WO2013002119A1 PCT/JP2012/065892 JP2012065892W WO2013002119A1 WO 2013002119 A1 WO2013002119 A1 WO 2013002119A1 JP 2012065892 W JP2012065892 W JP 2012065892W WO 2013002119 A1 WO2013002119 A1 WO 2013002119A1
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WIPO (PCT)
Prior art keywords
layer
current collector
electrode
insulating layer
layers
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Application number
PCT/JP2012/065892
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English (en)
Japanese (ja)
Inventor
原田　裕之
上田　安彦
幸夫 得原
昌治 板谷
恭丈 福田
景司 堀川
前田　智之
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 JP2013522803A priority Critical patent/JP5477609B2/ja
Publication of WO2013002119A1 publication Critical patent/WO2013002119A1/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
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a power storage device and a method for manufacturing the same, and more particularly to various power storage devices such as an electric double layer capacitor having a laminated structure, and a method for manufacturing the same.
  • the positive electrode layer 101 by which the positive electrode active material layer 101b was formed in both the main surfaces of the positive electrode collector layer 101a is clamped by a pair of porous separators 102 and 102.
  • the negative electrode layer 103 in which the negative electrode active material layer 103b is formed on both main surfaces of the negative electrode current collector layer 103a is sandwiched between a pair of porous separators 104 and 104, and formed integrally.
  • a laminated battery in which a porous separator 102 and a porous separator 104 are stacked to form a laminated body, and the laminated body is housed in a casing in which an electrolytic solution is held.
  • Patent Document 1 even when the porous separator 102 and the porous separator 104 are overlapped with each other so that the porous separators 102 and 104 form pinholes in the stacking direction of the stacked body, It is possible to reduce the probability that pinholes overlap each other, and thereby, it is intended to suppress the occurrence of a short circuit between the positive electrode active material layer 101b and the negative electrode active material layer 103b facing each other.
  • the porous separator 102 and the porous separator 104 are overlapped to suppress a short circuit between the positive electrode active material layer 101b and the negative electrode active material layer 103b.
  • the porous separators 102 and 104 are not integrally joined, the distance between the positive electrode layer 101 and the negative electrode layer 103 is not constant depending on the lamination state of the positive electrode side sheet 105 and the negative electrode side sheet 106. Further, a positional “displacement” is likely to occur between the positive electrode side sheet 105 and the negative electrode side sheet 106, which may cause a decrease in energy density.
  • the present invention has been made in view of such circumstances, and even when external stress is applied, an electricity storage device having high reliability by suppressing a decrease in energy density and a decrease in electrical characteristics and its An object is to provide a manufacturing method.
  • the present inventors manufactured a plurality of composite sheets having electrode layers formed on the surface of the insulating layer, and manufactured a cell sheet in which the insulating layers were joined and integrated so as not to cause gaps or misalignment between the insulating layers. Further, the electrode layers of the cell sheet were integrally joined to form a laminated structure.
  • the bonding force between the electrode layers is made smaller than the bonding force between the insulating layers, and when the external stress is applied, the electrode layers can be peeled preferentially to prevent the insulating layers from peeling.
  • an electric storage device can be obtained that has good impact resistance and can stably secure a desired energy density without deteriorating electrical characteristics even when a large external stress is applied.
  • the power storage device is a power storage device having a stacked structure in which an electrode layer and an insulating layer are stacked, and has the same polarity.
  • One electrode layer and another electrode layer are integrally bonded to form an integrated electrode layer, and one insulating layer and another insulating layer are integrally bonded to be integrated insulation.
  • a layer is formed, and the integrated electrode layer and the integrated insulating layer are laminated and integrally bonded, and the inter-electrode bonding force of the integrated electrode layer is the insulating layer indirect of the integrated insulating layer It is characterized by being smaller than the resultant force.
  • the electrode layers are peeled preferentially, so that the peeling between the insulating layers can be effectively suppressed, and the electrical characteristics are prevented from deteriorating. Can do.
  • the insulating layers are integrally joined, the distance between the electrode layers does not change and positional displacement does not occur between the insulating layers, and a highly reliable power storage device having a desired stable energy density. Can be obtained.
  • the laminated structure has a plurality of composite sheets in which the electrode layer and the insulating layer are integrally joined, and the integrated insulating layer is a single composite sheet. And an insulating layer constituting the other composite sheet are integrally joined, and electrode layers having different polarities are electrically insulated via the integrated insulating layer, and
  • the composite sheet is preferably laminated in a state where electrode layers having the same polarity are integrally joined.
  • the electrode layers having the same polarity are integrally joined via an adhesive layer.
  • these bonding forces can be easily adjusted such that the electrode interlayer bonding force is smaller than the insulating interlayer bonding force.
  • the electrode layer includes an electrode current collector layer and an electrode active material layer formed on a main surface of the electrode current collector layer, and the electrode current collector layer
  • the insulating layer is formed on one main surface of the adhesive layer, and the electrode current collector layers having the same polarity are integrally joined via the adhesive layer, and electrodes having different polarities It is also preferable that a space is formed between the active material layers.
  • the electricity storage device of the present invention is preferably provided with a communication port that communicates the space and the outside of the laminated structure.
  • the method for manufacturing an electricity storage device includes an electrode layer forming step of forming an electrode layer having a predetermined pattern after forming an adhesive layer on a substrate, and an insulating layer on a surface of the electrode layer or the adhesive layer.
  • the base material is peeled off from the cell sheet, and the step of exposing the surface of the adhesive layer and the electrode layers having the same polarity in the plurality of cell sheets are joined together via the adhesive layer,
  • Has an integrated electrode layer A laminated structure producing step of producing a laminated structure, and the adhesive layer and the insulating layer so that an interlayer bonding force of the integrated electrode layer is smaller than an interlayer bonding force of the integrated insulating layer It is characterized by selecting each material.
  • the method for manufacturing an electricity storage device of the present invention includes a heat treatment temperature and an applied temperature at the time of heating and pressurization so that an interlayer bonding force of the integrated electrode layer is smaller than an interlayer bonding force of the integrated insulating layer. It is preferred to control at least one of the pressures.
  • the electrode layer has an electrode current collector layer and an electrode active material layer formed on a main surface of the electrode current collector layer, and the laminated structure
  • the electrode current collector layers having the same polarity are integrally joined to each other through the adhesive layer.
  • an electricity storage device having a laminated structure in which an electrode layer and an insulating layer are laminated, wherein one electrode layer having the same polarity and the other electrode layer are integrated.
  • the one insulating layer and the other insulating layer are integrally bonded to form an integrated insulating layer, and the integrated electrode layer and the integrated insulating layer
  • the layers are laminated and integrally bonded, and the electrode interlayer bonding force of the integrated electrode layer is smaller than the insulating interlayer bonding force of the integrated insulating layer, and therefore, when external stress is applied.
  • the electrode layers are preferentially peeled off, it is possible to effectively suppress the peeling between the insulating layers, thereby suppressing the deterioration of the electrical characteristics.
  • the insulating layers are integrally joined, the distance between the electrode layers does not change and positional displacement does not occur between the insulating layers, and a highly reliable power storage device having a desired stable energy density. Can be obtained.
  • an electrode layer forming step of forming an electrode layer of a predetermined pattern, and insulating the surface of the electrode layer or the adhesive layer A composite sheet manufacturing step of forming a plurality of composite sheets in which the insulating layer and the electrode layer are integrally joined, and an insulating layer of one composite sheet of the plurality of composite sheets and another A cell sheet manufacturing process for forming a plurality of cell sheets in which the insulating layers of the composite sheet are superposed and heated and pressed to form an integrated insulating layer and the electrode layers having different polarities are electrically insulated by the integrated insulating layer.
  • FIG. 1 shows typically one Embodiment (1st Embodiment) of the electrical double layer capacitor as an electrical storage device which concerns on this invention. It is a principal part expanded sectional view of FIG. It is a manufacturing process figure (1/6) which shows one Embodiment of the manufacturing method of the said electrical double layer capacitor. It is a manufacturing process figure (2/6) which shows one Embodiment of the manufacturing method of the said electrical double layer capacitor. It is a manufacturing process figure (3/6) which shows one Embodiment of the manufacturing method of the said electrical double layer capacitor. It is a manufacturing process figure (4/6) which shows one Embodiment of the manufacturing method of the said electrical double layer capacitor.
  • an electric double layer capacitor will be exemplified as an electricity storage device, and embodiments of the present invention will be described in detail.
  • An electric double layer capacitor uses a physical phenomenon called an electric double layer. That is, when the positive electrode and the negative electrode are immersed in the electrolyte solution with a certain separation distance, the charged particles in the electrolyte solution are irregular in the electrolyte solution before voltage is applied between the positive electrode and the negative electrode. Distributed. However, when a voltage is applied between the positive electrode and the negative electrode, anions in the electrolyte and holes in the positive electrode are continuously distributed in pairs at the contact interface between the positive electrode and the electrolyte. Cations in the electrolyte and electrons in the negative electrode are continuously distributed in pairs at the contact interface with the electrolyte. As a result, holes and anions are distributed in layers at the contact interface on the positive electrode side, and electrons and cations are distributed in layers on the contact interface on the negative electrode side, thereby forming an electric double layer.
  • the electric double layer capacitor using such an electric double layer forms an electric double layer during charging, accumulates electric charge, and the charged particles return to the state before charging by discharging, so a chemical reaction is not used, Even if charging / discharging is repeated, it is considered that there is no heat generation or deterioration, rapid charging / discharging with high efficiency is possible, and good cycle characteristics can be obtained.
  • FIG. 1 is a cross-sectional view showing an embodiment of the electric double layer capacitor.
  • the element body 2 is accommodated in the casing 1, the gap between the inner surface of the casing 1 and the element body 2 is filled with the electrolyte 3, and the element body 2 is impregnated with the electrolyte 3. Has been.
  • the housing 1 includes a housing body 4 having a bottom surface portion 4a and a pair of side surface portions 4b and 4b connected to the bottom surface portion 4a, and a lid body 5 that closes the housing body 4.
  • external electrodes 6 and 7 are formed from the bottom surface portion 4a of the housing body 4 to the side surface portions 4b and 4b.
  • the housing body 4 and the lid body 5 are formed of a heat-resistant resin such as liquid crystal polymer resin or polyphenylene sulfide resin (PPS), and the housing body 4 and the lid body 5 are formed by laser welding, resistance heating welding, ultrasonic waves. It is joined in a sealed manner by an appropriate joining means according to materials used such as welding and high-frequency induction heating.
  • a heat-resistant resin such as liquid crystal polymer resin or polyphenylene sulfide resin (PPS)
  • PPS polyphenylene sulfide resin
  • the external electrodes 6 and 7 are made of a conductive material such as Al.
  • the element body 2 has a laminated structure 40 in which positive electrode layers 8 and negative electrode layers 9 and insulating layers 10 are alternately laminated, and end electrodes 11 and 12 are formed at both ends of the laminated structure 40. Yes.
  • the insulating layer 10 includes a separator layer 13 interposed between the positive electrode layer 8 and the negative electrode layer 9, a buried layer 14 that fills a gap between the electrode patterns, and an exterior insulating layer that covers the positive electrode layer 8 and the negative electrode layer 9. 15.
  • the positive electrode layer 8 includes a positive electrode current collector layer and a positive electrode active material layer.
  • the positive electrode layer 8a in the intermediate portion excluding the uppermost layer has a pair of positive electrode active material layers 17a and 17a formed on both main surfaces of the positive electrode current collector layer 16a.
  • a positive electrode current collector layer 17b is formed on one main surface of the positive electrode current collector layer 16b.
  • the negative electrode layer 9 is composed of a negative electrode current collector layer and a negative electrode active material layer.
  • the negative electrode layer 9a in the middle portion excluding the lowermost layer has a pair of negative electrode active material layers 19a and 19a formed on both main surfaces of the negative electrode current collector layer 18a, and the lowermost negative electrode layer 9b.
  • the positive electrode current collector layers 16a and 16b are electrically connected to one end face electrode 11, and the negative electrode current collector layers 18a and 18b are electrically connected to the other end face electrode 12, and the end face electrodes 11, 12 are electrically connected to the external electrodes 6 and 7, respectively.
  • FIG. 2 is an enlarged cross-sectional view of a main part of the laminated structure 40.
  • the separator layer 13 has a two-layer structure including a separator layer 13A and a separator layer 13B, and the separator layers 13A and 13B are integrally joined to form the separator layer 13 as an integrated insulating layer.
  • the positive electrode current collector layer 16a of the positive electrode layer 8a is formed by integrally bonding the positive electrode current collector layer 16A and the positive electrode current collector layer 16B via the adhesive layer 20. That is, the positive electrode current collector layer 16a has a two-layer structure in which two positive electrode current collector layers 16A and 16B are integrally joined, and is formed on one main surface of each positive electrode current collector layer 16A and 16B. The positive electrode current collector layer 16A and the positive electrode current collector layer 16B are integrally joined to each other through the adhesive layer 20A and the adhesive layer 20B, thereby forming the positive electrode current collector layer 16a.
  • the positive electrode active material layer 17a is formed on the surface opposite to the adhesive layers 20A and 20B on the positive electrode current collector layers 16A and 16B, thereby forming an integrated electrode layer. .
  • the negative electrode current collector layer 18a of the negative electrode layer 9a the negative electrode current collector layer 18A and the negative electrode current collector layer 18B are integrally bonded via the adhesive layer 20. That is, the negative electrode current collector layer 18a has a two-layer structure in which two negative electrode current collector layers 18A and 18B are integrally joined, and is formed on one main surface of each of the negative electrode current collector layers 18A and 18B. The negative electrode current collector layer 18A and the negative electrode current collector layer 18B are integrally joined to each other through the adhesive layer 20A and the adhesive layer 20B, thereby forming the negative electrode current collector layer 18a.
  • the negative electrode active material layer 19a is formed on the surface opposite to the adhesive layers 20A and 20B on the negative electrode current collector layers 18A and 18B in the same manner as the positive electrode layer 8a. Forming a layer.
  • the interlayer joining force of an integrated electrode layer may become smaller than the interlayer joining force of an integrated insulating layer. That is, the bonding force between the positive electrode current collector layer 16A and the positive electrode current collector layer 16B indicated by the arrow A, and the bonding force between the negative electrode current collector layer 18A and the negative electrode current collector layer 18B (hereinafter, “ Current collector interlayer bonding force ”) is smaller than the bonding force between the separator layer 13A and the separator layer 13B indicated by arrow B (hereinafter referred to as" separator interlayer bonding force "). Yes.
  • the distance between the positive electrode side sheet and the negative electrode side sheet may change or the separator layers may be misaligned only by stacking separator layers as in Patent Document 1.
  • a gap is formed between the separator layers, which may cause a decrease in electrical characteristics such as energy density and ESR.
  • the electrode current collector layers are integrally bonded, even if a large impact is applied from the outside and a gap is generated between the electrode current collector layers, the positive electrode active material layer 17a facing each other with the separator layer 13 interposed therebetween.
  • the distance between the negative electrode active material layer 19a and the distance between the positive electrode current collector layer 16A and the negative electrode current collector layer 18B (or the distance between the positive electrode current collector layer 16B and the negative electrode current collector layer 18A) does not change. The electric characteristics are hardly affected.
  • the electrode current collector layers are integrally bonded so that the current collector interlayer bonding force is smaller than the separator interlayer bonding force, and the electrode current collector is loaded when an external impact is applied.
  • the electrical layers are preferentially exfoliated, thereby suppressing the occurrence of delamination between the separator layers and avoiding the reduction in energy density and electrical characteristics as much as possible.
  • the current collector interlayer bonding force can be made smaller than the separator interlayer bonding force by appropriately selecting the material of the insulating layer 10 to be the adhesive layer 20 and the separator layer 13 and controlling the bonding force.
  • the insulating layer 10 that forms the adhesive layer 20 and the separator layer 13 includes a urethane resin, a polyvinylidene fluoride resin (hereinafter referred to as “PVDF”), a polyamideimide resin (hereinafter referred to as “PAI”), and a polyimide resin.
  • PVDF polyvinylidene fluoride resin
  • PAI polyamideimide resin
  • Polyamide resin, silicone resin, copolymer of PVDF and hexafluoropropylene (hereinafter referred to as “PVDF-HFP”), and the like can be used.
  • the superiority or inferiority of the bonding strength of these various materials can be determined, and the materials of the insulating layer 10 and the adhesive layer 20 can be appropriately combined so that the current collector interlayer bonding force is smaller than the separator interlayer bonding force.
  • the materials of the insulating layer 10 and the adhesive layer 20 can be appropriately combined so that the current collector interlayer bonding force is smaller than the separator interlayer bonding force.
  • urethane resin or PAI having a bonding strength smaller than that of the PVDF-HFP can be used for the adhesive layer 20.
  • PAI having a bonding force smaller than that of the PVDF can be used for the adhesive layer 20.
  • the positive electrode current collector layer 16a and the negative electrode current collector layer 18a are integrally bonded through the adhesive layer 20, but the separator layer 13A and the separator layer 13B are bonded together by heating and pressurizing. Therefore, the separator interlayer bonding force can be adjusted to be stronger than the current collector interlayer bonding force by controlling at least one of the heat treatment temperature and the applied pressure during heating and pressurization. Is possible.
  • the electric double layer capacitor includes the positive electrode current collector layer 16A and the positive electrode current collector layer 16B that form the positive electrode layer 8a, and the negative electrode current collector layer 18A and the negative electrode current collector layer 18B that form the negative electrode layer 9a.
  • the separator layer 13A and the separator layer 13B forming the insulating layer 10 are joined together, and the current collector interlayer joining force indicated by the arrow A Is smaller than the separator interlayer bonding force indicated by the arrow B, so that even when an external stress is applied, the current collectors are preferentially separated, thereby effectively suppressing the separation between the separator layers. be able to.
  • the distance between the layer 16B and the negative electrode current collector layer 18A) can be prevented from changing, and the electrical characteristics can be prevented from deteriorating.
  • the separator layers are integrally joined, the distance between the electrodes does not change and positional displacement does not occur between the separator layers. A double layer capacitor can be obtained.
  • the positive electrode current collector layer 16a and the negative electrode current collector layer 18a can be integrally bonded via the adhesive layer 20, and therefore, by selecting various materials for the adhesive layer 20, the current collector interlayer bonding force These bonding forces can be easily adjusted so that is smaller than the separator interlayer bonding force.
  • the positive electrode active material layer 17a and the negative electrode active material layer 19a are electrically insulated by the separator layer 13 which is an integrated insulating layer, even if pinholes occur in the separator layer 13A or the separator layer 13B, they are integrated.
  • the separator layer 13 bonded to each other almost eliminates the probability that the pinholes overlap each other, thereby effectively preventing the positive electrode active material layer 17a and the negative electrode active material layer 19a from being short-circuited.
  • 3 to 8 are cross-sectional views showing an embodiment of the manufacturing procedure of the electric double layer capacitor.
  • a film-like first base material 21 having a film thickness of 30 to 70 ⁇ m to which releasability is imparted is prepared.
  • the first substrate 21 is not particularly limited.
  • a polyethylene resin such as polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • a cellulose resin such as a cellulose acetate resin, a polypropylene resin, a polyester resin, a polycarbonate resin, Polyamide resin, polyamideimide resin, fluororesin, paper and the like
  • the material having releasability can be used directly as the first base material 21, and the material having no releasability is used for the first base material 21 with releasability. can do.
  • the method for imparting releasability is not particularly limited.
  • a silicone resin, wax, surfactant, metal oxide, fluororesin, or the like to the first substrate 21,
  • the first substrate 21 can be given releasability.
  • a PET film that has been subjected to a releasability treatment is preferably used.
  • an adhesive such as PAI or urethane is applied to the surface of the first base material 21 to form the adhesive layer 20, and then the conductive film 22 is formed on the surface of the adhesive layer 20 by a thin film forming method such as vacuum deposition. Form.
  • a mask pattern 23 is formed on the conductive film 22.
  • this mask pattern 23 a large number of electrode patterns are formed in a matrix so that a large number of composite sheets having an electrode layer and an insulating layer can be obtained.
  • the formation method of the mask pattern 23 is not particularly limited, and is formed by screen printing or gravure printing using an etching resist, or by photolithography using a coating type resist or dry film resist. In view of cost, screen printing and gravure printing are preferably used, and when pattern accuracy is required, photolithography is preferably used.
  • the first base material 21 on which the mask pattern 23 is formed is subjected to an etching process, whereby the surface exposed portion of the conductive film 22 is removed by etching. Thereafter, washing and drying are performed to form the positive electrode current collector layer 16 b in the lower layer portion of the mask pattern 23.
  • the mask pattern 23 is treated with a solvent to be dissolved and removed, and a positive electrode current collector layer 16b is formed on the surface of the adhesive layer 20 as shown in FIG.
  • an appropriate organic solvent such as butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, an amine solvent, or the like can be used.
  • the mask pattern 23 is formed, and after etching, the mask pattern 23 is dissolved and removed to form the positive electrode current collector layer 16b.
  • the positive electrode current collector layer 16b having a predetermined pattern may be directly formed on the adhesive layer 20 by a vacuum deposition method or the like using a metal mask or an oil mask.
  • the first base material 21 on which the positive electrode current collector layer 16b is patterned is surface-treated with a surface treatment liquid, and the oxide film on the surface of the positive electrode current collector layer 16b is removed.
  • the surface may be etched with acid or alkali, or the surface oxide film may be removed by electrolytic fluorination method or plasma fluorination method.
  • an active material layer slurry containing a carbon material such as activated carbon is prepared.
  • the positive electrode active material layer 17b of a predetermined pattern is produced.
  • a slurry for an insulating layer containing an organic insulating material such as PVDF or PVDF-HFP is prepared.
  • the insulating layer slurry is applied to the concave portions where the surface of the adhesive layer 20 and the positive electrode current collector layer 16b is exposed by screen printing or the like. 14 is formed and the surface is smoothed.
  • the insulating layer slurry is applied to the surfaces of the buried layer 14 and the positive electrode active material layer 17b to form the separator layer 13B.
  • the embedded layer 14 and the separator layer 13 ⁇ / b> B are formed by applying the same insulating layer slurry, whereby the positive electrode composite sheet 24 is formed on the surface of the first substrate 21.
  • the embedded layer 14 and the separator 13B are formed using the same insulating layer slurry, but the embedded layer 14 and the separator 13B are formed using different types of insulating layer slurries having different component compositions. May be formed.
  • the negative electrode composite sheet 25 is formed on the surface of the first base material 21 by the same method as shown in FIG. That is, the adhesive layer 20B is formed on the surface of the first substrate 21, the negative electrode current collector layer 18B and the negative electrode active material layer 19a are sequentially formed, and the buried layer 14 and the separator layer are formed using the insulating layer slurry. 13A is formed.
  • each of the positive electrode composite sheet 24 and the negative electrode composite sheet 25 is illustrated. However, since it is usually performed by a multi-cavity method, a large composite sheet is processed in the same process.
  • the positive electrode composite sheet 24 and the negative electrode composite sheet 25 are manufactured simultaneously by cutting.
  • the separator layer 13A and the separator layer 13B are arranged to face each other, the positive electrode composite sheet 24 and the negative electrode composite sheet 25 are overlaid, and are applied evenly using a pressure plate.
  • the positive electrode composite sheet 24 and the negative electrode composite sheet 25 are integrally joined by pressing and heating at a temperature of about 60 to 150 ° C. That is, the separator layer 13 ⁇ / b> A and the separator layer 13 ⁇ / b> B are integrated to form the separator layer (integrated insulating layer) 13, whereby the cell sheet 26 including the positive electrode composite sheet 24 and the negative electrode composite sheet 25 is manufactured.
  • the first substrate 21 on the negative electrode composite sheet 25 side is sucked by the suction disk 27 and the cell sheet 26 is lifted upward, and then the first base material 21 on the positive electrode composite sheet 24 side. 1 substrate 21 is peeled from the cell sheet 26.
  • a second substrate 28 is prepared, and the insulating layer slurry is used, and the surface of the second substrate 28 is formed by a molding method such as a doctor blade method.
  • the exterior insulating layer 15 is formed.
  • the second base material 28 on which the exterior insulating layer 15 is formed is pressed against and bonded to the adhesive layer 20 on the positive electrode composite sheet 24 side, and shown in FIG. 6 (l).
  • the cell sheet 26 is pulled down, and the first base material 21 sucked by the suction board 27 is peeled off from the negative electrode composite sheet 25.
  • FIG. 6 (m) another cell sheet 30 prepared by the same method as described above is prepared.
  • the cell sheet 26 and the cell sheet 30 are arranged so that the adhesive layer 20A and the adhesive layer 20B face each other, and the adhesive layer 20A and the adhesive layer 20B are overlapped as shown in FIG.
  • the cell sheet 26 and the cell sheet 30 are joined via the adhesive layer 20A and the adhesive layer 20B while heating at a temperature of ⁇ 150 ° C.
  • the negative electrode current collector layer 18A and the negative electrode current collector layer 18B are integrally joined via the adhesive layer 20, and the negative electrode current collector layer 18a is formed.
  • the cell sheet 30 is pulled downward, and the first base material 21 is drawn from the cell sheet 30 as shown in FIG. Peel off.
  • the uppermost cell sheet 31 is laminated, and the third base material 29 having the exterior insulating layer 15 formed on the surface is joined to the uppermost layer as shown in FIG. .
  • the laminated block body 41 is cut into a predetermined size and separated into individual pieces, whereby a laminated structure 40 (see FIG. 2) is formed.
  • end electrodes 11 and 12 are formed at the end of the laminated structure 40 by arc spraying or the like, whereby the end electrodes 11 and 12 are joined to the positive electrode layer 8, the negative electrode layer 9, and the insulating layer 10, and the element body 2. Is formed.
  • the laminated structure 40 in which the end face electrodes 11 and 12 are formed is housed together with the electrolytic solution in the casing body 4 in which the external electrodes 6 and 7 are formed, and sealed with the lid 5, thereby A multilayer capacitor is fabricated.
  • a conductive adhesive containing Au as conductive particles is applied to the end face electrodes 11 and 12 by dipping, and the element body 2 is attached to these conductive adhesives.
  • the agent is disposed in the housing body 4 so as to be bonded to the external electrodes 6 and 7.
  • the electrolyte solution is selected from commonly used organic solvents such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, acetonitrile, or the like, or mixed organic solvents such as tetramethylammonium tetrafluoro.
  • organic solvents such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, acetonitrile, or the like
  • mixed organic solvents such as tetramethylammonium tetrafluoro.
  • borate, triethylmethylammonium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide or the like can be used.
  • ionic liquids such as 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide may be used alone or dissolved in the organic solvent. it can.
  • the ionic liquid described above when used in a state 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 electric double layer capacitor with high heat resistance can be obtained. Obtainable.
  • 1-ethyl-3-methylimidazolium tetrafluoroborate has an ionic radius of tetrafluoroborate, which is an anion, compared to 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide. Since it is small and has high conductivity, an electric double layer capacitor with lower resistance can be obtained.
  • An electrolyte such as a gel electrolyte or a polymer solid electrolyte can also be used.
  • the electrode layer having a predetermined pattern that is, the positive electrode current collector layers 16A and 16B, the negative electrode current collector layer 18A, 18B, and a positive electrode active material layer 17a and a negative electrode active material layer 19a
  • a plurality of electrode layers forming step, separator layers 13A and 13B are formed on the surface of the electrode layers, and a plurality of separator layers and electrode layers are provided.
  • the composite sheet preparation step for preparing the composite sheet and the separator layer 13A of the positive electrode composite sheet 24 and the separator layer 13B of the negative electrode composite sheet 25 are superposed and heated and pressurized, and the separator layers 13A and 13B are integrally joined.
  • a negative electrode current collector layer 18A of one cell sheet 26 and a negative electrode current collector layer 18B of another cell sheet 30 are integrally joined via adhesive layers 20A and 20B to form a laminated structure.
  • Including the laminated structure manufacturing step for manufacturing the body 40, and the materials for the adhesive layer 20 and the insulating layer 13 are selected so that the current collector interlayer bonding force A is smaller than the separator bonding force B.
  • the materials of the layer 20 and the insulating layer 13 an electrical storage device that has favorable electrical characteristics and can secure a desired high output can be easily obtained.
  • a desired separator interlayer bonding force can be obtained by controlling the heat treatment temperature at the time of bonding between the separators.
  • FIG. 9 is an enlarged cross-sectional view of a main part showing a second embodiment of the electric double layer capacitor.
  • the positive electrode layer 45 includes a positive electrode current collector layer 47A in which a positive electrode active material layer 46A is formed on one main surface and one main layer.
  • the positive electrode current collector layer 47B having the positive electrode active material layer 46B formed on the surface is integrally bonded via an adhesive layer 48 (adhesive layers 48A and 48B), thereby forming an integrated electrode layer on the positive electrode side.
  • the negative electrode layer 49 includes a negative electrode current collector layer 51A in which a negative electrode active material layer 50A is formed on one main surface, and a negative electrode current collector layer 51B in which a negative electrode active material layer 50B is formed on one main surface.
  • Insulating layers 52A and 52B are formed on one main surface of the adhesive layers 48A and 48B together with the positive electrode current collector layers 47A and 47B and the negative electrode current collector layers 51A and 51B.
  • the positive electrode current collector layers 47A and 47B and the negative electrode current collector layers 51A and 51B are arranged to face each other, and the insulating layer 52A and the insulating layer 52B are integrally joined to form the integrated insulating layer 52. Yes.
  • the positive electrode composite sheet 54 is formed by the insulating layer 52A, the positive electrode current collector layer 47A (or the positive electrode current collector layer 47B), and the positive electrode active material layer 46A (or the positive electrode active material layer 46B), and the insulating layer 52B, the negative electrode
  • the current collector layer 51A (or the negative electrode current collector layer 51B) and the negative electrode active material layer 50A (or the negative electrode active material layer 50B) form a negative electrode composite sheet 55.
  • the positive electrode composite sheet 54 and the negative electrode composite sheet 55 are The cell sheet 56 is formed by being integrally joined via the integrated insulating layer 52. And many cell sheets 56 are laminated
  • a space 53 is formed between the positive electrode active material layer 46A and the negative electrode active material layer 50B and between the positive electrode active material layer 46B and the negative electrode active material layer 50A.
  • a communication port (not shown) that communicates the space 53 and the outside of the cell sheet 56 is provided.
  • the insulating layers 52A and 52B are required to have high mechanical strength. Therefore, it is necessary to reduce the porosity of the insulating layers 52A and 52B, which may cause a decrease in liquid permeability of the electrolytic solution. In this case, a method of injecting an electrolytic solution during the manufacturing process of the laminated block body 57 is conceivable. There is a fear.
  • a communication port that communicates the space portion 53 and the outside of the cell sheet 56 is provided, and the electrolyte solution is supplied from the communication port when the element body is disposed on the housing body. Can be supplied.
  • the interlayer bonding strength of the integrated electrode layer that is, between the positive electrode current collector layer 47A and the positive electrode current collector layer 47B or between the negative electrode current collector layer 51A and the negative electrode current collector layer.
  • the collector interlayer bonding force between 5B and 5B is formed to be smaller than the interlayer bonding force of the integrated insulating layer 52 in which the insulating layer 52A and the insulating layer 52B are bonded. Therefore, as in the first embodiment, even when external stress is applied, the current collector layers are preferentially peeled off, thereby effectively suppressing the peeling between the integrated insulating layers. it can.
  • the distance between the layer 46B and the negative electrode active material layer 50A and the distance between the positive electrode current collector layer 47B and the negative electrode current collector layer 51A) can be avoided, and deterioration of electrical characteristics can be suppressed. Can do.
  • the insulating layer 52A and the insulating layer 52B are integrally joined, the distance between the electrodes does not change and positional displacement between the insulating layers 52A and 52B does not occur. It is possible to obtain an electric double layer capacitor having high density and high reliability.
  • the separator layer as in the first embodiment is not interposed between the main surfaces of the positive electrode active material layers 46A and 46B and the negative electrode active material layers 50A and 50B, the resistance of the element can be reduced. It becomes possible.
  • the communication port for communicating the space 53 and the outside is provided, it becomes possible to inject the electrolyte into the space 53 after the cell sheet 56 is formed. Liquid permeability can be secured.
  • This second embodiment can be manufactured as follows.
  • the adhesive layer 48 and the positive electrode current collector layer 47A having a predetermined pattern are formed on the surface of the first base material 58 by the same method and procedure as in FIGS. To do.
  • the insulating layer slurry is applied to the surfaces of the positive electrode current collector layer 47A and the adhesive layer 48 by an appropriate means such as a screen printing method so as to have a predetermined columnar frame shape.
  • Layer 52A is formed.
  • a cut portion 60 is provided in the insulating layer 52A so as to be in contact with the positive electrode current collector layer 47A. The cut portion 60 penetrates the insulating layer 52A in FIG.
  • the active material layer slurry is applied to the surface of the positive electrode current collector layer 47A by an appropriate means such as a screen printing method to form a positive electrode active material layer 46A having a predetermined pattern.
  • the positive electrode composite sheet 54 is obtained.
  • the negative electrode composite sheet 55 obtained in the same manner is superimposed on the positive electrode composite sheet 54 as shown in FIG. 13, and heated and pressed to integrally bond the insulating layer 52A and the insulating layer 52B. An insulating layer 52 is formed, and thereby a cell sheet 56 is obtained.
  • the cut portion 60 of the positive electrode composite sheet 54 and the cut portion (not shown) of the negative electrode composite sheet 55 are overlapped so as to correspond to each other, thereby forming a communication port, and the outside of the space portion 53 and the cell sheet 56. And communicated with each other.
  • the multilayer block body 57 is formed by the same method and procedure as in the first embodiment (see FIGS. 5 to 8), and then the electric double layer capacitor is passed through a series of procedures as in the first embodiment. Is made.
  • the present invention is not limited to the above embodiment.
  • the positive electrode active material layer 46 and the negative electrode active material layer 50 are electrically insulated from each other by the space 53.
  • an insulating material is disposed in the space 53 to form a separator layer. In this case, the generation of leakage current can be more reliably suppressed.
  • the shape of the electric double layer capacitor, the pattern of the electrode layer, and the like described above are merely examples, and can be freely modified as necessary without departing from the gist of the present invention.
  • the electric double layer capacitor has been described as an example of the electric storage device.
  • the electric double layer capacitor is not limited to the electric double layer capacitor, and various types of stacked electric storage such as a lithium ion secondary battery and a lithium ion capacitor can be used. Can be widely applied to devices.
  • a positive electrode active material layer containing a lithium composite oxide such as LiCoO 2 is formed on a positive electrode current collector layer formed of Al foil or the like to form a positive electrode layer, and Cu
  • a negative electrode active material layer containing graphite is formed on a negative electrode current collector layer formed of foil or the like to form a negative electrode layer, and an electrolytic solution in which LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate is used.
  • a lithium ion secondary battery can be obtained.
  • a positive electrode active material layer containing activated carbon is formed on a positive electrode current collector layer formed of Al foil or the like to form a positive electrode layer, and a negative electrode current collector formed of copper foil or the like
  • a negative electrode active material layer containing graphite is formed on the layer to form a negative electrode layer, pre-doping lithium ions into the negative electrode layer, and using an electrolytic solution in which LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate A lithium ion capacitor can be obtained.
  • sample preparation (Sample No. 1) A sample No. 1 was prepared by the method described in the second embodiment.
  • a PET film (first base material) having a film thickness of 50 ⁇ m having a release property on the surface was prepared. And the urethane was apply
  • a resist is applied on the Al film by screen printing, and a rectangular pattern of 11 mm in length and 15.4 mm in width is arranged vertically and horizontally at an interval of 1 mm so that a large number of electrode patterns can be obtained.
  • a predetermined resist pattern was prepared and dried for 10 minutes in a hot air oven set at a temperature of 100 ° C.
  • the PET film on which the resist pattern was formed was passed through an aqueous ferric chloride solution adjusted to a temperature of 40 ° C. to perform etching treatment, and the Al film other than the resist pattern forming portion was dissolved and removed, and washed with shower water. After that, it was dried.
  • the PET film was treated with butyl acetate, the resist was dissolved and removed, the Al film was exposed on the surface, and electrode current collector layers (a positive electrode current collector layer and a negative electrode current collector layer) were produced on the PET film. Then, the PET film on which the electrode current collector layer was produced was treated with a mixed acid of hydrofluoric acid and sulfuric acid, and the oxide film on the surface of the electrode current collector layer was removed.
  • activated carbon having a BET specific surface area of 1668 m 2 / g, an average pore diameter of 1.83 nm, an average particle diameter D 50 of 1.26 ⁇ m: 29.0 g, and a carbon black having a BET specific surface area of 90 m 2 / g: 2. 7 g is weighed, and these weighed materials are put in a pot mill having a capacity of 1000 mL. Further, PSZ grinding media having a diameter of 2.0 mm and deionized water: 286 g are put in the pot mill and dispersed by mixing at a rotation speed of 150 rpm for 4 hours. I let you. Then, carboxymethyl cellulose: 3.0 g, 38.8 wt% polyacrylate resin aqueous solution: 2.0 g was added to the pot mill and mixed for 2 hours, thereby preparing an active material layer slurry.
  • a slurry for active material layer is screen-printed on the electrode current collector layer, dried at a temperature of 100 ° C. for 30 minutes, and an electrode active material layer having a length of 11 mm, a width of 7.2 mm, and a thickness of 5 ⁇ m (positive electrode active material layer and A negative electrode active material layer) was formed.
  • PVDF-HFP 160 g was added to a 1 L pot, and 1-methyl-2-pyrrolidone (hereinafter referred to as “NMP”): 640 g as an organic solvent was added.
  • NMP 1-methyl-2-pyrrolidone
  • a mixing treatment was performed at a rotational speed of 150 rpm for 24 hours, thereby obtaining a binder solution in which 20% by mass PVDF-HFP was present in NMP.
  • the insulating layer slurry is applied to the concave portion where the adhesive layer and the electrode current collector layer are exposed on the surface, and dried at a temperature of 60 ° C. for 2 minutes, whereby an insulating layer having a thickness of 15 ⁇ m (electrode current collector) The thickness on the layer was 14.5 ⁇ m).
  • the insulating layer of the composite sheet for the positive electrode and the insulating layer of the composite sheet for the negative electrode are overlapped, and uniformly heated at a pressure of 20 MPa for 10 seconds using a pressure plate while heating at a temperature of 100 ° C.,
  • the positive electrode composite sheet and the negative electrode composite sheet were joined and integrated to produce a cell sheet.
  • the negative electrode composite sheet of the cell sheet was adsorbed on the suction plate to lift the cell sheet upward, and then the PET film was peeled from the cell sheet.
  • PET film second base material
  • an insulating insulating layer having a thickness of 1 ⁇ m was formed on the surface of the PET film by the doctor blade method using the slurry for insulating layer.
  • the PET film on which the exterior insulating layer was formed was pressed against the adhesive layer on the lower surface of the cell sheet, joined, and pulled downward to peel the PET film sucked by the suction disk from the cell sheet.
  • both cell sheets were arranged so that the adhesive layers were opposed to each other, and both cell sheets were joined via the adhesive layer while being heated to 100 ° C., and then the PET film was peeled off from the cell sheet.
  • the cell sheets from which the PET film has been peeled are laminated, and thereafter, the same steps are repeated so that the positive electrode layer and the negative electrode layer are alternately positioned via the insulating layer on the PET film on which the exterior insulating layer is formed. 50 cell sheets were laminated.
  • this PET film was made to peel from a cell sheet, and, thereby, a positive electrode layer and a negative electrode layer Formed a laminated block body embedded in an insulating layer.
  • the joining process between insulating layers and the joining process between current collector layers were all performed by applying pressure uniformly at a pressure of 20 MPa for 10 seconds using a pressure plate while heating at a temperature of 100 ° C.
  • the laminated block body was cut into a predetermined size and separated into individual pieces to obtain a laminated structure.
  • an end face electrode made of Al was formed on the end of the laminated structure by arc spraying, thereby joining the end face electrode, the positive electrode layer, the negative electrode layer, and the insulating layer to obtain an element body.
  • the outer dimensions of the element body were 14 mm long, 8.5 mm wide, and 1 mm thick.
  • the element body was housed and arranged in a liquid crystal polymer case body having an external electrode made of Al. Then, the conductive adhesive was cured, the end face electrode of the element body was fixed to the external electrode, and the end face electrode and the external electrode were electrically connected. Thereafter, an electrolytic solution was injected into the casing body, and a liquid crystal polymer lid was joined by laser welding and sealed, thereby preparing a sample of sample number 1. As the electrolytic solution, 1-ethyl-3-methylimidazolium tetrafluoroborate was used.
  • Sample No. 2 was prepared in the same manner as Sample No. 1 except that PAI was used for the adhesive layer.
  • Sample No. 3 Sample number 1 except that PVDF is used for the insulating layer, the heat treatment temperature during heating / pressurization is 150 ° C., PAI is used for the adhesive layer, and the heat treatment temperature during bonding is 150 ° C. Thus, a sample No. 3 was prepared.
  • the slurry for insulating layers of PVDF was produced as follows.
  • Sample No. 4 was prepared in the same manner as Sample No. 1 except that PVDF was used for the insulating layer, the heat treatment temperature during heating / pressurization was 150 ° C., and the heat treatment temperature during bonding was 150 ° C.
  • Example evaluation (Electrical characteristics) The electrostatic capacity and ESR of each sample Nos. 1 to 4 were measured by the discharge method (discharge current 3A).
  • an Al film having a thickness of 0.5 ⁇ m is formed by vacuum deposition, and an insulating layer slurry is applied to the surface of the Al film at 60 ° C. It was dried for 2 minutes to form an insulating layer having a thickness of 14.5 ⁇ m, and two sheets each having a length of 100 mm and a width of 40 mm were produced.
  • the insulating layers of this sheet are overlapped with each other and heated uniformly at a temperature of 100 ° C. or 150 ° C., using a pressure plate, and uniformly pressed at a pressure of 20 MPa for 10 seconds to form an integrated insulating layer.
  • Four types of first test pieces for measuring the insulating interlayer bonding force corresponding to 1 to 4 were prepared. Then, the insulating interlayer bonding force was measured for each first test piece.
  • the measurement of the insulating interlayer bonding force was performed at a peeling rate of 100 mm / min and an ambient temperature of 23 ° C. in accordance with a 90 ° peeling test specified in JIS K 6854. The measurement was performed on 20 samples, and the peel angle was always kept at 90 ° during the measurement.
  • a second test piece for measuring the current collector interlayer bonding force was produced using the first test piece. That is, one PET film of each first test piece is peeled, the adhesive layers are overlapped, and the Al films are joined together while being heated to a temperature of 100 ° C. or 150 ° C.
  • Four types of second test pieces corresponding to ⁇ 4 were prepared. And about each 2nd test piece, the collector interlayer joining force was measured by the method similar to the measurement of an insulating interlayer joining force.
  • Drop test A drop test was performed on 50 samples of sample numbers 1 to 4, and the peeled portions of each sample were measured.
  • Each sample is solder-mounted on the center of the drop test substrate, dropped from a predetermined height with the drop test substrate attached to the frame jig, and subjected to a drop test by applying impact stress. went.
  • ESR equivalent series resistance
  • Table 1 shows the specifications and measurement results (average values) of the samples Nos. 1 to 4.
  • Sample Nos. 1 to 4 each had a capacitance of 402 to 405 mF, and the ESR before the drop test was 20.4 to 21.3 m ⁇ , which was almost the same between the samples.
  • Electric double layer capacitors with good energy density and no deterioration in electrical characteristics even when impact force is applied from the outside by making the bonding force between electrode layers smaller than the bonding force between insulating layers To realize the electricity storage device.

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Abstract

Selon l'invention, une couche de collecteur d'électrode positive (16A) avec une couche de collecteur d'électrode positive (16B), et une couche de collecteur d'électrode négative (18A) avec une couche de collecteur d'électrode négative (18B) sont liées d'un seul tenant par l'intermédiaire de couches adhésives (20A, 20B). Une couche de collecteur d'électrode positive (16a) sur la face principale de laquelle est formée une couche de substance active d'électrode positive (17a), et une couche de collecteur d'électrode négative (18a) sur la face principale de laquelle est formée une couche de substance active d'électrode négative (19a) sont placées en opposition par l'intermédiaire d'une couche de séparateur (13); une couche d'électrode positive et une couche d'électrode négative sont électriquement isolées par l'intermédiaire de la couche de séparateur (13). Cette couche de séparateur (13) présente une couche de séparateur (13A) et une couche de séparateur (13B) liées d'un seul tenant. En outre, la force de liaison entre les couches de collecteur représentée par une flèche (A), est formée de façon à être inférieure à la force de liaison entre les couches de séparateur représentée par une flèche (B). Ainsi, l'invention réalise un dispositif de stockage, tel qu'un condensateur électrique à couche double, qui empêche une baisse de densité énergétique ou une baisse de caractéristiques électriques, et qui possède une haute fiabilité, même lorsqu'une contrainte externe est appliquée.
PCT/JP2012/065892 2011-06-28 2012-06-21 Dispositif de stockage, et procédé de fabrication de celui-ci WO2013002119A1 (fr)

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CN110462883B (zh) * 2017-03-29 2022-10-11 株式会社村田制作所 二次电池的制造方法及制造装置
CN110462883A (zh) * 2017-03-29 2019-11-15 株式会社村田制作所 二次电池的制造方法及制造装置
WO2020022022A1 (fr) * 2018-07-26 2020-01-30 株式会社村田製作所 Dispositif de stockage d'électricité
JPWO2021024557A1 (fr) * 2019-08-06 2021-02-11
JP7192996B2 (ja) 2019-08-06 2022-12-20 株式会社村田製作所 蓄電デバイス
WO2021024557A1 (fr) * 2019-08-06 2021-02-11 株式会社村田製作所 Dispositif de stockage d'électricité
US11942270B2 (en) 2019-08-06 2024-03-26 Murata Manufacturing Co., Ltd. Electricity storage device with sintered body

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