WO2013118804A1 - フィルム外装電気デバイスの製造方法及び製造装置 - Google Patents
フィルム外装電気デバイスの製造方法及び製造装置 Download PDFInfo
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- WO2013118804A1 WO2013118804A1 PCT/JP2013/052807 JP2013052807W WO2013118804A1 WO 2013118804 A1 WO2013118804 A1 WO 2013118804A1 JP 2013052807 W JP2013052807 W JP 2013052807W WO 2013118804 A1 WO2013118804 A1 WO 2013118804A1
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- Prior art keywords
- pressure
- injection
- liquid injection
- electrolyte
- electrolytic solution
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000002347 injection Methods 0.000 claims abstract description 298
- 239000007924 injection Substances 0.000 claims abstract description 298
- 239000007788 liquid Substances 0.000 claims abstract description 180
- 239000003792 electrolyte Substances 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000005001 laminate film Substances 0.000 claims abstract description 41
- 239000008151 electrolyte solution Substances 0.000 claims description 147
- 230000008569 process Effects 0.000 claims description 50
- 230000009467 reduction Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 description 78
- 239000010410 layer Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 23
- 238000007789 sealing Methods 0.000 description 21
- 238000010248 power generation Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 9
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- 239000010408 film Substances 0.000 description 8
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- 239000007773 negative electrode material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
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- 239000011149 active material Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 230000002093 peripheral effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 101150004907 litaf gene Proteins 0.000 description 1
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Images
Classifications
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- 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
- H01M6/04—Cells with aqueous electrolyte
-
- 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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/04—Drying; Impregnating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/08—Housing; Encapsulation
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
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- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
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- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
- H01M50/618—Pressure control
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
- H01M50/627—Filling ports
- H01M50/636—Closing or sealing filling ports, e.g. using lids
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/53—Means to assemble or disassemble
- Y10T29/53274—Means to disassemble electrical device
- Y10T29/53278—Storage cell or battery
Definitions
- the present invention relates to a manufacturing method and a manufacturing apparatus for a film-covered electrical device represented by a battery or a capacitor, in which electrical device elements are accommodated in a laminate film.
- An electric device typified by an electrolytic capacitor or a battery is manufactured by injecting an electrolytic solution into a case made of metal or the like containing an electrode group to obtain an electric device element, and then closing the case.
- a state having a positive electrode and a negative electrode laminated via a separator and in a state (stage) before completion of a series of injection steps of the electrolytic solution is referred to as an “electrode group”.
- a state (stage) in which a series of injection steps of the electrolytic solution is completed is distinguished as an “electric device element”.
- Patent Document 1 discloses a method for injecting and impregnating an electrolytic solution in order to solve such a problem. That is, the opening of the case is hermetically closed and depressurized, and the electrolytic solution is injected into the depressurized case, and the gap between the electrode groups is impregnated with the electrolytic solution. Rather than injecting the electrolyte solution and reducing the pressure, the electrolyte solution is injected after reducing the opening of the case to form a liquid reservoir. After injecting the electrolytic solution into the decompressed case and allowing the electrolytic solution to penetrate into the gap between the electrode groups, the pressure in the case is further increased to allow the accumulated electrolytic solution to penetrate into the gap between the electrode groups.
- Laminate film exterior materials generally have a structure in which both surfaces of a thin metal layer such as aluminum are covered with a thin resin layer, are resistant to acids and alkalis, and are lightweight and flexible.
- the laminated film exterior material of the film exterior electrical device has flexibility unlike the metal case. That is, since the laminate film exterior material is easily deformed, there arises a problem that is not found in a metal case that is difficult to deform even when an electrolyte is injected.
- the electrolyte injected into the opening of the bag-like laminate film exterior material flows between the main surface of the electrode group and the laminate film without forming a liquid pool in the opening. Therefore, the electrode group is temporarily sealed to the outside by a liquid pool, and the electrode group is impregnated with an electrolytic solution forming a liquid pool by providing a pressure difference between the electrode group and the outside.
- the method disclosed in the above cannot be adopted as it is. Therefore, in a film-clad electrical device using a laminate film packaging material, as described above, it takes time to impregnate the gap between the electrode groups with the electrolytic solution. For example, it is necessary to leave the electrolyte solution standing still for a whole day and night until it naturally penetrates into the gap between the electrodes, and the production efficiency is extremely low.
- the electrolytic solution does not impregnate into the electrode group at a uniform rate, and causes a phenomenon (impregnation unevenness) that the electrolytic solution cannot be sufficiently impregnated in the impregnated portion, particularly in the central portion of the electrode group. There is a problem that it is easy.
- the uneven impregnation of the electrolytic solution may appear as wrinkles on the surface of the laminate film due to the flexibility of the laminate film.
- the uneven impregnation of the electrolytic solution in the electrode group partially causes a region having low ion conduction characteristics between the positive and negative electrodes in the plane, and as a result, deteriorates the electric characteristics of the battery. Arise.
- an object of the present invention is to provide a method for manufacturing a film-covered electrical device and an apparatus thereof that are less likely to cause uneven impregnation of the electrolyte in the electrode group and that can be injected in a short time.
- the film-clad electrical device manufacturing method of the present invention includes the following steps (1) to (3).
- the film-clad electrical device manufacturing apparatus of the present invention includes the following elements (1) to (3).
- It has a pressure adjusting device that adjusts the pressure in the injection chamber in which a bag-like laminate film exterior material having an opening that accommodates an electrode group having a positive electrode and a negative electrode laminated via a separator is installed.
- the controller has a controller that reduces the pressure in the injection chamber to a pressure lower than atmospheric pressure by the pressure adjusting device, and injects a part of the predetermined amount of electrolyte into the exterior material by the injection device.
- the pressure control device includes a control unit that increases the pressure in the liquid injection chamber to a pressure higher than the pressure after the pressure reduction, and causes the injection device to inject the remainder of the predetermined liquid injection amount into the exterior material.
- FIG. 1 is a cross-sectional view schematically showing the configuration of the film-covered battery according to the first embodiment of the present invention.
- FIG. 2A is a completed perspective view schematically showing the film-clad battery according to the first embodiment.
- FIG. 2B is an exploded perspective view schematically showing a state in which the film-clad battery of FIG. 2A is disassembled for each component.
- FIG. 3 is a schematic perspective view of the power generation element for explaining the main surface and laminated side surfaces of the power generation element in the film-clad battery according to the first embodiment.
- FIG. 4 shows a typical embodiment (first embodiment) of a film-clad electrical device manufacturing apparatus according to the present invention.
- Electrolysis is carried out in a bag-shaped laminate film packaging material (battery cell) having an opening containing an electrode group.
- FIG. 5 is a drawing showing an injection profile and an impregnation state by an electrolyte injection / impregnation method using the injection / impregnation apparatus of the present embodiment.
- FIG. 6 is a drawing showing the amount and pressure of liquid injected in each liquid injection step according to the liquid injection / impregnation method of the electrolytic solution by the liquid injection / impregnation apparatus of this embodiment.
- FIG. 7 is a diagram showing how bubbles are generated during injection.
- FIG. 1 is a cross-sectional view schematically showing the configuration of the film-clad battery 10 of the first embodiment.
- 2 is a perspective view schematically showing the film-clad battery of the first embodiment
- FIG. 2A is a completed perspective view of the film-clad battery
- FIG. 2B is the film-clad battery of the first embodiment of FIG. 2A.
- It is the disassembled perspective view which represented typically the state decomposed
- the film-clad battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a bag-shaped laminate film that is an exterior material 29.
- the film-clad battery 10 includes a positive electrode tab 27 connected to the positive electrode current collector 12b and a negative electrode tab 25 connected to the negative electrode current collector 11b.
- the electrolytic solution 20 is mainly used for the electrolyte layer 17 constituting the power generation element 21.
- the electrolyte layer 17 can be formed by impregnating the separator with the electrolytic solution 20.
- the electrolytic solution 20 does not necessarily need to be impregnated only in the separator, and is preferably impregnated in the electrode active material layers 13 and 15, and the gap between the power generation element 21 and the exterior material 29 ( It may also exist in the voids).
- the electrode current collectors 11b and 12b made of metal plates (or metal foils)
- the extending portions 11a and 12a extend.
- the extending portions 11a and 12a of the electrodes (current collectors 11 and 12) of each layer are connected to the negative electrode tab 25 and the positive electrode tab 27, respectively, in the positive electrode current collecting portion 12b and the negative electrode current collecting portion 11b.
- one end of each of the extending portions 11a and 12a is connected to each of the negative electrode current collector 11 and the positive electrode current collector 12, and each of the current collecting portions 11b, 12b is installed or connected.
- the negative electrode tab 25 and the positive electrode tab 27 are structured to be led out of the exterior material 29 so as to be sandwiched between end portions (sealing portion or seal portion 29f) of the exterior material 29 made of a bag-like laminate film.
- the respective connections between the negative electrode tab 25 and the positive electrode tab 27, the extending portions 11a and 12a of the electrode current collectors 11b and 12b, and the negative electrode current collector 11 and the positive electrode current collector 12 of each electrode are ultrasonic welding or resistance. It is desirable to attach by welding or the like.
- a recess 29e for housing the power generation element 21 is formed in an exterior material 29 made of a bag-like laminate film, and two laminate films are opposed to the exterior material 29.
- a type in which four sides are sealed is shown.
- the present embodiment is not limited to this, and a flat laminate film that does not form a recess may be used as the exterior material 29, or may be applied to a type in which one laminate film is folded and sealed on three sides. .
- two flat laminate films that do not form recesses may be used as the exterior material 29, or may be applied to a type in which two laminate films are overlapped to seal four sides. It is not something.
- the power generation element 21 includes a plurality of substantially rectangular negative plates (negative electrodes) 14 and a plurality of positive plates (positive electrodes) 16 that are alternately arranged through a substantially rectangular electrolyte layer 17.
- the negative electrode plate (negative electrode) 14 includes a negative electrode current collector 11 and a negative electrode active material layer 13 formed on both surfaces of the negative electrode current collector 11.
- the positive electrode plate (positive electrode) 16 includes a positive electrode current collector 12 and a positive electrode active material layer 15 formed on both surfaces of the positive electrode current collector 12.
- the electrolyte layer 17 is formed by impregnating a porous separator (including a nonwoven fabric separator) with the electrolytic solution 20.
- the film-clad battery 10 of the present embodiment has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
- the negative electrode active material layer 13 is disposed only on one side of the outermost layer negative electrode current collector located on both outermost layers of the power generation element 21, but the negative electrode active material layer 13 may be provided on both sides. Good.
- a current collector having an active material layer on both sides may be used as it is as an outermost current collector.
- the outermost positive electrode current collector is positioned on both outermost layers of the power generation element 21, and the outermost positive electrode current collector is disposed on one or both surfaces of the outermost layer positive electrode current collector.
- the positive electrode active material layer 15 may be disposed.
- the surface of the power generating element 21 viewed in the stacking direction is referred to as a main surface 21 a
- the surface viewed in the stacking direction from the lateral direction is referred to as a stacking side surface 21 b. .
- each negative electrode plate 14 has a negative electrode active material layer (negative electrode) 13 applied and formed on both surfaces of a negative electrode current collector 11 (for example, copper foil), and each positive electrode plate (positive electrode).
- a positive electrode active material layer (positive electrode) 15 is applied and formed on both surfaces of a positive electrode current collector 12 (for example, an aluminum foil).
- the negative electrode current collector 11 and the positive electrode current collector 12 extend from the stacked region.
- the extending portions where the electrode materials of the current collectors 11 and 12 are not applied are the extending portions 11 a on the negative electrode side and the extending portion 12 a on the positive electrode side. They are ultrasonically welded together.
- the positive electrode current collector 12b and the negative electrode current collector 11b which are relay parts, are formed.
- the connection of the negative electrode tab 25 to the negative electrode current collector 11b and the connection of the positive electrode tab 27 to the positive electrode current collector 12b are also ultrasonically welded.
- the laminate film packaging material 29 folds one rectangular laminate film in half as described above and surrounds the power generation element 21 from both sides in the thickness direction.
- the laminate film used for the exterior material 29 is formed by laminating a heat-fusible resin layer having heat-fusibility, a metal layer (for example, aluminum foil), and an (insulating) protective layer.
- the outer peripheral portion (outer edge portion) of the laminate film outer packaging material 29 is formed such that the heat-fusible resin layer made of PP (polypropylene) becomes an inner layer of the film outer battery 10 of the present embodiment.
- a sealing part (seal part) 29f is formed by heat-sealing the heat-sealing part. As a result, the housed power generation element 21 is sealed (sealed or insulated).
- the laminate film exterior material 29 of the present embodiment is not limited to the above configuration, and various conventionally known laminate film exterior materials can be appropriately used.
- the electrolytic solution 20 one using 1 mol / liter of LiPF 6 as a supporting salt and using a mixed solvent of propylene carbonate and ethylene carbonate (mass ratio 50:50) as a solvent can be used.
- the present embodiment is not limited to these. That is, the electrolytic solution 20 has a form in which an appropriate amount of a supporting salt is dissolved in a solvent.
- the solvent for example, carbonates such as dimethyl carbonate (DMC) and diethyl carbonate (DEC) can be used in addition to the above-described ethylene carbonate (EC) and propylene carbonate (PC). These may be used alone or in combination of two or more.
- LiPF 6 mentioned above other, Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, LiBF 4, LiAsF 6, LiTaF 6, LiClO 4, LiCF 3 SO 3 or the like can be used. These may be used alone or in combination of two or more. Further, the concentration of the supporting salt may be appropriately determined in the range of about 0.5 to 2 mol / liter, but is not limited to this range.
- FIG. 4 shows a configuration of a liquid injection / impregnation apparatus for injecting / impregnating an electrolyte into a film-clad battery cell as a typical embodiment (first embodiment) of the film-clad electrical device manufacturing method of the present invention. It is a schematic diagram which shows.
- the liquid injection / impregnation apparatus 1 of this embodiment includes a liquid injection chamber 2, a liquid injection magazine 3 having a holding jig 3 a, an electrolyte supply line 4, an exhaust line 5, a gas
- An introduction line 6 and a control unit 7 are included.
- the controller 7 controls the operation of the holding jig 3 a, the vacuum pump 5 b connected to the exhaust line 5, and the electrolyte storage tank 4 a connected to the electrolyte supply line 4. The operation of each unit controlled by the control unit 7 will be described in detail below.
- an injection magazine 3 having a holding jig 3 a for storing a large number of battery cells 10 a in which the electrolyte solution 20 has not been injected is installed, and the electrolyte solution is supplied to the wall surface of the injection chamber 2.
- Line 4, exhaust line 5, and gas introduction line 6 are connected to each other.
- the holding jig 3a provided in the liquid injection magazine 3 is a plate-shaped jig (plate member) that is installed so as to stably hold a large number of battery cells 10a that are not filled with an electrolyte.
- the electrolytic solution 20 is injected from the opening 29a into the bag-shaped laminate film exterior material 29 in which the electrode group 21 ′ is accommodated by the holding jig 3a, the exterior material 29 is disposed in the thickness direction of the electrode group 21 ′. It can be sandwiched and held from both sides (both main surfaces 21a side; see FIG. 3).
- the laminate film exterior material 29 that houses the electrode group 21 ′ sandwiched between the pressing jigs 3 a is formed in a bag shape. That is, the bag-shaped laminate film exterior material 29 is heat-sealed at sides other than the upper opening 29a, and only the opening 29a is opened. This is for making the bag shape into which the electrolyte solution 20 can be inject
- One end of the electrolyte supply line 4 constituting the injection device is connected to a storage tank 4a that stores the electrolyte.
- the other end of the electrolytic solution supply line 4 is divided into a plurality of systems on the way, and connected to the electrolytic solution transfer pump 4c for each system.
- the electrolyte transfer pump 4c is connected to the valve 4d. Opening and closing of the valve 4d is controlled by the control unit 7, and the opening degree is adjusted, so that the liquid can be injected in small portions several times for each system.
- the electrolyte transfer pump 4 c and the valve 4 d are installed outside the injection chamber 2 and are connected to the injection nozzles 4 b provided in the injection chamber 2.
- the liquid injection nozzle 4b on the other end side of the electrolytic solution supply line 4 is disposed so as to correspond to the opening 29a of the laminate film exterior material 29 that opens upward. This is because the electrolytic solution 20 supplied from the electrolytic solution supply line 4 is injected from the opening 29a.
- the liquid injection nozzle 4b is movable in a predetermined order above the openings 29a of the plurality of battery cells 10a juxtaposed with each other. Therefore, the electrolytic solution 20 can be repeatedly supplied to the plurality of battery cells 10a by one injection nozzle 4b.
- a traveling rail (not shown) provided in the liquid injection chamber 2 can be considered as a configuration that allows the liquid injection nozzle 4b to move. By forming this rail along the movement path of the liquid injection nozzle 4b, the liquid injection nozzle 4b can be moved along a desired path.
- the exhaust line 5 constituting the pressure adjusting device (mainly the pressure reducing side adjusting device) mainly has a valve 5a and a vacuum pump 5b, and is controlled so that the inside of the liquid injection chamber 2 can be evacuated and depressurized. Connected to the unit 7.
- the gas introduction line 6 constituting the pressure adjustment device (mainly the pressure side adjustment device) introduces dry air or inert gas into the liquid injection chamber 2 evacuated by the exhaust line 5 to inject liquid. This is for increasing the internal pressure of the chamber 2 from a vacuum state or a reduced pressure state.
- the gas introduction line 6 mainly includes a valve 6a and a gas storage tank 6b, and the valve 6a and the like are provided so that the inside of the injection chamber 2 can be raised (pressurized / pressured) from a vacuum state or a reduced pressure state. It is connected to the control unit 7.
- FIG. 5 is a drawing showing an injection profile and an impregnation state by the injection / impregnation method of the electrolytic solution 20 by the injection / impregnation apparatus 1 of the present embodiment.
- FIG. 6 is a drawing showing the amount and pressure of liquid injected in each liquid injection step by the liquid injection / impregnation method of the electrolytic solution 20 by the liquid injection / impregnation apparatus 1 of this embodiment.
- FIG. 7 is a diagram showing how bubbles are generated during injection.
- 5A to 5J are drawings showing the state in which the electrolyte is impregnated on the battery surface at the left end of the liquid injection magazine by the pressure operation after the liquid injection from the beginning to the end of the liquid injection. It is.
- the portion represented in white is the portion of the uninjected liquid before the outermost separator provided on the battery surface is impregnated with the electrolytic solution.
- the portion represented in black is a portion in which the outermost separator provided on the battery surface is impregnated with the electrolytic solution.
- electrodes are located on a normal battery surface.
- a separator is further installed on the battery surface in order to facilitate monitoring of the state of impregnation of the electrolyte into the separator. is there.
- the form which installs a separator in the outermost layer of an electrode group is not excluded at all.
- the graphs shown in FIGS. 5 and 6 show the relationship between the injection amount and time for the battery cell 10a injected by the injection nozzle 4b shown in FIG.
- FIG. 7 (a) shows an example in which the degree of pressure reduction during injection is increased to a pressure at which air expansion that impedes impregnation of the electrolytic solution occurs (as a high degree of vacuum), bubbles are generated, and the electrolytic solution is scattered. It is drawing which shows the liquid injection state.
- FIG. 7 (b) shows the embodiment according to the present embodiment in which the scattering of the electrolytic solution is suppressed by suppressing the generation of bubbles by suppressing the degree of decompression at the time of injection at a pressure at which air expansion that impedes the impregnation of the electrolytic solution does not occur. It is drawing which shows a liquid injection state.
- the electrolyte solution 20 is injected into the opening 29a of the bag-like laminate film packaging material 29 containing the electrode group 21 ', and the pressure (reduced pressure) is atmospheric pressure. Return to the side (below atmospheric pressure) and hold for a certain period of time. Specifically, as shown in FIGS. 5 and 6, the pressure (reduced pressure) is increased to the atmospheric pressure side (less than atmospheric pressure) between injection steps # 4 and # 5, and the pressure is increased to injection steps # 5 to ##. Hold for a certain time between 7. Therefore, the electrolytic solution 20 is injected by the following procedure.
- ⁇ Decompression step> As shown in FIG. 4, a plurality of battery cells 10 a are aligned in the liquid injection chamber 2.
- the vacuum pump 5b of the exhaust line 5 is driven with the valve 5a opened to reduce the pressure in the liquid injection chamber 2 to a pressure lower than the atmospheric pressure.
- the valve 5a When the predetermined degree of vacuum is reached, the valve 5a is closed. In this state, the inside of the liquid injection chamber 2 including the inside of the electrode group 21 ′ is equally reduced to a predetermined pressure.
- the liquid injection step for example, until time T 1 of the FIG. 5
- the degree of vacuum when the pressure operated after pouring is completed (e.g., time T 4 in FIG.
- T 5, T 6 a pressure higher than the pressure P C ) at T 7 (for example, the pressure P A or P B in FIG. 5) is desirable. By doing so, it is possible to effectively prevent foaming and scattering while the electrolytic solution 20 is impregnated into the separator or the like at the injection stage (FIGS. 7B and 7A). See contrast).
- the degree of decompression in the liquid injection chamber 2 may be a pressure lower than the atmospheric pressure, but is preferably within a range where the electrolytic solution 20 does not boil and become violently foamed. It is preferable to reduce the pressure to a pressure closer to vacuum.
- the pressure is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably in the range of about 1.5 to 2 kPa. However, in the present embodiment, the range is not limited at all.
- a predetermined amount of liquid injection (specified) is divided into several times (four times in FIGS. 5 and 6) from the electrolytic solution supply line 4 through the liquid injection nozzle 4b through the opening 29a in the upper part of the exterior material 29. Part of the electrolyte solution 20). For example, as shown in the injection profiles of FIGS. 5 and 6, about 60% of the electrolyte 20 having a predetermined injection volume (a prescribed electrolyte volume) is injected.
- the gap through which the electrolytic solution 20 flows to the central portion on the main surface 21a side of the electrode group 21 ′ is not present. Not formed. Further, by being held by the holding jig 3a, the gaps between the plurality of positive plates, separators, and negative plates constituting the electrode group 21 ′ are small, and the electrolyte 20 flows between the plurality of positive plates, separators, and negative plates. There is almost no.
- the electrolytic solution 20 is caused by the negative pressure in the electrode group 21 ′. It is not sucked into the electrode group 21 '. Therefore, in the first injection step, a part of the electrolyte solution 20 (about 60% of the total in FIGS. 5 and 6) having a predetermined injection amount (a prescribed amount of electrolyte solution) is divided into several small portions, and the electrode group 21 It inject
- a predetermined pressure for example, the pressure P A
- the electrolyte solution 20 is not impregnated up to the central portion on the main surface 21a side of the electrode group 21 ′ at the time of completion of the first injection step, and the separator In the impregnation state, the central portion remains white and is not impregnated.
- the electrolytic solution 20 is injected in small portions several times in this step in order to prevent the electrolytic solution from overflowing from the exterior material 29 and scattering. is there. It takes time to impregnate the electrode group 21 'with the electrolytic solution.
- the electrolyte solution 20 is slightly bubbled on the upper side of the electrode group 21 ′ (see FIG. 7B), but gradually gradually impregnates the electrode group 21 ′ (that is, there is a slight gap and a pressing force is applied). It is infiltrated (impregnated) from the outer periphery (difficult) (see FIG. 5B). As shown in FIGS. 5 and 6, the pressure in this step is kept constant while maintaining the state after the pressure is reduced to a pressure lower than atmospheric pressure (for example, pressure P A ) in the previous step. Yes.
- a pressure lower than atmospheric pressure for example, pressure P A
- a part of the electrolyte solution 20 having a predetermined injection volume (a prescribed electrolyte volume) is injected into the battery cell 10a in small portions several times through the injection nozzle 4b.
- the injection steps # 1 to # 4 are divided into four times and about 60% of the predetermined injection amount (the prescribed electrolyte amount). Until the liquid is gradually poured.
- one battery cell 10a is injected, and then in the next injection step, the battery cell 10a is injected again.
- another battery cell 10a juxtaposed with the one battery cell 10a is injected until the next battery cell 10a is injected.
- one battery cell 10a is maintained in a state without being injected, and during that time (during a certain time after each injection), the impregnation of the electrolyte proceeds. .
- it is not limited to the above, and the number of times of injection, the amount of injection, the time of injection, the degree of pressure reduction, etc.
- the number of injections may be appropriately determined according to the battery size, shape, electrolyte concentration, etc. Good.
- the number of injections can be reduced as much as possible within a range that does not cause a large amount of electrolyte to be blown out or splashed. Is desirable.
- the number of injections can be shortened by increasing the number of injections depending on pressure conditions, it is desirable to increase the number of injections.
- an optimal number of injections may be determined in the process of optimizing various conditions.
- the amount of liquid injection tends to decrease as the number of liquid injection steps increases in the liquid injection process.
- it is desirable that the amount to be injected while maintaining a pressure lower than the atmospheric pressure is approximately 50 to 70% of the predetermined injection amount (specified amount of electrolyte).
- the injection time of electrolyte solution can be shortened, preventing scattering of electrolyte solution.
- the injection time can be appropriately determined from the degree of vacuum and the impregnation rate into the electrode group.
- the degree of vacuum is preferably set to a higher degree of vacuum as long as the electrolyte can be prevented from boiling and violently bubbling and scattering. This is because if the air remains in the battery cell 10a, the electrolytic solution cannot penetrate into the remaining air portion even at the liquid injection stage, which may cause gas accumulation.
- the number of battery cells and the number of liquid injection nozzles may be determined as appropriate.
- the same number of battery cells 10a and injection nozzles 4b may be used, and a fixed type nozzle may be used to omit a movable mechanism or a system for controlling the mechanism, thereby reducing system trouble.
- a plurality of liquid injection magazines may be installed in a plane, or a plurality of liquid injection magazines may be stacked three-dimensionally at appropriate intervals. Or they may be combined. As shown in FIG.
- the liquid injection magazine 3 may have a form in which a plurality of battery cells 10 a are arranged in one row, or a form in which a plurality of battery cells 10 a are arranged in a plurality of rows.
- the injection magazine 3 may be box-shaped as shown in FIG. 4 or may be circular. In the case of a circular shape, the plurality of battery cells 10a may be arranged in order in the radial direction.
- the injection amount in each step from the injection step # 1 to # 4 gradually decreases because the electrolyte solution 20 moves from the periphery of the electrode group 21 ′ to the center as the injection step proceeds. This is because the amount of the electrolyte solution 20 that can be impregnated gradually decreases. Therefore, in a liquid injection method in which the pressure in the liquid injection chamber 2 is not changed from the start of liquid injection to the completion of liquid injection (for example, a point indicated by a circle A in FIG. 5), a predetermined liquid injection amount (a prescribed amount of electrolytic solution) is injected.
- ⁇ Second injection process> the pressure in the liquid injection chamber 2 is increased to a pressure (for example, pressure P B ) higher than the above pressure (pressure lower than atmospheric pressure, for example, pressure P A ), and then the pressure (pressure after pressure increase) is increased. Holding for a certain period of time, the remainder of the predetermined amount of electrolyte (a prescribed amount of electrolyte) is injected (see FIGS. 5 and 6).
- the valve 6a of the gas introduction line 6 is opened through the control unit 7, the gas is introduced into the injection chamber 2, and the pressure in the injection chamber 2 (pressure lower than atmospheric pressure, for example, pressure P, for example)
- the pressure is increased to a pressure higher than A ) (for example, the pressure P B ) (for details, see the step of increasing pressure from time Ta to time Tb shown in the injection profile of FIGS. 5 and 6).
- the impregnation state on the main surface 21a side of the electrode group 21 ′ is as shown in FIG. 5 (b) to FIG. 5 (c), but a large change is observed in the impregnation state of the separator before and after the pressure increase.
- the central part remains white. This is because the electrolyte solution 20 is not injected during the pressurizing operation, and there is no amount of electrolyte solution necessary for impregnation up to the central portion.
- the valve 6a of the gas introduction line 6 is closed and the pressure (after pressure increase). Pressure) for a certain period of time.
- the remaining portion of the predetermined injection amount (specified electrolyte amount) of the electrolyte solution 20 from the electrolyte solution supply line 4 through the injection nozzle 4b through the opening 29a in the upper portion of the outer packaging material 29 is little by little (see FIG. 5 and 6) 3 times).
- the remaining about 40% of the electrolyte solution 20 with a predetermined injection amount (a prescribed electrolyte amount) is injected.
- a predetermined injection amount a prescribed electrolyte amount
- the electrolytic solution 20 can be impregnated to the central portion on the main surface 21a side of the electrode group 21 ′.
- the electrolytic solution 20 is injected until the liquid level is above the upper end surface of the electrode group 21 ′.
- the predetermined injection amount specified electrolyte amount
- the lack of liquid injection may be caused by the fact that a part of the electrolytic solution is scattered during the injection, so that the desired total amount of the electrolytic solution is not injected into the battery cell 10a. Therefore, in such a case, it is desirable to inject the electrolytic solution 20 to a state where the liquid level is above the upper end surface of the electrode group 21 ′ by further injecting the electrolytic solution 20.
- the electrolytic solution 20 is impregnated up to the central portion on the main surface 21a side of the electrode group 21 ′, and the separator is impregnated only in a part of the central portion. Is still white and can be sufficiently impregnated.
- the pressure in the liquid injection chamber 2 is instantaneously increased to, for example, a pressure (for example, the pressure P B ) higher than the pressure (for example, the pressure P A ) by the introduction of the gas. Remains vacuumed and decompressed. Therefore, a pressure difference is produced between the inside of the electrode group 21 ′ of the battery cell 10 a and the inside of the liquid injection chamber 2.
- the inside of the electrode group 21 ′ is in a higher vacuum state (reduced pressure state)
- the negative pressure causes the electrolytic solution to be quickly impregnated (sucked) into the central portion of the electrode group 21 ′.
- the impregnation property of the electrolytic solution is improved, and the injection time can be shortened.
- the circular mark A shown in FIG. 5 is maintained with the degree of pressure reduction during the first liquid injection step (without increasing the pressure (for example, pressure P B ) higher than the pressure (for example, pressure P A ) at that time).
- this step may be repeated as an operation of injecting the solution in small portions.
- the pressure (for example, pressure P B ) when the pressure in the liquid injection chamber 2 is maintained for a certain time is a half value (average) of the pressure (for example, pressure P A ) and the atmospheric pressure in the first liquid injection process. Value) (see FIGS. 5 and 6).
- the pressure difference between the pressure to be held (for example, pressure P B ) and the pressure at the first injection step (for example, pressure P A ) does not become too large, and the scattering of the electrolyte is prevented. Yes (see FIG. 7B).
- the pressure difference ⁇ P is desirably at least 1 kPa or more, preferably 10 kPa or more, more preferably about 15 to 20 kPa. However, in the present embodiment, the range is not limited at all.
- the pressure of the liquid injection chamber 2 for example, from the pressure P A of the previous step (1) 15kPa ⁇ (2) 20kPa ⁇ (3)
- the electrolyte solution 20 may be injected while maintaining the pressure for a certain period of time at each step while increasing the pressure stepwise to 25 kPa.
- the pressure of 15 kPa is maintained for 5 minutes, and during this time, the electrolyte solution 20 is injected in small portions twice, and then the step (2) is performed in 1 minute.
- the pressure is increased to
- the pressure of 20 kPa is maintained for 5 minutes, and during this time, the electrolyte solution 20 is injected in small portions twice, and then the step (3) is performed in 1 minute. Increase to pressure.
- the pressure of 25 kPa may be maintained for 5 minutes, and the electrolyte solution 20 may be injected in small portions twice during this time.
- the liquid injection is performed in several steps (a small amount) in both the first liquid injection process and the second liquid injection process, and each injection in the second liquid injection process is performed. It is desirable that the liquid volume be larger than the final liquid injection volume in the first liquid injection process.
- the amount of liquid injected in each step (injection steps # 5 to # 7) in this step is the same as the amount of liquid injected in the final step (injection step # 4) of the previous step. Is desirable. Since the amount of liquid injection can be increased by the amount that the pressure is changed between the previous process and the main process and the electrolytic solution is easily impregnated in the main process, the injection time can be shortened by this operation.
- the impregnation utilizing the pressure difference can be promoted and the pouring time can be shortened.
- a flexible laminate film as an exterior material for a film-clad battery, it is possible to suppress the occurrence of wrinkles in the separator when the electrolyte solution is injected without causing a gap between the laminated surfaces.
- the sealing step After the above-described liquid injection step, the pressure is maintained (for example, the pressure P B at the time of (d) in FIG. 5 is maintained) or within a range where the electrolyte does not boil.
- the opening 29a In a state where the pressure is reduced to a low pressure (high vacuum state), the opening 29a is sealed (sealed or sealed) by heat sealing.
- the vacuum pump 5b of the exhaust line 5 is driven through the control unit 7 with the valve 5a open, and the pressure in the injection chamber 2 is reduced to a lower pressure (high vacuum state) within a range where the electrolyte does not boil. Reduce pressure.
- the valve 5a When the predetermined degree of vacuum is reached, the valve 5a is closed.
- the opening 29 a may be sealed (sealed / sealed) by thermally fusing the opening 29 a using a thermocompression bonding (fusion) device (not shown) provided in the liquid injection chamber 2.
- the sealing member such as the clip is removed and opened, and a relatively large amount of gas generated in the battery 10 is removed outside the film-covered battery 10 (for example, reduced pressure After the removal), it is desirable that the opening is finally sealed (sealed, sealed) by thermal fusion.
- the pressure in the liquid injection chamber 2 is changed during the liquid injection process ( Pressurize more than in the first and second liquid injection steps).
- the valve 6a of the gas introduction line 6 is opened through the controller 7, the gas is introduced into the injection chamber 2, and the inside of the injection chamber 2 is pressurized to a pressure higher than that in the injection step (see FIG. see boosting stages from the time T 1 of the 5,6 to time T 2).
- a large pressure difference is obtained from the time of pouring, and impregnation can be promoted.
- Impregnation can be promoted by maintaining the pressure for a certain time during pressurization.
- the impregnation state on the main surface 21a side of the electrode group 21 ′ is changed from that shown in FIG. 5 (e) to FIG. 5 (f), and the impregnation at the center is further promoted.
- the inside of the electrode group 21 ′ is pressurized, so that a larger pressure difference is obtained than in the liquid injection step, and the injected electrolytic solution 20 is further impregnated into the central portion.
- the pressure in the liquid injection chamber 2 is further reduced.
- depressurizing it is desirable to depressurize to a pressure (for example, pressure P C ) lower than the time of liquid injection in the liquid injection process (specifically, both the first and second liquid injection processes).
- a pressure for example, pressure P C
- the vacuum pump 5b of the exhaust line 5 is driven through the control unit 7 while the valve 5a is opened, and the inside of the liquid injection chamber 2 is preferably decompressed to a pressure lower than that during the liquid injection process. To do. Then, after reaching a predetermined degree of vacuum, the valve 5a is closed.
- the electrolytic solution 20 can be condensed and penetrated more than the time of pouring.
- the electrolytic solution 20 is condensed and impregnated (impregnated) inside the electrode group 21 ′, and the impregnation proceeds to the central portion of the separator.
- the unimpregnated white part of a center part further reduces (refer (g) of FIG. 5). Further, as shown in FIG.
- the pressure P C can be reduced in a short time. That is, the time required for the impregnation after the injection of the electrolytic solution can be significantly shortened by the pressurizing and depressurizing step in the present embodiment.
- FIG. 5 (e) at the time of pressurization in the first cycle, FIG. 5 (f) after maintaining the pressure for a certain time after pressurization, FIG. 5 (g) at the time of depressurization in the first cycle, and pressurization in the second cycle FIG. 5 (h) at the time and FIG. 5 (i) at the time of pressurization in the third cycle show that the impregnation is further promoted by repeating the pressurization and depressurization cycles a plurality of times. .
- the electrolyte solution was injected and impregnated by sequentially performing the sealing step and the pressure-raising step similar to those of the post-treatment (1) after the pressure-increasing step described above.
- the film-clad battery 10 can be obtained (taken out).
- the opening 29a is sealed (sealed / sealed) by heat sealing. Thereafter, when the pressure is increased, the battery cells in the impregnated state shown in FIG. 5 (i) to FIG. 5 (j) are obtained.
- the pressure in the injection chamber 2 is reduced to a pressure lower than that during the injection (during the first and second injection steps) after the injection step. Since the pressure in the liquid injection chamber 2 is reduced to a pressure lower than that at the time of liquid injection, the electrolytic solution can be condensed and penetrated more than at the time of liquid injection. Specifically, as shown by a thick white arrow in FIG. 5, the pressure (note) in FIG. 5 (g) is higher than the pressure in FIG. 5 (b) (maximum negative pressure P A during injection). The pressure is reduced so that the maximum negative pressure (P C ) after liquid has a lower value.
- the pressure may be reduced to a pressure (for example, pressure P C ) lower than that in the liquid injection process by following the shortest (bold broken line) route from FIG. 5 (d) to FIG. 5 (g).
- a pressure for example, pressure P C
- the pressure is reduced to a pressure (for example, pressure P C ) lower than that in the liquid injection step by the solid line route of FIG. 5 (d) ⁇ FIG. 5 (e) ⁇ FIG. 5 (f) ⁇ FIG. 5 (g). Is desirable.
- the pressure in the liquid injection step is set to a pressure at which air expansion that impedes impregnation of the electrolyte into the electrode group does not occur, and the pressure in the pressure reduction step after the liquid injection does not cause the electrolyte to boil It is desirable to use pressure. This is because the pressure remaining in the electrode group 21 ′ before completion of the liquid injection is such that bubbles are generated and impregnation does not proceed if the pressure is reduced too much (see FIG. 7 (a)). After completion of the injection, the pressure is set so that the boiling point of the electrolyte, not residual air, does not reach the working temperature. As shown in FIG.
- the pressure at which air expansion that impedes impregnation of the electrolytic solution does not occur, as long as the bubble generation is suppressed and the impregnation of the electrolytic solution can proceed.
- the pressure can be regarded as a pressure in which bubbles are generated vigorously and the electrolytic solution is scattered to cause air expansion that inhibits impregnation of the electrolytic solution.
- the temperature in the liquid injection chamber after the completion of liquid injection from the liquid injection is not particularly required to be controlled, and can be carried out at room temperature (approximately in the range of 0 to 40 ° C.).
- the pressure in consideration of the working temperature after completion of the pouring which is the working temperature not exceeding the boiling point of the electrolytic solution, may be the pressure indicated by the circle C in FIG. 5 (high vacuum state). Also in the impregnated state at the time of the circle C in FIG. 5 (FIG. 5 (g)), it is understood that the boiling of the electrolytic solution is not recognized and the above requirement is satisfied. That is, it can be said that the above requirements are satisfied if the pressure is within the range from the atmospheric pressure shown in FIGS. 5 and 6 to the maximum negative pressure (pressure at the time of pressure reduction after injection such as circle C in FIG. 5).
- the pressure in the liquid injection chamber 2 is set in advance. It may be pressurized. When pressurizing, it is desirable to pressurize to atmospheric pressure. By pressurizing to atmospheric pressure, a large pressure difference is obtained from the time of pouring, and impregnation can be promoted. In addition, in order to return to atmospheric pressure, it is only necessary to stop evacuation, which is also excellent in that it can be realized with a simple configuration. By such an operation, the impregnation state on the main surface 21a side of the electrode group 21 'is improved, and the impregnation at the central portion is promoted as shown in FIG.
- the inside of the electrode group 21 ′ is pressurized, so that a larger pressure difference than that in the liquid injection process is obtained, and the injected electrolytic solution 20 is further impregnated into the central portion.
- the injected electrolytic solution 20 is impregnated inside the electrode group 21 ′, and the impregnated electrolysis is also performed by the rapid pressurization (pressure increase) shown in FIGS.
- the liquid 20 can be returned to atmospheric pressure in a short time without scattering of the liquid 20, and the liquid injection process is shortened.
- Impregnation can be promoted by maintaining the pressure for a certain time during pressurization.
- the impregnation state on the main surface 21a side of the electrode group 21 ′ is as shown in FIG. 5 (e) to FIG. 5 (f), and it is recognized that the impregnation is further promoted in the central portion.
- the inside of the electrode group 21 ′ is pressurized, so that a larger pressure difference is obtained than in the liquid injection step, and the injected electrolytic solution 20 is further impregnated into the central portion.
- the pressure in the liquid injection chamber 2 is reduced to a pressure lower than that during the liquid injection step after being pressurized as necessary.
- the pressure in the liquid injection chamber may be reduced to a pressure lower than that during the liquid injection step without applying pressure after the liquid injection.
- the electrolytic solution 20 is impregnated in the power generation element 21 from the side of the laminated side surface 21b of the electrode group 21 ′.
- the rectangular power generation element 21 has four laminated side surfaces 21b.
- the injection of the electrolytic solution 20 by effectively using all of the four laminated side surfaces 21b shortens the injection time and laminates. This is important in that wrinkles are prevented from occurring on the film exterior material 29.
- the liquid injection nozzle 4b uniformly distributes a predetermined amount of the electrolytic solution 20 from one end to the other end of the opening 29a while traveling from one end to the other end of the opening 29a for each liquid injection. You may inject into. Further, the tip of the liquid injection nozzle 4b can be tilted (moved) up to about 45 ° from right to left to right and left, and is uniformly distributed from one end to the other end of the opening 29a for each liquid injection. Thus, a predetermined amount of the electrolytic solution 20 may be injected.
- the present embodiment is not particularly limited to these, and an existing liquid injection / impregnation method capable of uniformly liquid injection can be appropriately selected.
- the method and apparatus for manufacturing a film-clad battery and the method for injecting and impregnating an electrolytic solution into the film-clad battery cell and the apparatus thereof can achieve the following effects. . (1) Injecting while maintaining the inside of the injection chamber at a pressure lower than the atmospheric pressure, and then injecting while maintaining for a certain period of time at a pressure higher than the pressure, impregnation can be promoted using the pressure difference. . Moreover, (2) By making the pressure held for a certain period of time lower than the half value between the reduced pressure and the atmospheric pressure during the first injection step, the pressure difference from the previous pressure does not become too large, and scattering can be prevented. .
- Impregnation can be promoted in stages by increasing the pressure in stages and injecting while maintaining the pressure for a certain period of time in each stage.
- Impregnation can be promoted in stages by increasing the pressure in stages and injecting while maintaining the pressure for a certain period of time in each stage.
- (4) By increasing the amount of liquid each time at a pressure higher than the pressure lower than the atmospheric pressure to the amount of the final injection at a pressure lower than the atmospheric pressure, the pressure changed and it became easy to impregnate.
- the amount of injection can be increased, and the injection time can be shortened.
- the inside of the liquid injection chamber is increased from the above pressure.
- the pressure is increased to a high pressure, and the remainder of the predetermined injection amount of the electrolyte is injected, so that the impregnation utilizing the pressure difference can be promoted.
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Abstract
Description
まず、第1実施形態のフィルム外装電池10(フィルム外装電気デバイスの一例)の構成の概要を説明する。
以下に、フィルム外装電池セルに電解液を注液・含浸するための本実施形態における注液・含浸装置の構成について図面を用いて説明する。
次に本実施形態のフィルム外装電池の製造方法に含まれる工程について説明する。
以下に、フィルム外装電池セルに電解液を注液・含浸するための本実施形態の注液・含浸装置1による電解液20の注液・含浸方法について図面を用いて説明する。図5は、本実施形態の注液・含浸装置1による電解液20の注液・含浸方法による、注液プロファイルと含浸状態を表す図面である。図6は、本実施形態の注液・含浸装置1による電解液20の注液・含浸方法による、各注液ステップによる注液量と圧力を表す図面である。図7は、注液時の泡の発生の様子を示す図である。
図4に示すように、注液チャンバ2内に、複数の電池セル10aが整列される。制御部7を通じて、バルブ5aを開いた状態で排気ライン5の真空ポンプ5bを駆動して注液チャンバ2内を大気圧より低い圧力まで減圧する。所定の真空度に達したならバルブ5aを閉じる。この状態では、電極群21’の内部を含む注液チャンバ2の内部は、等しく所定の圧力に減圧されている。なお、図5に示すように、注液段階(例えば、図5の時刻T1まで)では、注液完了後に圧力操作する際の減圧度(例えば、図5の時刻T4、T5、T6、T7における圧力PC)よりも高い圧力(例えば、図5の圧力PAまたはPB)に設定することが望ましい。こうすることで、注液段階で電解液20がセパレータなどに含浸する間に、発泡して飛び散ったりするのを有効に防止することができる(図7(b)と図7(a)とを対比参照のこと)。また、図5、6に示すように、注液チャンバ2内の減圧度は、大気圧より低い圧力であればよいが、好ましくは電解液20が沸騰して激しく発泡する状態にならない範囲内で、より真空に近い圧力まで減圧するのが好ましい。これにより、電池セル10a内の余分な空気(ガス)を追い出し、ガス溜まりの発生を防止し、電解液を十分に含浸できるようにすることができる。当該圧力は、好ましくは5kPa以下、より好ましくは3kPa以下、特に好ましくは1.5~2kPa程度の範囲内である。但し、本実施形態では、かかる範囲に何ら制限されるものではない。
次に、注液チャンバ2内を上記減圧工程により達成した圧力(大気圧より低い圧力、例えば、図5の圧力PA)に維持したまま、開口部29aから外装材29内に所定注液量(規定の電解液量)の電解液の一部を注液する。
本工程では、注液チャンバ2内を上記圧力(大気圧より低い圧力、例えば、圧力PA)よりも高い圧力(例えば、圧力PB)に昇圧した後、当該圧力(昇圧後の圧力)を一定時間保持して前記電解液の所定注液量(規定の電解液量)の残部を注液する(図5、6参照)。
<後処理(1)>
上記第2注液工程後の後処理(1)として、開口部29aを封止する封止工程を行った後、注液チャンバ2内の圧力を大気圧に戻す昇圧工程を行う。これにより、電解液が注液されたフィルム外装電池10を得ることができる。封止工程および昇圧工程を説明する。
封止工程では、前記した注液工程後に、当該圧力を保持したままで(例えば、図5の(d)時の圧力PBを維持したままで)、あるいは電解液が沸騰しない範囲内でより低い圧力(高真空状態)まで減圧した状態で、開口部29aを熱融着により封止(密封・シール)する。後者の場合、制御部7を通じて、バルブ5aを開いた状態で排気ライン5の真空ポンプ5bを駆動して注液チャンバ2内を電解液が沸騰しない範囲内でより低い圧力(高真空状態)まで減圧する。所定の真空度に達したならバルブ5aを閉じる。次に、注液チャンバ2内に設けられた熱圧着(融着)装置(図示せず)を用いて、開口部29aを熱融着することにより封止(密封・シール)すればよい。
封止工程後、注液チャンバ2内の圧力を大気圧に戻す昇圧工程を行うことで、電解液20が注液され、含浸されたフィルム外装電池10を得る(取り出す)ことができる。詳しくは、制御部7を通じて、ガス導入ライン6のバルブ6aを開き、注液チャンバ2内にガスを導入し、注液チャンバ2内の圧力を大気圧に戻す。これにより本実施形態の注液・含浸装置1による電解液20の注液・含浸方法を達成することができる。
また、本実施形態では、図5、6に示すように、後処理(2)として、前記注液工程後、前記開口部を封止する前に、注液チャンバ内の圧力を、前記注液工程時よりも加圧し、さらに減圧する加減圧工程を繰り返してもよい。その後、上記後処理(1)と同様の封止工程、昇圧工程を順に行うことで、電解液が注液され、より含浸されたフィルム外装電池10を得ることができる。加減圧工程について、説明する。
加減圧工程では、前記注液工程後、開口部29aを封止する前に、注液チャンバ2内の圧力を、前記注液工程時(第1および第2注液工程時)よりも加圧し、さらに減圧する加減圧工程を行う。これにより、注液完了後封止前に加減圧を行うので、含浸を促進できる。注液後なので、セパレータに電解液20が保持されており、加減圧しても、飛び散りが起こらない点で優れている。
さらに、本実施形態では、図5、6に示すように、後処理(3)として、前記注液工程後、注液チャンバ2内の圧力を、前記注液工程時よりも低い圧力(例えば、圧力PC)まで減圧する注液後の減圧工程を行ってもよい。その後、必要に応じて後処理(2)と同様の加減圧工程を行い、後処理(1)と同様の封止工程、昇圧工程を行うことで、より含浸されたフィルム外装電池10を得ることもできる。
注液後の減圧工程では、前記注液工程後、注液チャンバ2内の圧力を、前記注液時(第1および第2注液工程時)よりも低い圧力まで減圧する。注液チャンバ2内の圧力を注液時よりも低い圧力に減圧するので、注液時よりも電解液を凝縮してより浸透させることができる。具体的には、図5中、白抜きの太い矢印で示すように、図5(b)での圧力(注液時の最大負圧PA)よりも図5(g)での圧力(注液後の最大負圧PC)の方がより低い値となるように減圧する。この際、図5(d)から図5(g)への最短(太破線)ルートをたどって、注液工程時よりも低い圧力(例えば、圧力PC)まで減圧してもよい。好ましくは、図5(d)→図5(e)→図5(f)→図5(g)の実線ルートにより、注液工程時よりも低い圧力(例えば、圧力PC)まで減圧するのが望ましい。
次に、本実施形態における電解液20の注液・含浸方法について、図4を用いて説明する。電解液20は電極群21’の積層側面21b側から発電要素21に含浸されている。矩形形状の発電要素21は4つの積層側面21bを有することとなるが、これら4つの積層側面21bの全てを有効に用いて電解液20の注液を行うのが注液時間の短縮化及びラミネートフィルム外装材29へのしわ発生を防止する点で重要となる。そのため、注液ノズル4bは、1回の注液ごとに、開口部29aの一端から他端まで走行しながら、所定量の電解液20を開口部29aの一端から他端まで均一に分布するように注液してもよい。さらに、注液ノズル4bの先端が直下から左右に45°程度上方まで傾ける(可動する)ことができるものを用い、1回の注液ごとに、開口部29aの一端から他端まで均一に分布するように、所定量の電解液20を注液してもよい。ただし、本実施形態ではこれらに何ら特に制限されるものではなく、均一に注液可能な既存の注液・含浸方法を適宜選択することができる。
2 注液チャンバ
3 注液マガジン
3a 押さえ治具
4 電解液供給ライン
4a 電解液の貯蔵タンク
4b 注液ノズル
4c 電解液供給ライン上の電解液移送ポンプ
4d 電解液供給ライン上の開閉ないし液流量調整バルブ
5 排気ライン
5a 排気用開閉バルブ
5b 排気用の真空ポンプ
6 ガス導入ライン
6a ガス導入ライン上の開閉ないしガス流量調整バルブ
6b ガスの貯蔵タンク
7 制御部
10 フィルム外装電池(フィルム外装電気デバイス)
10a フィルム外装電池セル
11 負極集電体
11a 負極(集電体からの)延出部
11b 負極集電部
12 正極集電体
12a 正極(集電体からの)延出部
12b 正極集電部
13 負極活物質層
14 負極板(=負極)
15 正極活物質層
16 正極板(=正極)
17 電解質層(電解液が含浸したセパレータ)
19 単電池層
20 電解液
20a 電解液の液滴
21 発電要素
21a 発電要素の主面
21b 発電要素の積層側面
25 負極タブ
27 正極タブ
29 ラミネートフィルム外装材
29a ラミネートフィルム外装材の開口部
29b ラミネートフィルム外装材の底部
29e ラミネートフィルム外装材の凹部
29f ラミネートフィルム外装材の封止部ないしシール部
Claims (5)
- セパレータを介して積層された正極と負極とを有する電極群を収納した開口部を有する袋状ラミネートフィルム外装材が設置された注液チャンバ内を、大気圧より低い圧力まで減圧し、前記開口部から前記外装材内に所定注液量の電解液の一部を注液する第1注液工程と、
前記第1注液工程の後、前記注液チャンバ内を前記圧力よりも高い圧力に昇圧し、前記電解液の所定注液量の残部を注液する第2注液工程と、を含むフィルム外装電気デバイスの製造方法。 - 前記第2注液工程における圧力は、前記第1注液工程における圧力と大気圧との半値よりも低いことを特徴とする請求項1に記載のフィルム外装電気デバイスの製造方法。
- 前記第2注液工程において、前記注液チャンバ内の圧力を、段階的に高めつつ、各段階で一定時間圧力を保持して前記電解液を注液することを特徴とする請求項1または2に記載のフィルム外装電気デバイスの製造方法。
- 前記第1注液工程と前記第2注液工程の両工程で数回に分けて注液を行うと共に、
前記第2注液工程での各回の注液量を、前記第1注液工程の最終回の注液量よりも多くすることを特徴とする請求項1~3のいずれか1項に記載のフィルム外装電気デバイスの製造方法。 - セパレータを介して積層された正極と負極とを有する電極群を収納した開口部を有する袋状ラミネートフィルム外装材が設置された注液チャンバ内の圧力を調整する圧力調整装置と、
前記開口部から前記外装材内に電解液を注入する注入装置と、
前記圧力調整装置により、前記注液チャンバ内を大気圧より低い圧力まで減圧させ、前記注入装置により、前記外装材内に所定注液量の電解液の一部を注液させ、さらに前記圧力調整装置により、前記注液チャンバ内を前記減圧後の圧力よりも高い圧力に昇圧させ、前記注入装置により、前記外装材内に前記電解液の所定注液量の残部を注液させる制御部と、
を有することを特徴とするフィルム外装電気デバイスの製造装置。
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- 2013-02-07 US US14/376,774 patent/US9859569B2/en active Active
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CN105917517A (zh) * | 2014-03-05 | 2016-08-31 | 松下知识产权经营株式会社 | 薄型电池和电池搭载设备 |
US10147914B2 (en) | 2014-03-05 | 2018-12-04 | Panasonic Intellectual Property Management Co., Ltd. | Thin battery and battery-mounted device |
JP2018106816A (ja) * | 2016-12-22 | 2018-07-05 | トヨタ自動車株式会社 | 電池の製造方法 |
JP2019169352A (ja) * | 2018-03-23 | 2019-10-03 | 株式会社豊田自動織機 | ニッケル水素電池及び蓄電モジュールの製造方法 |
JP7102825B2 (ja) | 2018-03-23 | 2022-07-20 | 株式会社豊田自動織機 | ニッケル水素電池及び蓄電モジュールの製造方法 |
KR20220081286A (ko) * | 2020-12-08 | 2022-06-15 | 프라임 플래닛 에너지 앤드 솔루션즈 가부시키가이샤 | 전지의 제조 방법 |
JP2022090917A (ja) * | 2020-12-08 | 2022-06-20 | プライムプラネットエナジー&ソリューションズ株式会社 | 電池の製造方法 |
JP7216696B2 (ja) | 2020-12-08 | 2023-02-01 | プライムプラネットエナジー&ソリューションズ株式会社 | 電池の製造方法 |
US11837755B2 (en) | 2020-12-08 | 2023-12-05 | Prime Planet Energy & Solutions, Inc. | Method for producing a battery |
KR102648710B1 (ko) | 2020-12-08 | 2024-03-19 | 프라임 플래닛 에너지 앤드 솔루션즈 가부시키가이샤 | 전지의 제조 방법 |
Also Published As
Publication number | Publication date |
---|---|
CN104106156B (zh) | 2016-05-25 |
US9859569B2 (en) | 2018-01-02 |
US20140373344A1 (en) | 2014-12-25 |
EP2814090A1 (en) | 2014-12-17 |
JP5786043B2 (ja) | 2015-09-30 |
CN104106156A (zh) | 2014-10-15 |
EP2814090A4 (en) | 2015-07-08 |
JPWO2013118804A1 (ja) | 2015-05-11 |
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