WO2020170607A1 - 電極製造システム、クリーニングユニット、及び電極製造方法 - Google Patents
電極製造システム、クリーニングユニット、及び電極製造方法 Download PDFInfo
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- WO2020170607A1 WO2020170607A1 PCT/JP2019/051291 JP2019051291W WO2020170607A1 WO 2020170607 A1 WO2020170607 A1 WO 2020170607A1 JP 2019051291 W JP2019051291 W JP 2019051291W WO 2020170607 A1 WO2020170607 A1 WO 2020170607A1
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Classifications
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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- H—ELECTRICITY
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- 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
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- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/02—Machines for winding capacitors
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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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
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E60/10—Energy storage using batteries
Definitions
- a process in which the electrode is preliminarily doped with an alkali metal is adopted for various purposes.
- a method of pre-doping the electrode with an alkali metal for example, there is a continuous method.
- pre-doping is performed while transferring the strip electrode in the dope solution.
- the continuous method is disclosed in Patent Documents 1 to 4.
- the strip-shaped electrode includes a current collector and an active material layer.
- a part of the surface of the current collector may be a part where the active material layer is not formed.
- the active material layer-unformed portion is a portion in which the active material layer is not formed.
- the dope solution also adheres to the part where the active material layer is not formed.
- the residue of the dope solution attached to the active material layer non-formed portion has an adverse effect on welding between the current collecting tab of the battery and the active material layer non-formed portion, and is therefore preferably removed.
- an electrode manufacturing system a cleaning unit, and an electrode manufacturing method capable of cleaning an active material layer-unformed portion.
- One aspect of the present disclosure is an active material layer forming part in which an active material layer containing an active material is formed on the surface of a current collector, and an active material layer in which the active material layer is not formed on the surface of the current collector.
- a doping unit configured to perform a treatment of doping the active material with an alkali metal in a strip electrode having an unformed portion, and the active material layer adjacent to the treated active material layer forming portion
- An electrode manufacturing system comprising: a cleaning unit configured to clean an unformed portion; and a transport unit configured to transport the electrode from the dope unit to the cleaning unit.
- Another aspect of the present disclosure is an active material layer forming part in which an active material layer containing an active material is formed on the surface of a current collector, and an active material in which the active material layer is not formed on the surface of the current collector.
- a cleaning unit for cleaning a strip-shaped electrode having a layer-unformed part, wherein the active-material-layer-unformed part adjacent to the active-material-layer-formed part in which the active material is doped with an alkali metal is formed.
- a cleaning unit configured to be cleaned.
- a cleaning unit according to another aspect of the present disclosure can clean an active material layer-unformed portion.
- Another aspect of the present disclosure is an active material layer forming part in which an active material layer containing an active material is formed on the surface of a current collector, and an active material in which the active material layer is not formed on the surface of the current collector.
- a band-shaped electrode having a layer-unformed part is subjected to a treatment of doping the active material with an alkali metal, and the electrode having been subjected to the treatment is transported, and the active material layer-formed portion is subjected to the treatment.
- the method for producing an electrode is to clean the portion where the active material layer is not formed.
- the active material layer-unformed portion can be cleaned.
- Electrode manufacturing system 15... Electrolyte treatment tank, 17,19, 21... Doping tank, 23... Cleaning tank, 25, 27, 29, 31, 33, 35, 37, 39, 40, 41, 43, 45, 46, 47, 49, 51, 52, 53, 55, 57, 58, 59, 61, 63, 64, 65, 67, 69, 70, 71, 73, 75, 77, 79, 81, 83, 85, 87, 89, 91, 93... Conveying rollers, 101... Supplying rolls, Reference numeral 103...
- Winding roll 105... Support base, 107... Circulation filtration unit, 109, 110, 111, 112, 113, 114... Power supply, 117... Tab cleaner, 119... Recovery unit, 121... End sensor, 131... Upstream Tank, 133... Downstream tank, 137, 139, 141, 143... Counter unit, 149, 151... Space, 153... Conductive base material, 155... Alkali metal containing plate, 157... Porous insulating member, 161... Filter, 163 ... pump, 165... piping, 201, 203... cleaning roller unit, 205... cleaning liquid tank, 207... pump, 209... drying unit, 211... first part, 213... second part, 215... support plate, 217...
- the configuration of the electrode 1 will be described based on FIGS. 1 and 2.
- the electrode 1 has a strip shape.
- the electrode 1 includes a current collector 3 and an active material layer 5.
- the current collector 3 has a strip shape.
- the active material layers 5 are formed on both sides of the current collector 3, respectively.
- the surface of the electrode 1 has an active material layer forming portion 6 and an active material layer non-forming portion 7.
- the active material layer forming portion 6 is a portion where the active material layer 5 is formed on the surface of the current collector 3.
- the active material layer-unformed portion 7 is a portion where the active material layer 5 is not formed on the surface of the current collector 3. In the active material layer-unformed portion 7, the current collector 3 is exposed.
- the active material layer-unformed portion 7 has a strip shape extending in the longitudinal direction L of the electrode 1.
- the active material layer-unformed portion 7 is located at the end of the electrode 1 in the width direction W of the electrode 1.
- the current collector 3 for example, a metal foil of copper, nickel, stainless steel or the like is preferable. Further, the current collector 3 may be one in which a conductive layer containing a carbon material as a main component is formed on the metal foil. The thickness of the current collector 3 is, for example, 5 to 50 ⁇ m.
- the active material layer 5 can be produced, for example, by applying a slurry containing an active material, a binder and the like onto the current collector 3 and drying it.
- binder examples include rubber-based binders such as styrene-butadiene rubber (SBR) and NBR; fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride; polypropylene, polyethylene; disclosed in JP 2009-246137 A.
- SBR styrene-butadiene rubber
- NBR fluorine-based resins
- polypropylene, polyethylene disclosed in JP 2009-246137 A.
- fluorine-modified (meth)acrylic binder is used.
- the slurry may contain other components in addition to the active material and the binder.
- Other components include, for example, conductive agents such as carbon black, graphite, vapor-grown carbon fibers, metal powders; carboxymethyl cellulose, its Na salt or ammonium salt, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, oxidation Thickening agents such as starch, phosphorylated starch and casein can be mentioned.
- the thickness of the active material layer 5 is not particularly limited.
- the thickness of the active material layer 5 is, for example, 5 to 500 ⁇ m, preferably 10 to 200 ⁇ m, and particularly preferably 10 to 100 ⁇ m.
- the active material contained in the active material layer 5 is not particularly limited as long as it is an electrode active material applicable to a battery or a capacitor utilizing insertion/desorption of alkali metal ions.
- the active material may be a negative electrode active material or a positive electrode active material.
- the negative electrode active material is not particularly limited.
- the negative electrode active material for example, carbon materials such as graphite, easily graphitizable carbon, non-graphitizable carbon, and composite carbon materials in which graphite particles are coated with a carbide of pitch or resin; Examples thereof include materials containing metals or semimetals or oxides thereof.
- Specific examples of the carbon material include the carbon material described in JP2013-258392A.
- Specific examples of the material containing a metal or metalloid capable of alloying with lithium or oxides thereof include those described in JP-A-2005-123175 and JP-A-2006-107795.
- the positive electrode active material examples include transition metal oxides such as cobalt oxide, nickel oxide, manganese oxide, and vanadium oxide; sulfur-based active materials such as elemental sulfur and metal sulfide. Both the positive electrode active material and the negative electrode active material may be composed of a single material or may be composed of a mixture of two or more kinds of materials.
- the active material contained in the active material layer 5 is pre-doped with an alkali metal using the electrode manufacturing system 11 described later.
- the alkali metal to be pre-doped in the active material lithium or sodium is preferable, and lithium is particularly preferable.
- the density of the active material layer 5 is preferably 1.30 to 2.00 g/cc, particularly preferably 1.40 to 1.90 g/cc. Is.
- the electrode manufacturing system 11 includes an electrolytic solution treatment tank 15, a dope tank 17, 19, 21, a cleaning tank 23, and conveyance rollers 25, 27, 29, 31, 33, 35, 37,.
- the dope tanks 17, 19 and 21 correspond to a part of the dope unit.
- the transport roller group corresponds to the transport unit.
- the electrolytic solution treatment tank 15 is a rectangular tank with an open top.
- the bottom surface of the electrolytic solution treatment tank 15 has a substantially U-shaped cross section.
- the electrolytic solution treatment tank 15 includes a partition plate 123.
- the partition plate 123 is supported by a support rod 125 penetrating its upper end.
- the support rod 125 is fixed to a wall or the like (not shown).
- the partition plate 123 extends in the vertical direction and divides the inside of the electrolytic solution treatment tank 15 into two spaces.
- the conveyance roller 33 is attached to the lower end of the partition plate 123.
- the partition plate 123 and the transport roller 33 are supported by a support rod 127 that penetrates them.
- the vicinity of the lower end of the partition plate 123 is cut out so as not to contact the transport roller 33.
- the configuration of the dope tank 17 will be described based on FIG.
- the dope tank 17 is composed of an upstream tank 131 and a downstream tank 133.
- the upstream tank 131 is arranged on the side of the supply roll 101 (hereinafter referred to as the upstream side), and the downstream tank 133 is arranged on the side of the winding roll 103 (hereinafter referred to as the downstream side).
- the upstream tank 131 is a rectangular tank having an open top.
- the bottom surface of the upstream tank 131 has a substantially U-shaped cross section.
- the upstream tank 131 includes a partition plate 135 and four counter electrode units 137, 139, 141 and 143.
- the partition plate 135 is supported by a support rod 145 that penetrates the upper end of the partition plate 135.
- the support rod 145 is fixed to a wall or the like (not shown).
- the partition plate 135 extends in the vertical direction and divides the inside of the upstream tank 131 into two spaces.
- the transport roller 40 is attached to the lower end of the partition plate 135.
- the partition plate 135 and the transport roller 40 are supported by a support rod 147 that penetrates them. The vicinity of the lower end of the partition plate 135 is cut out so as not to contact the transport roller 40. A space exists between the transport roller 40 and the bottom surface of the upstream tank 131.
- the counter electrode unit 137 is arranged on the upstream side of the upstream tank 131.
- the counter electrode units 139 and 141 are arranged so as to sandwich the partition plate 135 from both sides.
- the counter electrode unit 143 is arranged on the downstream side of the upstream tank 131.
- a space 149 exists between the counter electrode unit 137 and the counter electrode unit 139.
- a space 151 exists between the counter electrode unit 141 and the counter electrode unit 143.
- the counter electrode units 137, 139, 141, 143 are connected to the terminal 109B of the power source 109.
- the counter electrode units 137, 139, 141, 143 have the same structure. Here, the configuration of the counter electrode units 137 and 139 will be described with reference to FIG.
- the counter electrode units 137 and 139 have a configuration in which a conductive base material 153, an alkali metal containing plate 155, and a porous insulating member 157 are laminated.
- Examples of the material of the conductive base material 153 include copper, stainless steel, nickel and the like.
- the form of the alkali metal-containing plate 155 is not particularly limited, and examples thereof include an alkali metal plate and an alkali metal alloy plate.
- the thickness of the alkali metal containing plate 155 is, for example, 0.03 to 6 mm.
- the porous insulating member 157 has a plate shape.
- the porous insulating member 157 is laminated on the alkali metal containing plate 155.
- the plate-like shape of the porous insulating member 157 is a shape when the porous insulating member 157 is laminated on the alkali metal-containing plate 155.
- the porous insulating member 157 may be a member that maintains a constant shape by itself, or may be a member that can be easily deformed, such as a net.
- the porous insulating member 157 is porous. Therefore, the dope solution described below can pass through the porous insulating member 157. As a result, the alkali metal-containing plate 155 can come into contact with the dope solution.
- the porous insulating member 157 may be, for example, a resin mesh.
- the resin include polyethylene, polypropylene, nylon, polyether ether ketone, polytetrafluoroethylene and the like.
- the mesh openings can be set appropriately.
- the mesh opening is, for example, 0.1 ⁇ m to 10 mm, preferably 0.1 to 5 mm.
- the thickness of the mesh can be set appropriately.
- the thickness of the mesh is, for example, 1 ⁇ m to 10 mm, preferably 30 ⁇ m to 1 mm.
- the mesh opening ratio can be appropriately set.
- the mesh opening ratio is, for example, 5 to 98%, preferably 5 to 95%, and more preferably 50 to 95%.
- the entire porous insulating member 157 may be made of an insulating material, or a part thereof may be provided with an insulating layer.
- the downstream tank 133 basically has the same configuration as the upstream tank 131. However, inside the downstream tank 133, there is the transport roller 46 instead of the transport roller 40. Further, the counter electrode units 137, 139, 141, and 143 included in the downstream tank 133 are connected to one pole of the power source 110.
- the dope tank 19 basically has the same configuration as the dope tank 17. However, inside the dope tank 19, not the transport rollers 40 and 46, but the transport rollers 52 and 58 are present. Further, the counter electrode units 137, 139, 141 and 143 provided in the upstream tank 131 of the dope tank 19 are connected to one pole of the power source 111. Further, the counter electrode units 137, 139, 141 and 143 provided in the downstream tank 133 of the dope tank 19 are connected to one pole of the power source 112.
- the dope tank 21 basically has the same configuration as the dope tank 17. However, inside the dope tank 21, the conveying rollers 64 and 70 exist instead of the conveying rollers 40 and 46. Further, the counter electrode units 137, 139, 141 and 143 provided in the upstream tank 131 of the dope tank 21 are connected to one pole of the power source 113. Further, the counter electrode units 137, 139, 141 and 143 provided in the downstream tank 133 of the dope tank 21 are connected to one pole of the power source 114.
- the cleaning tank 23 basically has the same configuration as the electrolytic solution processing tank 15. However, inside the cleaning tank 23, there is the transport roller 75 instead of the transport roller 33.
- the transport rollers 37, 39, 43, 45, 49, 51, 55, 57, 61, 63, 67, 69 are made of a conductive material.
- the other transport rollers of the transport roller group are made of an elastomer except for the bearing portion.
- the transport roller group transports the electrode 1 along a fixed path.
- the path along which the transport roller group transports the electrode 1 is from the supply roll 101 to the electrolytic solution treatment tank 15, the dope tank 17, the dope tank 19, the dope tank 21, the cleaning tank 23, and the tab. It is a path that sequentially passes through the cleaner 117 and reaches the winding roll 103.
- the part of the path that passes through the electrolytic solution treatment tank 15 first moves downward via the transfer rollers 29 and 31, and then the transfer roller 33 can change the moving direction upward.
- the parts that pass through the dope tank 17 are as follows. First, the moving direction is changed downward by the transport roller 37, and the space 149 of the upstream tank 131 is moved downward. Next, the movement direction is changed upward by the conveyance roller 40, and the space 151 of the upstream tank 131 is moved upward. Next, the moving direction is changed downward by the transport rollers 41 and 43, and the space 149 of the downstream tank 133 is moved downward. Next, the moving direction is changed upward by the transport roller 46, and the space 151 of the downstream tank 133 is moved upward. Finally, the transport roller 47 changes the moving direction to the horizontal direction, and the head moves toward the dope tank 19.
- the parts that pass through the dope tank 19 are as follows. First, the moving direction is changed downward by the transport roller 49, and the space 149 of the upstream tank 131 is moved downward. Next, the moving direction is changed upward by the transport roller 52, and the space 151 of the upstream tank 131 is moved upward. Next, the moving direction is changed downward by the transport rollers 53 and 55, and the space 149 of the downstream tank 133 is moved downward. Next, the transport roller 58 changes the moving direction upward, and moves the space 151 of the downstream tank 133 upward. Finally, the moving direction is changed to the horizontal direction by the conveying roller 59, and it moves toward the dope tank 21.
- the parts that pass through the dope tank 21 are as follows. First, the moving direction is changed downward by the transport roller 61, and the space 149 of the upstream tank 131 is moved downward. Next, the moving direction is changed upward by the conveying roller 64, and the space 151 of the upstream tank 131 is moved upward. Next, the moving direction is changed downward by the transport rollers 65 and 67, and the space 149 of the downstream tank 133 is moved downward. Next, the moving direction is changed upward by the transport roller 70, and the space 151 of the downstream tank 133 is moved upward. Finally, the moving direction is changed to the horizontal direction by the transport roller 71, and the cleaning tank 23 is headed.
- a portion passing through the cleaning tank 23 is first moved downward by the conveying roller 73 and moved downward, and then changed by the conveying roller 75 in the upward direction. It is a route to be done.
- the supply roll 101 winds around the electrode 1. That is, the supply roll 101 holds the electrode 1 in a wound state.
- the active material in the electrode 1 held by the supply roll 101 has not yet been doped with an alkali metal.
- the transport roller group pulls out and transports the electrode 1 held by the supply roll 101.
- the winding roll 103 winds up and stores the electrode 1 conveyed by the conveying roller group.
- the electrode 1 stored in the winding roll 103 is subjected to pre-doping treatment in the dope tanks 17, 19 and 21. Therefore, the active material in the electrode 1 stored in the winding roll 103 is doped with alkali metal.
- the support table 105 supports the electrolytic solution treatment tank 15, the dope tanks 17, 19, 21 and the cleaning tank 23 from below.
- the height of the support 105 can be changed.
- the circulation filtration unit 107 is provided in each of the dope tanks 17, 19, and 21.
- the circulation filtration unit 107 includes a filter 161, a pump 163, and a pipe 165.
- a pipe 165 is a circulation pipe that goes out from the dope tank 17, sequentially passes through the pump 163 and the filter 161, and returns to the dope tank 17.
- the dope solution in the dope tank 17 is circulated in the pipe 165 and the filter 161 by the driving force of the pump 163, and returns to the dope tank 17 again.
- foreign substances and the like in the dope solution are filtered by the filter 161.
- Examples of the foreign matter include foreign matter deposited from the dope solution and foreign matter generated from the electrode 1.
- the material of the filter 161 is, for example, resin such as polypropylene or polytetrafluoroethylene.
- the hole diameter of the filter 161 can be set appropriately.
- the pore diameter of the filter 161 is, for example, 0.2 ⁇ m or more and 50 ⁇ m or less.
- the circulation filtration unit 107 provided in the dope tanks 19 and 21 also has the same configuration and has the same operation effect. 3 and 4, the description of the dope solution is omitted for convenience.
- the terminal 109A of the power supply 109 is connected to the transport rollers 37 and 39. Further, the terminal 109B of the power source 109 is connected to the counter electrode units 137, 139, 141, 143 provided in the upstream tank 131 of the dope tank 17.
- the electrode 1 contacts the transport rollers 37 and 39.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the upstream tank 131 of the dope tank 17, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
- the terminal 110A of the power supply 110 is connected to the transport rollers 43 and 45. Further, the terminal 110B of the power source 110 is connected to the counter electrode units 137, 139, 141, 143 provided in the downstream tank 133 of the dope tank 17.
- the electrode 1 contacts the transport rollers 43 and 45.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the downstream tank 133 of the dope tank 17, the electrode 1 and the counter electrode units 137, 139, 141 and 143 are electrically connected via the electrolytic solution.
- One terminal of the power supply 111 is connected to the transport rollers 49 and 51.
- the other terminal of the power source 111 is connected to the counter electrode units 137, 139, 141, 143 provided in the upstream tank 131 of the dope tank 19.
- the electrode 1 contacts the transport rollers 49 and 51.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the upstream tank 131 of the dope tank 19, the electrode 1 and the counter electrode units 137, 139, 141 and 143 are electrically connected via the electrolytic solution.
- One terminal of the power supply 112 is connected to the transport rollers 55 and 57.
- the other terminal of the power supply 112 is connected to the counter electrode units 137, 139, 141, 143 provided in the downstream tank 133 of the dope tank 19.
- the electrode 1 contacts the transport rollers 55 and 57.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the downstream tank 133 of the dope tank 19, the electrode 1 and the counter electrode units 137, 139, 141 and 143 are electrically connected via the electrolytic solution.
- One terminal of the power supply 113 is connected to the transport rollers 61 and 63.
- the other terminal of the power supply 113 is connected to the counter electrode units 137, 139, 141, 143 provided in the upstream tank 131 of the dope tank 21.
- the electrode 1 contacts the transport rollers 61 and 63.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the upstream tank 131 of the dope tank 21, the electrode 1 and the counter electrode units 137, 139, 141 and 143 are electrically connected via the electrolytic solution.
- One terminal of the power supply 114 is connected to the transport rollers 67 and 69.
- the other terminal of the power supply 114 is connected to the counter electrode units 137, 139, 141, 143 provided in the downstream tank 133 of the dope tank 21.
- the electrode 1 contacts the transport rollers 67 and 69.
- the electrode 1 and the counter electrode units 137, 139, 141, 143 are in a dope solution which is an electrolytic solution. Therefore, in the downstream tank 133 of the dope tank 21, the electrode 1 and the counter electrode units 137, 139, 141 and 143 are electrically connected via the electrolytic solution.
- the tab cleaner 117 cleans the active material layer-unformed portion 7 of the electrode 1.
- the detailed configuration of the tab cleaner 117 will be described later.
- the recovery unit 119 is arranged in each of the electrolytic solution treatment tank 15, the dope tanks 17, 19, 21 and the cleaning tank 23. The recovery unit 119 recovers the liquid brought out of the tank by the electrode 1 and returns it to the tank.
- the end sensor 121 detects the position of the end of the electrode 1 in the width direction W.
- the end position adjusting unit 241 described later adjusts the positions of the supply roll 101 and the winding roll 103 in the width direction W based on the detection result of the end sensor 121.
- the configuration of the tab cleaner 117 will be described based on FIGS. 6 to 9.
- the tab cleaner 117 corresponds to a cleaning unit.
- the tab cleaner 117 includes cleaning roller units 201 and 203, a cleaning liquid tank 205, a pump 207, a drying unit 209, an overflow pipe 248, and a waste liquid tank 250.
- the cleaning roller unit 201 is provided between the transport roller 79 and the transport roller 81.
- the cleaning roller unit 201 includes a first part 211 and a second part 213.
- the first portion 211 and the second portion 213 are arranged so as to sandwich the electrode 1 from both sides.
- the first part 211 includes a support plate 215, a brush roller 217, a cleaning tank 219, and a motor 221.
- the brush roller 217 corresponds to the cleaning roller.
- the cleaning tank 219 corresponds to a tab cleaning tank.
- the first portion 211 also includes a pulley 223, a pulley 225, and a shaft 227, as shown in FIG. 7. In FIG. 6, the pulley 223 and the pulley 225 are omitted for convenience.
- the support plate 215 is a plate-shaped member.
- the brush roller 217 is attached to the shaft 227.
- the outer peripheral portion of the brush roller 217 is composed of a brush.
- Hardness of the brush roller 217 which is defined by JIS S 3016-1995 usually, 1N / cm 2 or more 1000 N / cm 2 or less, preferably 5N / cm 2 or more 500 N / cm 2 or less, 10 N / more preferably cm 2 or more 300N / cm 2 or less, particularly preferably 20 N / cm 2 or more 100 N / cm 2 or less.
- the hardness of the brush roller 217 means the hardness of the brush existing in the outer peripheral portion.
- the brush material is a material of the brush roller 217.
- the plastic include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylic, nylon, polycarbonate, polyphenylene sulfide, polyether ether ketone, polytetrafluoroethylene and the like.
- animal fibers include horse hair, pig hair, goat hair and the like.
- the shaft 227 is pivotally supported by a bearing 229 provided on the support plate 215.
- the axial direction of the shaft 227 and the brush roller 217 is parallel to the width direction W of the electrode 1.
- the brush roller 217 is used as the cleaning roller, but a sponge roller may be used as the cleaning roller.
- a sponge roller is used as the cleaning roller, it is preferable that the hardness of the sponge roller measured by a type E durometer specified in JIS K 6253-3 is 1 or more and 40 or less.
- a sponge material having such hardness is an elastomer.
- the sponge material is a material for the sponge roller.
- the elastomer include polyolefin rubber, styrene rubber, styrene butadiene rubber, polyurethane, chloroprene rubber, ethylene propylene diene rubber, nitrile rubber, silicone rubber, fluororubber, polyvinyl alcohol and the like.
- the cleaning tank 219 is fixed to the support plate 215 below the brush roller 217.
- the cleaning tank 219 contains a cleaning liquid.
- the cleaning liquid contained in the cleaning tank 219 is, for example, a carbonate-based solvent.
- Examples of the carbonate-based solvent include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate and the like.
- the cleaning tank 219 is open on the upper side. A part of the lower side of the brush roller 217 enters the inside of the cleaning tank 219 and is immersed in the cleaning liquid.
- the motor 221 is attached to the support plate 215.
- the pulley 223 is attached to the motor 221.
- the pulley 225 is attached to the shaft 227.
- the second part 213 basically has a configuration in which the first part 211 is horizontally inverted in FIG. 6. However, the second portion 213 does not include the motor 221. A pulley 231 is attached to the shaft 227 of the second portion 213, as shown in FIG. 7.
- the first part 211 and the second part 213 are respectively movable between a position close to the electrode 1 (hereinafter referred to as an approach position) and a position separated from the electrode 1 (hereinafter referred to as a separated position). is there.
- the positions of the first portion 211 and the second portion 213 are set to the approaching position.
- the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 respectively have the electrode 1 And contact the active material layer-unformed portion 7 of.
- the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 do not contact the active material layer forming portion 6.
- the brush roller 217 of the first part 211 and the brush roller 217 of the second part 213 do not contact any part of the electrode 1.
- the positions of the first part 211 and the second part 213 are set to the separated positions.
- a belt 233 is stretched over the pulley 223, the pulley 225, and the pulley 231.
- the belt 233 is bridged in a figure 8 shape at the pulley 225 and the pulley 231.
- the pulley 225 and the brush roller 217 of the first portion 211 also rotate clockwise.
- the pulley 231 and the brush roller 217 of the second portion 213 rotate counterclockwise. That is, the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 rotate in opposite directions.
- the cleaning roller unit 203 is provided between the transport roller 83 and the transport roller 85.
- the cleaning roller unit 203 has the same configuration as the cleaning roller unit 201.
- the cleaning liquid tank 205 holds the cleaning liquid.
- the cleaning liquid tank 205 communicates with the cleaning tanks 219 of the cleaning roller units 201 and 203 via the pump 207 and the pipe 235.
- the pump 207 supplies the cleaning liquid to the cleaning tank 219 of the cleaning roller units 201 and 203.
- the cleaning liquid tank 205, the pump 207, and the pipe 235 correspond to the cleaning liquid supply unit.
- the drying unit 209 is provided between the cleaning roller unit 203 and the transport roller 85.
- the drying unit 209 includes a plurality of blow nozzles 237.
- the plurality of blow nozzles 237 blow nitrogen having a dew point of ⁇ 40° C. or lower onto the electrode 1 to dry the electrode 1.
- the overflow pipe 248 causes the cleaning liquid overflowing in the cleaning tank 219 to flow into the waste liquid tank 250.
- the waste liquid tank 250 stores the cleaning liquid flowing down the overflow pipe 248.
- the electrode manufacturing system 11 includes a control system 239 shown in FIG.
- the control system 239 includes an end position adjustment unit 241, two end sensors 121, and a roll drive unit 243.
- One of the two end sensors 121 is arranged near the supply roll 101 as shown in FIG.
- the other of the two end sensors 121 is arranged near the winding roll 103.
- the end position adjustment unit 241 is a computer including a CPU, a memory and the like.
- the roll driving unit 243 can change the positions of the supply roll 101 and the winding roll 103 in the width direction W. When the positions of the supply roll 101 and the winding roll 103 in the width direction W change, the positions of the electrode 1 in the width direction W change.
- the processing executed by the control system 239 is as follows.
- the end position adjusting unit 241 uses the end sensor 121 to detect the position of the end part of the electrode 1 in the width direction W near the supply roll 101 and near the winding roll 103.
- the end position adjustment unit 241 adjusts the positions of the supply roll 101 and the winding roll 103 in the width direction W using the roll drive unit 243 based on the detection result.
- the positions of the supply roll 101 and the winding roll 103 after the adjustment are positions where the brush roller 217 comes into contact with the active material layer-unformed portion 7 and does not come into contact with the active material layer-formed portion 6.
- the electrolytic solution treatment tank 15 and the dope tanks 17, 19 and 21 contain the dope solution.
- the dope solution contains an alkali metal ion and a solvent.
- the dope solution is an electrolytic solution.
- the solvent examples include organic solvents.
- an aprotic organic solvent is preferable.
- the aprotic organic solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1-fluoroethylene carbonate, ⁇ -butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride.
- an ionic liquid such as a quaternary imidazolium salt, a quaternary pyridinium salt, a quaternary pyrrolidinium salt or a quaternary piperidinium salt can be used.
- the organic solvent may be composed of a single component, or may be a mixed solvent of two or more components.
- the organic solvent may be composed of a single component, or may be a mixed solvent of two or more components.
- the alkali metal ion contained in the dope solution is an ion that constitutes an alkali metal salt.
- the alkali metal salt is preferably a lithium salt or a sodium salt.
- a phosphorus anion having a fluoro group such as PF 6 ⁇ , PF 3 (C 2 F 5 ) 3 ⁇ , PF 3 (CF 3 ) 3 ⁇ ; BF 4 ⁇ , BF 2 Boron anion having a fluoro group or a cyano group such as (CF) 2 - , BF 3 (CF 3 ) - , and B(CN) 4 - ; N(FSO 2 ) 2 - , N(CF 3 SO 2 ) 2 - , Examples thereof include a sulfonylimide anion having a fluoro group such as N(C 2 F 5 SO 2 ) 2 ⁇ and an organic sulfonate anion having a fluoro
- the concentration of the alkali metal salt in the dope solution is preferably 0.1 mol/L or more, more preferably 0.5 to 1.5 mol/L. When the concentration of the alkali metal salt is within this range, pre-doping of the alkali metal proceeds efficiently.
- the dope solution further contains additives such as vinylene carbonate, vinyl ethylene carbonate, 1-fluoroethylene carbonate, 1-(trifluoromethyl)ethylene carbonate, succinic anhydride, maleic anhydride, propane sultone and diethyl sulfone. be able to.
- additives such as vinylene carbonate, vinyl ethylene carbonate, 1-fluoroethylene carbonate, 1-(trifluoromethyl)ethylene carbonate, succinic anhydride, maleic anhydride, propane sultone and diethyl sulfone.
- the above dope solution may further contain a flame retardant such as a phosphazene compound.
- the amount of the flame retardant added is preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the dope solution, from the viewpoint of effectively controlling the thermal runaway reaction at the time of doping the alkali metal. It is more preferable that the amount is 5 parts by mass or more.
- the amount of the flame retardant added is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the dope solution. It is more preferable that the amount is not more than part.
- Electrode Manufacturing Method Using Electrode Manufacturing System 11 The manufacturing method for manufacturing the pre-doped electrode 1 is as follows. The electrode 1 before pre-doping is wound around the supply roll 101. Next, the electrode 1 before pre-doping is pulled out from the supply roll 101 and is passed through the winding roll 103 along the above-mentioned path. At this time, the positions of the first portion 211 and the second portion 213 forming the cleaning roller units 201 and 203 of the tab cleaner 117 are set to the separated positions. Then, the electrolytic solution treatment tank 15, the dope tanks 17, 19, 21 and the cleaning tank 23 are raised and set to the fixed positions shown in FIG.
- the dope solution is stored in the electrolytic solution treatment tank 15 and the dope tanks 17, 19 and 21.
- the dope solution is as described in “4. Composition of dope solution” above.
- a cleaning liquid is stored in the cleaning tank 23.
- the cleaning liquid contained in the cleaning tank 23 is an organic solvent. Examples of the organic solvent include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate and the like.
- the positions of the first portion 211 and the second portion 213 that form the cleaning roller units 201 and 203 of the tab cleaner 117 are referred to as approaching positions.
- the path for transporting the electrode 1 is a path that passes through the inside of the dope tanks 17, 19 and 21.
- the active material contained in the active material layer 5 is pre-doped with alkali metal.
- the transport roller group transports the electrode 1 to the cleaning tank 23.
- the electrode 1 is cleaned in the cleaning tank 23 while being transported by the transport roller group.
- the transport roller group continuously transports the electrode 1 to the tab cleaner 117.
- the portion of the electrode 1 that has been transported to the tab cleaner 117 is the portion that has been pre-doped.
- the cleaning roller units 201 and 203 of the tab cleaner 117 respectively clean the active material layer-unformed portion 7 of the electrode 1.
- the portion to be cleaned is the active material layer-unformed portion 7 adjacent to the active material layer-formed portion 6 on which the pre-doping process has already been performed.
- To be adjacent means to be adjacent in the width direction W, for example.
- the cleaning performed by the cleaning roller units 201 and 203 is as follows.
- the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 contact the active material layer-unformed portion 7 while rotating. Since the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 are respectively immersed in the cleaning liquid in the cleaning tank 219, the active material layer-unformed portion in the state containing the cleaning liquid. Touch 7. As a result, the active material layer-unformed portion 7 is cleaned.
- the peripheral speed of the brush roller 217 at the portion in contact with the electrode 1 is V1.
- the transport speed of the electrode 1 is V2.
- V2 is a positive value.
- the unit of V1 and the unit of V2 are the same. If the portion of the brush roller 217 that contacts the electrode 1 is moving in the transport direction of the electrode 1, V1 has a positive value. When the portion of the brush roller 217 that contacts the electrode 1 is moving in the direction opposite to the transport direction of the electrode 1, V1 is a negative value.
- the ratio of V1 to V2 is defined as V1/V2 ratio.
- the V1/V2 ratio is a value obtained by dividing V1 by V2.
- the V1/V2 ratio is ⁇ 5.0 or more and 0.99 or less, or 1.01 or more and 5 or more from the viewpoint of effectively cleaning the active material layer-unformed portion 7 and stably transporting the electrode 1. It is preferably 0 or less.
- the V1/V2 ratio is more preferably 0.01 or more and 0.95 or less, or 1.05 or more and 3.0 or less.
- the V1/V2 ratio is more preferably 0.1 or more and 0.9 or less, or 1.1 or more and 2.0 or less.
- the V1/V2 ratio is preferably not 0.
- the drying unit 209 of the tab cleaner 117 dries the electrode 1 that has passed through the cleaning roller units 201 and 203. Next, the electrode 1 is wound around the winding roll 103.
- the electrode 1 may be a positive electrode or a negative electrode.
- the electrode manufacturing system 11 dopes the positive electrode active material with an alkali metal
- the electrode manufacturing system 11 dopes the negative electrode active material with an alkali metal.
- the amount of the alkali metal doped is preferably 70 to 95% of the theoretical capacity of the negative electrode active material when the negative electrode active material of the lithium ion capacitor stores lithium. In the case of occluding TiO2, it is preferably 10 to 30% with respect to the theoretical capacity of the negative electrode active material.
- the tab cleaner 117 cleans the active material layer-unformed portion 7. Therefore, the electrode manufacturing system 11 can suppress the dope solution and the like from remaining in the active material layer-unformed portion 7 of the manufactured electrode 1.
- the hardness of the brush roller 217 defined by JIS S 3016-1995 is 1 N/cm 2 or more and 1000 N/cm 2 or less. Therefore, it is possible to clean the active material layer-unformed portion 7 while suppressing damage to the active material layer-unformed portion 7.
- the V1/V2 ratio is -5.0 or more and 0.99 or less, or particularly in the range of 1.01 or more and 5.0 or less, 0.01 or more and 0.95 or less, or 1.05 or more and 3.0.
- the tab cleaner 117 includes a cleaning tank 219.
- the cleaning tank 219 contains a part of the brush roller 217 and a cleaning liquid. Therefore, the brush roller 217 comes into contact with the active material layer-unformed portion 7 while containing the cleaning liquid. As a result, the tab cleaner 117 can more effectively clean the active material layer-unformed portion 7.
- the (1F) tab cleaner 117 can supply the cleaning liquid to the cleaning tank 219 by the pump 207. Further, the tab cleaner 117 can sequentially discharge the cleaning liquid used for the cleaning process from the cleaning tank 219 to the waste liquid tank 250 through the overflow pipe 248. Therefore, it is possible to prevent the cleaning liquid contained in the cleaning tank 219 from decreasing or becoming dirty.
- the (1G) active material layer-unformed portion 7 has a strip shape extending in the longitudinal direction of the electrode 1. Therefore, the tab cleaner 117 can easily clean the active material layer-unformed portion 7.
- the brush roller 217 of the cleaning roller units 201 and 203 is rotated by the mechanism shown in FIG.
- the second embodiment is different from the first embodiment in that the brush roller 217 of the cleaning roller units 201 and 203 is rotated by the mechanism shown in FIG.
- a gear 245 and a small motor 247 are attached to the shaft 227 of the first portion 211.
- the small motor 247 is fixed.
- the shaft 227, the brush roller 217, and the gear 245 are rotated by the driving force of the small motor 247.
- a gear 249 is attached to the shaft 227 of the second portion 213.
- the gear 249 meshes with the gear 245.
- the gear 245 rotates
- the gear 249, the shaft 227 of the second portion 213, and the brush roller 217 also rotate. Therefore, the brush roller 217 of the first portion 211 and the brush roller 217 of the second portion 213 are rotated by the driving force of the small motor 247.
- the rotation direction of the brush roller 217 of the first portion 211 is opposite to the rotation direction of the brush roller 217 of the second portion 213.
- the tab cleaner 117 includes the cleaning roller units 201 and 203 shown in FIGS. 6 and 7.
- a cleaning roller unit 301 shown in FIGS. 11 and 12 is provided instead of the cleaning roller units 201 and 203.
- the cleaning roller unit 301 is provided at the positions of the cleaning roller units 201 and 203 in the first embodiment.
- the cleaning roller unit 301 includes a first part 311 and a second part 313.
- the first portion 311 and the second portion 313 are arranged so as to sandwich the electrode 1 from both sides.
- the first portion 311 includes a brush arm 315, a support shaft 317, a fixing portion 318, a brush roller 217, a brush shaft 319, and a motor 321.
- the brush arm 315 is rotatably attached to the support shaft 317.
- the brush arm 315 is provided with a greaseless bearing 323 at a portion to which the support shaft 317 is attached.
- the brush arm 315 includes a main body 325, a first protrusion 327, a second protrusion 329, a third protrusion 331, and a fourth protrusion 333.
- the main body portion 325 is a portion through which the support shaft 317 passes. As shown in FIG. 12, the first projecting portion 327, the second projecting portion 329, and the third projecting portion 331 project more toward the electrode 1 than the body portion 325.
- the first protruding portion 327, the second protruding portion 329, and the third protruding portion 331 are arranged along the width direction W at intervals.
- the fourth protrusion 333 protrudes from the main body 325 in the direction opposite to the electrode 1.
- the support shaft 317 and the fixing portion 318 are fixed to the frame of the electrode manufacturing system 11, respectively.
- the fixing portion 318 may be a part of the frame of the electrode manufacturing system 11. Therefore, the positions of the support shaft 317 and the fixed portion 318 are fixed with respect to the transport roller group.
- the axial direction of the support shaft 317 is parallel to the width direction W.
- the fourth projecting portion 333 is fixed to the fixing portion 318 with the fixing screw 335. As a result, the position of the brush arm 315 is fixed.
- the brush shaft 319 is rotatably supported by the first protrusion 327 and the second protrusion 329.
- the first protrusion 327 and the second protrusion 329 each include a greaseless bearing 323 at a portion to which the brush shaft 319 is attached.
- the axial direction of the brush shaft 319 is parallel to the width direction W.
- the brush roller 217 is pivotally supported by the brush shaft 319.
- the brush roller 217 is in contact with the active material layer-unformed portion 7.
- the brush roller 217 does not contact the active material layer forming portion 6.
- the position of the brush arm 315 in the width direction W can be adjusted. By adjusting the position of the brush arm 315 in the width direction W, the position of the brush roller 217 in the width direction W can be adjusted.
- the motor 321 is arranged between the second protrusion 329 and the third protrusion 331.
- the motor 321 rotationally drives the brush shaft 319 and the brush roller 217.
- the second portion 313 basically has a configuration in which the first portion 311 is horizontally inverted in FIGS. 11 and 12. However, the second portion 313 does not include the fixing portion 318.
- the brush arm 315 of the second portion 313 can rotate around the support shaft 317.
- a weight 337 is suspended from the fourth protrusion 333 of the second portion 313. Therefore, the brush arm 315 of the second portion 313 is biased in the direction in which the brush roller 217 is pressed against the electrode 1.
- the tab cleaner 117 may clean the active material layer non-formed portion 7 by a method other than the method using the cleaning roller.
- the number of cleaning roller units included in the tab cleaner 117 may be other than 2, and can be 1, 3, 4, 5,...
- the following processing may be performed.
- the electrode 1 that has been treated to dope the alkali metal is placed on the supply roll 101.
- the electrode 1 is conveyed from the supply roll 101 to the tab cleaner 117 for cleaning.
- the cleaned electrode 1 is wound on a winding roll 103 and stored.
- each of the above embodiments may be shared by a plurality of constituent elements, or the function of a plurality of constituent elements may be exerted by one constituent element. Moreover, you may omit a part of structure of each said embodiment. Further, at least a part of the configuration of each of the above-described embodiments may be added to or replaced with the configuration of the other above-described embodiments.
- a higher-level system having the electrode manufacturing system as a component, a program for causing a computer to function as the end position adjustment unit 241, and a non-transition such as a semiconductor memory storing this program
- the present disclosure can be realized in various forms such as a physical recording medium and a doping method.
- a long strip-shaped current collector 3 was prepared.
- the current collector 3 is a negative electrode current collector.
- the size of the current collector 3 was 150 mm in width, 100 m in length, and 8 ⁇ m in thickness.
- the surface roughness Ra of the current collector 3 was 0.1 ⁇ m.
- the current collector 3 was made of copper foil. Negative electrode active material layers 5 were formed on both surfaces of the current collector 3.
- the coating amount of the negative electrode active material layer 5 formed on one side of the current collector 3 was 50 g/m 2 .
- the negative electrode active material layer 5 was formed along the longitudinal direction of the current collector 3.
- the negative electrode active material layer 5 was formed over a width of 130 mm from the end portion of the current collector 3 in the width direction W.
- the negative electrode active material layer-unformed portion at the other end in the width direction W of the current collector 3 was 20 mm.
- the negative electrode active material layer-unformed portion is a portion where the negative electrode active material layer 5 is not formed. Then, the electrode 1 was obtained by performing drying and pressing.
- the negative electrode active material layer 5 contained the negative electrode active material, carboxymethyl cellulose, acetylene black, a binder, and a dispersant in a mass ratio of 88:3:5:3:1.
- the negative electrode active material was a mixture of Si-based active material and graphite-based active material.
- the negative electrode active material contained a Si-based active material and a graphite-based active material in a mass ratio of 2:8. Acetylene black corresponds to a conductive agent.
- the electrode manufacturing system 11 shown in FIG. 3 was prepared, and the electrode 1 was passed through. Further, counter electrode units 139, 141 and 143 were installed in the dope tanks 17, 19 and 21, respectively. Next, the dope solution was supplied into the dope tanks 17, 19 and 21.
- the dope solution was a solution containing 1.4 M LiPF 6 .
- the solvent of the dope solution was a mixed solution containing EC (ethylene carbonate), EMC (ethyl methyl carbonate), and DMC (dimethyl carbonate) at a volume ratio of 1:1:1.
- the electrode 1 passed through the electrode manufacturing system 11 and the counter electrode units 139, 141, and 143 were connected to a DC power supply with a current/voltage monitor, and the electrode 1 was conveyed at a speed of 0.1 m/min, and a 5 A Energized with current.
- the center in the width direction W of the negative electrode active material layer 95 included in the electrode 1 was aligned with the center in the width direction W of the lithium metal plate included in the counter electrode unit 51.
- the energization time was set such that the lithium doping ratio in the negative electrode active material layer 5 was 15% of the negative electrode discharge capacity C2 in consideration of the irreversible capacity.
- the irreversible capacity was estimated in advance by measuring the discharge capacity of the electrode 1 after doping lithium. Through this step, the negative electrode active material in the negative electrode active material layer 95 was doped with lithium, and the electrode 1 became a pre-doped negative electrode.
- the electrode 1 is a negative electrode for a lithium ion secondary battery.
- the electrode 1 was passed through the cleaning tank 23 and then wound up.
- the cleaning tank 23 contained DMC (dimethyl carbonate) at 25° C.
- the pre-doped electrode 1 was manufactured as described above.
- Example 1 The electrode 1 manufactured as described above was passed through the electrode manufacturing system 11 of the third embodiment again.
- the brush roller 217 a polypropylene brush roller having a wire diameter of 0.1 mm was used.
- the hardness of the brush roller defined by JIS S 3016-1995 was 40 N/cm 2 .
- the weight of the weight 337 was set to 300 g.
- the dope solution was supplied to the dope tanks 17, 19 and 21.
- the 4 m long portion of the electrode 1 wound on the winding roll 103 was laminated using a winding machine.
- the laminated electrode 1 and the battery current collector were laser-welded. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 1 the V1/V2 ratio was smaller than 1. As a result, the active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion could be welded well.
- Example 2 Basically, the same operation as in Example 1 was performed. However, the peripheral velocity V1 of the brush roller 217 was set to 1.0 m/min. The V1/V2 ratio was 1. The active material layer-unformed portion 7 was cleaned. However, a certain amount of copper spatter was generated during laser welding. In addition, a blowhole was found in part of the weld.
- Example 2 the V1/V2 ratio was 1. As a result, compared to Example 2, in Example 1, the active material layer-unformed portion 7 was cleaned more sufficiently.
- Example 3 Basically, the same operation as in Example 1 was performed. However, the peripheral speed V1 of the brush roller 217 was set to 1.18 m/min. The V1/V2 ratio was 1.18. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 3 the V1/V2 ratio was larger than 1. As a result, the active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion could be welded well.
- Example 4 Basically, the same operation as in Example 1 was performed. However, the peripheral speed V1 of the brush roller 217 was set to 1.57 m/min. The V1/V2 ratio was 1.57. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 4 the V1/V2 ratio was larger than 1. As a result, the active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion could be welded well.
- Example 5 Basically, the same operation as in Example 1 was performed. However, the peripheral velocity V1 of the brush roller 217 was set to 2.36 m/min. The V1/V2 ratio was 2.36. The active material layer-unformed portion 7 was cleaned. However, since the brush rollers 217 were easily caught in each other, wrinkles were generated in the electrode 1 and the position shift of the active material layer-unformed portion 7 was generated. Therefore, the transportation of the electrode 1 became unstable. As a result, compared with Example 5, in Example 1, the active material layer-unformed portion 7 was cleaned more sufficiently.
- Example 6 Basically, the same operation as in Example 1 was performed. However, the peripheral speed V1 of the brush roller 217 was set to 4.71 m/min. The transport speed V2 of the electrode 1 was set to 3.0 m/min. The V1/V2 ratio was 1.57. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 6 even if the transport speed V2 was high, by setting the V1/V2 ratio within an appropriate range, the active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion was welded well. ..
- Example 7 Basically, the same operation as in Example 1 was performed. However, the peripheral speed V1 of the brush roller 217 was set to -0.39 m/min. Further, the transport speed V2 of the electrode 1 was set to 1.0 m/min. The V1/V2 ratio was -0.39.
- Example 7 The part 7 where the active material layer was not formed was cleaned. However, since the brush rollers 217 were easily caught in each other, wrinkles were generated in the electrode 1 and the position shift of the active material layer-unformed portion 7 was generated. Therefore, the transportation of the electrode 1 became unstable. As a result, compared to Example 7, in Example 1, the active material layer-unformed portion 7 was cleaned more sufficiently.
- Example 8 Basically, the same operation as in Example 4 was performed. However, a brush roller having a wire diameter of 0.3 mm was used as the brush roller 217. The V1/V2 ratio was 1.57. The active material layer-unformed portion 7 was cleaned. However, a certain amount of copper spatter was generated during laser welding. In addition, a blowhole was found in part of the weld.
- Example 8 since the wire diameter of the brush roller 217 was too large, the contact area between the active material layer-unformed portion 7 and the brush roller 217 was reduced. Therefore, as compared with Example 8, in Example 1, the active material layer-unformed portion 7 was cleaned more sufficiently, and the tab portion was welded more favorably.
- Example 9 Basically, the same operation as in Example 4 was performed. However, a goat wool brush roller was used as the brush roller 217. The hardness of the brush roller defined by JIS S 3016-1995 was 10 N/cm 2 . The V1/V2 ratio was 1.57. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 9 since the brush roller 217 made of an appropriate material was used, the active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion could be welded well.
- Example 10 Basically, the same operation as in Example 4 was performed. However, a goat wool brush roller was used as the brush roller 217. The peripheral speed V1 of the brush roller 217 was set to -0.39 m/min. The V1/V2 ratio was -0.39.
- Example 10 even if the material of the brush rollers 217 was a soft natural material, if the direction of V1 was opposite to the direction of V2, the brush rollers 217 could easily bite into each other.
- Example 11 Basically, the same operation as in Example 10 was performed. However, the tab cleaner 117 including the cleaning roller units 201 and 203 shown in FIG. 10 was used. The V1/V2 ratio was -0.39.
- the brush rollers 217 did not bite each other, and the current collector 3 did not break. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 11 the position of the brush roller 217 was fixed, and the distance between the brush roller 217 and the electrode 1 was constant. By keeping the distance between the brush roller 217 and the electrode 1 constant, even if the direction of V1 is opposite to the direction of V2, the electrode 1 does not break and the active material layer-unformed portion 7 is sufficiently cleaned. The tab portion was welded well.
- Example 12 Basically, the same operation as in Example 11 was performed. However, the peripheral speed V1 of the brush roller 217 was set to 1.57 m/min. The V1/V2 ratio was ⁇ 1.57. No copper spatter occurred during laser welding. No blowhole was found in the weld.
- Example 12 the position of the brush roller 217 was fixed, and the distance between the brush roller 217 and the electrode 1 was constant. By keeping the distance between the brush roller 217 and the electrode 1 constant, the rotation of the brush roller 217 is high speed, and even if the direction of V1 is reversed with respect to the direction of V2, the electrode 1 does not break, The active material layer-unformed portion 7 was sufficiently cleaned, and the tab portion was welded well.
- Example 13 Basically, the same operation as in Example 4 was performed. However, instead of the brush roller 217 used in Example 4, a sponge roller whose material is an olefin sponge was used. JIS The sponge roller had a hardness of 20 as measured by a type E durometer specified by K 6253-3. The V1/V2 ratio was 1.57.
- Example 13 even if the cleaning roller was a sponge roller, the active material layer-unformed portion 7 was sufficiently cleaned and the tab portion was well welded.
- Comparative Example 1 Basically, the same operations as in Examples 1 to 5 and 7 to 13 were performed. However, the tab cleaner 117 was not used. A large amount of copper spatter was generated during laser welding. In addition, blow holes were occasionally found in the welds. When the tab cleaner 117 was not used, laser welding had a problem.
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Abstract
Description
<第1実施形態>
1.電極1の構成
図1、図2に基づき、電極1の構成を説明する。電極1は帯状の形状を有する。電極1は、集電体3と、活物質層5とを備える。集電体3は帯状の形状を有する。活物質層5は、集電体3の両面にそれぞれ形成されている。
電極製造システム11の構成を、図3~図5に基づき説明する。図3に示すように、電極製造システム11は、電解液処理槽15と、ドープ槽17、19、21と、洗浄槽23と、搬送ローラ25、27、29、31、33、35、37、39、40、41、43、45、46、47、49、51、52、53、55、57、58、59、61、63、64、65、67、69、70、71、73、75、77、79、81、83、85、87、89、91、93(以下ではこれらをまとめて搬送ローラ群と呼ぶこともある)と、供給ロール101と、巻取ロール103と、支持台105と、循環濾過ユニット107と、6つの電源109、110、111、112、113、114と、タブクリーナー117と、回収ユニット119と、端部センサ121と、を備える。
タブクリーナー117の構成を、図6~図9に基づき説明する。タブクリーナー117はクリーニングユニットに対応する。図6に示すように、タブクリーナー117は、洗浄ローラユニット201、203、洗浄液タンク205、ポンプ207、乾燥ユニット209、オーバーフロー配管248、及び廃液タンク250を備える。
電極製造システム11を使用するとき、電解液処理槽15、及びドープ槽17、19、21に、ドープ溶液を収容する。ドープ溶液は、アルカリ金属イオンと、溶媒とを含む。ドープ溶液は電解液である。
プレドープされた電極1を製造する製造方法は以下のとおりである。プレドープ前の電極1を供給ロール101に巻き回す。次に、プレドープ前の電極1を供給ロール101から引き出し、上述した経路に沿って巻取ロール103まで通紙する。このとき、タブクリーナー117の洗浄ローラユニット201、203を構成する第1部211及び第2部213の位置は、離間位置にしておく。そして、電解液処理槽15と、ドープ槽17、19、21と、洗浄槽23とを上昇させ、図3に示す定位置へセットする。
(1A)タブクリーナー117は活物質層未形成部7をクリーニングする。そのため、電極製造システム11は、製造した電極1の活物質層未形成部7にドープ溶液等が残留することを抑制できる。
<第2実施形態>
1.第1実施形態との相違点
第2実施形態は、基本的な構成は第1実施形態と同様であるため、相違点について以下に説明する。なお、第1実施形態と同じ符号は、同一の構成を示すものであって、先行する説明を参照する。
以上詳述した第2実施形態によれば、前述した第1実施形態の効果を奏する。
<第3実施形態>
1.第1実施形態との相違点
第3実施形態は、基本的な構成は第1実施形態と同様であるため、相違点について以下に説明する。なお、第1実施形態と同じ符号は、同一の構成を示すものであって、先行する説明を参照する。
<他の実施形態>
以上、本開示の実施形態について説明したが、本開示は上述の実施形態に限定されることなく、種々変形して実施することができる。
(各実施例及び比較例1で使用する電極1の製造)
長尺の帯状の集電体3を用意した。集電体3は負極集電体である。集電体3のサイズは、幅150mm、長さ100m、厚さ8μmであった。集電体3の表面粗さRaは0.1μmであった。集電体3は銅箔から成っていた。集電体3の両面に、それぞれ負極活物質層5を形成した。
上記のように製造した電極1を、再び、第3実施形態の電極製造システム11に通紙した。ブラシローラ217として、ポリプロピレン製の線径0.1mmのブラシローラを用いた。JIS S 3016‐1995で規定されるブラシローラの硬さは40N/cm2であった。重り337の重さを300gとした。ドープ槽17、19、21にドープ溶液を供給した。
(実施例2)
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を1.0m/minとした。V1/V2比は、1であった。活物質層未形成部7はクリーニングされていた。ただし、レーザー溶接のとき、銅のスパッタが一定量発生した。また、溶接部の一部にブロウホールが見られた。
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を1.18m/minとした。V1/V2比は、1.18であった。レーザー溶接のとき、銅のスパッタは発生しなかった。また、溶接部にブロウホールは見られなかった。
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を1.57m/minとした。V1/V2比は、1.57であった。レーザー溶接のとき、銅のスパッタは発生しなかった。また、溶接部にブロウホールは見られなかった。
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を2.36m/minとした。V1/V2比は、2.36であった。活物質層未形成部7はクリーニングされていた。ただし、ブラシローラ217同士が噛み込み易くなることで電極1にしわが発生し、活物質層未形成部7の位置ずれが発生した。このため、電極1の搬送が不安定になった。その結果、実施例5と比べて、実施例1の方が、活物質層未形成部7のクリーニングが一層十分に行われていた。
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を4.71m/minとした。また、電極1の搬送速度V2を3.0m/minとした。V1/V2比は、1.57であった。レーザー溶接のとき、銅のスパッタは発生しなかった。また、溶接部にブロウホールは見られなかった。
基本的には実施例1と同様の操作を行った。ただし、ブラシローラ217の周速度V1を-0.39m/minとした。また、電極1の搬送速度V2を1.0m/minとした。V1/V2比は-0.39であった。
基本的には実施例4と同様の操作を行った。ただし、ブラシローラ217として、線径が0.3mmのブラシローラを使用した。V1/V2比は、1.57であった。活物質層未形成部7はクリーニングされていた。ただし、レーザー溶接のとき、銅のスパッタが一定量発生した。また、溶接部の一部にブロウホールが見られた。
基本的には実施例4と同様の操作を行った。ただし、ブラシローラ217として、素材が山羊毛のブラシローラを使用した。JIS S 3016‐1995で規定されるブラシローラの硬さは10N/cm2であった。V1/V2比は、1.57であった。レーザー溶接のとき、銅のスパッタは発生しなかった。また、溶接部にブロウホールは見られなかった。
(実施例10)
基本的には実施例4と同様の操作を行った。ただし、ブラシローラ217として、素材が山羊毛のブラシローラを使用した。また、ブラシローラ217の周速度V1を-0.39m/minとした。V1/V2比は、-0.39であった。
基本的には実施例10と同様の操作を行った。ただし、図10に示す洗浄ローラユニット201、203を備えたタブクリーナー117を使用した。V1/V2比は、-0.39であった。
基本的には実施例11と同様の操作を行った。ただし、ブラシローラ217の周速度V1を1.57m/minとした。V1/V2比は、-1.57であった。レーザー溶接のとき、銅のスパッタは発生しなかった。また、溶接部にブロウホールは見られなかった。
基本的には実施例4と同様の操作を行った。ただし、実施例4で使用したブラシローラ217に代えて、素材がオレフィン系スポンジであるスポンジローラを使用した。JIS
K 6253‐3で規定されるタイプEデュロメーターで測定したスポンジローラの硬さは20であった。V1/V2比は、1.57であった。
基本的には実施例1~5、7~13と同様の操作を行った。ただし、タブクリーナー117を使用しなかった。レーザー溶接のとき、銅のスパッタが大量に発生した。また、溶接部にブロウホールが散見された。タブクリーナー117を使用しない場合、レーザー溶接に不具合が発生した。
Claims (16)
- 集電体の表面に活物質を含む活物質層が形成された活物質層形成部と、前記集電体の表面に前記活物質層が形成されていない活物質層未形成部とを有する帯状の電極における前記活物質にアルカリ金属をドープする処理を行うように構成されたドープユニットと、
前記処理が行われた前記活物質層形成部に隣接する前記活物質層未形成部をクリーニングするように構成されたクリーニングユニットと、
前記電極を前記ドープユニットから前記クリーニングユニットに搬送するように構成された搬送ユニットと、
を備える電極製造システム。 - 請求項1に記載の電極製造システムであって、
前記搬送ユニットは、前記電極を前記ドープユニットから前記クリーニングユニットに連続的に搬送するように構成された、
電極製造システム。 - 請求項1又は2に記載の電極製造システムであって、
前記クリーニングユニットは、前記活物質層未形成部と接触する洗浄ローラを有する電極製造システム。 - 請求項3に記載の電極製造システムであって、
前記洗浄ローラがブラシローラである電極製造システム。 - 請求項3又は4に記載の電極製造システムであって、
JIS S 3016‐1995で規定される前記洗浄ローラの硬さが、1N/cm2以上1000N/cm2以下である電極製造システム。 - 請求項3~5のいずれか1項に記載の電極製造システムであって、
前記洗浄ローラの少なくとも一部、及び洗浄液を収容するように構成されたタブクリーニング槽をさらに備える電極製造システム。 - 請求項6に記載の電極製造システムであって、
前記タブクリーニング槽に前記洗浄液を供給するように構成された洗浄液供給ユニットをさらに備える電極製造システム。 - 請求項1~7のいずれか1項に記載の電極製造システムであって、
前記活物質層未形成部は、前記電極の長手方向に延びる帯状の形態を有する電極製造システム。 - 請求項1~8のいずれか1項に記載の電極製造システムであって、
前記ドープユニットは、
アルカリ金属イオンを含む溶液を収容するように構成されたドープ槽と、
前記ドープ槽に収容される対極ユニットと、
を備え、
前記搬送ユニットは、前記電極を、前記ドープ槽内を通過する経路に沿って搬送するように構成された電極製造システム。 - 集電体の表面に活物質を含む活物質層が形成された活物質層形成部と、前記集電体の表面に前記活物質層が形成されていない活物質層未形成部とを有する帯状の電極をクリーニングするクリーニングユニットであって、
前記活物質にアルカリ金属をドープする処理が行われた前記活物質層形成部に隣接する前記活物質層未形成部をクリーニングするように構成されたクリーニングユニット。 - 請求項10に記載のクリーニングユニットと、
前記電極における前記活物質にアルカリ金属をドープする処理を行うように構成されたドープユニットと、
を備える電極製造システム。 - 集電体の表面に活物質を含む活物質層が形成された活物質層形成部と、前記集電体の表面に前記活物質層が形成されていない活物質層未形成部とを有する帯状の電極における前記活物質にアルカリ金属をドープする処理を行い、
前記処理が行われた前記電極を搬送し、
前記処理が行われた前記活物質層形成部に隣接する前記活物質層未形成部をクリーニングする電極製造方法。 - 請求項12に記載の電極製造方法であって、
前記処理が行われた前記電極を連続的に搬送する、
電極製造方法。 - 請求項12又は13に記載の電極製造方法であって、
洗浄ローラを前記活物質層未形成部に接触させることで、前記活物質層未形成部をクリーニングする電極製造方法。 - 請求項14に記載の電極製造方法であって、
前記電極の搬送速度V2(m/min)に対する、前記洗浄ローラの周速度V1(m/min)の比であるV1/V2比が、-5.0以上0.99以下、又は、1.01以上5.0以下である電極製造方法。 - 請求項15に記載の電極製造方法であって、
前記V1/V2比が、0.1以上0.9以下、又は、1.1以上2.0以下である電極製造方法。
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