WO2012111699A1 - 三次元網状アルミニウム多孔体を用いた電極、該電極を用いた非水電解質電池、非水電解液を用いたキャパシタ及びリチウムイオンキャパシタ - Google Patents
三次元網状アルミニウム多孔体を用いた電極、該電極を用いた非水電解質電池、非水電解液を用いたキャパシタ及びリチウムイオンキャパシタ Download PDFInfo
- Publication number
- WO2012111699A1 WO2012111699A1 PCT/JP2012/053514 JP2012053514W WO2012111699A1 WO 2012111699 A1 WO2012111699 A1 WO 2012111699A1 JP 2012053514 W JP2012053514 W JP 2012053514W WO 2012111699 A1 WO2012111699 A1 WO 2012111699A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- aluminum
- region
- porous body
- skeleton
- Prior art date
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their 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
- 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
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
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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
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a tertiary used as an electrode for a non-aqueous electrolyte battery (such as a lithium battery), a capacitor using a non-aqueous electrolyte (hereinafter also referred to as “capacitor”), a lithium ion capacitor using a non-aqueous electrolyte, and the like.
- a non-aqueous electrolyte battery such as a lithium battery
- capacitor using a non-aqueous electrolyte hereinafter also referred to as “capacitor”
- a lithium ion capacitor using a non-aqueous electrolyte and the like.
- the present invention relates to an original reticulated aluminum porous body.
- Metal porous bodies having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes.
- Celmet manufactured by Sumitomo Electric Industries, Ltd .: registered trademark
- nickel porous body made of a three-dimensional network nickel porous body (hereinafter referred to as “nickel porous body”) is used as an electrode material for batteries such as nickel metal hydride batteries and nickel cadmium batteries.
- Celmet is a metal porous body having continuous air holes, and has a feature of high porosity (90% or more) compared to other porous bodies such as a metal nonwoven fabric.
- aluminum like nickel, has excellent characteristics such as conductivity, corrosion resistance, and light weight.
- a positive electrode of a lithium battery is coated with an active material such as lithium cobaltate on the surface of an aluminum foil. Things are used.
- aluminum porous body having a large aluminum surface area, and to fill the active material into the aluminum. This is because the active material can be used even if the electrode is thickened, and the active material utilization rate per unit area is improved.
- Patent Document 1 discloses that a metal aluminum layer having a thickness of 2 to 20 ⁇ m is formed by subjecting a three-dimensional net-like plastic substrate having an internal communication space to aluminum vapor deposition by an arc ion plating method. A method is described. According to this method, it is said that an aluminum porous body having a thickness of 2 to 20 ⁇ m can be obtained, but it is difficult to manufacture in a large area because of the vapor phase method, and depending on the thickness and porosity of the substrate, It is difficult to form a uniform layer. In addition, there are problems such as a slow formation rate of the aluminum layer and an increase in manufacturing cost due to expensive equipment. Further, when a thick film is formed, there is a risk that the film may crack or aluminum may fall off.
- Patent Document 2 a film made of a metal (such as copper) that forms a eutectic alloy below the melting point of aluminum is formed on the skeleton of a foamed resin molding having a three-dimensional network structure, and then an aluminum paste is applied.
- a method is described in which a heat treatment is performed at a temperature of 550 ° C. or higher and 750 ° C. or lower in a non-oxidizing atmosphere so that the organic component (foamed resin) disappears and the aluminum powder is sintered to obtain an aluminum porous body.
- a layer that forms a eutectic alloy with aluminum is formed, and a high-purity aluminum layer cannot be formed.
- Patent Document 3 uses a low melting point composition in which onium halide and aluminum halide are mixed and melted as a plating bath, and the amount of moisture in the bath
- An aluminum electroplating method is disclosed, in which aluminum is deposited on the cathode while maintaining 2% by mass or less.
- aluminum electroplating is only possible on a metal surface, and electroplating on the surface of a resin molded body, in particular, a method of electroplating on the surface of a resin molded body having a three-dimensional network structure is known. There wasn't.
- the present inventors diligently studied about a method of performing electroplating of aluminum on the surface of a urethane resin molded body having a three-dimensional network structure. At least, in a molten salt bath, aluminum was added to a urethane resin molded body having a conductive surface. It was found that plating was possible by plating with, and a method for producing a porous aluminum body was completed. According to this manufacturing method, an aluminum structure having a urethane resin molded body as a skeleton core is obtained. Depending on applications such as various filters and catalyst carriers, it may be used as a composite of resin and metal as it is. However, due to restrictions in the usage environment, when using as a metal structure without resin, the resin is removed and aluminum is used.
- Removal of the resin can be performed by any method such as decomposition (dissolution) with an organic solvent, molten salt, or supercritical water, and thermal decomposition.
- methods such as thermal decomposition at high temperatures are simple, but involve oxidation of aluminum. Unlike nickel and the like, aluminum is difficult to reduce once oxidized. For example, when used as an electrode material for a battery or the like, it cannot be used because conductivity is lost due to oxidation.
- the present inventors immersed an aluminum structure formed by forming an aluminum layer on the surface of the porous resin molded body in a molten salt, A method for producing an aluminum porous body was completed by heating the aluminum layer to a temperature below the melting point of aluminum while applying a negative potential to thermally decompose and remove the porous resin molded body.
- a lead wire is attached to the aluminum porous body by a process as shown in FIG. It is necessary to fill the aluminum porous body as a current collector with an active material and perform processing such as compression, cutting, etc., but from the aluminum porous body to a non-aqueous electrolyte battery, a capacitor using a non-aqueous electrolyte, a lithium ion capacitor, etc.
- the practical technology for industrially manufacturing the electrode is not yet known.
- the present invention is to provide a practical technology for industrially producing an electrode from an aluminum porous body, an electrode using a three-dimensional network aluminum porous body, a non-aqueous electrolyte battery using the electrode, a capacitor, An object is to provide a lithium ion capacitor.
- the configuration of the present invention is as follows.
- the cell of the three-dimensional network aluminum porous body has an elliptical shape with a short axis in the thickness direction of the electrode in a cross section parallel to the width direction and the thickness direction of the electrode.
- the ratio of the number of cross sections of the aluminum skeleton in region 1 to the number of cross sections of the aluminum skeleton in region 2 is 0.8 or more and 1.2 or less, Any of (1) to (4) above, wherein the ratio of the number of cross sections of the aluminum solid angle in the region 3 to the number of cross sections of the aluminum skeleton in the region 2 is 0.8 or more and 1.2 or less An electrode according to the above.
- the outermost surface of the three-dimensional network aluminum porous body is covered with an active material, and the three-dimensional network aluminum porous body is not exposed from the active material.
- the electrode in any one. (9) The electrode according to any one of (1) to (7) above, wherein no active material is present from the outermost surface of the three-dimensional network aluminum porous body to a depth of 0.02 mm. (10) A nonaqueous electrolyte battery using the electrode according to any one of (1) to (9) above. (11) A capacitor using a non-aqueous electrolyte, wherein the electrode according to any one of (1) to (9) is used. (12) A lithium ion capacitor using a non-aqueous electrolyte, wherein the electrode according to any one of (1) to (9) is used.
- the electrode according to the present invention can be manufactured by a continuous production process, and industrial production costs can be reduced.
- the electrode of the present invention can be used for a nonaqueous electrolyte battery, a capacitor using a nonaqueous electrolyte, a lithium ion capacitor, etc., and can improve the output characteristics of such a battery, capacitor, lithium ion capacitor, Or a long life.
- FIG. 1 shows the process for manufacturing an electrode material from an aluminum porous body.
- the electrode according to the present invention can obtain various effects by using a sheet-like three-dimensional network aluminum porous body as an electrode substrate.
- the electrode of the present invention preferably has the following configuration. [1] Make the cell shape into a specific state in the cross section in the thickness direction of the electrode. [2] The distribution of the amount of aluminum forming the skeleton is set to a specific state in the thickness direction of the electrode. [3] Making the state of filling the active material into the aluminum porous body a specific state. Each configuration will be specifically described below.
- ⁇ 1-1> A mode in which the shape of the cell in the cross section in the thickness direction of the electrode is an ellipse having a short axis in the thickness direction.
- ⁇ 1-2> A mode in which the shape of the cell in the cross section in the thickness direction of the electrode is an ellipse having a short axis in the width direction.
- ⁇ 1-3> The cell shape of the cross section in the thickness direction of the electrode is made circular.
- the cells of the three-dimensional network aluminum porous body are elliptical with a short axis in the thickness direction of the electrode in a cross section parallel to the longitudinal direction and the thickness direction of the sheet-like electrode, and It is preferable that the cells of the three-dimensional reticulated aluminum porous body have an elliptical shape with a short axis in the thickness direction of the electrode in a cross section parallel to the width direction and the thickness direction of the electrode.
- the electrode according to the present invention is preferably obtained by subjecting a three-dimensional reticulated aluminum porous body to at least a current collecting lead welding step, an active material filling step, and a compression step.
- the shape of the cell of the three-dimensional reticulated aluminum porous body as a substrate is in a cross section parallel to the thickness direction of the sheet-like electrode. It is also preferable that it is an ellipse having a short axis in the width direction of the electrode.
- the electrode of the present invention it is preferable that the shape of the cell of the three-dimensional reticulated aluminum porous body, which is the base material, is circular in the cross section parallel to the thickness direction of the sheet-like electrode. Accordingly, since the distance between the active material and the base material skeleton is not varied, the current collection distance is uniform, the current distribution is small, and the electrode can provide a battery, a capacitor, a lithium ion capacitor, or the like having a long life.
- the electrode is produced without being compressed.
- ⁇ 2-1> A mode in which the number of cross sections of the aluminum skeleton is made uniform in the aluminum direction so as not to have a distribution in the cross section in the thickness direction of the electrode.
- ⁇ 2-2> As shown in FIG. 2, in the cross section in the thickness direction of the electrode, the number of cross sections of the aluminum skeleton on the outer surface portion (front surface and back surface) is increased, and the aluminum skeleton of the inner portion (center portion) is increased. A mode in which the number of cross sections is reduced.
- ⁇ 2-3> As shown in FIG.
- the number of aluminum skeletons in region 1 is larger than the number of aluminum skeleton cross sections in region 2.
- the ratio of the number of cross sections is 0.8 or more and 1.2 or less, and the ratio of the number of cross sections of the aluminum skeleton in region 3 to the number of cross sections of the aluminum skeleton in region 2 is 0.8 or more and 1.2 or less.
- the ratio of the number of aluminum skeleton cross sections in region 1 to the number of aluminum skeleton cross sections in region 2 is 0.9 or more and 1.1 or less, and the aluminum skeleton in region 3 with respect to the number of aluminum skeleton cross sections in region 2 It is more preferable that the ratio of the number of cross-sections is 0.9 or more and 1.1 or less.
- the number of cross sections of the aluminum skeleton in each region of the cross section in the thickness direction of the electrode can be measured as follows. First, the electrode is polished to obtain a cross section, and the cross section is observed with a microscope to take a photograph. Subsequently, the photograph is divided into three in the thickness direction of the electrodes, and are defined as region 1, region 2, and region 3, respectively. Then, the total number of aluminum skeleton cross sections (that is, the number of metal portions of the porous skeleton) included in each region in the photograph is calculated. This measurement is performed five times in different cross sections, and the average value is calculated. Note that the measurement method can be similarly applied to an aluminum porous body. In that case, a resin is filled in the opening of the aluminum porous body, and when the resin is solidified, a cross-section may be obtained by polishing. . Examples of the resin to be filled include an epoxy resin, an acrylic resin, and a polyester resin.
- the cross section in the thickness direction of the aluminum porous body is divided into region 1, region 2, and region 3 in this order as a base material
- the cross section of the aluminum skeleton in region 2 The ratio of the number of aluminum skeleton cross sections in region 1 to the number of aluminum skeletons is 0.8 or more and 1.2 or less, and the ratio of the number of aluminum skeleton cross sections in region 3 to the number of aluminum skeleton cross sections in region 2
- a porous aluminum body having a thickness of 0.8 or more and 1.2 or less may be used.
- a general urethane resin molded body used as a starting material for the electrode metal porous body may be used in the aluminum porous body manufacturing process described later.
- the region where the active material and the skeleton are in contact with each other increases in the portion where the number of skeletons is large. That is, in a portion where the number of skeletons is large, the active material is difficult to fall off, and the active material retention performance is high. Therefore, as the electrode substrate of the present invention, in the cross section in the thickness direction, the number of cross sections of the aluminum skeleton on the outer surface portion (front surface and back surface) is large, and the number of cross sections of the aluminum skeleton on the inner portion (center portion) is large. If a small amount of porous aluminum is used, the active material can be prevented from falling off, and the active material retention performance can be improved.
- the electrode of the present invention when the cross section in the thickness direction of the electrode is divided into region 1, region 2, and region 3 in this order, region 1 and region 3 with respect to the number of cross sections of the aluminum skeleton in region 2
- the average ratio of the number of cross sections of the aluminum skeleton in is preferably greater than 1.2, and more preferably greater than 1.5.
- the ratio of the average number of cross sections of the aluminum skeleton in the regions 1 and 3 to the number of cross sections of the aluminum skeleton in the region 2 is 1.2 or less, the above active material retention performance is sufficiently exhibited. It becomes difficult to be done.
- the ratio of the number of cross sections of the aluminum skeleton can be obtained from this ratio by measuring the number of cross sections of the aluminum skeleton in each region in the same manner as the number of cross sections of the aluminum skeleton in each region described above. That is, the average of the number of cross sections of the aluminum skeleton in region 1 and the number of cross sections of the aluminum skeleton in region 3 may be calculated and divided by the number of cross sections of the aluminum skeleton in region 2.
- the cross section in the thickness direction of the aluminum porous body is divided into region 1, region 2, and region 3 in this order as a base material
- the cross section of the aluminum skeleton in region 2 An aluminum porous body in which the average ratio of the number of cross sections of the aluminum skeleton in the region 1 and the region 3 to the number of regions is larger than 1.2 may be used.
- Such an aluminum porous body can be obtained, for example, by stacking and integrating aluminum porous bodies having different numbers of cross sections of the aluminum skeleton in the cross section in the thickness direction.
- a three-dimensional reticulated aluminum porous body in which three aluminum porous bodies A, B, and C are laminated and integrated in this order in the thickness direction as a base material.
- the ratio of the average number of cross sections of the aluminum skeleton in the cross section in the thickness direction of the porous aluminum bodies A and C to the number of cross sections of the aluminum skeleton in the cross section in the thickness direction of the aluminum porous body B is greater than 1.2 It is also effective to use a three-dimensional network aluminum porous body.
- an aluminum porous body having a large number of aluminum skeleton cross sections in a thickness direction cross section, and an aluminum porous body having a small number of aluminum skeleton cross sections in a thickness direction cross section Two types of porous aluminum are prepared. Then, two aluminum porous bodies A and C having a large number of cross sections of the aluminum skeleton in the cross section in the thickness direction are stacked so as to sandwich the aluminum porous body B having a small number of cross sections of the skeleton, and these are integrated.
- the number of cross sections of the aluminum skeleton in the thickness direction of the outer surface layer portion (front and back surfaces) is large, and conversely, the number of cross sections of the aluminum skeleton in the thickness direction of the inner portion (center layer portion) is small.
- a reticulated aluminum porous body can be produced.
- the thickness of the three-dimensional network aluminum porous body can be made thicker than before.
- the average ratio of the number of aluminum skeleton cross sections in the cross section in the thickness direction of the aluminum porous bodies A and C to the number of aluminum skeleton cross sections in the cross section in the thickness direction of the porous aluminum body B is from 1.2.
- the ratio is more preferably larger than 1.5.
- An example of a method for integrating the laminated aluminum porous bodies A to C includes a method of compressing them in layers. Among them, a method in which a plurality of roll presses are performed and partial welding is performed to make electrical contact is preferable. For example, in a state where pressure is applied to the aluminum porous body sheet, by raising the temperature to near the melting point of aluminum, the contacting skeletons can be fused and integrated.
- the substrate of the electrode of the present invention in the cross section in the thickness direction, the number of cross sections of the aluminum skeleton on the outer surface portion (front surface and back surface) is small, and the number of cross sections of the aluminum skeleton on the inner portion (center portion) is small. If many aluminum porous bodies are used, the current collecting property inside the electrode can be enhanced, and the active material inside can be used 100%.
- the electrode of the present invention when the cross section in the thickness direction of the electrode is divided into region 1, region 2, and region 3 in this order, region 1 and region 3 with respect to the number of cross sections of the aluminum skeleton in region 2
- the average ratio of the number of cross sections of the aluminum skeleton is preferably less than 0.8, more preferably less than 0.7.
- the ratio of the average number of cross sections of the aluminum skeleton of the regions 1 and 3 to the number of cross sections of the aluminum skeleton of the region 2 is 0.8 or more, the improvement of the current collecting property inside the electrode as described above It becomes difficult to fully exhibit the effect.
- the ratio of the number of cross sections of the aluminum skeleton can be obtained from this ratio by measuring the number of cross sections of the aluminum skeleton in each region in the same manner as the number of cross sections of the aluminum skeleton in each region described above. That is, the average of the number of cross sections of the aluminum skeleton in region 1 and the number of cross sections of the aluminum skeleton in region 3 may be calculated and divided by the number of cross sections of the aluminum skeleton in region 2.
- the cross section in the thickness direction of the aluminum porous body is divided into region 1, region 2, and region 3 in this order as a base material
- the cross section of the aluminum skeleton in region 2 A porous aluminum body in which the average ratio of the number of cross-sections of the aluminum skeleton in the region 1 and the region 3 to the number of regions is smaller than 0.8 may be used.
- Such an aluminum porous body can be obtained, for example, by stacking and integrating aluminum porous bodies having different numbers of cross sections of the aluminum skeleton in the cross section in the thickness direction.
- three aluminum porous bodies D, E, and F are three-dimensional reticulated aluminum porous bodies formed by laminating and integrating in this order in the thickness direction.
- the ratio of the average number of cross sections of the aluminum skeleton in the cross section in the thickness direction of the porous aluminum bodies D and F to the number of cross sections of the aluminum skeleton in the cross section in the thickness direction of the aluminum porous body E is less than 0.8. It is also effective to use a three-dimensional network aluminum porous body.
- an aluminum porous body having a large number of aluminum skeleton cross sections in a thickness direction cross section, and an aluminum porous body having a small number of aluminum skeleton cross sections in a thickness direction cross section Two types of porous aluminum are prepared. Then, two aluminum porous bodies D and F having a small number of cross sections of the aluminum skeleton in the cross section in the thickness direction are laminated so as to sandwich the aluminum porous body E having a large number of skeleton cross sections, and these are integrated.
- the number of cross sections of the aluminum skeleton in the thickness direction of the outer surface layer portion (front and back surfaces) is small, and conversely, the number of cross sections of the aluminum skeleton in the thickness direction of the inner portion (center layer portion) is large.
- An original reticulated aluminum porous body can be produced.
- the thickness of the three-dimensional network aluminum porous body can be made thicker than before.
- the average ratio of the number of aluminum skeleton cross sections in the cross section in the thickness direction of the aluminum porous bodies D and F to the number of cross sections of the aluminum skeleton in the cross section in the thickness direction of the porous aluminum body E is from 0.8.
- the active material retention performance can be improved as described above.
- the ratio is more preferably smaller than 0.7.
- An example of a method for integrating the laminated aluminum porous bodies D to F includes a method of compressing them in layers. Among them, a method in which a plurality of roll presses are performed and partial welding is performed to make electrical contact is preferable. For example, in a state where pressure is applied to the aluminum porous body sheet, by raising the temperature to near the melting point of aluminum, the contacting skeletons can be fused and integrated.
- an active material is filled (shown as a slurry filling step D in FIG. 1). And it becomes an electrode through the drying process and the compression process, but if the skeleton part of the aluminum porous body that is the current collector is exposed from the surface of the electrode after completion, a short circuit and current concentration are likely to occur, and the life is shortened. The problem of becoming may occur. Moreover, in order to avoid these, the separator needs to be thickened.
- the outermost surface of the three-dimensional network aluminum porous body serving as the base material is covered with the active material, and the skeleton of the three-dimensional network aluminum porous body is exposed from the active material. Preferably not. Thereby, a short circuit and current concentration do not occur, and a long-life electrode can be provided. Further, since the separator can be made thin, the battery, the capacitor, and the lithium ion capacitor can be made compact.
- the outermost surface of the porous aluminum body means a surface formed by connecting the respective topmost portions of the skeleton of the outermost portion of the porous aluminum body as shown in FIG. Since FIG. 5 is a conceptual diagram, the outermost surface of the aluminum porous body is displayed only in the upper part of the drawing, but in the actual sheet-like aluminum porous body, each surface is considered in the same manner.
- an active material is filled (shown as a slurry filling step D in FIG. 1), and then an electrode is obtained through a drying step and a compression step. .
- the capacity of the binder filled together with the active material is not sufficient, the active material tends to drop off from the electrode surface after completion of the electrode, and a micro short circuit is likely to occur.
- the electrode of the present invention preferably has no active material from the outermost surface of the three-dimensional network aluminum porous body serving as a base material to a depth of 0.02 mm.
- an electrode can be provided in which the active material is sufficiently held inside the electrode, does not fall off from the electrode surface, and does not cause a micro short circuit.
- the outermost surface of the aluminum porous body refers to a surface formed by connecting the respective topmost portions of the skeleton of the outermost portion of the aluminum porous body. Since FIG. 6 is a conceptual diagram, the outermost surface of the porous aluminum body is displayed only in the upper part in the figure, and the other parts are covered with the active material, but the actual sheet-like porous aluminum body In, we consider the same for each aspect. In order to produce such an electrode of the present invention, for example, a method of scraping the active material from the electrode surface with a brush after the compression step of FIG. 1F can be mentioned.
- FIG. 7 is a flowchart showing the manufacturing process of the aluminum structure.
- FIG. 8 schematically shows a state in which an aluminum plating film is formed using a resin molded body as a core material corresponding to the flowchart. The flow of the entire manufacturing process will be described with reference to both drawings.
- preparation 101 of a resin molded body to be a base is performed.
- FIG. 8A is an enlarged schematic view in which the surface of the resin molded body having continuous air holes is enlarged as an example of the resin molded body serving as the base. The pores are formed with the resin molded body 1 as a skeleton.
- the surface 102 of the resin molded body is made conductive. By this step, as shown in FIG.
- a thin conductive layer 2 made of a conductive material is formed on the surface of the resin molded body 1.
- aluminum plating 103 in molten salt is performed to form an aluminum plating layer 3 on the surface of the resin molded body on which the conductive layer is formed (FIG. 8C).
- an aluminum structure in which the aluminum plating layer 3 is formed on the surface using the resin molded body as a base material is obtained.
- removal 104 of the resin molded body is performed for the resin molded body that is the base.
- the aluminum structure (porous body) in which only the metal layer remains can be obtained by dissociating and disappearing the resin molded body 1 (FIG. 8D).
- each step will be described in order.
- a porous resin molded body having a three-dimensional network structure and continuous air holes is prepared.
- Arbitrary resin can be selected as a raw material of a porous resin molding.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a resin molded article having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes). For example, what has a shape like a nonwoven fabric entangled with a fibrous resin can be used instead of the foamed resin molded article.
- the foamed resin molded article preferably has a porosity of 80% to 98% and a pore diameter of 50 ⁇ m to 500 ⁇ m.
- Foamed urethane and foamed melamine can be preferably used as a foamed resin molded article because they have high porosity, have pore connectivity and are excellent in thermal decomposability.
- Urethane foam is preferable in terms of pore uniformity and availability, and urethane foam is preferable in that a material having a small pore diameter can be obtained.
- the porous resin molded body often has residues such as foaming agents and unreacted monomers in the foam production process, and it is preferable to perform a washing treatment for the subsequent steps.
- FIG. 9 shows a product obtained by washing urethane foam as a pretreatment.
- the resin molded body forms a three-dimensional network as a skeleton, thereby forming continuous pores as a whole.
- the urethane skeleton has a substantially triangular shape in a cross section perpendicular to the extending direction.
- the porosity is defined by the following equation.
- Porosity (1 ⁇ (weight of porous material [g] / (volume of porous material [cm 3 ] ⁇ material density))) ⁇ 100 [%]
- the surface of the foamed resin is subjected to a conductive treatment in advance.
- a conductive treatment can provide a conductive layer on the surface of the resin molded body, electroless plating of a conductive metal such as nickel, vapor deposition and sputtering of aluminum, or conductive particles such as carbon.
- coating of the conductive paint containing this, can be selected.
- Formation of aluminum layer molten salt plating
- electrolytic plating is performed in a molten salt to form an aluminum plating layer on the surface of the resin molded body.
- a uniformly thick aluminum layer can be formed on the surface of a complicated skeleton structure, particularly a resin molded body having a three-dimensional network structure.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and aluminum having a purity of 99.0% as an anode.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used, and specifically, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable. Since the molten salt deteriorates when moisture or oxygen is mixed in the molten salt, the plating is preferably performed in an atmosphere of an inert gas such as nitrogen or argon and in a sealed environment.
- an inert gas such as nitrogen or argon
- a molten salt bath containing nitrogen is preferable, and among them, an imidazolium salt bath is preferably used.
- an imidazolium salt bath is preferably used.
- a salt that melts at a high temperature is used as the molten salt, the resin is dissolved or decomposed in the molten salt faster than the growth of the plating layer, and the plating layer cannot be formed on the surface of the resin molded body.
- the imidazolium salt bath can be used without affecting the resin even at a relatively low temperature.
- a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- AlCl 3 + EMIC aluminum chloride + 1-ethyl-3-methylimidazolium chloride
- molten salt is stable. Is most preferably used because it is high and difficult to decompose. Plating onto foamed urethane resin or foamed melamine resin is possible, and the temperature of the molten salt bath is 10 ° C to 65 ° C, preferably 25 ° C to 65 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate on the entire porous body surface. At a high temperature exceeding 65 ° C., a problem that the shape of the base resin is impaired tends to occur.
- an organic solvent to the molten salt bath, and 1,10-phenanthroline is particularly preferably used.
- the amount added to the plating bath is preferably 0.2 to 7 g / L. If it is 0.2 g / L or less, it is brittle with plating having poor smoothness, and it is difficult to obtain the effect of reducing the difference in thickness between the surface layer and the inside. On the other hand, if it is 7 g / L or more, the plating efficiency is lowered and it is difficult to obtain a predetermined plating thickness.
- FIG. 10 is a diagram schematically showing a configuration of an apparatus for continuously performing the aluminum plating process on the above-described belt-shaped resin.
- a configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure.
- the first plating tank 21a includes a cylindrical electrode 24, an anode 25 made of aluminum provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, a uniform current can easily flow through the entire resin molded body, and uniform plating can be obtained.
- the plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks.
- Plating is performed by passing the belt-like resin 22 having a conductive surface through a plating bath 28 while sequentially feeding the belt-like resin 22 by an electrode roller 26 that also serves as a feeding roller and an out-of-vessel feeding cathode.
- anodes 27 made of aluminum provided on both surfaces of the resin molded body via a plating bath 28, and uniform plating can be applied to both surfaces of the resin molded body. After sufficiently removing the plating solution from the plated aluminum porous body by nitrogen blowing, the aluminum porous body can be obtained by washing with water.
- an inorganic salt bath can be used as the molten salt as long as the resin is not dissolved.
- the inorganic salt bath is typically a binary or multicomponent salt of AlCl 3 —XCl (X: alkali metal).
- Such an inorganic salt bath generally has a higher melting temperature than an organic salt bath such as an imidazolium salt bath, but is less restricted by environmental conditions such as moisture and oxygen, and can be put into practical use at a low cost overall.
- the resin is a foamed melamine resin, it can be used at a higher temperature than the foamed urethane resin, and an inorganic salt bath at 60 ° C. to 150 ° C. is used.
- an aluminum structure having a resin molded body as a skeleton core is obtained.
- the resin and metal composite may be used as they are, but the resin is removed when used as a porous metal body without resin due to restrictions on the use environment.
- the resin is removed by decomposition in a molten salt described below so that oxidation of aluminum does not occur.
- Decomposition in the molten salt is carried out by the following method.
- a porous resin molded body with an aluminum plating layer formed on the surface is immersed in molten salt and heated while applying a negative potential (potential lower than the standard electrode potential of aluminum) to the aluminum layer to remove the porous resin molded body.
- a negative potential potential lower than the standard electrode potential of aluminum
- the porous resin molded body can be decomposed without oxidizing aluminum.
- the heating temperature can be appropriately selected according to the type of the porous resin molded body.
- the temperature of the molten salt bath needs to be 380 ° C. or higher.
- the melting point of the aluminum 660 ° C. or lower is required. It is necessary to process at temperature.
- a preferable temperature range is 500 ° C. or more and 600 ° C. or less.
- the amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of the cation in the molten salt.
- an alkali metal or alkaline earth metal halide salt in which the electrode potential of aluminum is low can be used.
- FIG. 1 is a diagram for explaining an example of a process for continuously producing an electrode from an aluminum porous body.
- the process includes a porous sheet unwinding step A for unwinding the porous sheet from the unwinding roller 41, a thickness adjusting step B using the compression roller 42, and a lead using the compression / welding roller 43 and the lead welding roller 49.
- a winding process H using a winding roller 48.
- the porous aluminum sheet is unwound from the raw roll on which the porous aluminum sheet is wound, and the thickness is adjusted to an optimum thickness by a roller press in the thickness adjusting step, and the surface is flattened.
- the final thickness of the porous aluminum body is appropriately determined depending on the application of the electrode, but this thickness adjusting step is a compression step before the final thickness, and the thickness is easy to process the next step. Compress to a certain extent.
- a flat plate press or a roller press is used as the pressing machine.
- a flat plate press is preferable for suppressing the elongation of the current collector, but is not suitable for mass production, and therefore, it is preferable to use a roller press capable of continuous processing.
- FIG. 11 schematically shows the compression process.
- a rotating roller can be used as the compression jig.
- a predetermined mechanical strength can be obtained by setting the thickness of the compression portion to 0.05 mm or more and 0.2 mm or less (for example, about 0.1 mm).
- the compression portion 33 is formed by compressing the central portion of the aluminum porous body 34 having a width of two sheets by a rotating roller 35 using a compression jig. After compression, the central portion of the compression portion 33 is cut to obtain two electrode current collectors having the compression portion at the end.
- a plurality of band-like compression portions are formed in the central portion of the porous aluminum body using a plurality of rotating rollers, and each of the band-like compression portions is cut along the center line to thereby collect a plurality of collections. An electric body can be obtained.
- a tab lead is joined to the end compression part of the current collector obtained as described above.
- the tab lead it is preferable to use a metal foil to reduce the electric resistance of the electrode and to bond the metal foil to the surface on at least one side of the peripheral edge of the electrode.
- welding it is preferable to use welding as a joining method. If the width of the metal foil to be welded is too large, useless space increases in the battery and the capacity density of the battery decreases, so that it is preferably 10 mm or less. If it is too thin, welding becomes difficult and the current collecting effect is lowered, so 1 mm or more is preferable.
- a welding method a method such as resistance welding or ultrasonic welding can be used, but ultrasonic welding is preferable because the bonding area is wide.
- metal foil As a material of the metal foil, aluminum is preferable in consideration of electric resistance and resistance to an electrolytic solution. In addition, since impurities are eluted and reacted in the battery, capacitor, and lithium ion capacitor, it is preferable to use an aluminum foil having a purity of 99.99% or more. Moreover, it is preferable that the thickness of a welding part is thinner than the thickness of electrode itself. The thickness of the aluminum foil is preferably 20 to 500 ⁇ m.
- the metal foil may be welded either before or after the current collector is filled with the active material, but the active material can be prevented from falling off before being filled. In particular, in the case of ultrasonic welding, it is preferable to perform welding before filling. Moreover, although activated carbon paste may be attached to the welded portion, it may be peeled off during the process, so it is preferable to mask it so that it cannot be filled.
- the compression process of the end portion and the tab lead bonding process are described as separate processes, but the compression process and the bonding process may be performed simultaneously.
- the compression roller a roller part that can be resistance-welded with the roller part that contacts the tab lead joining end of the aluminum porous sheet is used, and the aluminum porous sheet and the metal foil are simultaneously supplied to this roller. The compression and the welding of the metal foil to the compressed portion can be performed simultaneously.
- An electrode is obtained by filling the current collector obtained as described above with an active material.
- the active material is appropriately selected according to the purpose for which the electrode is used.
- a known method such as a dip filling method or a coating method can be used for filling the active material.
- Coating methods include, for example, roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor blade Examples thereof include a coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- FIG. 13 shows a method of filling a porous material with slurry by a roll coating method. As shown in the figure, slurry is supplied onto the porous sheet, and this is passed through a pair of rotating rolls facing each other with a predetermined gap. The slurry is pressed and filled into the porous body when passing through the rotating roll.
- the porous material filled with the active material is carried into a dryer, and the organic solvent is evaporated and removed by heating to obtain an electrode material in which the active material is fixed in the pores of the porous material.
- compression process The electrode material after drying is compressed to a final thickness in a compression process.
- a flat plate press or a roller press is used as the pressing machine.
- a flat plate press is preferable for suppressing the elongation of the current collector, but is not suitable for mass production, and therefore, it is preferable to use a roller press capable of continuous processing.
- the compression process F of FIG. 1 the case where it compresses with a roller press was shown.
- the width of the porous aluminum sheet is set to the width of a plurality of final products, and this is cut by a plurality of blades along the sheet traveling direction. It is preferable to use a long sheet-like electrode material.
- This cutting step is a step of dividing the long electrode material into a plurality of long electrode materials.
- This step is a step of winding a plurality of long sheet-like electrode materials obtained in the cutting step onto a take-up roller.
- Electrodes for non-aqueous electrolyte batteries such as lithium batteries and molten salt batteries
- capacitor electrodes using non-aqueous electrolytes such as lithium batteries and molten salt batteries
- non-aqueous electrolytes such as lithium ion capacitors
- lithium ion capacitors There are lithium ion capacitors. Below, these uses are described.
- Lithium battery Next, a battery electrode material and a battery using an aluminum porous body will be described.
- a positive electrode of a lithium battery including a lithium ion secondary battery
- an active material lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium nickelate (LiNiO 2 ) Etc.
- the active material is used in combination with a conductive additive and a binder.
- a conventional positive electrode material for a lithium battery an electrode in which an active material is applied to the surface of an aluminum foil is used.
- Lithium batteries have a higher capacity than nickel metal hydride batteries and capacitors, but there is a need for higher capacities in applications such as automobiles.
- the active material coating thickness must be increased.
- the aluminum foil as the current collector and the active material are in electrical contact with each other. It is used.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, since the contact area between the current collector and the active material is increased, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive additive can be reduced.
- the positive electrode material described above is used as a positive electrode, and a copper or nickel foil, a punching metal, a porous body, or the like is used as a current collector for the negative electrode.
- Graphite, lithium titanate (Li 4 Ti 5 O 12 ), Sn An alloy system such as Si or Si, or a negative electrode active material such as lithium metal is used.
- a negative electrode active material is also used in combination with a conductive additive and a binder. Since such a lithium battery can improve capacity even with a small electrode area, the energy density of the battery can be made higher than that of a lithium battery using a conventional aluminum foil.
- the effect on the secondary battery has been mainly described above. However, the effect of increasing the contact area when the porous aluminum body is filled with the active material is the same as that of the secondary battery in the primary battery. Can be improved.
- the electrolyte used for the lithium battery includes a non-aqueous electrolyte and a solid electrolyte.
- FIG. 14 is a longitudinal sectional view of an all-solid lithium battery using a solid electrolyte.
- the all solid lithium battery 60 includes a positive electrode 61, a negative electrode 62, and a solid electrolyte layer (SE layer) 63 disposed between both electrodes.
- the positive electrode 61 includes a positive electrode layer (positive electrode body) 64 and a positive electrode current collector 65
- the negative electrode 62 includes a negative electrode layer 66 and a negative electrode current collector 67.
- a non-aqueous electrolyte described later is used as the electrolyte.
- a separator a porous polymer film, a nonwoven fabric, paper, or the like
- the non-aqueous electrolyte is impregnated in both electrodes and the separator.
- an aluminum porous body When an aluminum porous body is used for a positive electrode of a lithium battery, a material capable of removing and inserting lithium can be used as an active material, and it is suitable for a lithium secondary battery by filling such an aluminum porous body. An electrode can be obtained.
- the material for the positive electrode active material include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium nickel cobaltate (LiCo 0.3 Ni 0.7 O 2 ), lithium manganate (LiMn 2 O 4 ), and titanate.
- the active material is used in combination with a conductive additive and a binder.
- transition metal oxides such as olivine compounds which are conventional lithium iron phosphate and its compounds (LiFePO 4 , LiFe 0.5 Mn 0.5 PO 4 ). Further, the transition metal element contained in these materials may be partially substituted with another transition metal element.
- Still other positive electrode active materials include, for example, TiS 2 , V 2 S 3 , FeS, FeS 2 , LiMSx (M is a transition metal element such as Mo, Ti, Cu, Ni, Fe, or Sb, Sn, Pb) ) And the like, and lithium metal having a skeleton of a metal oxide such as TiO 2 , Cr 3 O 8 , V 2 O 5 , and MnO 2 .
- the lithium titanate obtained by the ((Li 4 Ti 5 O 12 ) it is also possible to use as a negative electrode active material.
- Non-aqueous electrolyte a polar aprotic organic solvent is used, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and the like are used.
- the supporting salt lithium tetrafluoroborate, lithium hexafluorophosphate, and an imide salt are used.
- concentration of the supporting salt serving as an electrolyte is high, a concentration around 1 mol / L is generally used because there is a limit to dissolution.
- Solid electrolyte filled in aluminum porous body In addition to the active material, a solid electrolyte may be added and filled.
- a solid electrolyte By filling an aluminum porous body with an active material and a solid electrolyte, it can be made suitable for an electrode of an all-solid-state lithium battery.
- the proportion of the active material in the material filled in the aluminum porous body is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of securing the discharge capacity.
- a sulfide-based solid electrolyte having high lithium ion conductivity is preferably used.
- a sulfide-based solid electrolyte having high lithium ion conductivity examples include a sulfide-based solid electrolyte containing lithium, phosphorus, and sulfur. It is done.
- the sulfide solid electrolyte may further contain an element such as O, Al, B, Si, and Ge.
- Such a sulfide-based solid electrolyte can be obtained by a known method.
- lithium sulfide (Li2S) and diphosphorus pentasulfide (P 2 S 5 ) are prepared as starting materials, and Li 2 S and P 2 S 5 are mixed in a molar ratio of about 50:50 to 80:20.
- a method of melting and quenching this (melting and quenching method) and a method of mechanically milling this (nokanal milling method) can be mentioned.
- the sulfide-based solid electrolyte obtained by the above method is amorphous. Although it can be used in this amorphous state, it may be heat-treated to obtain a crystalline sulfide solid electrolyte. Crystallization can be expected to improve lithium ion conductivity.
- the active material for filling the active material (the active material and the solid electrolyte)
- a known method such as an immersion filling method or a coating method
- the coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive or binder is added, and an organic solvent or water is mixed therewith to produce a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT)
- AB acetylene black
- KB ketjen black
- CNT carbon nanotube
- polyfluoride can be used as the binder, for example.
- Vinylidene (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- the conventional positive electrode material for lithium batteries has apply
- the coating thickness of the active material is increased, and in order to effectively use the active material, the aluminum foil and the active material must be in electrical contact. For this reason, the active material is used in combination with a conductive aid.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, since the contact area between the current collector and the active material is increased, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive additive can be reduced.
- FIG. 15 is a schematic cross-sectional view showing an example of a capacitor using a capacitor electrode material.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the polarizable electrode 141 is connected to the lead wire 144 and is entirely housed in the case 145.
- the aluminum porous body as a current collector, the surface area of the current collector is increased and the contact area with the activated carbon as the active material is increased, so that a capacitor capable of high output and high capacity can be obtained.
- activated carbon is filled as an active material in an aluminum porous body current collector.
- Activated carbon is used in combination with a conductive additive or binder.
- the activated carbon is preferably 90% or more in terms of the composition ratio after drying (after removal of the solvent).
- a conductive auxiliary agent and a binder are necessary, it is a factor of a capacity
- the conductive auxiliary agent is preferably 10% by mass or less, and the binder is preferably 10% by mass or less.
- Activated carbon has a specific surface area of preferably 1000 m 2 / g or more because the capacitor has a larger surface area as the surface area becomes larger.
- Activated carbon can use plant-derived coconut shells, petroleum-based materials, and the like. In order to improve the surface area of the activated carbon, it is preferable to perform activation treatment using water vapor or alkali.
- An activated carbon paste can be obtained by mixing and stirring the electrode material mainly composed of activated carbon.
- the activated carbon paste is filled in the current collector, dried, and compressed by a roller press or the like as necessary, thereby improving the density and obtaining a capacitor electrode.
- the activated carbon can be filled using a known method such as a dip filling method or a coating method.
- a coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive or a binder is added as necessary, and an organic solvent or water is mixed therewith to prepare a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT)
- AB acetylene black
- KB ketjen black
- CNT carbon nanotube
- polyfluoride can be used as the binder, for example.
- Vinylidene (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- Capacitor production Two of the electrodes obtained as described above are punched out to a suitable size, and are opposed to each other with a separator interposed therebetween.
- the separator it is preferable to use a porous film or non-woven fabric made of cellulose, polyolefin resin, or the like. And it accommodates in a cell case using a required spacer, and impregnates electrolyte solution.
- the electric double layer capacitor can be manufactured by sealing the case with an insulating gasket.
- a non-aqueous material it is preferable to sufficiently dry materials such as electrodes in order to reduce the moisture in the capacitor as much as possible.
- the capacitor may be manufactured in an environment with little moisture, and the sealing may be performed in a reduced pressure environment.
- the capacitor is not particularly limited as long as the current collector and electrode of the present invention are used, and the capacitor may be manufactured by other methods.
- Electrolyte can be used for both aqueous and non-aqueous, but non-aqueous is preferable because the voltage can be set higher.
- potassium hydroxide or the like can be used as an electrolyte.
- non-aqueous systems there are many ionic liquids in combination of cations and anions.
- cation lower aliphatic quaternary ammonium, lower aliphatic quaternary phosphonium, imidazolinium and the like are used, and as the anion, imide compounds such as metal chloride ion, metal fluoride ion, and bis (fluorosulfonyl) imide Etc. are known.
- polar aprotic organic solvents there are polar aprotic organic solvents, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and the like are used.
- the supporting salt in the non-aqueous electrolyte lithium tetrafluoroborate, lithium hexafluorophosphate, or the like is used.
- FIG. 16 is a schematic cross-sectional view showing an example of a lithium ion capacitor using a lithium ion capacitor electrode material.
- an electrode material having a positive electrode active material supported on an aluminum porous body is disposed as a positive electrode 146
- an electrode material having a negative electrode active material supported on a current collector is disposed as a negative electrode 147.
- the positive electrode 146 and the negative electrode 147 are connected to lead wires 148 and 149, respectively, and are entirely housed in the case 145.
- the aluminum porous body as a current collector, the surface area of the current collector is increased, and a lithium ion capacitor capable of increasing the output and capacity can be obtained even when activated carbon as an active material is thinly applied.
- activated carbon is filled as an active material in an aluminum porous body current collector.
- Activated carbon is used in combination with a conductive additive or binder.
- the activated carbon is preferably 90% or more in terms of the composition ratio after drying (after solvent removal).
- a conductive auxiliary agent and a binder are necessary, it is a factor of a capacity
- the conductive auxiliary agent is preferably 10% by mass or less, and the binder is preferably 10% by mass or less.
- the specific surface area is preferably 1000 m 2 / g or more.
- Activated carbon can use plant-derived coconut shells, petroleum-based materials, and the like. In order to improve the surface area of the activated carbon, it is preferable to perform activation treatment using water vapor or alkali.
- ketjen black, acetylene black, carbon fiber, or a composite material thereof can be used as the conductive auxiliary.
- the binder polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, or the like can be used.
- water or an organic solvent may be appropriately selected depending on the kind of the binder.
- organic solvents N-methyl-2-pyrrolidone is often used.
- surfactant when using water for a solvent, you may use surfactant in order to improve a filling property.
- An activated carbon paste can be obtained by mixing and stirring the electrode material mainly composed of activated carbon.
- the activated carbon paste is filled in the current collector, dried, and compressed by a roller press or the like as necessary, thereby improving the density and obtaining an electrode for a lithium ion capacitor.
- the activated carbon can be filled using a known method such as a dip filling method or a coating method.
- a coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive or a binder is added as necessary, and an organic solvent or water is mixed therewith to prepare a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT)
- AB acetylene black
- KB ketjen black
- CNT carbon nanotube
- polyfluoride can be used as the binder, for example.
- Vinylidene (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- the negative electrode is not particularly limited, and a conventional negative electrode for a lithium battery can be used.
- the conventional electrode using a copper foil as a current collector has a small capacity, it is made of copper or nickel such as the aforementioned foamed nickel.
- An electrode in which a porous material is filled with an active material is preferable.
- the negative electrode is doped with lithium ions in advance. A known method can be used as the doping method.
- the remaining capacity of the negative electrode is smaller than the positive electrode capacity, the capacity of the lithium ion capacitor is reduced, so the positive electrode capacity is not doped. It is preferable to leave it in
- Electrolytic solution used for lithium ion capacitors The same electrolyte as the nonaqueous electrolyte used for the lithium battery is used.
- a polar aprotic organic solvent is used, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and the like are used.
- the supporting salt lithium tetrafluoroborate, lithium hexafluorophosphate, and an imide salt are used.
- the electrode obtained as described above is punched out to an appropriate size, and is opposed to the negative electrode with a separator interposed therebetween.
- the negative electrode may be doped with lithium ions by the above-described method, and when a method of doping after assembling the cell is taken, an electrode connected with lithium metal may be arranged in the cell.
- the separator it is preferable to use a porous film or non-woven fabric made of cellulose, polyolefin resin, or the like. And it accommodates in a cell case using a required spacer, and impregnates electrolyte solution. Finally, the case is covered and sealed with an insulating gasket, so that a lithium ion capacitor can be produced.
- the material such as the electrode is sufficiently dried.
- the lithium ion capacitor may be manufactured in an environment with little moisture, and the sealing may be performed in a reduced pressure environment. Note that the lithium ion capacitor is not particularly limited as long as the current collector and the electrode of the present invention are used, and may be manufactured by a method other than this.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating cations of molten salt as an electrolyte such as sodium chromite (NaCrO 2 ) and titanium disulfide (TiS 2 ) as an active material Is used.
- the active material is used in combination with a conductive additive and a binder.
- a conductive assistant acetylene black or the like can be used.
- PTFE polytetrafluoroethylene
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to alloy sodium with other metals (Si, Sn, In, etc.). Of these, an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal (such as Si) that is alloyed with sodium is attached to the aluminum porous body by a method such as plating, a sodium alloy can be obtained by charging in a molten salt battery.
- FIG. 17 is a schematic cross-sectional view showing an example of a molten salt battery using the battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature can be 90 ° C. or lower.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, a porous resin molding, etc. can be used.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- Example 1 (Formation of conductive layer) As a urethane resin molded body, a urethane foam having a porosity of 95%, the number of pores per 1 inch (number of cells), a pore diameter of about 552 ⁇ m, and a thickness of 1 mm was prepared and cut into a 100 mm ⁇ 30 mm square. . An aluminum film having a basis weight of 10 g / m 2 was formed on the surface of the polyurethane foam by a sputtering method and subjected to a conductive treatment.
- a urethane foam with a conductive layer formed on the surface is set as a work piece in a jig with a power supply function, and then placed in a glove box with an argon atmosphere and low moisture (dew point -30 ° C or less), and melted at a temperature of 40 ° C. It was immersed in a salt aluminum plating bath (33 mol% EMIC-67 mol% AlCl 3 ). The jig on which the workpiece was set was connected to the cathode side of the rectifier, and a counter electrode aluminum plate (purity 99.99%) was connected to the anode side.
- An aluminum structure in which an aluminum plating layer having a weight of 150 g / m 2 was formed on the surface of the urethane foam was obtained by plating by applying a direct current of a current density of 3.6 A / dm 2 for 90 minutes. Stirring was performed with a stirrer using a Teflon (registered trademark) rotor.
- the current density is a value calculated by the apparent area of the urethane foam.
- the aluminum structure was immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and a negative potential of ⁇ 1 V was applied for 30 minutes. Bubbles were generated in the molten salt due to the decomposition reaction of the polyurethane. Then, after cooling to room temperature in the atmosphere, the molten salt was removed by washing with water to obtain a porous aluminum body from which the resin was removed. The obtained aluminum porous body had continuous air holes, and the porosity was as high as the urethane foam used as the core material.
- the obtained aluminum porous body was adjusted to a thickness of 0.96 mm by a roller press and cut into 5 cm square.
- a SUS block bar
- a width of 5 mm as a jig for compression and a hammer
- a compressed portion having a thickness of 100 ⁇ m was formed by compression.
- the tab lead was welded by spot welding under the following conditions.
- lithium cobaltate powder positive electrode active material having an average particle diameter of 5 ⁇ m is prepared, and the lithium cobaltate powder, acetylene black (conductive aid), and PVDF (binder) are 90% by mass. Mixing at a ratio of 5: 5.
- N-methyl-2-pyrrolidone organic solvent
- this positive electrode mixture slurry was filled in an aluminum porous body.
- the positive electrode 1 was obtained by making it dry at 100 degreeC for 40 minute (s), and removing the organic solvent.
- the obtained positive electrode 1 was sectioned by polishing. And when the cross section of the electrode was observed by SEM, it was confirmed that the cell of the aluminum porous body was an ellipse having a short axis in the thickness direction with respect to both the width direction and the longitudinal direction of the electrode.
- Example 2 A positive electrode 2 was obtained in the same manner as in Example 1 except that the electrode was produced while applying tension in Example 1. As a result of observing the cross section of the obtained aluminum porous body in the same manner as in Example 1, it was confirmed that the cells of the aluminum porous body were elliptical with a short axis in the width direction of the electrode.
- Example 3 A positive electrode 3 was obtained in the same manner as in Example 1 except that it was used without being compressed in Example 1. As a result of observing the cross section of the obtained aluminum porous body in the same manner as in Example 1, it was confirmed that the cells of the aluminum porous body were circular.
- Example 4 The urethane resin molded body was the same as Example 1 except that a urethane foam having a porosity of 95%, the number of pores per inch (number of cells), a pore diameter of about 438 ⁇ m, and a thickness of 1 mm was used as a starting material. A positive electrode 4 having a thickness of 1 mm and a basis weight of 140 g / m 2 was obtained.
- the obtained positive electrode 4 was cross-sectioned by polishing. And the cross section of the electrode was observed by SEM, and the photograph was image
- Example 5 As the urethane resin molded body, the same procedure as in Example 1 was performed except that a urethane foam having a porosity of 95%, the number of pores per inch (number of cells), a cell diameter of about 438 ⁇ m, and a thickness of 1 mm was used as a starting material. , the thickness was 1 mm, and the aluminum porous body a having a basis weight of 140 g / m 2, the thickness was 1 mm, basis weight was obtained porous aluminum C of 140 g / m 2.
- Example 1 As a urethane resin molded body, Example 1 is used except that a urethane foam having a porosity of 95%, the number of pores per one inch (number of cells), a cell diameter of about 635 ⁇ m, and a thickness of 1 mm is used as a starting material. Similarly, a porous aluminum body B having a thickness of 1 mm and a basis weight of 140 g / m 2 was obtained. And the aluminum porous body was laminated
- Example 4 In the same manner as in Example 4, the cross section of the obtained positive electrode 5 was observed. As a result, the number of the area 1 was 40, the area 2 was 30, and the area 3 was 42. The average ratio of the number of cross sections of the aluminum skeleton in regions 1 and 3 to the number of cross sections of the aluminum skeleton in region 2 was 1.37.
- Example 6 The urethane resin molded body was the same as in Example 1 except that a urethane foam having a porosity of 95%, the number of pores per 1 inch (number of cells), a cell diameter of about 635 ⁇ m, and a thickness of 1 mm was used as a starting material. , the thickness was 1 mm, and the aluminum porous body D having a basis weight of 140 g / m 2, the thickness was 1 mm, basis weight was obtained porous aluminum F of 140 g / m 2.
- Example 1 As a urethane resin molded body, Example 1 except that a urethane foam having a porosity of 95%, the number of pores per one inch (number of cells), a cell diameter of about 438 ⁇ m, and a thickness of 1 mm is used as a starting material.
- a porous aluminum body E having a thickness of 1 mm and a basis weight of 140 g / m 2 was obtained.
- the aluminum porous body was laminated
- Example 4 In the same manner as in Example 4, the cross section of the obtained positive electrode 6 was observed. As a result, the area 1 was 31, the area 2 was 41, and the area 3 was 32. The average ratio of the number of cross sections of the aluminum skeleton in regions 1 and 3 to the number of cross sections of the aluminum skeleton in region 2 was 1.3.
- Example 7 The urethane resin molded body was the same as in Example 1 except that a urethane foam having a porosity of 95%, the number of pores per inch (number of cells), a pore diameter of about 508 ⁇ m, and a thickness of 1 mm was used as a starting material. Thus, a positive electrode 7 having a thickness of 1 mm and a basis weight of 140 g / m 2 was obtained. In the same manner as in Example 1, the cross section of the obtained positive electrode 7 was observed. As a result, the outermost surface of the aluminum porous body was covered with the active material, and the aluminum porous body skeleton was not exposed from the electrode surface.
- Example 8 As a urethane resin molded body, a urethane foam having a porosity of 95%, the number of pores per one inch (number of cells), a pore diameter of about 508 ⁇ m, and a thickness of 1 mm was used as a starting material. And the electrode was produced like Example 1, and the active material on the electrode surface was finally removed with the brush, and the collector 8 for positive electrodes was obtained. The obtained electrode had a thickness of 1 mm and a basis weight of 140 g / m 2 . In the same manner as in Example 1, the cross section of the obtained positive electrode 8 was observed. As a result, the active material was not present at a depth of 0.02 mm from the outermost surface of the aluminum porous body.
- the electrode of the present invention can be suitably used for non-aqueous electrolyte batteries (such as lithium batteries), non-aqueous electrolyte capacitors, non-aqueous electrolyte lithium ion capacitors, and the like.
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Abstract
Description
この方法によれば、2~20μmの厚さのアルミニウム多孔体が得られるとされているが、気相法によるため大面積での製造は困難であり、基体の厚さや気孔率によっては内部まで均一な層の形成が難しい。またアルミニウム層の形成速度が遅い、設備が高価などにより製造コストが増大するなどの問題点がある。さらに、厚膜を形成する場合には、膜に亀裂が生じたりアルミニウムの脱落が生じたりするおそれがある。
しかしながら、この方法によればアルミニウムと共晶合金を形成する層が出来てしまい、純度の高いアルミニウム層が形成できない。
しかしながら、アルミニウムの電気めっきについては金属表面へのめっきが可能であるのみで、樹脂成形体表面への電気めっき、とりわけ三次元網目構造を有する樹脂成形体の表面に電気めっきする方法は知られていなかった。
樹脂の除去は、有機溶媒、溶融塩、又は超臨界水による分解(溶解)、加熱分解等任意の方法で行うことができる。
ここで、高温での加熱分解等の方法は簡便であるが、アルミニウムの酸化を伴う。アルミニウムはニッケル等と異なり、一旦酸化すると還元処理が困難であるため、たとえば電池等の電極材料として使用する場合には、酸化により導電性が失われることから用いることが出来ない。そこで、本発明者等はアルミニウムの酸化が起こらないようにして樹脂を除去する方法として、多孔質樹脂成形体の表面にアルミニウム層を形成してなるアルミニウム構造体を溶融塩に浸漬した状態で、該アルミニウム層に負電位を印加しながらアルミニウムの融点以下の温度に加熱して多孔質樹脂成形体を熱分解して除去することによってアルミニウム多孔体を製造する方法を完成した。
(1)三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の長手方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であり、かつ、電極の幅方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であることを特徴とする電極。
(2)三次元網状アルミニウム多孔体に、少なくとも、集電リード溶接工程と、活物質充填工程と、圧縮工程と、を施して得られたことを特徴とする上記(1)に記載の電極。
(3)三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の厚さ方向に平行な断面において、三次元網状アルミニウム多孔体のセルが電極の幅方向に短軸の楕円形であることを特徴とする電極。
(4)三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の厚さ方向に平行な断面において、三次元網状アルミニウム多孔体のセルが円形であることを特徴とする電極。
(5)前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1におけるアルミニウム骨格の断面の数の比が0.8以上、1.2以下であり、
領域2におけるアルミニウム骨格の断面の数に対する、領域3におけるアルミニウム固角の断面の数の比が0.8以上、1.2以下であることを特徴とする上記(1)~(4)のいずれかに記載の電極。
(6)前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1と領域3とにおけるアルミニウム骨格の断面の数の平均の比が1.2より大きいことを特徴とする上記(1)~(4)のいずれかに記載の電極。
(7)前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1と領域3とにおけるアルミニウム骨格の断面の数の平均の比が0.8より小さいことを特徴とする上記(1)~(4)のいずれかに記載の電極。
(8)前記三次元網状アルミニウム多孔体の最表面が活物質で覆われていて、三次元網状アルミニウム多孔体が活物質から露出していないことを特徴とする上記(1)~(7)のいずれかに記載の電極。
(9)前記三次元網状アルミニウム多孔体の最表面から、0.02mmの深さまで活物質が存在しないことを特徴とする上記(1)~(7)のいずれかに記載の電極。
(10)上記(1)~(9)のいずれかに記載の電極を用いたことを特徴とする非水電解質電池。
(11)上記(1)~(9)のいずれかに記載の電極を用いたことを特徴とする非水電解液を用いたキャパシタ。
(12)上記(1)~(9)のいずれかに記載の電極を用いたことを特徴とする非水電解液を用いたリチウムイオンキャパシタ。
また、本発明の電極は非水電解質電池、非水電解液を用いたキャパシタ、リチウムイオンキャパシタ等に利用することが可能であり、かかる電池、キャパシタ、リチウムイオンキャパシタの出力特性を向上させたり、長寿命にしたりすることができる。
本発明の電極は、次のような構成を有することが好ましい。
[1]電極の厚さ方向の断面においてセルの形状を特定の状態にすること。
[2]電極の厚さ方向において、骨格を形成するアルミニウムの量の分布を特定の状態にすること。
[3]アルミニウム多孔体への活物質の充填状態を特定の状態にすること。
以下、それぞれの構成について具体的に説明する。
本発明の電極に上記[1]の構成を加える場合に、例えば、次の<1-1>~<1-3>の態様を考えることができる。
<1-1>電極の厚さ方向の断面のセルの形状を、厚さ方向に短軸の楕円形にする態様。
<1-2>電極の厚さ方向の断面のセルの形状を、幅方向に短軸の楕円形にする態様。
<1-3>電極の厚さ方向の断面のセルの形状を、円形にすること。
以下、それぞれの態様について説明する。
電極の出力特性を高めるためには、活物質の利用率を高めることが有効である。活物質の利用率を高める方法としては、例えば、電極の骨格と活物質との距離を短くすることが挙げられる。
この観点から本発明の電極においては、シート状の電極の長手方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であり、かつ、電極の幅方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であることが好ましい。これにより、活物質と基材骨格との距離が短くなるため、集電距離が小さく、高出力な電池、キャパシタ、リチウムイオンキャパシタ等を提供可能な電極となる。
このため、本発明に係る電極は、三次元網状アルミニウム多孔体に、少なくとも、集電リード溶接工程と、活物質充填工程と、圧縮工程と、を施して得られたものであることが好ましい。
上記<1-1>の態様について同様の観点から、本発明の電極においては、シート状の電極の厚さ方向に平行な断面において、基材である三次元網状アルミニウム多孔体のセルの形状が電極の幅方向に短軸の楕円形であることも好ましい。これにより、活物質と基材骨格との距離が短くなるため、集電距離が小さく、高出力な電池、キャパシタ、リチウムイオンキャパシタ等を提供可能な電極となる。
電極の内部において活物質と基材骨格との距離にばらつきがある場合には、活物質の集電距離にばらつきがあるため、電流分布が大きく、短寿命になってしまう。
この観点から本発明の電極においては、シート状の電極の厚さ方向に平行な断面において、基材である三次元網状アルミニウム多孔体のセルの形状が円形であることが好ましい。これにより、活物質と基材骨格との距離にばらつきがなくなるため、集電距離が均一になり電流分布が小さく、長寿命な電池、キャパシタ、リチウムイオンキャパシタ等を提供可能な電極となる。
本発明の電極に上記[2]の構成を加える場合に、例えば、次の<2-1>~<2-3>の態様を考えることができる。
<2-1>電極の厚さ方向の断面において、アルミニウム骨格の断面の数をアルミ方向において均一にして分布を持たせない態様。
<2-2>図2に示すように、電極の厚さ方向の断面において、外側表面部分(表面と裏面)のアルミニウム骨格の断面の数を多くし、内側部分(中心部分)のアルミニウム骨格の断面の数を少なくする態様。
<2-3>図3に示すように、電極の厚さ方向の断面において、内側部分(中心部分)のアルミニウム骨格の断面の数を多くし、外側表面部分(表面と裏面)のアルミニウム骨格の断面の数を少なくする態様。
以下、それぞれの態様について説明する。
アルミニウム多孔体において、厚さ方向の断面におけるアルミニウム骨格断面の数が厚さ方向に均一であると、当該アルミニウム多孔体に電圧を印加した場合、電流が多孔体中に一様に流れる。したがって、このようなアルミニウム多孔体を電極の基材として使用すれば、集電が均一に行われ、長寿命化を実現することができる。
まず、電極を研磨することにより断面出しを行い、当該断面を顕微鏡により観察して写真撮影を行う。続いて当該写真を電極の厚さ方向に3分割し、それぞれ順に、領域1、領域2、領域3と定める。そして、当該写真中のそれぞれの領域に含まれるアルミニウム骨格断面の数(すなわち、多孔体骨格の金属部分の数)の合計を算出する。この測定を、異なる断面において、5回実施し、その平均値を算出する。
なお、当該測定方法は、アルミニウム多孔体についても同様に行うことが可能であり、その場合には、アルミニウム多孔体の開口部分に樹脂を充填し、樹脂が固化したら研磨により断面出を行えばよい。充填する樹脂としては、例えば、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂が挙げられる。
このようなアルミニウム多孔体を作製するには、後述するアルミニウム多孔体の製造工程において、電極用金属多孔体の出発材料として使用される一般的なウレタン樹脂成形体を使用すればよい。
アルミニウム多孔体の開口部に活物質を充填した場合、骨格の本数が多い部分では活物質と骨格とが接触する領域が多くなっている。即ち、骨格の本数が多い部分では、活物質が脱落し難く、活物質の保持性能が高くなっている。したがって、本発明の電極の基材として、厚さ方向の断面において、外側表面部分(表面と裏面)のアルミニウム骨格の断面の数が多く、内側部分(中心部分)のアルミニウム骨格の断面の数が少なくいアルミニウム多孔体を使用すれば、活物質の脱落を防止して、活物質の保持性能を高めることができる。
当該アルミニウム骨格の断面の数の比は、前述の各領域におけるアルミニウム骨格の断面の数と同様に、各領域におけるアルミニウム骨格の断面の数を計測し、この比により求めることができる。すなわち、領域1のアルミニウム骨格の断面の数と領域3のアルミニウム骨格の断面の数との平均を算出し、これを領域2のアルミニウム骨格の断面の数で割ればよい。
このようなアルミニウム多孔体は、例えば、厚さ方向の断面におけるアルミニウム骨格の断面の数が異なるアルミニウム多孔体を積層して一体化することにより得ることができる。
これにより、外側表面層部分(表面と裏面)の厚さ方向におけるアルミニウム骨格の断面の数が多く、逆に内側部分(中心層部分)の厚さ方向におけるアルミニウム骨格の断面の数が少ない三次元網状アルミニウム多孔体を作製することができる。また、複数のアルミニウム多孔体を積層して一体化することにより、三次元網状アルミニウム多孔体の厚さを従来よりも厚くすることが可能となる。
なお、積層させたアルミニウム多孔体A~Cを一体化させる手法としては、重ねて圧縮する方法が挙げられる。なかでも、重ねてロールプレスし、電気的接触を取るために部分的に溶接する方法が好ましい。例えば、アルミニウム多孔体シートに圧力を付加した状態で、アルミニウムの融点付近まで昇温することで、接触している骨格同士が融着して一体化させることができる。
前述のように、アルミニウム多孔体の開口部に活物質を充填した場合、骨格の本数が多い部分では活物質と骨格とが接触する領域が多くなっており、活物質と骨格との距離も短くなっている。このため、骨格の本数が多い部分では、活物質の保持性能が高くなると同時に、集電性が高くなっている。したがって、本発明の電極の基材として、厚さ方向の断面において、外側表面部分(表面と裏面)のアルミニウム骨格の断面の数が少なく、内側部分(中心部分)のアルミニウム骨格の断面の数が多いアルミニウム多孔体を使用すれば、電極内部での集電性を高めることができ、内部の活物質を100%利用することが可能となる。
このようなアルミニウム多孔体は、例えば、厚さ方向の断面におけるアルミニウム骨格の断面の数が異なるアルミニウム多孔体を積層して一体化することにより得ることができる。
これにより、外側表面層部分(表面と裏面)の厚さ方向におけるアルミニウム骨格の断面の数が少なく、逆に、内側部分(中心層部分)の厚さ方向におけるアルミニウム骨格の断面の数が多い三次元網状アルミニウム多孔体を作製することができる。また、複数のアルミニウム多孔体を積層して一体化することにより、三次元網状アルミニウム多孔体の厚さを従来よりも厚くすることが可能となる。
なお、積層させたアルミニウム多孔体D~Fを一体化させる手法としては、重ねて圧縮する方法が挙げられる。なかでも、重ねてロールプレスし、電気的接触を取るために部分的に溶接する方法が好ましい。例えば、アルミニウム多孔体シートに圧力を付加した状態で、アルミニウムの融点付近まで昇温することで、接触している骨格同士が融着して一体化させることができる。
本発明の電極に上記[3]の構成を加える場合に、例えば次の<3-1>、<3-2>の態様を考えることができる。
<3-1>アルミニウム多孔体の最表面を活物質で完全に覆うこと。
<3-2>アルミニウム多孔体の最表面よりも外側に活物質を露出させないこと。
以下、それぞれの態様について説明する。
図1に示すように、アルミニウム多孔体から電極を作製するには、活物質の充填(図1ではDのスラリー充填工程として示す)が行われる。そして、乾燥工程、圧縮工程を経て電極となるが、完成後に電極の表面から集電体であるアルミニウム多孔体の骨格部分が露出していると、微小短絡や電流集中が起こりやすく、寿命が短くなるという問題が発生する場合がある。また、これらを回避するためにセパレータを厚くする必要が生じる。
このような本発明の電極を作製するためには、図1に示すスラリー充填工程において、活物質をアルミニウム多孔体の骨格が埋もれるほど充分に供給することが好ましい。
図1に示すように、アルミニウム多孔体から電極を作製するには、活物質の充填(図1ではDのスラリー充填工程として示す)が行われ、その後、乾燥工程、圧縮工程を経て電極となる。このとき、活物質と一緒に充填したバインダの能力が充分でない場合には、電極完成後に電極表面から活物質が脱落しやすく、微小短絡が生じやすくなってしまう。
このような本発明の電極を作製するためには、例えば図1Fの圧縮工程後にブラシにより電極表面から活物質をかき出す方法が挙げられる。
図7は、アルミニウム構造体の製造工程を示すフロー図である。また図8は、フロー図に対応して樹脂成形体を芯材としてアルミニウムめっき膜を形成する様子を模式的に示したものである。両図を参照して製造工程全体の流れを説明する。まず基体となる樹脂成形体の準備101を行う。図8(a)は、基体となる樹脂成形体の例として、連通気孔を有する樹脂成形体の表面を拡大視した拡大模式図である。樹脂成形体1を骨格として気孔が形成されている。次に樹脂成形体表面の導電化102を行う。この工程により、図8(b)に示すように樹脂成形体1の表面には薄く導電体による導電層2が形成される。
続いて溶融塩中でのアルミニウムめっき103を行い、導電層が形成された樹脂成形体の表面にアルミニウムめっき層3を形成する(図8(c))。これで、樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。基体である樹脂成形体については、樹脂成形体の除去104を行う。
樹脂成形体1を分解等して消失させることにより金属層のみが残ったアルミニウム構造体(多孔体)を得ることができる(図8(d))。以下各工程について順を追って説明する。
三次元網目構造を有し連通気孔を有する多孔質樹脂成形体を準備する。多孔質樹脂成形体の素材は任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。発泡樹脂成形体と表記したが、連続した気孔(連通気孔)を有するものであれば任意の形状の樹脂成形体を選択できる。例えば繊維状の樹脂を絡めて不織布のような形状を有するものも発泡樹脂成形体に代えて使用可能である。発泡樹脂成形体の気孔率は80%~98%、気孔径は50μm~500μmとするのが好ましい。発泡ウレタン及び発泡メラミンは気孔率が高く、また気孔の連通性があるとともに熱分解性にも優れているため発泡樹脂成形体として好ましく使用できる。
発泡ウレタンは気孔の均一性や入手の容易さ等の点で好ましく、発泡ウレタンは気孔径の小さなものが得られる点で好ましい。
気孔率=(1-(多孔質材の重量[g]/(多孔質材の体積[cm3]×素材密度)))×100[%]
また、気孔径は、樹脂成形体表面を顕微鏡写真等で拡大し、1インチ(25.4mm)あたりの気孔数をセル数として計数して、平均孔径=25.4mm/セル数として平均的な値を求める。
電解めっきを行うために、発泡樹脂の表面をあらかじめ導電化処理する。樹脂成形体の表面に導電性を有する層を設けることができる処理である限り特に制限はなく、ニッケル等の導電性金属の無電解めっき、アルミニウム等の蒸着及びスパッタ、又はカーボン等の導電性粒子を含有した導電性塗料の塗布等任意の方法を選択できる。
次に溶融塩中で電解めっきを行い、樹脂成形体表面にアルミニウムめっき層を形成する。溶融塩浴中でアルミニウムのめっきを行うことにより特に三次元網目構造を有する樹脂成形体のように複雑な骨格構造の表面に均一に厚いアルミニウム層を形成することができる。表面が導電化された樹脂成形体を陰極、純度99.0%のアルミニウムを陽極として溶融塩中で直流電流を印加する。溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなくめっきができ好ましい。有機系ハロゲン化物としてはイミダゾリウム塩、ピリジニウム塩等が使用でき、具体的には1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。溶融塩中に水分や酸素が混入すると溶融塩が劣化するため、めっきは窒素、アルゴン等の不活性ガス雰囲気下で、かつ密閉した環境下で行うことが好ましい。
溶融塩中での分解は以下の方法で行う。表面にアルミニウムめっき層を形成した多孔質樹脂成形体を溶融塩に浸漬し、アルミニウム層に負電位(アルミニウムの標準電極電位より卑な電位)を印加しながら加熱して多孔質樹脂成形体を除去する。溶融塩に浸漬した状態で負電位を印加すると、アルミニウムを酸化させることなく多孔質樹脂成形体を分解することができる。加熱温度は多孔質樹脂成形体の種類に合わせて適宜選択できる。樹脂成形体がウレタンである場合には分解は約380℃で起こるため溶融塩浴の温度は380℃以上にする必要があるが、アルミニウムを溶融させないためにはアルミニウムの融点(660℃)以下の温度で処理する必要がある。好ましい温度範囲は500℃以上600℃以下である。また、印加する負電位の量は、アルミニウムの還元電位よりマイナス側で、かつ溶融塩中のカチオンの還元電位よりプラス側とする。このような方法によって、連通気孔を有し、表面の酸化層が薄く酸素量の少ないアルミニウム多孔体を得ることができる。
図1はアルミニウム多孔体から電極を連続的に製造するためのプロセスの一例を説明する図である。当該プロセスは、巻き出しローラ41から多孔体シートを巻き出す多孔体シート巻き出し工程Aと、圧縮ローラ42を用いた調厚工程Bと、圧縮・溶接ローラ43及びリード溶接ローラ49を用いたリード溶接工程Cと、充填ローラ44、スラリー供給ノズル50及びスラリー51を用いたスラリー充填工程Dと、乾燥機45を用いた乾燥工程Eと、圧縮ローラ46を用いた圧縮行程Fと、切断ローラ47を用いた切断工程Gと、巻取ローラ48を用いた巻取工程Hとを含んでいる。以下、このような工程について具体的に説明する。
アルミニウム多孔体のシートが巻き取られた原反ロールからアルミニウム多孔体シートを巻き出して、調厚工程でローラプレスにより最適な厚さに調厚すると共に表面を平坦にする。アルミニウム多孔体の最終的な厚さはその電極の用途によって適宜に定められるが、この調厚工程は最終的な厚さとする前の段階の圧縮工程であり、次工程の処理が行いやすい厚みとなる程度に圧縮する。プレス機としては平板プレスやローラプレスが用いられる。平板プレスは集電体の伸びを抑制するためには好ましいが、量産には不向きなため、連続処理可能なローラプレスを用いることが好ましい。
-アルミニウム多孔体の端部の圧縮-
アルミニウム多孔体を二次電池等の電極集電体として用いるに際してはアルミニウム多孔体に外部引き出し用のタブリードを溶着する必要がある。アルミニウム多孔体を使用する電極の場合、強固な金属部が存在しないため、リード片を直接溶接することが出来ない。このため、アルミニウム多孔体の端部を圧縮することによって端部を箔状とすることで機械的強度を付加してタブリードを溶接する。
アルミニウム多孔体の端部の加工方法の一例について述べる。
図11はその圧縮工程を模式的に示したものである。
圧縮用治具としては回転ローラを用いることができる。
圧縮部の厚みは0.05mm以上0.2mm以下(例えば0.1mm程度)とすることにより、所定の機械的強度を得ることができる。
図12において、2枚分の幅を有するアルミニウム多孔体34の中央部を圧縮用治具として回転ローラ35によって圧縮して圧縮部33を形成する。圧縮後に圧縮部33の中央部を切断して端部に圧縮部を有する2枚の電極集電体を得る。
また、複数個の回転ローラを用いてアルミニウム多孔体の中央部に複数本の帯状の圧縮部を形成し、この帯状の圧縮部のそれぞれをその中心線に沿って切断することにより複数個の集電体を得ることができる。
前記のようにして得た集電体の端部圧縮部にタブリードを接合する。タブリードとしては電極の電気抵抗を低減するために金属箔を用いて、電極の周縁部の少なくとも一方の側の表面に金属箔を接合することが好ましい。また、電気抵抗を低減するために接合方法としては溶接を用いることが好ましい。金属箔を溶接する幅は、あまり太いと電池内に無駄なスペースが増えて電池の容量密度が低下するため、10mm以下が好ましい。あまり細いと溶接が困難になると共に集電効果も下がるため、1mm以上が好ましい。
溶接方法としては抵抗溶接や超音波溶接などの方法が使用できるが、超音波溶接の方が、接着面積が広いため好ましい。
金属箔の材質としては、電気抵抗や電解液に対する耐性を考慮するとアルミニウムが好ましい。また、不純物があると電池、キャパシタ、リチウムイオンキャパシタ内で溶出・反応したりするため、純度99.99%以上のアルミニウム箔を用いることが好ましい。また、溶接部分の厚さが電極自体の厚さより薄いことが好ましい。
アルミ箔の厚さは20~500μmとすることが好ましい。
また、金属箔の溶接は集電体に活物質を充填する前・後どちらで行なってもかまわないが、充填前に行なう方が活物質の脱落を抑えられる。特に超音波溶接の場合は充填前に溶接する方が好ましい。また、溶接した部分に活性炭ペーストがついてもよいが、工程途中で剥離する可能性もあるため、充填できないようにマスキングしておくことが好ましい。
上記のようにして得た集電体に活物質を充填することにより電極を得る。活物質は電極が使用される目的に応じて適宜選択される。
活物質の充填には浸漬充填法や塗工法など公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケータ塗工法、静電塗工法、粉黛塗工法、スプレー塗工法、スプレーコータ塗工法、バーコータ塗工法、ロールコータ塗工法、ディップコータ塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコータ塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
活物質を充填するときは、必要に応じて導電助剤やバインダを加え、これに有機溶剤を混合してスラリーを作製し、これを上記の充填法を用いてアルミニウム多孔体に充填する。
図13にはロール塗工法によってスラリーを多孔体に充填する方法を示した。図示のように多孔体シート上にスラリーを供給しこれを所定の間隙を開けて対向する一対の回転ロールに通す。スラリーは回転ロールを通過する際に多孔体中に押圧充填される。
活物質を充填された多孔体は乾燥機に搬入され、加熱することによって有機溶剤を蒸発除去することにより、多孔体孔内に活物質が固定された電極材料を得る。
乾燥後の電極材料は圧縮工程において最終的な厚さに圧縮される。プレス機としては平板プレスやローラプレスが用いられる。平板プレスは集電体の伸びを抑制するためには好ましいが、量産には不向きなため、連続処理可能なローラプレスを用いることが好ましい。
図1の圧縮工程Fではローラプレスによって圧縮する場合を示した。
電極材料の量産性を高めるためには、アルミニウム多孔体のシートの幅を最終製品の複数枚分の幅とし、これをシートの進行方向に沿って複数の刃で切断することによって複数枚の長尺シート状の電極材料とすることが好ましい。この切断工程は長尺状の電極材料を複数枚の長尺状の電極材料に分割する工程である。
この工程は上記切断工程で得た複数枚の長尺シート状の電極材料としこれを巻取ローラに巻き取る工程である。
アルミニウム多孔体を集電体として用いた電極材料の主な用途としては、リチウム電池や溶融塩電池等の非水電解質電池用電極、非水電解液を用いるキャパシタ用電極、非水電解液を用いるリチウムイオンキャパシタなどがある。
以下では、これらの用途について述べる。
次にアルミニウム多孔体を用いた電池用電極材料及び電池について説明する。例えばリチウム電池(リチウムイオン二次電池等を含む。)の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は導電助剤及びバインダと組み合わせて使用する。
従来のリチウム電池用正極材料は、アルミニウム箔の表面に活物質を塗布した電極が用いられている。リチウム電池はニッケル水素電池やキャパシタに比べれば高容量であるが、自動車用途などでは更なる高容量化が求められており、単位面積当たりの電池容量を向上するために、活物質の塗布厚みを厚くしており、また活物質を有効に利用するためには集電体であるアルミニウム箔と活物質とが電気的に接触している必要があるので、活物質は導電助剤と混合して用いられている。
これに対し、本発明のアルミニウム多孔体は気孔率が高く単位面積当たりの表面積が大きい。よって集電体と活物質の接触面積が大きくなるため活物質を有効に利用でき、電池の容量を向上できるとともに、導電助剤の混合量を少なくすることができる。リチウム電池は、上記の正極材料を正極とし、負極には銅やニッケルの箔やパンチングメタル、多孔体などが集電体として用いられ、黒鉛、チタン酸リチウム(Li4Ti5O12)、SnやSi等の合金系、あるいはリチウム金属等の負極活物質が使用される。負極活物質も導電助剤及びバインダと組み合わせて使用する。
このようなリチウム電池は、小さい電極面積でも容量を向上できるため、従来のアルミ箔を用いたリチウム電池よりも電池のエネルギー密度を高くすることができる。また、上記では主に二次電池についての効果を説明したが、一次電池についてもアルミニウム多孔体に活物質を充填したときに接触面積が大きくなる効果は二次電池の場合と同じであり、容量の向上が可能である。
リチウム電池に使用される電解質には、非水電解液と固体電解質がある。
図14は、固体電解質を使用した全固体リチウム電池の縦断面図である。この全固体リチウム電池60は、正極61、負極62、および、両電極間に配置される固体電解質層(SE層)63を備える。正極61は、正極層(正極体)64と正極集電体65とからなり、負極62は、負極層66と負極集電体67とからなる。
電解質として、固体電解質以外に、後述する非水電解液が用いられる。この場合、両極間には、セパレータ(多孔質ポリマーフィルムや不織布、紙等)が配置され、非水電解液は両極およびセパレータ中に含浸される。
アルミニウム多孔体をリチウム電池の正極に使用する場合は、活物質としてリチウムを脱挿入できる材料を使用することができ、このような材料をアルミニウム多孔体に充填することでリチウム二次電池に適した電極を得ることができる。正極活物質の材料としては、例えばコバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、ニッケルコバルト酸リチウム(LiCo0.3Ni0.7O2)、マンガン酸リチウム(LiMn2O4)、チタン酸リチウム(Li4Ti5O12)、リチウムマンガン酸化合物(LiMyMn2-yO4);M=Cr、Co、Ni)、リチウム酸等を使用する。活物質は導電助剤及びバインダと組み合わせて使用する。従来のリチウムリン酸鉄及びその化合物(LiFePO4、LiFe0.5Mn0.5PO4)であるオリビン化合物などの遷移金属酸化物が挙げられる。また、これらの材料の中に含まれる遷移金属元素を、別の遷移金属元素に一部置換してもよい。
非水電解液としては、極性非プロトン性有機溶媒で使用され、具体的にはエチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、プロピレンカーボネート、γ-ブチロラクトン及びスルホラン等が使用される。支持塩としては4フッ化ホウ酸リチウム、6フッ化リン酸リチウム、およびイミド塩等が使用されている。電解質となる支持塩の濃度は高い方が好ましいが、溶解に限度があるため1mol/L付近のものが一般に用いられる。
活物質の他に、さらに、固体電解質を加えて充填してもよい。アルミニウム多孔体に活物質と固体電解質とを充填することで、全固体リチウム電池の電極に適したものとすることができる。ただし、アルミニウム多孔体に充填する材料のうち活物質の割合は、放電容量を確保する観点から、50質量%以上、より好ましくは70質量%以上とすることが好ましい。
活物質(活物質と固体電解質)の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケータ塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコータ塗工法、バーコータ塗工法、ロールコータ塗工法、ディップコータ塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコータ塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
図15はキャパシタ用電極材料を用いたキャパシタの一例を示す断面模式図である。セパレータ142で仕切られた有機電解液143中に、アルミニウム多孔体に電極活物質を担持した電極材料を分極性電極141として配置している。分極性電極141はリード線144に接続しており、これら全体がケース145中に収納されている。アルミニウム多孔体を集電体として使用することで、集電体の表面積が大きくなり、活物質としての活性炭との接触面積が大きくなるため高出力、高容量化可能なキャパシタを得ることができる。
キャパシタの容量を大きくするためには主成分である活性炭の量が多い方が良く、乾燥後(溶媒除去後)の組成比で活性炭が90%以上あることが好ましい。また導電助剤やバインダは必要ではあるが容量低下の要因であり、バインダは更に内部抵抗を増大させる要因となるためできる限り少ない方がよい。導電助剤は10質量%以下、バインダは10質量%以下が好ましい。
活性炭の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケータ塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコータ塗工法、バーコータ塗工法、ロールコータ塗工法、ディップコータ塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコータ塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
上記のようにして得られた電極を適当な大きさに打ち抜いて2枚用意し、セパレータを挟んで対向させる。セパレータはセルロースやポリオレフィン樹脂などで構成された多孔膜や不織布を用いるのが好ましい。そして、必要なスペーサを用いてセルケースに収納し、電解液を含浸させる。最後に絶縁ガスケットを介してケースに蓋をして封口することにより電気二重層キャパシタを作製することができる。非水系の材料を使用する場合は、キャパシタ内の水分を限りなく少なくするため、電極などの材料を十分乾燥することが好ましい。キャパシタの作製は水分の少ない環境下で行い、封止は減圧環境下で行ってもよい。なお、本発明の集電体、電極を用いていればキャパシタとしては特に限定されず、これ以外の方法により作製されるものでも構わない。
図16はリチウムイオンキャパシタ用電極材料を用いたリチウムイオンキャパシタの一例を示す断面模式図である。セパレータ142で仕切られた有機電解液143中に、アルミニウム多孔体に正極活物質を担持した電極材料を正極146として配置し、集電体に負極活物質を担持した電極材料を負極147として配置している。正極146及び負極147はそれぞれリード線148、149に接続しており、これら全体がケース145中に収納されている。アルミニウム多孔体を集電体として使用することで、集電体の表面積が大きくなり、活物質としての活性炭を薄く塗布しても高出力、高容量化可能なリチウムイオンキャパシタを得ることができる。
リチウムイオンキャパシタ用の電極を製造するには、アルミニウム多孔体集電体に活物質として活性炭を充填する。活性炭は導電助剤やバインダと組み合わせて使用する。
リチウムイオンキャパシタの容量を大きくするためには主成分である活性炭の量が多い方が良く、乾燥後(溶媒除去後)の組成比で活性炭が90%以上あることが好ましい。また導電助剤やバインダは必要ではあるが容量低下の要因であり、バインダは更に内部抵抗を増大させる要因となるためできる限り少ない方がよい。導電助剤は10質量%以下、バインダは10質量%以下が好ましい。
活性炭の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケータ塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコータ塗工法、バーコータ塗工法、ロールコータ塗工法、ディップコータ塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコータ塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
負極は特に限定されず従来のリチウム電池用負極を使用可能であるが、銅箔を集電体に用いた従来の電極では容量が小さいため、前述の発泡状ニッケルのような銅やニッケル製の多孔体に活物質を充填した電極が好ましい。また、リチウムイオンキャパシタとして動作させるために、あらかじめ負極にリチウムイオンをドープしておくことが好ましい。ドープ方法としては公知の方法を用いることができる。たとえば、負極表面にリチウム金属箔を貼り付けて電解液中に浸してドープする方法や、リチウムイオンキャパシタ内にリチウム金属を取り付けた電極を配置し、セルを組み立ててから負極とリチウム金属電極の間で電流を流して電気的にドープする方法、あるいは負極とリチウム金属で電気化学セルを組み立て、電気的にリチウムをドープした負極を取り出して使用する方法などが挙げられる。
いずれの方法でも、負極の電位を十分に下げるためにリチウムドープ量は多いほうがよいが、負極の残容量が正極容量より小さくなるとリチウムイオンキャパシタの容量が小さくなるため、正極容量分はドープせずに残しておく方が好ましい。
電解液はリチウム電池に使用する非水電解液と同じものが用いられる。非水電解液としては、極性非プロトン性有機溶媒で使用され、具体的にはエチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、プロピレンカーボネート、γ-ブチロラクトン及びスルホラン等が使用される。支持塩としては4フッ化ホウ酸リチウム、6フッ化リン酸リチウム、およびイミド塩等が使用されている。
上記のようにして得られた電極を適当な大きさに打ち抜き、セパレータを挟んで負極と対向させる。負極は、前述の方法でリチウムイオンをドープしたものを用いても構わないし、セルを組み立て後にドープする方法をとる場合は、リチウム金属を接続した電極をセル内に配置すればよい。セパレータはセルロースやポリオレフィン樹脂などで構成された多孔膜や不織布を用いるのが好ましい。そして、必要なスペーサを用いてセルケースに収納し、電解液を含浸させる。最後に絶縁ガスケットを介してケースに蓋をして封口することによりリチウムイオンキャパシタを作製することができる。リチウムイオンキャパシタ内の水分を限りなく少なくするため、電極などの材料は十分乾燥することが好ましい。また、リチウムイオンキャパシタの作製は水分の少ない環境下で行い、封止は減圧環境下で行ってもよい。なお、本発明の集電体、電極を用いていればリチウムイオンキャパシタとしては特に限定されず、これ以外の方法により作製されるものでも構わない。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質として亜クロム酸ナトリウム(NaCrO2)、二硫化チタン(TiS2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は導電助剤及びバインダと組み合わせて使用する。導電助剤としてはアセチレンブラック等が使用できる。またバインダとしてはポリテトラフルオロエチレン(PTFE)等を使用できる。活物質として亜クロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、PTFEはこの両者をより強固に固着することができ好ましい。
(導電層の形成)
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)約46個、気孔径約552μm、厚さ1mmのウレタン発泡体を準備し、これを100mm×30mm角に切断した。このポリウレタンフォームの表面にスパッタ法で目付量10g/m2のアルミニウム膜を形成して導電化処理した。
表面に導電層を形成したウレタン発泡体をワークとして、給電機能を有する治具にセットした後、アルゴン雰囲気かつ低水分(露点-30℃以下)としたグローブボックス内に入れ、温度40℃の溶融塩アルミめっき浴(33mol%EMIC-67mol%AlCl3)に浸漬した。ワークをセットした治具を整流器の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続した。電流密度3.6A/dm2の直流電流を90分間印加してめっきすることにより、ウレタン発泡体表面に150g/m2の重量のアルミニウムめっき層が形成されたアルミニウム構造体を得た。攪拌はテフロン(登録商標)製の回転子を用いてスターラにて行った。ここで、電流密度はウレタン発泡体の見かけの面積で計算した値である。
前記アルミニウム構造体を温度500℃のLiCl-KCl共晶溶融塩に浸漬し、-1Vの負電位を30分間印加した。溶融塩中にポリウレタンの分解反応による気泡が発生した。その後大気中で室温まで冷却した後、水洗して溶融塩を除去し、樹脂が除去されたアルミニウム多孔体を得た。得られたアルミニウム多孔体は連通気孔を有し、気孔率が芯材としたウレタン発泡体と同様に高いものであった。
得られたアルミニウム多孔体をローラプレスにより厚さ0.96mmに調厚し、5cm角に切断した。
溶接の準備として、圧縮用治具として幅5mmのSUSブロック(棒)とハンマーを用いて、アルミニウム多孔体の1辺の端から5mm部分にSUSブロックを載置してSUSブロックをハンマーで叩いて圧縮して厚み100μmの圧縮部を形成した。
その後、以下の条件でタブリードをスポット溶接によって溶接した。
溶接装置: パナソニック社製 Hi-Max100、型番YG-101UD
(最大250Vまで印加可能)
容量100Ws、0.6kVA
電極 : 2mmφの銅電極
荷重 : 8kgf
電圧 : 140V
<タブリード>
材質 : アルミニウム
寸法 : 幅5mm、長さ7cm、厚み100μm
表面状態: ベーマイト加工
活物質としては平均粒径が5μmのコバルト酸リチウム粉末(正極活物質)を用意し、このコバルト酸リチウム粉末と、アセチレンブラック(導電助剤)と、PVDF(バインダ)とを質量%で90:5:5の割合で混合した。この混合物にN-メチル-2-ピロリドン(有機溶剤)を滴下して混合し、ペースト状の正極合剤スラリーを作製した。次に、この正極合剤スラリーをアルミニウム多孔体に充填した。その後、100℃で40分間乾燥させて有機溶剤を除去することにより正極用電極1を得た。
実施例1において張力をかけながら電極作製した以外は実施例1と同様にして正極用電極2を得た。実施例1と同様にして、得られたアルミニウム多孔体の断面を観察した結果、アルミニウム多孔体のセルが、電極の幅方向に短軸の楕円形であることが確認された。
実施例1において圧縮せずに使用とした以外は実施例1と同様にして正極用電極3を得た。
実施例1と同様にして、得られたアルミニウム多孔体の断面を観察した結果、アルミニウム多孔体のセルが円形であることが確認された。
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)58個、気孔径約438μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2の正極用電極4を得た。
その結果、領域1は41個であり、領域2は40個であり、領域3は42個であった。領域2におけるアルミニウム骨格の断面の数に対する、領域1のアルミニウム骨格の断面の数の比は1.03であった。領域2におけるアルミニウム骨格の断面の数に対する、領域3のアルミニウム骨格の断面の数の比は1.05であった。
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)58個、セル径約438μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Aと、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Cを得た。
同様に、ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)40個、セル径約635μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Bを得た。
そして、アルミニウム多孔体をA、B、Cの順に積層して、電極作製前にロールプレスし、部分的に溶接して処理をすることにより一体化させた。
その後、実施例1と同様の操作を行い、正極用電極5を得た。
その結果、領域1は40個であり、領域2は30個であり、領域3は42個であった。領域2におけるアルミニウム骨格の断面の数に対する、領域1、3のアルミニウム骨格の断面の数の平均の比は1.37であった。
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)40個、セル径約635μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Dと、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Fを得た。
同様に、ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)約58個、セル径約438μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2のアルミニウム多孔体Eを得た。
そして、アルミニウム多孔体をD、E、Fの順に積層して、ロールプレスし、部分的に溶接する処理をすることにより一体化させた。
その後、実施例1と同様の操作を行い、正極用電極6を得た。
その結果、領域1は31個であり、領域2は41個であり、領域3は32個であった。領域2におけるアルミニウム骨格の断面の数に対する、領域1、3のアルミニウム骨格の断面の数の平均の比は1.3であった。
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)約50個、気孔径約508μm、厚さ1mmのウレタン発泡体を出発材料とする以外は実施例1と同様にして、厚みが1mmで、目付量が140g/m2の正極用電極7を得た。
実施例1と同様にして、得られた正極用電極7の断面を観察した。
その結果、アルミニウム多孔体の最表面は活物質で覆われており、電極表面からアルミニウム多孔体骨格が露出していなかった。
ウレタン樹脂成形体として、気孔率95%、1インチ当たりの気孔数(セル数)約50個、気孔径約508μm、厚さ1mmのウレタン発泡体を出発材料とした。そして、実施例1と同様にして電極を作製し、最後にブラシによって電極表面の活物質を除去して正極用集電体8を得た。得られた電極の厚さは1mmで、目付量は140g/m2であった。
実施例1と同様にして、得られた正極用電極8の断面を観察した。
その結果、活物質は、アルミニウム多孔体の最表面から0.02mmの深さまでは活物質が存在していなかった。
2 導電層
3 アルミニウムめっき層
21a,21b めっき槽
22 帯状樹脂
23,28 めっき浴
24 円筒状電極
25,27 陽極
26 電極ローラ
32 圧縮用治具
33 圧縮部
34 アルミニウム多孔体
35 回転ローラ
36 ローラ回転軸
37 タブリード
38 絶縁・封止用テープ
41 巻き出しローラ
42 圧縮ローラ
43 圧縮溶接ローラ
44 充填ローラ
45 乾燥機
46 圧縮ローラ
47 切断ローラ
48 巻取りローラ
49 リード供給ローラ
50 スラリー供給ノズル
51 スラリー
60 リチウム電池
61 正極
62 負極
63 電解質層
64 正極層(正極体)
65 正極集電体
66 負極層
67 負極集電体
121 正極
122 負極
123 セパレータ
124 押さえ板
125 バネ
126 押圧部材
127 ケース
128 正極端子
129 負極端子
130 リード線
141 分極性電極
142 セパレータ
143 有機電解液
144 リード線
145 ケース
146 正極
147 負極
148 リード線
149 リード線
Claims (12)
- 三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の長手方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であり、かつ、電極の幅方向と厚さ方向に平行な断面において三次元網状アルミニウム多孔体のセルが電極の厚さ方向に短軸の楕円形であることを特徴とする電極。
- 三次元網状アルミニウム多孔体に、少なくとも、集電リード溶接工程と、活物質充填工程と、圧縮工程と、を施して得られたことを特徴とする請求項1に記載の電極。
- 三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の厚さ方向に平行な断面において、三次元網状アルミニウム多孔体のセルが電極の幅方向に短軸の楕円形であることを特徴とする電極。
- 三次元網状アルミニウム多孔体を基材とする電極であって、該電極がシート状であり、該電極の厚さ方向に平行な断面において、三次元網状アルミニウム多孔体のセルが円形であることを特徴とする電極。
- 前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1におけるアルミニウム骨格の断面の数の比が0.8以上、1.2以下であり、
領域2におけるアルミニウム骨格の断面の数に対する、領域3におけるアルミニウム固角の断面の数の比が0.8以上、1.2以下であることを特徴とする請求項1~4のいずれかに記載の電極。 - 前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1と領域3とにおけるアルミニウム骨格の断面の数の平均の比が1.2より大きいことを特徴とする請求項1~4のいずれかに記載の電極。 - 前記電極の厚さ方向の断面を、領域1、領域2、領域3とこの順に3分割したとき、
領域2におけるアルミニウム骨格の断面の数に対する、領域1と領域3とにおけるアルミニウム骨格の断面の数の平均の比が0.8より小さいことを特徴とする請求項1~4のいずれかに記載の電極。 - 前記三次元網状アルミニウム多孔体の最表面が活物質で覆われていて、三次元網状アルミニウム多孔体が活物質から露出していないことを特徴とする請求項1~7のいずれかに記載の電極。
- 前記三次元網状アルミニウム多孔体の最表面から、0.02mmの深さまで活物質が存在しないことを特徴とする請求項1~7のいずれかに記載の電極。
- 請求項1~9のいずれかに記載の電極を用いたことを特徴とする非水電解質電池。
- 請求項1~9のいずれかに記載の電極を用いたことを特徴とする非水電解液を用いたキャパシタ。
- 請求項1~9のいずれかに記載の電極を用いたことを特徴とする非水電解液を用いたリチウムイオンキャパシタ。
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DE112012000859.6T DE112012000859T8 (de) | 2011-02-18 | 2012-02-15 | Elektrode unter Verwendung eines porösen Aluminiumkörpers mit dreidimensionalem Netzwerk und nicht-wässrige Elektrolytbatterie, Kondensator und Lithiumionenkondensator mit einer nicht-wässrigen elektrolytischen Lösung, die jeweils die Elektrode verwenden |
US13/569,300 US8541134B2 (en) | 2011-02-18 | 2012-08-08 | Electrode using three-dimensional network aluminum porous body, and nonaqueous electrolyte battery, capacitor and lithium-ion capacitor with nonaqueous electrolytic solution, each using the electrode |
US13/969,994 US20130330614A1 (en) | 2011-02-18 | 2013-08-19 | Electrode using three-dimensional network aluminum porous body, and nonaqueous electrolyte battery, capacitor and lithium-ion capacitor with nonaqueous electrolytic solution, each using the electrode |
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JP2015011823A (ja) * | 2013-06-27 | 2015-01-19 | 住友電気工業株式会社 | リチウム電池 |
JP2015159021A (ja) * | 2014-02-24 | 2015-09-03 | 住友電気工業株式会社 | 多孔質集電体及び電気化学装置 |
US10243240B2 (en) * | 2014-11-13 | 2019-03-26 | Basf Corporation | Electrolytes and metal hydride batteries |
CN114628772B (zh) * | 2020-12-10 | 2023-07-07 | 北京好风光储能技术有限公司 | 一种卷绕式电池 |
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- 2012-02-15 DE DE112012000859.6T patent/DE112012000859T8/de not_active Expired - Fee Related
- 2012-02-15 WO PCT/JP2012/053514 patent/WO2012111699A1/ja active Application Filing
- 2012-02-15 KR KR1020137022858A patent/KR20140012076A/ko not_active Application Discontinuation
- 2012-08-08 US US13/569,300 patent/US8541134B2/en active Active
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KR20140012076A (ko) | 2014-01-29 |
DE112012000859T8 (de) | 2014-01-16 |
DE112012000859T5 (de) | 2013-12-24 |
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