Classifications

• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
  • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • 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
  • H01G11/30—Electrodes characterised by their material
• • 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
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
  • H01G11/38—Carbon pastes or blends; Binders or additives therein
• • 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
  • H01G11/30—Electrodes characterised by their material
  • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• • 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
  • H01G11/54—Electrolytes
  • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • 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
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
• • 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
  • H01M10/54—Reclaiming serviceable parts of waste accumulators
• • 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
  • H01M4/0433—Molding
• • 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
  • H01M4/0435—Rolling or calendering
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/665—Composites
  • H01M4/667—Composites in the form of layers, e.g. coatings
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/668—Composites of electroconductive material and synthetic resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • 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
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a method for manufacturing or recycling a member for an electrochemical device, a method for manufacturing an electrochemical device, a member for an electrochemical device, and an electrochemical device.
• primary batteries such as lithium primary batteries; non-aqueous secondary batteries such as lithium ion secondary batteries, lithium metal secondary batteries, sodium ion secondary batteries, potassium ion secondary batteries, magnesium secondary batteries, aluminum secondary batteries, etc.
• Air batteries such as dye-sensitized solar batteries; Capsules such as electric double layer capacitors and lithium ion capacitors; Electrochromic display devices; Electrochemical light emitting elements; Electrochemical double layer transistors; Electrochemical devices such as electrochemical actuators In, electrodes containing active materials are used.
• Patent Document 1 it is a problem to provide an electrode paste having a uniform contact surface area of active material particles with a solution, and an active material solid using a chemically dried material.
• the particle component is mixed with the liquid non-volatile plastic component and the volatile anhydrous pulverizing solvent to form a slurry, and the slurry is pulverized until the particle size and the particle size distribution reach the desired values, and the volatile anhydrous pulverizing solvent is removed. It is described that the electrode paste is produced by this.
• Patent Document 2 mainly contains a solution of an active material powder such as manganese dioxide, a binder made of a fluororesin that is fibroticized in an unsintered state to form a bonding network, and a viscous agent made of polyethylene oxide. Described is a method for producing a positive electrode plate for a non-aqueous battery by applying the containing paste to a electrode plate core body and then heat-treating at a temperature equal to or lower than the decomposition temperature of the polyethylene oxide to remove water.
• an active material powder such as manganese dioxide
• a viscous agent made of polyethylene oxide made of polyethylene oxide.
• Patent Document 3 describes an electrolyte composition for an electrochemical device containing an ionic substance and a plasticizer composed of an organic compound containing a high boiling point organic compound, and an electrolyte composition for the electrochemical device and an electrode active material. Described are electrodes for electrochemical devices including an electrode mixture layer obtained by molding a mixture obtained by mixing and, and a method for producing these.
• a molding material obtained by kneading an active material with an electrolytic solution is applied to a current collector or molded on the current collector, and a non-aqueous system in the electrolytic solution is used.
• the electrode is manufactured so that the organic solvent does not completely volatilize.
• the non-aqueous organic solvent volatilizes more than necessary when the atmosphere becomes open during the molding process, it becomes difficult to replenish the volatilized organic solvent, and also.
• moisture absorption occurs, it becomes difficult to remove the absorbed moisture, so it becomes difficult to recover the quality once changed, and the amount of volatilization is controlled in order to obtain stable production and stable device performance. There was a problem that we had to. Further, in the electrode production, if proper management is not performed, there is a risk that the worker is exposed to the volatilized non-aqueous organic solvent, which has been a problem.
• Patent Document 2 has been studied for its applicability to the manufacture of positive electrodes for lithium primary batteries, but its applicability to the manufacture of members used for other batteries such as lithium ion secondary batteries has been investigated. Not considered. Further, the technique described in Patent Document 2 has not studied the quality change and the quality recovery of the member due to the fluctuation of the solvent amount in the manufacturing process. In particular, in a secondary battery, the electrode texture accuracy (eg, electrode thickness, electrode surface roughness accuracy) is more important than in a primary battery, but in the technique described in Patent Document 2, the electrode texture accuracy is examined. Not. Moreover, the member is not formed by the shaping operation.
• the electrode texture accuracy eg, electrode thickness, electrode surface roughness accuracy
• an object of the present invention is to provide a method for manufacturing a member for an electrochemical device, which is unlikely to cause a problem of irreversible change in the composition of the electrochemical device due to solvent reduction, moisture absorption, etc. at the time of manufacturing the electrochemical device.
• the present inventor contains a filler and a plasticizer which is water, an ionic liquid, or a mixture thereof, and a polymer, and substantially contains no organic solvent. Electricity in which irreversible quality changes in the manufacturing process are suppressed by performing a predetermined shaping operation on a molding material composition having plasticity and independence and the polymer being plasticized with a plasticizer.
• the present invention has been completed by finding that a member for a chemical device can be manufactured.
• group A Extrusion, injection into mold, stretching, compression molding, thickness reduction by pressure, thickness homogenization by pressure, cutting, drilling, cutting, final shape to be housed in electrochemical device container Bending to, bonding of molding material compositions with different compositions
• an electrochemical device eg. an electrode
• the irreversible change in the composition of the electrochemical device due to solvent reduction, moisture absorption, etc. during the manufacture of the electrochemical device can be observed. It can be suppressed.
• the polymer (P1) may be an electrolytic solution solvent (ES) or a polymer that is plasticized. Further, the polymer (P1) may be a deliquescent polymer.
• the polymer (P1) is preferably a polymer containing ethylene oxide (EO) as a monomer unit, a polyoxazoline-based polymer, a poly-N-vinylacetamide-based polymer, or an epichlorohydrin-organic amine condensate.
• EO ethylene oxide
• the filler (F) may contain the active material (A). Further, the filler (F) may contain an inorganic solid electrolyte. Further, the filler (F) may contain a fibrous substance. Further, the filler (F) may contain a solid lubricant.
• the fibrous substance may have a fiber length of 10 ⁇ m or more. Further, the fibrous material may have a fiber length equal to or larger than the thickness of the member for an electrochemical device. Further, the fibrous material may have a nano-sized fiber diameter.
• the solid lubricant may be selected from the following group B.
• group B graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metal soap]
• group B graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metal soap
• the filler (F) may be nano-sized.
• the volume fraction occupied by the filler (F) in the molding material composition may be 50% by volume or more.
• the molding material composition may further contain a polymer (P2) that is plasticized with a plasticizer (PS) but is insoluble in the electrolytic solution.
• P2 polymer that is plasticized with a plasticizer (PS) but is insoluble in the electrolytic solution.
• the method for producing a member for an electrochemical device of the present invention may include irreversibly cross-linking a polymer (P1).
• the method of crosslinking may be thermal crosslinking.
• the method of cross-linking may be UV cross-linking.
• the cross-linking agent may be added to the molding material composition.
• the cross-linking agent may be added to the electrolytic solution.
• the polymer (P1) may be a self-crosslinking polymer.
• the method for manufacturing a member for an electrochemical device of the present invention may include managing the basis weight by measuring the thickness of the member and providing feedback. Further, the method for producing a member for an electrochemical device of the present invention may include crushing a plurality of strands made of a molding material composition to form a sheet. In addition, the method for producing a member for an electrochemical device of the present invention may include obtaining a member by scraping from a bulk molding material composition.
• the method for manufacturing a member for an electrochemical device of the present invention may include attaching a molding material composition to a base material.
• the method for producing a member for an electrochemical device of the present invention may include molding a molding material composition to a desired thickness and then attaching it to a substrate.
• the method for producing a member for an electrochemical device of the present invention may include attaching a molding material composition from the front and back surfaces of a base material substantially at the same time.
• the method for producing a member for an electrochemical device of the present invention may include attaching the molding material composition to the front side of the base material and then attaching it to the back side as well.
• the base material may have a conductive coating on the surface in contact with the molding material composition.
• the base material may contain a polymer as a main component.
• the member may be an electrode or an insulating layer.
• the shaping operation selected from the group A may be performed at least once in a state where the molding material composition is not in contact with the current collecting foil. Further, the shaping operation selected from the group A may be performed at least once in a state where the molding material composition is not in contact with the porous separator film.
• the method for producing a member for an electrochemical device of the present invention is when the molding material composition is placed on the device. After shaping to the final shape, it may include removing water by a drying operation to bring it into a non-plasticized state.
• the drying operation may be performed by vacuum or heating. Further, the drying operation may be performed in a state where the molding material composition is not in contact with the current collector foil. Further, the drying operation may be performed in a state where the molding material composition is not in contact with the porous separator membrane.
• the method for manufacturing a member for an electrochemical device of the present invention may include a step of peeling a molding material composition already attached to a base material from the base material. Further, in the method for producing a member for an electrochemical device of the present invention, after the molding material composition or the molding material composition subjected to the cross-linking operation is in the non-plasticized state, it is rehydrated or humidified to be in the plasticized state. May include restoring. In addition, the method for manufacturing a member for an electrochemical device of the present invention may include manufacturing the next member again using the scraps of the molding material composition produced in the process of shaping the molding material composition. ..
• the method for recycling the member for an electrochemical device of the present invention includes a step of peeling the molding material composition already attached to the base material from the base material in the above-mentioned method for manufacturing the member for an electrochemical device.
• the plasticized state is restored by adding water or humidifying again.
• the next member is manufactured again using the scraps of the molding material composition produced in the process of shaping the molding material composition. including.
• the molding material composition used in the present invention can suppress irreversible changes in the electrochemical device composition due to solvent reduction, moisture absorption, etc. during the manufacture of the electrochemical device, the quality of the electrochemical device member varies. Can be recycled without.
• the method for manufacturing an electrochemical device of the present invention includes obtaining a member by the above-mentioned manufacturing method or recycling method.
• the polymer (P1) may be a polymer that is also plasticized with an electrolytic solution solvent (ES). Further, in the method for producing an electrochemical device of the present invention, the molding material composition further contains a polymer (P2) that is plasticized with a plasticizer (PS) but is insoluble in an electrolytic solution. May be good. Further, in the method for producing an electrochemical device of the present invention, the cross-linking agent may be added to the electrolytic solution.
• the member for an electrochemical device of the present invention can be obtained by the above-mentioned manufacturing method or recycling method.
• the member for the electrochemical device may be an electrode or an insulating layer.
• the electrochemical device of the present invention includes the above-mentioned member for an electrochemical device.
• the electrochemical device of the present invention may include an electrode obtained by the above-mentioned manufacturing method or recycling method, and a counter electrode to the electrode, and the counter electrode is an alkali metal, an alkaline earth metal, metallic aluminum, and a metal aluminum. It may contain at least one selected from silver.
• carrier ions are alkali metal ion, alkaline earth metal ion, aluminum ion, silver ion, organic nitrogen cation, and halide anion, bis (fluoromethanesulfonyl) imidebis (trifluoromethanesulfonyl) imide anion.
• Trifluoromethanesulfonate anion may be at least one of the water-containing electrochemical devices.
• the hydrous electrochemical device include an electrochemical device containing water in an electrolytic solution (eg, a hydrous battery such as a hydrous lithium ion secondary battery and a manganese zinc primary battery).
• the electrochemical device of the present invention may be a non-aqueous electrochemical device.
• carrier ions are alkali metal ion, alkaline earth metal ion, aluminum ion, silver ion, organic nitrogen cation, and halide anion, bis (fluoromethanesulfonyl) imidebis (trifluoromethanesulfonyl). It may be a non-aqueous electrochemical device having at least one of an imide anion and a trifluoromethanesulfonic acid anion.
• non-aqueous electrochemical device examples include a non-aqueous battery such as a non-aqueous lithium ion secondary battery, a lithium primary battery, and a manganese lithium primary battery in which an electrolytic solution is dissolved in an organic solvent and does not contain water. ).
• a non-aqueous battery such as a non-aqueous lithium ion secondary battery, a lithium primary battery, and a manganese lithium primary battery in which an electrolytic solution is dissolved in an organic solvent and does not contain water.
• Electrochemical devices can be provided.
• the method for manufacturing and recycling the member for an electrochemical device of the present invention is not particularly limited, and is, for example, a non-aqueous system such as a lithium primary cell, a manganese primary cell (eg, a manganese zinc primary cell, a manganese lithium primary cell), or a non-aqueous system.
• Hydrous primary cell Lithium ion secondary battery (non-aqueous, hydrous), lithium metal secondary battery, sodium ion secondary battery, potassium ion secondary battery, magnesium secondary battery, aluminum secondary battery, etc.
• Hydrous secondary batteries Air batteries; Solar cells such as dye-sensitized solar cells; Capsules such as electric double-layer capacitors and lithium-ion capacitors; Electrochromic display devices; Electrochemical light-emitting elements; Electrochemical double-layer transistors; Electrochemical actuators It can be used when manufacturing or recycling a member used for an electrochemical device such as. Further, the member for an electrochemical device of the present invention may be one manufactured or recycled by the method for manufacturing or recycling the member for an electrochemical device of the present invention. Further, the electrochemical device of the present invention may use the member for the electrochemical device of the present invention.
• the electrochemical device described above is preferably a non-aqueous secondary battery, and more preferably a lithium ion secondary battery.
• the method for manufacturing a member for an electrochemical device of the present invention is At least one filler (F); A plasticizer (PS) that is water, an ionic liquid, or a mixture thereof; and a polymer (P1). Includes performing at least one shaping operation selected from Group A below on a plastic and self-supporting molding material composition that is substantially free of organic solvents.
• the polymer (P1) may be plasticized with a plasticizer (PS).
• PS plasticizer
• the "molding material composition” is a semi-solid material for forming a member for an electrochemical device.
• the molding material composition contains at least one of the above-mentioned fillers (F), plasticizers (PS), and polymers (P1), and optionally additional components, under conditions substantially free of organic solvents. It can be obtained by mixing with. These components may be mixed at the same time or sequentially, and the order in which the components constituting the molding material composition are added does not matter.
• the mixing operation may be a batch type mixer or a continuous type kneader, or both may be used in combination.
• the polymer may be added as a powder or as a solution dissolved in a solvent.
• the mixing operation is not particularly limited, and for example, a multi-screw extruder, a bead mill, a roll kneader, a closed kneader (for example, a kneader, a Banbury mixer, a planetary stirrer, etc.), a high-speed stirring mixer (for example, a Henschel mixer). , Coffee mill, etc.), rolling granulators, fluidized layer granulators, and other known mixing devices.
• the operating temperature of the mixing is preferably not more than the melting point of the polymer (P1), and usually preferably not more than room temperature (35 ° C. or less).
• the operating temperature of the mixing is preferably 0 ° C. or higher, preferably 0 ° C. or higher, preferably equal to or higher than the freezing point of the plasticizer (PS).
• PS plasticizer
• the molding material composition used in the present invention has plasticity and independence.
• “having plasticity” means that a molding material composition has “plasticity” even after a mass of the molding material composition is divided into two or more portions under the condition of 25 ° C. to be united into one mass. Refers to what can be done.
• “having independence” means having resistance to deformation and collapse due to its own weight when standing and moving in space, and maintaining its shape, that is, keeping the material stationary for a long period of time. It means that when placed, the shape is maintained without being affected by its own weight, etc., and it can move in the air while maintaining the shape.
• "having self-sustaining” means that it can be shaped into a sheet of at least 10 x 10 x 2 mm under the condition of 25 ° C., and does not flow when the sheet is placed on a flat table. It means that the shape does not change for at least 1 hour or more, and this can be grasped and lifted with tweezers having an area of 1/10 cm 2 or less from the edge of the sheet. It can be said that it has a high degree of independence so that it can be lifted with a larger area and thinner thickness.
• the filler (F) refers to a solid substance that forms a member for an electrochemical device.
• the filler (F) is usually granular or powdery.
• the filler (F) may preferably be a solid substance having a minor axis smaller than the member thickness.
• Examples of the filler (F) include active material (A), inorganic solid electrolyte, fibrous material, solid lubricant, conductive material (eg, conductive carbon), reinforcing material, output improver, flame retardant, and gas generation. Examples include agents, resistance-increasing plastic particles, and other simple fillers with no particular function.
• These classifications of the filler (F) are classifications based on function, use, physical properties, etc., and the same substance may belong to a plurality of classifications in duplicate.
• the filler When the filler is in the form of particles, it is preferable to reduce the particle size because the specific surface area increases and the cohesive force becomes stronger.
• the filler (F) it is preferable to use a filler having a nano size (maximum diameter is less than 1 ⁇ m), and it is more preferable to use a filler having a volume average particle diameter of 100 nm or more and 900 nm or less. If a nano-sized filler is used, the contact boundary area with the electrolyte becomes large, so that a member having excellent strength (eg, an electrode) can be formed and a member capable of satisfactorily advancing an electrochemical reaction (a member). For example, electrodes) can be formed.
• a member having excellent strength eg, an electrode
• a member capable of satisfactorily advancing an electrochemical reaction a member capable of satisfactorily advancing an electrochemical reaction
• the diameter of the filler is preferably smaller than the thickness of the member itself, but even when the major axis is larger than the thickness of the member itself, if the minor diameter is smaller than the thickness of the member, it can be used because it is oriented laterally.
• the volume average particle size of the particulate filler can be measured according to JIS K8825.
• the content ratio of the filler (F) in the molding material composition is preferably 50% by volume or more, and more preferably 60% by volume or more.
• a member eg, electrode
• an electrochemical device having high functionality eg, high capacity
• the solid content in the molding material composition is preferably 40 vol% or more, 50 vol% or more, 60 vol% or more, and 70 vol% or more.
• the content of the solid content in the molding material composition becomes inferior in plasticity when it exceeds 80 vol%, and therefore it is preferably 80 vol% or less.
• the active material density is high from the viewpoint of energy density.
• the active material (A) is not particularly limited, and any active material depending on the type of the electrochemical device can be used.
• the active material (A) contained in the molding material composition may be composed of only one type of active material, or may be a mixture of two or more types of active materials.
• Examples of the active material (A) include an electrode active material (when the member for an electrochemical device is an electrode).
• the electrode contains an electrode active material as the active material (A).
• the electrode active material an electrode active material corresponding to the type of the electrochemical device using the electrode to be manufactured can be used.
• the electrochemical device is a battery (eg, a non-aqueous or hydrous secondary battery such as a lithium ion secondary battery (non-aqueous, hydrous), a lithium primary cell, a manganese primary cell (manganese zinc primary cell, manganese lithium primary cell).
• a non-aqueous or hydrous primary cell such as a battery
• the following electrode active material can be used without particular limitation as the electrode active material.
• Non-aqueous or hydrous secondary batteries such as batteries (eg, lithium ion secondary batteries (non-aqueous, hydrous), lithium primary batteries, manganese primary batteries (manganese zinc primary batteries, manganese lithium primary batteries), etc.
• batteries eg, lithium ion secondary batteries (non-aqueous, hydrous), lithium primary batteries, manganese primary batteries (manganese zinc primary batteries, manganese lithium primary batteries), etc.
• Examples of the positive electrode active material to be blended in the positive electrode mixture layer of the positive electrode of a (hydraulic primary cell) are a compound containing a transition metal, for example, a transition metal oxide, a transition metal sulfide, or a composite of lithium and a transition metal. Metal oxides, single sulfur, redox-active organic compounds, and the like can be used.
• the transition metal examples include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
• the positive electrode active material is not particularly limited, and is limited to lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2 ), and Co-.
• the above-mentioned positive electrode active material may be used alone or in combination of two or more.
• Non-aqueous or water-containing secondary batteries such as batteries (eg, lithium ion secondary batteries (non-aqueous, water-containing), lithium primary batteries, manganese primary batteries (manganese-zinc primary batteries, manganese lithium primary batteries), etc.
• Examples of the negative electrode active material blended in the negative electrode mixture layer of the negative electrode of the water-containing primary battery include a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material combining these.
• the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton to which lithium can be inserted (also referred to as “dope”).
• the carbon-based negative electrode active material examples include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, thermally decomposed vapor-grown carbon fiber, phenol resin calcined product, and polyacrylonitrile-based carbon fiber.
• Examples include carbonic materials such as pseudoisotropic carbon, furfuryl alcohol resin calcined product (PFA) and hard carbon, and graphite materials such as natural graphite and artificial graphite.
• the metal-based negative electrode active material is an active material containing a metal, and usually contains an element into which lithium can be inserted in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh /. An active material having a mass of g or more.
• the metal-based active material for example, a lithium metal or a simple substance metal capable of forming a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Mg, Ni, P, Pb, Sb) , Si, Sn, Sr, Zn, Ti, etc.) and their oxides, sulfides, nitrides, silides, carbides, phosphates, oxalates, formates and the like. Further, oxides such as lithium titanate can be mentioned.
• the above-mentioned negative electrode active material may be used alone or in combination of two or more.
• the insulating member may contain a filler for an insulating layer.
• a filler for the insulating layer can be used according to the type of the electrochemical device that uses the insulating layer to be manufactured.
• the filler for the insulating layer can be arbitrarily selected from substances other than substances having electrical conductivity (conductive materials), for example, simple fillers, solid electrolytes, fibrous substances, solid lubricants, reinforcing materials, output improvers, etc.
• One or more combinations may be selected from flame retardant, gas generating agent, resistance-increasing plastic, and the like.
• the amount may be any amount as long as it does not exhibit conductivity as an insulating layer.
• the filler for the insulating layer is not particularly limited as long as it is not a conductive material, and exists stably under the usage environment of the electrochemical device.
• examples thereof include particles made of an inorganic material (that is, non-conductive inorganic particles) and particles made of an organic material (that is, non-conductive organic particles) that are electrochemically stable. Of these, non-conductive inorganic particles are preferable.
• Preferred examples of the non-conductive inorganic particles include simple fillers other than substances having electrical conductivity (conductive materials).
• the molding material composition may contain an inorganic solid electrolyte as the filler (F).
• the inorganic solid electrolyte may be, for example, an ionic conductive ceramic.
• Examples of the inorganic solid electrolyte include Li-Ge-PS -based conductors (eg, Li 10 GeP 2 S 12 ) and Li-Si-PS-Cl-based conductors (eg, Li 9.54 Si 1).
• Li-La-Zr-O conductor eg, Li 7 La 3 Zr 2 O 12
• ⁇ -alumina Sodium ion conductor
• copper ion conductors such as Rb-Cu-IC conductors (eg, RbCu 4 I 1.75 Cl 3.25 ), Ag-I-W-O conductors (eg, RbCu 4 I 1.75 Cl 3.25).
• Ag 6 I 4 WO 4 silver ion conductors and the like can be mentioned.
• the material composition may further contain a fibrous substance as a filler (F).
• a fibrous substance a substance having a fiber diameter at least equal to or less than the member thickness and having an aspect ratio of 100 or more is preferable.
• the fibrous substance include fibers such as carbon, metal, plastic, natural polymer, and ceramic. Of these, nanofibers having a fiber diameter of 1 ⁇ m or less are preferable, and nanosizes (maximum diameter is less than 1 ⁇ m) are preferable.
• nanofibers having such a fiber diameter include carbon nanotubes (CNT), carbon nanofibers, cellulose nanofibers, polytetrafluoroethylene (PTFE), and ceramic nanofibers.
• the fiber length of the fibrous substance is not particularly limited, but may be, for example, 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more from the viewpoint of joining the fillers, and from the viewpoint of handleability of the raw material. For example, it may be 5 cm or less, preferably 1 cm or less, and more preferably 1 mm or less. Further, the fiber length of the fibrous substance is preferably equal to or larger than the thickness of the member (eg, electrode) for an electrochemical device from the viewpoint of aligning the fiber in the plane direction to improve the tensile strength.
• the member eg, electrode
• the amount of the fibrous substance is preferably 8 parts by weight or less, more preferably 5 parts by weight or less, still more preferably 3 parts by weight, based on the entire molding material composition. It may be as follows. There is a conventional technique for producing an electrode using only PTFE as a binder, but a large amount of PTFE of 10 parts by weight or more is required, and the density of the electrode tends to be low. In the present invention, since the force of binding fillers such as active materials and conductive particles is mainly due to the adhesiveness of the plasticized polymer, the fibrous material plays an auxiliary role and does not require a large amount of addition. ..
• the molding material composition may contain a solid lubricant as the filler (F).
• the solid lubricant include those listed in Group B below. [Group B: graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metal soap]
• metal soaps include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, calcium 12-hydroxystearate, calcium montanate, barium stearate, barium oleate, and lauric acid.
• metal soaps include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, calcium 12-hydroxystearate, calcium montanate, barium stearate, barium oleate, and lauric acid.
• examples thereof include barium, barium arachidate, barium behenate, zinc stearate, zinc oleate, zinc laurate, and lithium stearate.
• the concentration of the solid lubricant with respect to the molding material composition is not particularly limited, but is, for example, 0.5% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more from the viewpoint of exhibiting lubricity. From the viewpoint of increasing the ratio of the active material and the insulating layer filler, for example, it may be 5% by weight or less, preferably 8% by weight or less, and more preferably 10% by weight or less.
• the molding material composition may contain a conductive material as the filler (F).
• the conductive material include conductive carbon (eg, graphite (graphite), expanded graphite, graphene, acetylene black, Ketjen black (registered trademark), carbon nanohorn, fullerene, CNT), metal powder (eg, aluminum, etc.). Zinc, iron, copper, silver, gold, nickel, titanium).
• the concentration of the conductive material with respect to the molding material composition is not particularly limited, but may be, for example, 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more from the viewpoint of exhibiting conductivity. From the viewpoint of increasing the ratio of the active material, it may be, for example, 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less.
• the molding material composition may contain a reinforcing material as the filler (F).
• the reinforcing material include whiskers having a large aspect ratio.
• the molding material composition may contain an output improver as the filler (F).
• the output improver include a filler that imparts ion dissociation assistance and a filler that imparts output to an electrochemical device.
• the filler that imparts ion dissociation assistance include nanofillers (eg, silica, alumina, zirconia, titania).
• the filler that imparts output to the electrochemical device include a ferroelectric substance such as barium titanate.
• the molding material composition may contain a flame retardant as the filler (F).
• Flame retardants include, for example, red phosphorus, aluminum hydroxide, magnesium hydroxide, antimony (eg, antimon trioxide), phosphinate metal salts, cyclophosphazene oligomers, polyphosphazene, aliphatic phosphate amidate (eg, DAIGUARD-850). : Daihachi Chemical Industry Co., Ltd.), chlorinated paraffin (eg, Empara 70: Ajinomoto Fine Techno), melamine cyanurate.
• the concentration of the flame retardant with respect to the molding material composition is not particularly limited, but may be, for example, 5% by weight or more, preferably 8% by weight or more, and more preferably 10% by weight or more from the viewpoint of exhibiting flame retardancy. From the viewpoint of not interfering with the operation of the electrochemical device, for example, it may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less.
• the molding material composition is used as a filler (F) as a gas generating agent (gas is generated when abnormal heat is generated). It has the effect of increasing the electrode resistance).
• the gas generating agent include melamine, melamine cyanurate, ammonium carbonate, ammonium chloride, baking soda, and OBSH.
• the molding material composition may contain the resistance-increasing plastic particles as the filler (F) from the viewpoint of imparting the effect of melting at the time of abnormal heat generation of the electrochemical device to increase the electrode resistance and enhancing the safety.
• the resistance-increasing plastic particles include polyethylene and polypropylene.
• the molding material composition may contain other simple fillers having no particular function as the filler (F).
• a filler composed of a substance having no electrical conductivity can also be used as a filler for an insulating layer.
• Fillers that can be used both as a simple filler and as a filler for an insulating layer include, for example, aluminum oxide (alumina, Al 2 O 3 ), aluminum oxide hydrate (bemite, Al OOH), and gibsite (Al (OH).
• Inorganic oxide particles such as silicon oxide, magnesium oxide (magnesia), magnesium hydroxide, calcium oxide, titanium oxide (titania), barium titanate (BaTIO 3 ), ZrO, silica, alumina-silica composite oxide, etc.
• Nitride particles such as aluminum oxide and boron nitride; Covalently bonded crystal particles such as silicon and diamond; Poorly soluble ion crystal particles such as barium sulfate, calcium fluoride and barium fluoride; Clay fine particles such as talc and montmorillonite; etc. Can be mentioned.
• the non-conductive particles include particles made of alumina (alumina particles), particles made of boehmite (boehmite particles), particles made of titania (titania particles), and barium sulfate.
• Particles made of (barium sulfate particles) are preferable, alumina particles, boehmite particles, and barium sulfate particles are more preferable, and alumina particles and barium sulfate particles are even more preferable.
• these particles may be subjected to element substitution, surface treatment, solid solution formation, etc., if necessary.
• one type of these particles may be used alone, or two or more types may be used in combination.
• ⁇ Selection of filler (F)> As the selection of the filler (F), the effect of contributing to the improvement of production efficiency or safety in the manufacture of the member for the electrochemical device, the improvement of the performance or safety of the member for the electrochemical device, the constant quality, etc. You can expect and choose.
• the filler expected to improve the ionic conductivity for example, the above-mentioned inorganic solid electrolyte may be selected.
• the above-mentioned reinforcing material may be selected as the filler that imparts reinforcing properties to the electrochemical device.
• the filler that imparts flame retardancy to the electrochemical device for example, the above-mentioned flame retardant may be selected.
• the filler for improving the output of the electrochemical device for example, the above-mentioned output improver (eg, a filler for imparting ion dissociation assistance, a filler for imparting output to the electrochemical device) may be selected.
• the above-mentioned gas generating agent may be selected as a filler that gives the effect of generating gas to increase the electrode resistance when the electrochemical device generates abnormal heat.
• the filler which has the effect of increasing the electrode resistance by melting when the electrochemical device generates abnormal heat
• the above-mentioned plastic particles may be selected.
• the filler for improving the conductivity of the electrode for example, the above-mentioned conductive material may be selected.
• the above-mentioned solid lubricant may be selected as a filler having an effect of smoothing the molding process and enabling processing of the molding material composition with a small force.
• the molding material composition used in the present invention may further contain a second polymer (P2) that is plasticized with a plasticizer (PS) but is insoluble in the electrolytic solution.
• P2 second polymer
• PS plasticizer
• the molding material composition used in the present invention may further contain other additional components. Additional ingredients include, for example, cross-linking agents.
• the "polymer” (polymer (P1), polymer (P2)) contained in the molding material composition means a molecule having a weight average molecular weight of 10,000 or more.
• the main chain of the polymer used in the present invention include an aromatic ring, a sugar chain, a peptide chain, a carbonic acid ester chain, a methylene chain, a polyether chain, a chain containing nitrogen in the main chain, or a composite thereof. ..
• the main chain of the polymer used in the present invention is a non-cellulosic sugar chain, a peptide chain, a methylene chain, from the viewpoint of imparting flexibility to the molding material composition.
• a polyether chain and a polyethyleneimine chain are preferable, and a chain containing a methylene chain, a polyether chain, and nitrogen in the main chain is most preferable.
• the substituent or side chain bonded to the main chain of the polymer used in the present invention include a cyano group, a hydroxyl group, a carboxylic acid, a carboxylate, a chain ester, a cyclic ester, a chain amide, a cyclic amide, and a pyridyl group. Examples thereof include oxazoline groups, polyether chains, amines, ammoniums, organic ammoniums, etc., and one type of polymer may have a plurality of types of substituents or side chains.
• the substituent or side chain of the polymer used in the present invention may be appropriately selected from the viewpoint of adjusting the solubility in a plasticizer or an electrolytic solution. For example, increasing the number of polar groups makes them water-soluble, and decreasing them makes them water-insoluble. Further, the design may be made with reference to the SP value. From the viewpoint of imparting viscosity to the polymer solution, a higher weight average molecular weight is preferable, and it is 50,000 or more, more preferably 100,000 or more. On the other hand, if there are many components having an excessively high molecular weight, the skin of the molded product may become rough or the molding speed may decrease. Therefore, it is preferable that the components exceeding 10 million are 5% by weight or less of the total polymer solution. More preferably, more than 5 million components are 5% by weight or less of the total polymer solution.
• polymer (polymer (P1), polymer (P2)) include polyethylene oxide, sodium polyacrylate, lithium polyacrylate, polyacrylic acid ester, polyvinyl alcohol, poly-N-vinylpyrrolidone, and polyvinyl acetate.
• Synthetic polymers such as deliquescent polymers such as polyamideamine epichlorohydrin), dextrins, cyclodextrins ( ⁇ -cyclodextrin, ⁇ -cyclodextrin or ⁇ -cyclodextrin, etc.), tamarind gum, Arabic gum , Gua gum, carrageenan, quince seed, pregelatinized starch, tragacanth gum, carob gum, pectin, galactan, karaya gum, canten, algae colloid, xanthan gum, dextran, succinoglucan, purulan, collagen, gelatin, casein, albumin alginic acid, glucomannan, mutin , Fucoidan, sulfated fucose, polyglutamic acid ( ⁇ polyglutamic acid), mannan, mannose and other natural polymers, carboxymethyl starch, methyl hydroxypropyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl
• the polymer used in the present invention is a polymer containing ethylene oxide (EO) as a monomer unit (eg, polyethylene oxide, high ethylene oxide content ethylene oxide copolymer, low ethylene oxide).
• EO ethylene oxide
• Ethylene oxide copolymer polyoxazoline-based polymer (eg, polyoxazoline, oxazoline copolymer), poly-N-vinylacetamide-based polymer (eg, poly-N-vinylacetamide, N-vinylacetamide copolymer weight) (Combined), poly-N-vinylpyrrolidone, polyvinylacetate, and epichlorohydrin-organicamine condensates (eg, dimethylamine-epichlorohydrin-ethylenediamine copolymer, polyamideamine epichlorohydrin) are preferred.
• polyoxazoline-based polymer eg, polyoxazoline, oxazoline copolymer
• poly-N-vinylacetamide-based polymer eg, poly-N-vinylacetamide, N-vinylacetamide copolymer weight
• epichlorohydrin-organicamine condensates eg, dimethylamine-epichlorohydr
• high content means that the ratio of monomer units to all monomer units in the copolymer is, for example, 50 mol% or more, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more. , Or 90 mol% or more.
• low content means that the ratio of monomer units to all monomer units in the copolymer is, for example, less than 50 mol%, preferably 40 mol% or less, 30 mol% or less, 20 mol% or less. , Or 10 mol% or less.
• the polymer used in the present invention is preferably a poly-N-vinylacetamide, poly-N-vinylpyrrolidone, polyacrylic acid-based or alginic acid-based polymer.
• the polymer used in the present invention is deliquescent such as an epichlorohydrin-dimethylamine condensate (eg, dimethylamine-epichlorohydrin-ethylenediamine copolymer). Polymers are preferred.
• the viscosity of the polymer used in the present invention is preferably high from the viewpoint of retaining the filler well in the member, and the viscosity of the polymer solution is, for example, 100 cP or more, preferably 500 cP or more, more preferably 1000 cP or more. 5000 cP or more is preferable.
• the polymer used in the present invention is preferably one that is not gelled.
• the viscosity of the polymer solution can be measured by the following method.
• viscosity means that the composition of the polymer solution does not change under closed conditions using an EMS viscometer (EMS-1000S, manufactured by Kyoto Electronics Industry Co., Ltd.) at a temperature of 25 ° C. Refers to the viscosity measured at 1000 rotations.
• the viscosity measured by this measuring method is basically the same as the value measured in accordance with JIS Z8803.
• the amount of the polymer in the polymer solution is preferably 90 wt% or less from the viewpoint of flexibility of the electrochemical device member (eg, electrode), 1 wt% or more is necessary for the development of moldability, and 3 wt% or more is preferable. ..
• the polymers In order to meet the requirements for "polymers" in molding material compositions, they must be “polymers” during the molding process and include those that polymerize in electrochemical devices (eg batteries) to become polymers. Absent. If the polymer is not plasticized by the electrolyte solvent, the flexibility of the electrode is low, and there is a risk of damage due to deformation due to external force or deformation due to a chemical reaction accompanying the operation of the device. If the member contains a polymer soluble in the electrolyte solvent, the flexibility of the electrode is maintained and there is less risk of damage even if the device is deformed.
• the first polymer (P1) is plasticized with a plasticizer (PS). Therefore, the polymer (P1) is a plasticizer (P1) used in the present invention. A polymer having the property of being plasticized in —S) is used. Further, the polymer (P1) is preferably a polymer having a property of being plasticized even with an electrolytic solution solvent (ES) from the viewpoint of maintaining flexibility even after becoming an electrochemical device. Further, when the method for producing a member for an electrochemical device of the present invention includes cross-linking a polymer (P1), the polymer (P1) may be a cross-linking polymer.
• crosslinkable polymer examples include an irreversible crosslinkable polymer and a reversible crosslinkable polymer, and an irreversible crosslinkable polymer is preferable.
• examples of the crosslinkable polymer include a heat crosslinkable polymer and a UV crosslinkable polymer.
• examples of the crosslinkable polymer include a polymer crosslinked with a crosslinking agent and a self-crosslinkable polymer.
• Examples of the polymer cross-linked with a cross-linking agent examples include those having a cross-linking group such as an unsaturated bond, an epoxy group, and an oxetane group in the molecule.
• the polymer (P1) can be appropriately selected from the above-mentioned polymers according to the types of the plasticizer (PS) and the electrolytic solution solvent (ES). Examples of the combination of the polymer (P1), the plasticizer (PS), and the electrolytic solution solvent (ES) include those described below.
• the molding material composition may further contain a second polymer (P2) that is plasticized with a plasticizer (PS) but is insoluble in the electrolyte.
• the first polymer (P1) and the second polymer (P2) are plasticized with a plasticizer (PS).
• PS plasticizer
• the inclusion of the polymer (P2) in the molding material composition is advantageous in limiting the contact between the filler and the electrolyte. By limiting the contact between the filler and the electrolyte, unnecessary reactions are suppressed and the life of the electrochemical device is extended.
• the polymer (P1) can be appropriately selected from the above-mentioned polymers according to the types of the plasticizer (PS) and the electrolytic solution. Examples of the combination of the polymer (P1), the plasticizer (PS), and the electrolytic solution include those described below.
• the plasticizer (PS) is water, an ionic liquid, or a mixture thereof.
• the ionic liquid include N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI, water-insoluble ionic liquid), 1-ethyl-3.
• EMI-TFSI water-insoluble ionic liquid
• DEME-BF4 N, N-diethyl-N-methyl-N- (2-methoxyethyl) -tetrafluoroborate
• ES electrolyte solvent
• the amount of plasticizer (PS) for plasticizing the polymer is not particularly limited, but it is often 5% by weight or more based on the weight of the polymer, and 10% by weight or more is often plasticized. it can.
• the plasticizer (PS) content in the molding material composition may be, for example, 3% by weight or more, preferably 5% by weight or more. In any case, it is better to confirm by looking at the actual properties, not the amount.
• the electrolytic solution solvent (ES) and the electrolytic solution are not particularly limited, and any electrolytic solution used in the electrochemical device can be used.
• the electrolytic solution solvent (ES) include substances (water, ionic liquid, or a mixture thereof) used as a plasticizer (PS), propylene carbonate (PC), ethylene carbonate, and chain carbonate.
• examples thereof include organic solvents such as lactones, chain carboxylic acid esters, acetonitrile, sulfolanes, glides, chain sulfones, dinitrile compounds, cyclic ethers and fluorinated ethers.
• electrolyte examples include electrolytes (eg, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, lithium sulfate, magnesium sulfate, sulfuric acid, sodium hydroxide, lithium hexafluorophosphate (LiPF 6 ), lithium bis (fluorosulfonyl).
• electrolytes eg, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, lithium sulfate, magnesium sulfate, sulfuric acid, sodium hydroxide, lithium hexafluorophosphate (LiPF 6 ), lithium bis (fluorosulfonyl).
• Imido LiFSI
• LiTFSI Lithium bis (trifluoromethanesulfonyl) imide
• LiBF 4 Lithium tetrafluoroborate
• Magnesium bis (trifluoromethanesulfonyl) imide Mg (TFSI) 2
• ES electrolyte solvent
• ES electrolyte solvent
• a solvent or salt having high ionic conductivity for a device having a thick electrode exceeding 100 ⁇ m, it is preferable to select a solvent or salt having high ionic conductivity, and specifically, as the solvent, water, acetonitrile, ethylene glycol dimethyl ether, methyl acetate, etc. It is preferable to contain any of bis (2,2,2-trifluoroethyl) ether and 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether as the electrolyte salt. , A salt of FSI anion, is preferably included.
• polymers (P1) and (P2) ⁇ Examples of polymers (P1) and (P2)>
• the plasticizer (PS) is water and the electrolyte solvent (ES) is propylene carbonate (PC)
• the polymer that can be selected as the polymer (P1) is, for example, polyethylene oxide (PEO) or ethylene oxide.
• PEO polyethylene oxide
• EO High content EO copolymer, polyoxazoline, poly-N-vinylacetamide, carboxymethyl cellulose (CMC), Na polyacrylate, Na alginate, polyvinyl alcohol (PVOH) can be mentioned.
• examples of the polymer that can be selected as the polymer (P1) that is also plasticized with the electrolyte solvent (ES) include PEO, EO high content EO copolymer, polyoxazoline, and poly-N-vinylacetamide. Can be mentioned.
• examples of the polymer that can be selected as the polymer (P2) include CMC, sodium polyacrylate, sodium alginate, and PVOH.
• the polymer that can be selected as the polymer (P1) includes, for example, PEO, EO high content EO copolymer, and the like. Examples thereof include CMC, Na polyacrylic acid, Na alginate, PVOH, polyethyleneimine, polyoxazoline, and poly-N-vinylacetamide.
• the polymer (P1) that is also plasticized with the electrolyte solvent (ES) may be selected from these polymers.
• the polymer (P1) may be, for example, PEO, EO high content EO copolymer, or low EO. Examples thereof include EO copolymers, styrene-acrylic copolymers, celluloses, polyoxazolines, and poly-N-vinylacetamides. In this case, the polymer (P1) that is also plasticized with the electrolyte solvent (ES) may be selected from these polymers.
• the polymer (P1) includes, for example, both PEO and EO high content EO.
• examples thereof include polymers, polyoxazoline, poly-N-vinylacetamide, EO low content EO copolymer, styrene acrylic copolymer, and cellulose.
• examples of the polymer that can be selected as the polymer (P1) that is also plasticized with the electrolyte solvent (ES) include PEO, EO high content EO copolymer, polyoxazoline, and poly-N-vinylacetamide.
• examples of the polymer that can be selected as the polymer (P2) include an EO low content EO copolymer, a styrene-acrylic copolymer, and cellulose.
• ⁇ Plasticized polymer> When a polymer is "plasticized”, it loses its shape by mixing the polymer with a solvent (eg, plasticizer (PS), electrolyte solvent (ES), electrolyte) ( Liquid or rubbery), which means that a mass of plasticized polymer can be united into a mass even after being divided into two or more portions. However, since the determination cannot be made after the cross-linking operation is performed, the properties in the non-cross-linked state are also applied to the cross-linked body.
• the plasticizer (PS) is an ionic liquid having a repeating structure, the ionic liquid itself is regarded as a "polymer (P1) plasticized with the plasticizer (PS)".
• the amount of the plasticizer (PS) for plasticizing the polymer (P1) is not particularly limited, but may be any amount as long as the polymer (P1) is plasticized.
• the amount of the plasticizer (PS) is usually 5% by weight or more with respect to the polymer (P1), and 10% by weight or more can be plasticized in many cases.
• Organic solvent refers to a nonionic organic compound with a molecular weight of 1000 or less that is neither a polymer nor an ionic liquid.
• the inclusion of an organic solvent is not preferable from the viewpoint of fire and worker health, but since the addition of a small amount does not hinder the practice of the present invention, the polymer and plasticizer (PS) in the molding material composition Up to 10% by weight or less can be added based on the total amount.
• PS polymer and plasticizer
• the molding material composition used in the present invention may further contain the following components and configurations (formation of pseudo-crosslinks).
• pseudo-crosslinks can be formed to increase the strength of the member without losing its plasticity.
• Polyvalent ions especially polyether and polyvalent cations, carboxylic acids and polyvalent cations, polyvinyl alcohol and polyvalent cations, polymers with cation groups and polyvalent anions, polyethyleneimine and polyvalent ions); Polyethylenimine and polycarboxylic acid compounds; Polyvinyl alcohol and borate / borax (sodium tetraborate / lithium tetraborate); Or a triblock polymer with both ends hydrophobicized.
• the molding material composition used in the present invention may further contain an acid, a base, and an electrolyte salt for operating the device.
• the member for an electrochemical device of the present invention is produced by performing at least one shaping operation selected from the following group A on the above-mentioned molding material composition.
• group A Extrusion, injection into mold, stretching, compression molding, thickness reduction by pressure, thickness homogenization by pressure, cutting, drilling, cutting, final shape to be housed in electrochemical device container Bending to, bonding of molding material compositions with different compositions
• the molding material composition used in the present invention has plasticity and self-supporting property, the shape of the desired electrochemical device member can be imparted by the shaping operation, and the imparted shape is maintained throughout the manufacturing process. be able to.
• the amount of solvent such as water in the manufacturing process fluctuates as compared with the case where the slurry is applied and dried to form a device member. It is possible to suppress the quality change of the member due to the above, and to recover the quality by absorbing a solvent such as water after the formation.
• the shaping operation selected from the group A may be performed by a different type of operation, or the same operation may be repeated a plurality of times.
• the shaping operation may be performed at least once by using the molding material composition on the current collecting foil. It may be done in a non-contact state. Further, the shaping operation selected from the group A may be performed at least once in a state where the molding material composition is not in contact with the porous separator film.
• the shaping operation can be performed using known processing equipment such as rollers, presses, cutters, milling cutters, and drills.
• the surface of the roller or the like is preferably a metal, ceramic, glass, fluorine-based polymer, or silicone-based polymer.
• the surface is preferably non-adhesive. It is also possible to control the adhesiveness by making fine irregularities on the roller.
• the member When the member is temporarily placed in the shaping operation, it may be placed on a net, a perforated plate, or a pick-up jig processed into a textured or satin-like shape.
• a tape having a constant thickness may be attached to a roller or the like to control the thickness. If the roller is patterned, the member can be shaped so as to transfer the shape.
• a smaller diameter is preferable because the amount of material adhering to the member is smaller and cleaning is better.
• the molding material composition may be molded into a sheet shape.
• the thickness accuracy when molded into a sheet shape is preferably within ⁇ 10%, more preferably within ⁇ 5%. Adhesion with current collector foil and other members is improved.
• it is preferable to make the surface of the sheet corrugated because it is difficult to stick to a shaping device such as a roller, and it is easy to be crushed so that the thickness can be easily controlled.
• the operation of making the sheet surface corrugated may be performed by making the die outlet corrugated, extruding it in a flat shape and then shaping it with a grooved roller or embossing roller, or cutting it with a blade. It may be formed by lacking.
• the height difference between the highest portion and the lowest portion of the unevenness is preferably 10% or more of the average thickness.
• the thicker the member the less it sticks to the device and the easier it is to manufacture.
• the thickness of the member is preferably 100 ⁇ or more. More preferably, it may be 200 ⁇ or more.
• the insulating layer is thin from the viewpoint of adhesiveness to other members and followability. If the insulating layer is too thick, it tends to peel off at the interface.
• the thickness of the insulating layer may be preferably 100 ⁇ or less, more preferably 50 ⁇ or less, still more preferably 20 ⁇ or less.
• the molding material composition should be stored in a closed container as much as possible when not in use.
• a protective film that prevents moisture absorption and drying may be attached to the molding material composition during the process or storage.
• the method for manufacturing a member for an electrochemical device of the present invention may further include, for example, the following additional steps.
• the method for producing a member for an electrochemical device of the present invention may further include cross-linking a polymer (P1).
• the cross-linking include irreversible cross-linking and reversible cross-linking, and irreversible cross-linking is preferable.
• known cross-linking methods such as thermal cross-linking, UV cross-linking, electron beam cross-linking, and radiation cross-linking can be used.
• the cross-linking of the electrode and the conductive layer is preferably thermal cross-linking or electron beam cross-linking. UV cross-linking is preferable for cross-linking the insulating layer because the material is transparent.
• cross-linking examples include cross-linking with a cross-linking agent (eg, UV initiator) and self-cross-linking.
• a cross-linking agent eg, UV initiator
• the cross-linking agent is preferably added in the electrochemical device, for example, may be added in the molding material composition, and a portion other than the molding material composition (eg, electrolysis). It may be added in the liquid).
• a low-molecular-weight co-crosslinking agent having a plurality of cross-linking groups such as TAIC (triallyl isocyanurate) may be used in combination.
• the polymer (P1) and the cross-linking agent can be appropriately selected depending on the mode of cross-linking.
• the polymer (P1) when the cross-linking is self-cross-linking, can be selected as a self-cross-linking polymer.
• the polymer in order to make the polymer a self-crosslinking polymer, for example, it may be a polymer containing an acetoacetyl group, an epoxy group, an oxetane group, an azetidineium group, a pyrrolidonyl group and the like.
• Such self-crosslinking polymers can be self-crosslinked by heating.
• Cross-linking of the polymer (P1) may be performed either during or after plasticizing the polymer (P1) with a plasticizer (PS), before, during, or after the shaping operation. You may go to either.
• PS plasticizer
• the cross-linking operation is preferably performed in a polymer (P1) plasticized state, and may be performed before assembling the device or by heating the device itself after assembling the device. Further, in the manufacture of an electrochemical device, each member may be crosslinked and then assembled, but if the structure of the electrochemical device is completed and then crosslinked, the whole can be integrated and the durability is improved, which is preferable.
• the method for manufacturing a member for an electrochemical device of the present invention may further include a feedback control step.
• a feedback management process for example, the basis weight is managed and feedback is given by measuring the characteristics (eg, thickness) of the member. (Since it is not impossible with other compositions, it has been deleted.)
• the basis weight can be measured by measuring the characteristics (eg, thickness) of the member.
• a manufacturing method in which the basis weight is controlled and fed back can be implemented by measuring the thickness. In such a feedback management step, it is not always necessary to mark the members with X-rays or gamma rays, and measurement using a contact type film thickness meter or a laser type film thickness meter may be used.
• the method for producing a member for an electrochemical device of the present invention may include crushing a plurality of strands made of a molding material composition to form a sheet.
• the method for producing a member for an electrochemical device of the present invention may include obtaining a member by scraping from a bulk molding material composition.
• the method for producing a member for an electrochemical device of the present invention may include attaching a molding material composition to a base material (eg, a current collector, a porous separator membrane). The attachment to the base material may be performed, for example, after the molding material composition is molded to a desired thickness.
• the attachment to the base material may be performed, for example, by attaching the molding material composition from the front and back sides of the base material substantially at the same time, and after the molding material composition is attached to the front side of the base material, also on the back side. It may be done by pasting.
• the base material is a conductive base material (for example, a current collector such as a current collector foil)
• the base material may have a conductive coat on the surface in contact with the molding material composition. Examples of the conductive coating include carbon paint, ITO, and metal plating.
• the conductive coat may be applied to the current collecting foil side, or may be applied to the member side or sprayed. If the conductive coat has sufficient strength and conductivity, it can itself be a conductive substrate (eg, a current collector).
• the current collector may be a metal or a non-metal main body.
• a non-metallic current collector for example, a polymer such as polyethylene, polypropylene, cellulose, or rubber mixed with a conductive carbon or metal material to make it conductive can be used.
• the base material is an insulating base material (for example, a separator base material such as a porous separator membrane)
• the base material may mainly contain a polymer.
• Examples of the base material containing a polymer as a main component include polyethylene, polypropylene, cellulose, rubber and the like.
• the method for manufacturing a member for an electrochemical device of the present invention may include a step of peeling a molding material composition already attached to the base material from the base material.
• the method for producing a member for an electrochemical device of the present invention may include removing water by a drying operation to bring it into a non-plasticized state.
• the drying operation may be performed before or after the molding material composition is incorporated (eg, shaped) into the final shape when the member is placed in the device.
• the drying operation may be performed, for example, in a vacuum, in a low humidity atmosphere, or by heating.
• the vacuum means reducing the pressure to such an extent that the water contained in the member is removed, and may be reduced to, for example, 100 Pa, preferably 10 Pa, and more preferably 1 Pa.
• the low humidity atmosphere is a humidity sufficient to remove the moisture contained in the member, and is, for example, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30 at room temperature.
• the atmosphere may have a relative humidity of% or less, 20% or less, and 10% or less.
• Heating means placing the member at a temperature at which the moisture contained in the member is removed and the member is not denatured, and the temperature is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, and more preferably 100 ° C. or higher. It may be, for example, 300 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
• the drying operation may be performed in a state where the molding material composition is not in contact with the current collector foil. Further, the drying operation may be performed in a state where the molding material composition is not in contact with the porous separator membrane.
• the drying operation by the drying oven in the previous stage which normally exists, can be omitted. In this case, since the shape is formed in the plasticized state, it is possible to prevent the member from being damaged without applying an excessive force to obtain the final shape.
• the method for producing a member for an electrochemical device of the present invention may include restoring the plasticized state by watering or humidifying again after the molding material composition is in the non-plasticized state.
• Water may be added, for example, under the condition that dropping or spraying is performed at 25 ° C. for 1 second. Humidification may be performed under the condition of, for example, 25 ° C. and 99% RH.
• the molding material composition may be incorporated (eg, shaped) into the final shape when the member is placed on the device after the plasticized state has been restored.
• the plasticizer (PS) reduction operation for storage does not need to be performed until the polymer is no longer liquid or rubbery.
• the plasticizer (PS) reduction operation is preferably reduced to 90% or less, more preferably 80% or less, based on the total amount of the added plasticizer (PS).
• PS plasticizer
• the plasticizer (PS) reduction operation cannot be performed.
• the member for the electrochemical device is strongly attached, it is preferable to sandwich the plastic film during storage.
• the material is not particularly limited, but PE, PP, PET, PTFE and the like are preferable, and may be subjected to a mold release treatment or a concavo-convex treatment.
• the method for manufacturing a member for an electrochemical device of the present invention may include manufacturing the next member again using the scraps of the molding material composition produced in the process of shaping the molding material composition. Since the molding material composition used in the present invention has plasticity and independence, irreversible quality fluctuations are suppressed in the manufacturing process. Can be used. When the scraps of the molding material composition are reused, it is preferable to dry them to the equilibrium moisture of the environment and then rehydrate them from the viewpoint of quantitativeness. When rehydrating the member, operations such as raising the atmospheric humidity, spraying, dropping, electrostatic spraying, and dipping can be preferably used. When an ionic liquid, an organic solvent, or the like is added to the member, operations such as spraying, dropping, electrostatic spraying, and dipping can be preferably used.
• the method for manufacturing a member for an electrochemical device of the present invention may be carried out in a normal humidity environment or a dry environment (dry room, glove box).
• a dry environment 50% RH or less
• the molding material composition used in the present invention has plasticity and independence, irreversible quality fluctuations are suppressed in the manufacturing process. Therefore, for example, the molding material composition in the intermediate process of manufacturing (eg, already a base material).
• the members for the electrochemical device can be recycled by using the molding material composition attached to the molding material composition, the molding material composition in the non-plasticized state, and the scraps of the molding material composition.
• the method for recycling the member for an electrochemical device may include, for example, a step of peeling the molding material composition already attached to the base material from the base material.
• the method for recycling the member for an electrochemical device may include, for example, restoring the plasticized state by adding water or humidifying again after the molding material composition is in the non-plasticized state. Further, the method for recycling a member for an electrochemical device may include, for example, manufacturing the next member again by using the scrap of the molding material composition produced in the process of shaping the molding material composition. Good.
• the method for manufacturing an electrochemical device of the present invention includes obtaining a member by the above-mentioned method for manufacturing or recycling a member for an electrochemical device.
• the member for an electrochemical device of the present invention can be obtained by the method for manufacturing or recycling the member for an electrochemical device described above.
• Examples of the member for an electrochemical device of the present invention include an electrode (eg, positive electrode, negative electrode), an insulating layer (eg, insulating film), and an adhesive layer.
• the member for the electrochemical device is preferably an electrode or an insulating layer.
• the electrodes also include the air electrode of the air battery.
• the insulating layer may be used as an insulating layer of a power storage device such as a lithium ion battery, or may be attached to glass or the like on which a conductive ITO (indium tin oxide) layer is formed to be attached to a dye-sensitized solar cell or electro. It can also be used for chromic devices.
• the insulating layer may be used in the device assembly in the plasticized state, or may be dried and used in the non-plasticized state. It is also a preferable embodiment that the device is assembled without cross-linking and finally cross-linked with ultraviolet rays, heat or the like.
• the electrochemical device of the present invention includes the above-mentioned member for an electrochemical device.
• Examples of the electrochemical device of the present invention include non-aqueous or hydrous primary batteries such as lithium primary batteries and manganese primary batteries (eg, manganese zinc primary batteries, manganese lithium primary batteries); lithium ion secondary batteries (non-aqueous, non-aqueous batteries).
• Non-aqueous or hydrous secondary batteries such as (hydrous), lithium metal secondary batteries, sodium ion secondary batteries, potassium ion secondary batteries, magnesium secondary batteries, aluminum secondary batteries; air batteries; dye-sensitized sun Solar batteries such as batteries; capacitors such as electric double layer capacitors and lithium ion capacitors; electrochromic display devices; electrochemical light emitting elements; electric double layer transistors; electrochemical actuators.
• the electrochemical device is preferably a non-aqueous secondary battery, more preferably a lithium ion secondary battery.
• the electrochemical device of the present invention may include, for example, an electrode as a member for the electrochemical device.
• the electrochemical device of the present invention may include an electrode obtained by a manufacturing method or a recycling method described later, and one electrode (counter electrode).
• the counter electrode is at least one selected from, for example, alkali metals (eg, lithium, sodium, potassium, rubidium, cesium), alkaline earth metals (eg, beryllium, magnesium, calcium, strontium, barium), metallic aluminum, and silver. May be included.
• the electrochemical device of the present invention is a Li-ion battery
• a perforated current collector foil is used in the manufacture of the Li-ion battery
• a Li metal electrode is arranged inside the cell in addition to the positive and negative electrodes to perform vertical predoping. Can be carried out. This is an effective method when using an active material having an initial irreversible capacity.
• the electrochemical device of the present invention may be either a hydrous-based electrochemical device or a non-aqueous electrochemical device.
• the hydrous electrochemical device include an electrochemical device containing water in an electrolytic solution (eg, a hydrous battery such as a hydrous lithium ion secondary battery and a manganese zinc primary battery).
• the non-aqueous electrochemical device include a non-aqueous battery such as a non-aqueous lithium ion secondary battery, a lithium primary battery, and a manganese lithium primary battery in which an electrolytic solution is dissolved in an organic solvent and does not contain water. ).
• Hydrous and non-aqueous electrochemical devices include, for example, carrier ions as alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and alkaline earth metal ions (eg, beryllium ion, magnesium ion, calcium ion). ), Aluminum ion, silver ion, organic nitrogen cation (eg, triethylmethylammonium 1-ethyl-3-methylimidazolium), and halide anion (eg, bromide ion, iodide ion). It may be an electrochemical device.
• carrier ions as alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and alkaline earth metal ions (eg, beryllium ion, magnesium ion, calcium ion).
• the following shows an example of an experiment using a lithium ion battery and a manganese battery, but the effect is the same for other devices.
• Example 1 Manufacture and evaluation of an electrode sheet using polyethylene oxide (PEO)
• PEO polyethylene oxide
• a temperature of 25 ° C and a humidity of 90% RH 100 g of lithium cobalt acetate (Celseed C manufactured by Nippon Chemical Industries, Ltd., average particle size 20 ⁇ m) as an active material, 3 g of acetylene black as a conductive auxiliary agent, and a processing solvent.
• Electrode sheet 1 8 g of ion-exchanged water as a polymer P1, 1 g of polyethylene oxide (PEO) (Sigma-Aldrich) having a weight average molecular weight of 1 million as a polymer P1, and 1 g of polytetrafluoroethylene (PTFE) (Sigma-Aldrich) as a fibrous substance. Weighed and mixed to obtain a uniform electrode composition. 1 g of this electrode composition was taken and molded into a sheet having a thickness of 200 ⁇ m on a releasable polyethylene terephthalate (PET) film using a SUS hand roller having a diameter of 3 cm (electrode sheet 1-1).
• PEO polyethylene oxide
• PTFE polytetrafluoroethylene
• the sheet Upon immediate evaluation, the sheet was self-supporting and plastic, and could be bent to a diameter of 2 mm. At this time, polyethylene oxide became an aqueous solution, which is considered to have contributed to the flexibility of the electrode.
• the thickness of the edge of the sheet tended to be slightly thinner than that of the center, and the average thickness at a location 5 mm from the edge was 197 ⁇ m. If necessary, the end portion may be cut off. The cut material can be used again for electrode production.
• Example 2 Production, evaluation, and regeneration of an electrode sheet using a PEO-based polymer
• 1 g of a molar ratio of 9: 1) and 1 g of PTFE were weighed in a dairy pot and mixed to obtain a uniform electrode composition.
• Electrode sheet 2-1 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 2-1). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 2-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm. At this time, the copolymer was an aqueous solution, which is considered to have contributed to the flexibility of the electrode.
• the electrode sheet 2-2 When the electrode sheet 2-2 was left in a laboratory having a temperature of 25 ° C. and a humidity of 55%, the surface became dry in about 1 minute and the adhesiveness was reduced. When it was left as it was for one day, the thickness did not change, but the weight decreased by 7% from the initial stage, and 99% of the added water was volatilized (comparative electrode sheet 2-2). It was judged that polyethylene oxide was not plasticized. When I tried to bend it, it broke at an internal angle of about 120 ° before it was wound around the cylinder. The density of the electrode sheet before breaking in the dry state was 3 g / cm 3 . The volume fraction of the filler in this electrode sheet was 61% by volume when lithium cobalt oxide and acetylene black were added. After that, the density can be improved by further pressing with a high-pressure roll press.
• the electrode sheet 2-2 is further pressed with a roller having a linear pressure of 200 N / cm to reduce the average thickness to 50 ⁇ m (49 to 51 ⁇ m) (electrode sheet 2-3), and contains conductive carbon separately prepared as a current collector. by attaching the thickness 50 ⁇ m of conductive polyethylene film (surface resistance 10 4 ⁇ / sq. or less) to produce a lithium-ion battery cathode (positive electrode 2-4).
• the electrode sheets 2-1, 2-2, 2-3, and the positive electrode 2-4 were cut with scissors in a laboratory at a temperature of 25 ° C and a humidity of 55%, they could be cut in two in a straight line. At this time, small pieces such as fine powder were not generated, and the molding material did not adhere to the scissors. When these were piled up again and stretched with a hand roller, they were united and the same sheet as the first one was regenerated.
• Comparative Example 1 Evaluation of Sheet with Volatilized Moisture
• Electrodes were prepared by the slurry coating method, which is common in the manufacture of lithium-ion batteries and electric double layer capacitor electrodes. All of the electrode slurries using lithium cobalt oxide, graphite, and activated carbon were found to be plastic, but not self-sustaining. When an electrode slurry using graphite was applied to an aluminum foil having a thickness of 25 ⁇ m and an attempt was made to cut it with scissors while it was still undried, a large amount of slurry was attached to the blade. In addition, the slurry flowed out of the current collector foil from the cut portion.
• Comparative Example 3 Manufacture and evaluation of slurry-coated dry electrode
• the coated electrode of Comparative Example 2 was dried in an oven at 60 ° C., and in a dry state, an attempt was made to peel off the electrode mixture of 5 mm from the end of the electrode.
• the interface between the aluminum and the mixture was peeled off with a plastic spatula, but fine powder was generated by the peeling and adhered to the surroundings.
• Example 3 Evaluation of adhesion of electrode sheet using PEO polymer
• the electrode sheet 2-3 of Example 2 is cut into a size of 5 cm square, placed on an aluminum foil having a thickness of 25 ⁇ m in a laboratory at a temperature of 25 ° C. and a humidity of 55%, and the entire surface of the electrode sheet 2-3 is lightly pressed from above with a hand roller.
• the electrode sheet 2-2 and the aluminum foil were in close contact with each other.
• the edge of the sheet was a little thin, so I made a notch at the outer circumference of 5 mm so that it would not reach the current collector foil, pinched the edge with tweezers and peeled it off, without producing small pieces or fine powder.
• the outer molding material could be removed as a square frame shape (positive electrode 3).
• positive electrode 3 When the 4 cm square electrode sheet was further left in a laboratory at a temperature of 25 ° C. and a humidity of 55% for 24 hours, a weight loss due to volatilization of water was observed as in Example 1, but the electrode sheet was observed. The adhesion between 2-3 and the aluminum foil was maintained.
• Example 4 Manufacture and evaluation of an electrode sheet using a polymer other than PEO
• a sheet was prepared in the same manner as in Example 1 except that the polymer P1 was changed to poly-2-ethyloxazoline (sigma-aldrich) having a weight average molecular weight of 500,000. Upon immediate evaluation, this sheet was self-supporting and could be bent with a diameter of 2 mm.
• Example 5 Production and evaluation of an electrode sheet containing the second polymer (P2))
• a lithium ion battery positive electrode having a thickness of 50 ⁇ m was prepared in the same manner as in Example 2 except that 1 g of carboxymethyl cellulose (CMC) was further added as the second polymer (polymer P2) (positive electrode 5).
• the positive electrode capacity retention rate after 200 cycles with respect to the initial capacity was 91% for the positive electrode 2-4 and 95% for the positive electrode 5, and the one containing the polymer P2 was superior. It is considered that this functioned as a protective film on the surface of the positive electrode active material by containing a component (polymer P2) that does not dissolve or swell after being immersed in the electrolytic solution.
• Example 6 Production and evaluation of an electrode sheet using a deliquescent polymer
• This polymer showed deliquescent property, absorbed moisture equivalent to 15% by weight of its own weight in a laboratory at a temperature of 25 ° C. and a humidity of 55%, and spontaneously plasticized into an aqueous solution.
• 9 g of this spontaneously plasticized polymer solution 100 g of lithium cobalt oxide, 3 g of acetylene black, and 1 g of PTFE were weighed in a mortar and mixed to obtain a uniform electrode composition.
• Electrode sheet 6 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 6). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 6-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed with a hand roller could be bent with a diameter of 2 mm.
• the copolymer is an aqueous solution, which is considered to have contributed to the flexibility of the electrode. When this was left for 24 hours, there was no change in weight and the flexibility of the sheet was maintained.
• Example 7 Manufacture and evaluation of electrode sheet using ionic liquid
• the experiment was carried out in a dry room controlled at a dew point temperature of ⁇ 40 ° C. or lower and an air temperature of 25 ° C., and the raw materials used were well dried in advance.
• DEME-TFSI N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide
• the electrode sheet 7 was vacuum dried at 100 ° C. for 24 hours in order to remove water more carefully.
• the moisture content of this sheet was measured with a Karl Fischer titer and found to be 4 ppm.
• Example 8 Combined use of water and ionic liquid, and cross-linking of electrodes
• 100 g of lithium cobaltate, 3 g of acetylene black, and (N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethane) as a water-insoluble ionic liquid.
• the sheet 8-1 When the sheet 8-1 was left in a laboratory with a temperature of 25 ° C and a humidity of 55%, the surface became dry in about 1 minute and the adhesiveness was reduced. Further, the sheet was vacuum dried in a vacuum dryer at 150 ° C. for 30 minutes for the purpose of dehydration and cross-linking by heating. The weight has decreased by 3.5%, and it is considered that almost 100% of the added water has become a volatilized sheet (comparison sheet 8-2), and it is judged that the sheet is plasticized by the polymer ionic liquid. ..
• the comparison sheet 8-2 maintained flexibility and could be bent with a diameter of 5 mm.
• the cross-linking operation is preferably performed in a polymer (P1) plasticized state, and may be performed before assembling the device as in this embodiment, or may be performed by heating the device itself after assembling the device.
• Example 9 Manufacture and evaluation of electrode sheet using cellulose nanofibers
• 1 g of 5: 5) and 2 g of cellulose nanofibers were weighed in a dairy pot and mixed to obtain a uniform electrode composition.
• Electrode sheet 9-1 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having a thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 9-1). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (sheet 9-2) having a thickness of 200 ⁇ m pressed by a hand roller could be bent with a diameter of 2 mm. Polyethylene oxide is an aqueous solution and is thought to have contributed to the flexibility of the electrodes.
• Example 10 Spraying the electrode
• the electrode When a small amount of water was sprayed onto the comparison sheet 2-2 obtained in Example 1, the electrode absorbed the sprayed water and the flexibility was restored. This sheet was able to bend with a diameter of 2 mm.
• the electrode weight was measured, a weight recovery corresponding to 80% of the water content initially contained was observed.
• Example 11 Rehydration to the electrode
• Example 12 Impregnation of the electrode with an electrolytic solution
• a separately prepared 1M LiTFSI / propylene carbonate solution was added dropwise in a small amount so that the electrolytic solution did not overflow from the electrode. It was confirmed that the electrolytic solution permeated into the electrode, and the flexibility of the electrode was restored and the electrode could be bent at 2 mm. Since the random copolymer of ethylene oxide-propylene oxide (molar ratio 9: 1) is soluble in propylene carbonate, it was confirmed that it can be plasticized with an electrolytic solution and maintain its flexibility even in the device.
• Example 13 Graphite electrode
• graphite 604A manufactured by Nippon Carbon Co., Ltd.
• ion-exchanged water 7 g
• ethylene oxide-propylene oxide having a weight average molecular weight of 1 million.
• 1 g of a random copolymer (molar ratio: 9: 1) and 0.2 g of PTFE were weighed in a dairy pot and mixed to obtain a uniform electrode composition.
• Electrode sheet 13-1 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 13-1). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 13-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm.
• a lithium ion battery negative electrode was manufactured by further pressing this with a hand roller to thin it to an average thickness of 50 ⁇ m (49 to 51 ⁇ m) (electrode sheet 13-3) and attaching it to an electrolytic copper foil having a thickness of 25 ⁇ m (negative electrode). 13-3).
• the density of the electrodes in the dry state was 1.74 g / cm 3 .
• the volume fraction of the filler at this electrode is 70 Vol% for graphite alone. After that, the density can be improved by further pressing with a high-pressure roll press.
• Example 14 Addition of solid lubricant
• a molding material was prepared in the same manner as in Example 1 except that 5 g of graphite powder (KS4 manufactured by TIMCAL) was added as a solid lubricant.
• KS4 graphite powder
• TIMCAL graphite powder
• Example 15 Electrode using nano-sized Si 10 g of silicon powder (average particle size 100 nm) as the negative electrode active material of the lithium ion battery, 8 g of ion-exchanged water, and a random copolymer of ethylene oxide-propylene oxide having a weight average molecular weight of 1 million (molar ratio 9: 1). was weighed in a 1 g dairy pot and mixed to obtain a uniform electrode composition. 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 15-1). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 15-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm.
• Example 16 Activated carbon and carbon nanotubes (CNT) 10 g of activated carbon MSP-20 (Kansai Thermochemical), carbon nanotubes (CNT) as a component that doubles as a conductive material and a fibrous substance (ZEONANO SG101 manufactured by Zeon Nanotechnology, Inc., average diameter: 4 nm, average length: 400 ⁇ m, BET Specific surface area: 1150 m2 / g) 0.1 g, DEME-BF4 (N, N-diethyl-N-methyl-N- (2-methoxyethyl) -tetrafluoroborate) as a water-soluble ionic liquid, and 11 g.
• activated carbon MSP-20 Kansai Thermochemical
• CNT carbon nanotubes
• ZONANO SG101 manufactured by Zeon Nanotechnology, Inc., average diameter: 4 nm, average length: 400 ⁇ m
• BET Specific surface area 1150 m2 / g
• a random copolymer of ethylene oxide-propylene oxide having a weight average molecular weight of 1 million (molar ratio 9: 1) was weighed in a 1 g dairy pot and mixed to obtain a uniform electrode composition. 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 16-1). Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 16-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm. Such a sheet can be used as a capacitor electrode, a fuel cell electrode, an air battery electrode, an electrochemical actuator, and the like.
• Example 17 Preparation of insulating layer
• Aerosil 380 registered trademark
• EVONIK ethylene oxide-propylene oxide random copolymer
• ethylene oxide-propylene oxide random copolymer molar ratio 90:10
• 1-butyl 1-butyl
• -3-Methylimidazolium tetrafluoroborate was weighed in a 70 g dairy pot and mixed to obtain a uniform insulating layer composition.
• a 50 ⁇ m sheet (insulating layer 17) was obtained in the same manner as in Example 1. This sheet was self-supporting and plastic, and could be bent with a diameter of 1 mm.
• Such an insulating layer may be used as an insulating layer of a power storage device such as a lithium ion battery, or may be attached to glass or the like on which a conductive ITO (indium tin oxide) layer is formed to be attached to a dye-sensitized solar cell. It can also be used for batteries and electrochromic devices.
• a power storage device such as a lithium ion battery
• a conductive ITO (indium tin oxide) layer is formed to be attached to a dye-sensitized solar cell. It can also be used for batteries and electrochromic devices.
• Example 18 Cross-linking of insulating layer
• Random copolymer of ethylene oxide-propylene oxide-allylglycidyl ether with 40 g of Aerosil R711 (registered trademark) (manufactured by EVONIK, treated with methacryloxysilane), 20 g of alumina, and 1 million molecular weight as a nano-sized filler (molar ratio) 90: 5: 5) was weighed out, 70 g of water as a solvent, and 500 mg of Irg651 as an ultraviolet cross-linking agent were weighed to obtain a 50 ⁇ m sheet (insulating layer 18) in the same manner as in Example 1. This sheet was self-supporting and could be bent with a diameter of 1 mm.
• a crosslinked insulating layer 18 was obtained by irradiating the insulating layer 1 with ultraviolet rays while maintaining its plasticity without rubbing the insulating layer 1 while being sandwiched between the release PET films.
• the insulating layer 18 was cut into strips having a width of 1 cm, and when pulled while maintaining plasticity without being rubbed by a drying operation, it broke when it was stretched by 5%. When the crosslinked insulating layer 18 was pulled in the same manner, it did not break even when it was stretched by 10%. It can be expected that the crosslinked insulating layer is less likely to break due to mechanical stress and is more effective in preventing an internal short circuit of the device.
• the insulating layer may be used for device assembly in a plasticized state, or may be dried and used in a non-plasticized state. It is also a preferable embodiment that the device is assembled without cross-linking and finally cross-linked with ultraviolet rays, heat or the like.
• Example 19 Preparation of solid electrolyte-containing insulating layer
• LAGP Li 1.5 Al 0.5 Ge 1.5 P 3 O 12
• molar ratio 90:10 molecular weight 1 million Ethylene oxide-propylene oxide random copolymer
• 1-methyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide sigmaaldrich
• a 50 ⁇ m sheet (insulating layer 19) was obtained in the same manner as in Example 17. This sheet was self-supporting and plastic, and could be bent with a diameter of 1 mm. The volume fraction of the filler in this sheet was 53 v réellel% for LAGP alone. When the ionic conductivity of this sheet is measured by the AC impedance method , it has an ionic conductivity of 1.0 ⁇ 10 -3 S / cm, which is suitable as an insulating layer for a lithium ion battery.
• Example 20 Alkaline production example
• 70 g of lithium nickelate (Sigma Aldrich), which is the positive electrode active material of lithium ion batteries and is strongly alkaline, 3 g of acetylene black, 8 g of ion-exchanged water, 1 g of carboxymethyl cellulose (BSH-12 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and PTFE was weighed into a 1 g dairy pot and mixed to give a uniform electrode composition.
• 1 g of this electrode composition was taken, sandwiched between releasable PET films, and a sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm (electrode sheet 20-1).
• Electrode sheet 20-2 Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet (electrode sheet 20-2) having an average thickness of 200 ⁇ m (195 to 205 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm. CMC is an aqueous solution, which is considered to have contributed to the flexibility of the electrodes.
• Example 21 Bonding of electrode and insulating layer
• Example 22 Fabrication and composite of low-density electrode
• the first electrode sheet (electrode sheet 22-1) was prepared in the same manner as in Example 1 except that the thickness was 100 ⁇ m. Further, a second electrode sheet was prepared using 50 g of lithium cobalt oxide, which is half the amount of Example 1 (electrode sheet 22-2).
• the first electrode sheet was pasted on an aluminum foil having a thickness of 25 ⁇ m, the second electrode sheet was placed on the first electrode sheet, and the second electrode sheet was brought into close contact with each other so as not to contain air bubbles. In this way, composite electrode sheets having different densities in the upper layer and the lower layer were manufactured. At this time, the first electrode sheet may be bonded after it has dried.
• the density measured by drying the second electrode sheet was 2.64 g / cm 3 . Therefore, the volume fraction of the filler in this electrode is 61 Vol% in the lower layer and Vol% in the upper layer 47 by adding lithium cobalt oxide and acetylene black.
• Such an electrode whose density decreases as the distance from the current collector increases, has an ion conduction resistance that is lower than the electrode thickness, which is advantageous for increasing the output and operating speed of the device.
• Example 23 Manufacturing method of extruding into blocks and slicing
• a steel cutter that moves laterally with respect to the cylinder was installed here, and the cylinder was continuously sliced into a disk shape having a thickness of 200 ⁇ m and a diameter of 15 ⁇ m to prepare an electrode sheet.
• a hollow cylinder such as macaroni can be manufactured by changing the base. If you don't like the metal powder coming out when the metals rub against each other, the base and cutter can be made of ceramic or plastic.
• Example 24 Manufacturing method of extruding into a tube and making an incision
• the outlet was changed to a ring-shaped mouthpiece having an outer diameter of 50 mm and an inner diameter of 49 mm, and extrusion was performed in a tube shape having a film thickness of 500 ⁇ m.
• a steel cutter was placed at a position where the extruded product protruded about 100 mm from the base, and one part of the tube cross section was continuously incised. By continuously opening the incised tube, a sheet of uniform thickness with the same thickness variation at the center and the end was obtained (494-506 ⁇ m). If you don't like the metal powder coming out when the metals rub against each other, the base and cutter can be made of ceramic or plastic.
• Example 25 Manufactured with a large number of strands
• the die outlet was changed by arranging 20 cylinders with a diameter of 300 ⁇ m at intervals of 4 mm, and this was changed with two metal rollers (roll diameter 30 mm, linear pressure 200 N).
• roll diameter 30 mm, linear pressure 200 N rollers
• Example 26 Device manufacturing example
• An aluminum foil having a thickness of 25 ⁇ m, an electrode sheet 2-3 of Example 2, an insulating layer 18 of Example 18 and an electrode sheet 13-3 of Example 13, and a rolled copper foil having a thickness of 25 ⁇ m are wound around a metal rod having an outer diameter of 2 mm in this order.
• a wound body having a diameter of 10 mm was obtained. Since all the sheets were in a plasticized state, they were flexible and were not damaged during winding.
• This wound body was housed in an aluminum laminated package and lightly pressed from the outside to flatten it. This was transferred to a vacuum dryer at 100 ° C. and dried for 6 hours.
• a lithium ion battery was prepared by injecting 1MLiPF6 EC / DMC (30/70) as an electrolytic solution and sealing with a vacuum. When this was charged and discharged at a rate of 4.2 V to 3.0 V and 0.1 C, a reversible capacity of 145 mAh / g was obtained per positive electrode active material, and it was found that the battery functions as a battery.
• Example 27 Manganese battery production example
• an aqueous solution containing 20% by weight of zinc chloride and 5% by weight of ammonium chloride was prepared. 100 parts of manganese dioxide (MnO 2 , 99.5%, Fuji Film Wako Pure Chemical Industries, 133-09681), 6 parts of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Black granules), weight average molecular weight of 100 as polymer P1 2 parts of a random copolymer of ethylene oxide-propylene oxide (molecular ratio 9: 1), 2 parts of PTFE, and 40 parts of the above electrolyte are weighed in a dairy pot and kneaded well to obtain a uniform electrode composition.
• manganese dioxide MnO 2 , 99.5%, Fuji Film Wako Pure Chemical Industries, 133-09681
• 6 parts of acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Black gran
• this electrode composition was taken, sandwiched between releasable PET films, and a self-supporting sheet having an average thickness of 2 mm was obtained using a SUS hand roller having a diameter of 3 cm. Upon immediate evaluation, the sheet was slightly sticky, self-supporting and plastic. Further, a sheet having an average thickness of 500 ⁇ m (497 to 503 ⁇ m) pressed by a hand roller could be bent with a diameter of 2 mm. This sheet was cut into a 14 mm ⁇ circle and attached to a graphite sheet (15 mm ⁇ circle) as a current collector to form a positive electrode.
• a separator a piece of paper (manufactured by Nippon Kodoshi Kogyo Co., Ltd., trade name "TF4535", thickness 35 ⁇ m) cut into a circle of 16 mm was prepared and immersed in the above-mentioned electrolytic solution to contain the electrolytic solution.
• a zinc foil manufactured by Niraco, 99.99% pure, 15 mm ⁇ circular, thickness 50 ⁇ m was prepared as the negative electrode, and these were superposed in this order in the order of the positive electrode, the separator, and the negative electrode to form a manganese battery, which was a 2032 type. Attached to the coin cell.
• Electrochemical devices can be provided.

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