WO2021201294A1 - 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス - Google Patents

蓄電デバイス用外装材、その製造方法、及び蓄電デバイス Download PDF

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Publication number
WO2021201294A1
WO2021201294A1 PCT/JP2021/014413 JP2021014413W WO2021201294A1 WO 2021201294 A1 WO2021201294 A1 WO 2021201294A1 JP 2021014413 W JP2021014413 W JP 2021014413W WO 2021201294 A1 WO2021201294 A1 WO 2021201294A1
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WIPO (PCT)
Prior art keywords
power storage
heat
storage device
layer
exterior material
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Ceased
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PCT/JP2021/014413
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English (en)
French (fr)
Japanese (ja)
Inventor
純 景山
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to US17/915,774 priority Critical patent/US12573691B2/en
Priority to JP2021566132A priority patent/JP7036290B2/ja
Publication of WO2021201294A1 publication Critical patent/WO2021201294A1/ja
Priority to JP2022031992A priority patent/JP2022081564A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/134—Hardness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • 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

  • This disclosure relates to an exterior material for a power storage device, a manufacturing method thereof, and a power storage device.
  • an exterior material is an indispensable member for sealing the power storage device elements such as electrodes and electrolytes.
  • a metal exterior material has been widely used as an exterior material for a power storage device.
  • a base material layer / barrier layer / adhesive layer / heat-sealing resin layer is sequentially laminated.
  • a film-like laminate has been proposed (see, for example, Patent Document 1).
  • a recess is generally formed by cold forming, and a heat-sealing resin such as an electrode or an electrolytic solution is arranged in the space formed by the recess.
  • the heat-sealing resin layer of the exterior material for a power storage device in the form of a laminated film has been used as the heat-sealing resin layer of the exterior material for a power storage device in the form of a laminated film from the viewpoint of excellent heat resistance. Therefore, the heat sealing of the heat-sealing resin layer is performed at a high temperature of about 200 ° C.
  • the present disclosure is an exterior material for a power storage device composed of at least a laminate including a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • the heat-sealing resin layers are heat-sealed at a temperature lower than the conventional heat-sealing temperature (around 200 ° C.) (for example, about 120 ° C.) to form a power storage device, and the power storage device is exposed to an environment of about 100 ° C.
  • the main purpose of the present invention is to provide an exterior material for a power storage device, which does not open the exterior material for the power storage device even if it is used.
  • the inventors of the present disclosure have made diligent studies to solve the above problems.
  • it is an exterior material for a power storage device composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order, and is a heat-sealing resin layer.
  • the melting peak temperature was observed below 130 ° C.
  • the melting peak temperature was observed above 135 ° C. for the adhesive layer
  • the resin constituting the heat-sealing resin layer had a polyolefin skeleton and was an adhesive layer.
  • the exterior material for a power storage device having a polyolefin skeleton heat-seals the heat-sealing resin layers at a temperature lower than the conventional heat-sealing temperature (around 200 ° C.) (for example, about 120 ° C.). It was found that even if the power storage device is exposed to an environment of about 100 ° C., the exterior material for the power storage device is not opened.
  • An exterior material for a power storage device composed of a laminate including a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • a melting peak temperature was observed below 130 ° C.
  • a melting peak temperature was observed above 135 ° C.
  • the resin constituting the heat-sealing resin layer has a polyolefin skeleton and has a polyolefin skeleton.
  • the resin constituting the adhesive layer is an exterior material for a power storage device having a polyolefin skeleton.
  • the inventors of the present disclosure are exterior materials for power storage devices, which are composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • the Martens hardness measured by pushing a Vickers indenter to a depth of 1 ⁇ m in the thickness direction from the surface of the exterior material for a power storage device on the heat-sealing resin layer side is measured.
  • the heat-sealing resin layers are heat-sealed at a lower temperature (for example, about 120 ° C.) than the conventional heat-sealing temperature (around 200 ° C.) to heat-seal the power storage device. It was found that even if the power storage device is exposed to an environment of about 100 ° C., the exterior material for the power storage device is not opened.
  • An exterior material for a power storage device composed of a laminate including a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order. Based on the indentation method, the Vickers hardness measured by pushing the Vickers indenter to a depth of 1 ⁇ m in the thickness direction from the surface of the exterior material for the power storage device on the heat-sealing resin layer side at a measurement temperature of 25 ° C. Exterior material for power storage devices, which is 30.0 MPa or more.
  • the present disclosure is an exterior material for a power storage device composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order, and is a conventional heat storage device. Even if the heat-sealing resin layers are heat-sealed at a temperature lower than the sealing temperature (around 200 ° C.) (for example, about 120 ° C.) to form a power storage device, and the power storage device is exposed to an environment of about 100 ° C. It is possible to provide an exterior material for a power storage device that does not open the exterior material for the power storage device. Further, according to the present disclosure, it is also possible to provide a method for manufacturing an exterior material for a power storage device and a power storage device.
  • the exterior material for a power storage device is composed of a laminated body including at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • the heat-sealing resin layer which is an exterior material for devices, has a melting peak temperature observed at 130 ° C. or lower, and the adhesive layer has a melting peak temperature observed at 135 ° C. or higher, forming a heat-sealing resin layer.
  • the resin used has a polyolefin skeleton, and the resin constituting the adhesive layer has a polyolefin skeleton.
  • the exterior material for a power storage device has this configuration, it has heat-sealing properties at a temperature lower than the conventional heat seal temperature (around 200 ° C.) (for example, about 120 ° C.).
  • the resin layers are heat-sealed to form a power storage device, and even if the power storage device is exposed to an environment of about 100 ° C., the exterior material for the power storage device is not opened.
  • the exterior material for a power storage device is composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • An exterior material for a power storage device based on the indentation method, at a measurement temperature of 25 ° C., a Vickers indenter from the surface of the exterior material for a power storage device on the heat-sealing resin layer side to a depth of 1 ⁇ m in the thickness direction. It is also characterized in that the Martens hardness measured by pushing in is 30.0 MPa or more.
  • the exterior material for a power storage device according to the second embodiment of the present disclosure has this configuration, it has heat-sealing properties at a temperature lower than the conventional heat seal temperature (around 200 ° C.) (for example, about 120 ° C.).
  • the resin layers are heat-sealed to form a power storage device, and even if the power storage device is exposed to an environment of about 100 ° C., the exterior material for the power storage device is not opened.
  • the exterior material for the power storage device of the present disclosure will be described in detail.
  • the numerical range indicated by “-” means “greater than or equal to” and “less than or equal to”.
  • the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.
  • the barrier layer 3 described later in the exterior material for a power storage device it is usually possible to discriminate between MD (Machine Direction) and TD (Transverse Direction) in the manufacturing process thereof.
  • MD Machine Direction
  • TD Transverse Direction
  • the barrier layer 3 is made of a metal foil such as an aluminum alloy foil or a stainless steel foil
  • RD Rolling Direction
  • Shaped streaks are formed. Since the rolling marks extend along the rolling direction, the rolling direction of the metal foil can be grasped by observing the surface of the metal foil.
  • the MD of the laminated body and the RD of the metal foil usually match, the surface of the metal foil of the laminated body is observed and the rolling direction (RD) of the metal foil is specified. Thereby, the MD of the laminated body can be specified. Further, since the TD of the laminated body is in the direction perpendicular to the MD of the laminated body, the TD of the laminated body can also be specified.
  • the MD of the exterior material for the power storage device cannot be specified due to the rolling marks of a metal foil such as an aluminum alloy foil or a stainless steel foil, it can be specified by the following method.
  • a method of confirming the MD of the exterior material for the electricity storage device there is a method of observing the cross section of the heat-sealing resin layer of the exterior material for the electricity storage device with an electron microscope to confirm the sea-island structure.
  • MD can be determined to be the direction parallel to the cross section in which the average diameter of the island shapes in the direction perpendicular to the thickness direction of the heat-sealing resin layer is the maximum.
  • the angle is changed by 10 degrees from the cross section of the heat-sealing resin layer in the length direction and the direction parallel to the cross section in the length direction to the direction perpendicular to the cross section in the length direction.
  • Each cross section (10 cross sections in total) is observed with an electron micrograph to confirm the sea-island structure.
  • the shape of each island is observed.
  • the diameter y is the linear distance connecting the leftmost end in the direction perpendicular to the thickness direction of the heat-sealing resin layer and the rightmost end in the vertical direction.
  • the average of the top 20 diameters y is calculated in descending order of the diameter y of the island shape.
  • the direction parallel to the cross section in which the average of the diameter y of the island shape is the largest is determined as MD.
  • the exterior material 10 for power storage device of the present disclosure is, for example, as shown in FIG. 1, a base material layer 1, a barrier layer 3, an adhesive layer 5, and a heat-sealing resin layer 4. It is composed of a laminated body having the above in this order.
  • the base material layer 1 is on the outermost layer side
  • the heat-sealing resin layer 4 is on the innermost layer.
  • the power storage device element is housed in the space formed by.
  • the heat-sealing resin layer 4 side is inside the barrier layer 3 and the base material layer 1 side is more than the barrier layer 3 with the barrier layer 3 as a reference. It is the outside.
  • the exterior material 10 for a power storage device is used, if necessary, for the purpose of enhancing the adhesiveness between the base material layer 1 and the barrier layer 3 and the like. It may have an adhesive layer 2. Further, as shown in FIG. 3, a surface coating layer 6 or the like may be provided on the outside of the base material layer 1 (the side opposite to the heat-sealing resin layer 4 side), if necessary.
  • the thickness of the laminate constituting the exterior material 10 for the power storage device is not particularly limited, but is preferably about 180 ⁇ m or less, about 155 ⁇ m or less, and about 120 ⁇ m or less from the viewpoint of cost reduction, energy density improvement, and the like. Further, the thickness of the laminate constituting the exterior material 10 for the power storage device is preferably about 35 ⁇ m or more, about 45 ⁇ m or more, and about from the viewpoint of maintaining the function of the exterior material for the power storage device of protecting the power storage device element. 60 ⁇ m or more can be mentioned.
  • the preferred range of the laminated body constituting the exterior material 10 for the power storage device is, for example, about 35 to 180 ⁇ m, about 35 to 155 ⁇ m, about 35 to 120 ⁇ m, about 45 to 180 ⁇ m, about 45 to 155 ⁇ m, about 45 to 120 ⁇ m. , About 60 to 180 ⁇ m, about 60 to 155 ⁇ m, about 60 to 120 ⁇ m, and particularly preferably about 60 to 155 ⁇ m.
  • the base material layer 1, the adhesive layer 2, the barrier layer 3, and the adhesive layer 5 provided as necessary with respect to the thickness (total thickness) of the laminate constituting the power storage device exterior material 10.
  • the ratio of the total thickness of the heat-sealing resin layer 4 and the surface coating layer 6 provided as needed is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more. Is.
  • the exterior material 10 for a power storage device of the present disclosure includes a base material layer 1, an adhesive layer 2, a barrier layer 3, an adhesive layer 5, and a heat-sealing resin layer 4, the exterior for a power storage device
  • the ratio of the total thickness of each of these layers to the thickness (total thickness) of the laminate constituting the material 10 is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more.
  • the exterior material 10 for a power storage device of the present disclosure heats the heat-sealing resin layers 4 to each other under the conditions of a temperature of 120 ° C. and a surface pressure of 1.0 MPa for 3 seconds.
  • the heat seal strength is preferably about 35 N / 15 mm or more, more preferably about 40 N / 15 mm or more, still more preferably. It is about 45 N / 15 mm or more, more preferably about 50 N / 15 mm or more.
  • the heat seal strength is preferably about 80 N / 15 mm or less, more preferably about 70 N / 15 mm or less, and further preferably about 60 N / 15 mm or less.
  • the preferred range of the heat seal strength is about 35 to 80 N / 15 mm, about 35 to 70 N / 15 mm, about 35 to 60 N / 15 mm, about 40 to 80 N / 15 mm, about 40 to 70 N / 15 mm, and about 40 to 60 N / 15 mm.
  • the exterior material 10 for a power storage device of the present disclosure includes heat-sealing resin layers 4 under the conditions of a temperature of 190 ° C. and a surface pressure of 1.0 MPa for 3 seconds.
  • the heat seal strength is preferably about 80 N / 15 mm or more, more preferably about 90 N / 15 mm or more, and further. It is preferably about 95 N / 15 mm or more.
  • the heat seal strength is preferably about 130 N / 15 mm or less, more preferably about 120 N / 15 mm or less, and further preferably about 110 N / 15 mm or less.
  • the preferred range of the heat seal strength is about 80 to 130 N / 15 mm, about 80 to 120 N / 15 mm, about 80 to 110 N / 15 mm, about 90 to 130 N / 15 mm, about 90 to 120 N / 15 mm, and about 90 to 110 N / 15 mm.
  • the degree is about 95 to 130 N / 15 mm, about 95 to 120 N / 15 mm, and about 95 to 110 N / 15 mm.
  • the method for measuring the heat seal strength at 120 ° C. or 190 ° C. is as follows.
  • the seal strength of the exterior material for the power storage device is measured as follows.
  • an exterior material for a power storage device cut into strips having a width in the TD direction of 15 mm is prepared. Specifically, as shown in FIG. 5, first, the exterior material for each power storage device is cut into 60 mm (TD direction) ⁇ 200 mm (MD direction) (FIG. 5a). Next, the heat-sealing resin layers are made to face each other, and the exterior material for the power storage device is folded in half in the MD direction at the position of the crease P (middle in the MD direction) (FIG. 5b).
  • the heat-sealing resin layers are heat-sealed with each other under the conditions of a seal width of 7 mm, a temperature of 120 ° C. or 190 ° C., and a surface pressure of 1.0 MPa for 3 seconds in the direction of MD about 10 mm from the crease P (FIG. 5c).
  • the shaded portion S is a heat-sealed portion.
  • a test piece is obtained by cutting in the direction of MD (cutting at the position of the alternate long and short dash line in FIG. 5d) so that the width in the direction of TD is 15 mm (FIG. 5e).
  • the test piece 13 was left in an environment of 25 ° C.
  • the heat of the exterior material 10 for the power storage device of the present disclosure is set at a measurement temperature (sample temperature) of 25 ° C. based on the indentation method.
  • the Vickers hardness measured by pushing a Vickers indenter to a depth of 1 ⁇ m from the surface on the fusion resin layer 4 side in the thickness direction is preferably 25.0 MPa or more, more preferably 30.0 MPa or more, still more preferably 40. It is 0.0 MPa or more.
  • the Martens hardness is preferably 80.0 MPa or less, more preferably 70.0 MPa.
  • the preferred range of the Martens hardness is about 25.0 to 80.0 MPa, about 25.0 to 70.0 MPa, about 30.0 to 80.0 MPa, about 30.0 to 70.0 MPa, and about 40.0 to.
  • About 80.0 MPa, about 40.0 to 70.0 MPa can be mentioned.
  • the heat of the exterior material 10 for the power storage device of the present disclosure is set at a measurement temperature (sample temperature) of 25 ° C. based on the indentation method.
  • the Martens hardness measured by pushing a Vickers indenter to a depth of 1 ⁇ m in the thickness direction from the surface on the fusion resin layer 4 side is preferably 35.0 MPa or more, more preferably 40.0 MPa or more. From the same viewpoint, the Martens hardness is preferably 80.0 MPa or less, more preferably 70.0 MPa. The preferred range of the Martens hardness is about 30.0 to 80.0 MPa, about 30.0 to 70.0 MPa, about 35.0 to 80.0 MPa, about 35.0 to 70.0 MPa, and 40.0 to. About 80.0 MPa, about 40.0 to 70.0 MPa can be mentioned. As a further effect of the Martens hardness at 25 ° C.
  • the heat-sealing resin layer there is an effect of suppressing the smoothness from being impaired by touching the transport roll. Therefore, it is possible to heat-seal the heat-sealing without impairing the smoothness at the time of heat-sealing, and even if the heat-sealing resin layers are heat-sealed at a low temperature (for example, about 120 ° C.), high sealing performance can be exhibited.
  • the impaired smoothness means that the exterior material for the power storage device rubs against the transport roll, causing scratches on the heat-sealing resin layer.
  • the method for measuring the Martens hardness is as follows.
  • Martens hardness calculates the surface area A (mm 2) of the indenter at the maximum indentation depth of the Vickers indenter is obtained dividing the maximum load F (N) (F / A ) that in the surface area A (mm 2).
  • a picodenter HM-500 manufactured by Fisher Instruments is used as the measuring device.
  • an exterior material for a power storage device is adhered to one side of a slide glass (76 mm ⁇ 26 mm ⁇ 1 mm) to which a double-sided adhesive tape is attached so that the heat-sealing resin layer side is opposite to the slide glass, and used as a measurement sample.
  • the surface hardness of the surface of the measurement sample on the heat-sealing resin layer side is measured.
  • the exterior material for the power storage device of the present disclosure is not opened when it is subjected to the following opening test.
  • the exterior material for the power storage device was cut into a size of 100 mm ⁇ 200 mm, and the heat-sealing resin layers were folded so as to face each other at the center position of the long side of the exterior material for the power storage device.
  • the short side is heat-sealed under the conditions of a temperature of 120 ° C., a surface pressure of 1.0 MPa, and a seal width of 7 mm for 3 seconds.
  • one long side was heat-sealed in the same manner, 2.0 g of water was added to the bag-shaped sample, and then the opening side (long side) was heat-sealed in the same manner to seal the water.
  • Use as a test sample The test sample is placed in an oven and allowed to stand in an environment of 105 ° C. for 8 hours to check whether the test sample has been opened.
  • each layer forming the exterior material for the power storage device [base material layer 1]
  • the base material layer 1 is a layer provided for the purpose of exerting a function as a base material of an exterior material for a power storage device.
  • the base material layer 1 is located on the outer layer side of the exterior material for the power storage device.
  • the material forming the base material layer 1 is not particularly limited as long as it has a function as a base material, that is, at least an insulating property.
  • the base material layer 1 can be formed by using, for example, a resin, and the resin may contain an additive described later.
  • the base material layer 1 may be, for example, a resin film formed of a resin or a resin film applied to the base material layer 1.
  • the resin film may be an unstretched film or a stretched film.
  • the stretched film include a uniaxially stretched film and a biaxially stretched film, and a biaxially stretched film is preferable.
  • the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, an inflation method, and a simultaneous biaxial stretching method.
  • the method for applying the resin include a roll coating method, a gravure coating method, and an extrusion coating method.
  • the resin forming the base material layer 1 examples include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, and phenol resin, and modified products of these resins. Further, the resin forming the base material layer 1 may be a copolymer of these resins or a modified product of the copolymer. Further, it may be a mixture of these resins.
  • the resin forming the base material layer 1 include polyester and polyamide.
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester.
  • copolymerized polyester examples include a copolymerized polyester containing ethylene terephthalate as a repeating unit as a main component.
  • copolymer polyester (hereinafter abbreviated after polyethylene (terephthalate / isophthalate)), polyethylene (terephthalate / adipate), polyethylene (terephthalate / terephthalate / (Sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate), polyethylene (terephthalate / decandicarboxylate) and the like.
  • polyesters may be used alone or in combination of two or more.
  • polyamide examples include an aliphatic polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid.
  • Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I stands for isophthalic acid, T stands for terephthalic acid), polyamide MXD6 (polymethaki Polyamide containing aromatics such as silylene adipamide); Alicyclic polyamide such as polyamide PACM6 (polybis (4-aminocyclohexyl) methaneadipamide); Further, lactam component and isocyanate component such as 4,4'-diphenylmethane-diisocyanate Examples thereof include a copolymerized polyamide, a polyesteramide copolymer or a polyether esteramide copolymer
  • the base material layer 1 preferably contains at least one of a polyester film, a polyamide film, and a polyolefin film, and preferably contains at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film. It is more preferable to contain at least one of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, and a stretched polypropylene film, and a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, and a biaxially stretched nylon film. , It is more preferable to contain at least one of the biaxially stretched polypropylene films.
  • the base material layer 1 may be a single layer or may be composed of two or more layers.
  • the base material layer 1 may be a laminated body in which a resin film is laminated with an adhesive or the like, or the resin is co-extruded to form two or more layers. It may be a laminated body of the resin film. Further, the laminated body of the resin film obtained by co-extruding the resin into two or more layers may be used as the base material layer 1 without being stretched, or may be uniaxially stretched or biaxially stretched as the base material layer 1.
  • the laminate of two or more layers of resin film in the base material layer 1 include a laminate of a polyester film and a nylon film, a laminate of two or more layers of nylon film, and a laminate of two or more layers of polyester film. And the like, preferably, a laminate of a stretched nylon film and a stretched polyester film, a laminate of two or more layers of stretched nylon film, and a laminate of two or more layers of stretched polyester film are preferable.
  • the base material layer 1 is a laminate of two layers of resin film, a laminate of polyester resin film and polyester resin film, a laminate of polyamide resin film and polyamide resin film, or a laminate of polyester resin film and polyamide resin film.
  • a laminate is preferable, and a laminate of a polyethylene terephthalate film and a polyethylene terephthalate film, a laminate of a nylon film and a nylon film, or a laminate of a polyethylene terephthalate film and a nylon film is more preferable.
  • the polyester resin is difficult to discolor when the electrolytic solution adheres to the surface, for example, when the base material layer 1 is a laminate of two or more resin films, the polyester resin film is the base material layer 1. It is preferably located in the outermost layer.
  • the two or more layers of resin films may be laminated via an adhesive.
  • Preferred adhesives include those similar to the adhesives exemplified in the adhesive layer 2 described later.
  • the method of laminating two or more layers of resin films is not particularly limited, and known methods can be adopted. Examples thereof include a dry laminating method, a sandwich laminating method, an extrusion laminating method, and a thermal laminating method, and a dry laminating method is preferable.
  • the laminating method can be mentioned.
  • the thickness of the adhesive is, for example, about 2 to 5 ⁇ m.
  • an anchor coat layer may be formed on the resin film and laminated. Examples of the anchor coat layer include the same adhesives as those exemplified in the adhesive layer 2 described later. At this time, the thickness of the anchor coat layer is, for example, about 0.01 to 1.0 ⁇ m.
  • additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent are present on at least one of the surface and the inside of the base material layer 1. good. Only one type of additive may be used, or two or more types may be mixed and used.
  • the lubricant is present on the surface of the base material layer 1.
  • the lubricant is not particularly limited, but an amide-based lubricant is preferable.
  • Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides.
  • saturated fatty acid amide examples include lauric acid amide, palmitic acid amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide and the like.
  • unsaturated fatty acid amide examples include oleic acid amide and erucic acid amide.
  • substituted amide examples include N-oleyl palmitate amide, N-stearyl stearyl amide, N-stearyl oleate amide, N-oleyl stealic acid amide, N-stearyl erucate amide and the like.
  • methylolamide examples include methylolstearic amide.
  • saturated fatty acid bisamide examples include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstearic.
  • Acid amides, hexamethylene bisbechenic acid amides, hexamethylene hydroxystearic acid amides, N, N'-distearyl adipate amides, N, N'-distearyl sebacic acid amides and the like can be mentioned.
  • unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucate amide, hexamethylene bisoleic acid amide, N, N'-diorail adipate amide, and N, N'-diorail sebacic acid amide. And so on.
  • Specific examples of the fatty acid ester amide include stearoamide ethyl stearate and the like.
  • Specific examples of the aromatic bisamide include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, and N, N'-distearyl isophthalic acid amide.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the abundance thereof is not particularly limited, but is preferably about 3 mg / m 2 or more, more preferably about 4 to 15 mg / m 2 , and further preferably 5 to 14 mg. / M 2 is mentioned.
  • the lubricant existing on the surface of the base material layer 1 may be one in which the lubricant contained in the resin constituting the base material layer 1 is exuded, or one in which the lubricant is applied to the surface of the base material layer 1. You may.
  • the thickness of the base material layer 1 is not particularly limited as long as it functions as a base material, but for example, it may be about 3 to 50 ⁇ m, preferably about 10 to 35 ⁇ m.
  • the thickness of the resin films constituting each layer is preferably about 2 to 25 ⁇ m, respectively.
  • the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as necessary for the purpose of enhancing the adhesiveness between the base material layer 1 and the barrier layer 3.
  • the adhesive layer 2 is formed by an adhesive capable of adhering the base material layer 1 and the barrier layer 3.
  • the adhesive used for forming the adhesive layer 2 is not limited, but may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a hot pressure type and the like. Further, it may be a two-component curable adhesive (two-component adhesive), a one-component curable adhesive (one-component adhesive), or a resin that does not involve a curing reaction. Further, the adhesive layer 2 may be a single layer or a multilayer.
  • the adhesive component contained in the adhesive include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester; polyether; polyurethane; epoxy resin; Phenolic resin; Polyethylene such as nylon 6, nylon 66, nylon 12, copolymerized polyamide; Polyethylene resin such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin; Polyvinyl acetate; Cellulose; (Meta) acrylic resin; Polyethylene; polycarbonate; amino resin such as urea resin and melamine resin; rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; silicone resin and the like.
  • polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene
  • adhesive components may be used alone or in combination of two or more.
  • a polyurethane adhesive is preferable.
  • the resins used as these adhesive components can be used in combination with an appropriate curing agent to increase the adhesive strength.
  • An appropriate curing agent is selected from polyisocyanate, polyfunctional epoxy resin, oxazoline group-containing polymer, polyamine resin, acid anhydride and the like, depending on the functional group of the adhesive component.
  • the polyurethane adhesive examples include a polyurethane adhesive containing a first agent containing a polyol compound and a second agent containing an isocyanate compound.
  • a two-component curable polyurethane adhesive using a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol as a first agent and an aromatic or aliphatic polyisocyanate as a second agent can be mentioned.
  • the polyurethane adhesive examples include a polyurethane adhesive in which a polyol compound and an isocyanate compound are reacted in advance, and a polyurethane adhesive containing the isocyanate compound.
  • examples of the polyurethane adhesive include a polyurethane adhesive in which a polyol compound and an isocyanate compound are reacted in advance, and a polyurethane adhesive containing the polyol compound.
  • examples of the polyurethane adhesive include a polyurethane adhesive obtained by reacting a polyurethane compound in which a polyol compound and an isocyanate compound are previously reacted with water such as in the air to cure the polyurethane compound.
  • the polyol compound it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit.
  • Examples of the second agent include aliphatic, alicyclic, aromatic, and aromatic aliphatic isocyanate compounds.
  • Examples of the isocyanate-based compound include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalenediocyanate (NDI) and the like.
  • a polyfunctional isocyanate modified product from one kind or two or more kinds of these diisocyanates and the like can be mentioned.
  • a multimer for example, a trimer
  • a multimer include an adduct body, a biuret body, a nurate body and the like. Since the adhesive layer 2 is formed of the polyurethane adhesive, excellent electrolytic solution resistance is imparted to the exterior material for the power storage device, and even if the electrolytic solution adheres to the side surface, the base material layer 1 is suppressed from peeling off. ..
  • the adhesive layer 2 may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, etc., as long as the addition of other components is permitted as long as the adhesiveness is not impaired. Since the adhesive layer 2 contains a colorant, the exterior material for the power storage device can be colored. As the colorant, known ones such as pigments and dyes can be used. Further, only one type of colorant may be used, or two or more types may be mixed and used.
  • the type of pigment is not particularly limited as long as it does not impair the adhesiveness of the adhesive layer 2.
  • organic pigments include azo-based, phthalocyanine-based, quinacridone-based, anthracinone-based, dioxazine-based, indigothioindigo-based, perinone-perylene-based, isowearnine-based, and benzimidazolone-based pigments, which are inorganic.
  • the pigment include carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, and iron-based pigments, and other examples include fine powder of mica (mica) and fish scale foil.
  • carbon black is preferable in order to make the appearance of the exterior material for the power storage device black, for example.
  • the average particle size of the pigment is not particularly limited, and examples thereof include about 0.05 to 5 ⁇ m, preferably about 0.08 to 2 ⁇ m.
  • the average particle size of the pigment is the median diameter measured by a laser diffraction / scattering type particle size distribution measuring device.
  • the content of the pigment in the adhesive layer 2 is not particularly limited as long as the exterior material for the power storage device is colored, and examples thereof include about 5 to 60% by mass, preferably 10 to 40% by mass.
  • the thickness of the adhesive layer 2 is not particularly limited as long as the base material layer 1 and the barrier layer 3 can be adhered to each other, but is, for example, about 1 ⁇ m or more and about 2 ⁇ m or more.
  • the thickness of the adhesive layer 2 is, for example, about 10 ⁇ m or less and about 5 ⁇ m or less.
  • the preferable range of the thickness of the adhesive layer 2 is about 1 to 10 ⁇ m, about 1 to 5 ⁇ m, about 2 to 10 ⁇ m, and about 2 to 5 ⁇ m.
  • the colored layer is a layer provided between the base material layer 1 and the barrier layer 3 as needed (not shown).
  • a colored layer may be provided between the base material layer 1 and the adhesive layer 2 and between the adhesive layer 2 and the barrier layer 3. Further, a colored layer may be provided on the outside of the base material layer 1. By providing the colored layer, the exterior material for the power storage device can be colored.
  • the colored layer can be formed, for example, by applying an ink containing a colorant to the surface of the base material layer 1 or the surface of the barrier layer 3.
  • a colorant known ones such as pigments and dyes can be used. Further, only one type of colorant may be used, or two or more types may be mixed and used.
  • colorant contained in the colored layer include the same as those exemplified in the column of [Adhesive layer 2].
  • the barrier layer 3 is at least a layer that suppresses the infiltration of water.
  • Examples of the barrier layer 3 include a metal foil having a barrier property, a thin-film deposition film, a resin layer, and the like.
  • Examples of the vapor deposition film include a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, and the like, and examples of the resin layer include polymers and tetras mainly composed of polyvinylidene chloride and chlorotrifluoroethylene (CTFE).
  • CTFE chlorotrifluoroethylene
  • examples thereof include polymers containing fluoroethylene (TFE) as a main component, polymers having a fluoroalkyl group, fluorine-containing resins such as polymers containing a fluoroalkyl unit as a main component, and ethylene vinyl alcohol copolymers.
  • examples of the barrier layer 3 include a resin film provided with at least one of these vapor-deposited films and a resin layer. A plurality of barrier layers 3 may be provided.
  • the barrier layer 3 preferably includes a layer made of a metal material. Specific examples of the metal material constituting the barrier layer 3 include an aluminum alloy, stainless steel, titanium steel, and a steel plate. When used as a metal foil, the metal material includes at least one of an aluminum alloy foil and a stainless steel foil. Is preferable.
  • the aluminum alloy foil is more preferably a soft aluminum alloy foil composed of, for example, an annealed aluminum alloy, and from the viewpoint of further improving the moldability. Therefore, it is preferable that the aluminum alloy foil contains iron.
  • the iron content is preferably 0.1 to 9.0% by mass, more preferably 0.5 to 2.0% by mass.
  • the iron content is 0.1% by mass or more, an exterior material for a power storage device having more excellent moldability can be obtained.
  • the iron content is 9.0% by mass or less, a more flexible exterior material for a power storage device can be obtained.
  • the soft aluminum alloy foil examples include an aluminum alloy having a composition specified by JIS H4160: 1994 A8021HO, JIS H4160: 1994 A8079HO, JIS H4000: 2014 A8021PO, or JIS H4000: 2014 A8077P-O. Foil is mentioned. Further, if necessary, silicon, magnesium, copper, manganese and the like may be added. Further, softening can be performed by annealing or the like.
  • stainless steel foils examples include austenite-based, ferrite-based, austenite-ferritic-based, martensitic-based, and precipitation-hardened stainless steel foils. Further, from the viewpoint of providing an exterior material for a power storage device having excellent moldability, the stainless steel foil is preferably made of austenitic stainless steel.
  • austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferable.
  • the thickness of the barrier layer 3 may at least exhibit a function as a barrier layer that suppresses the infiltration of water, and is, for example, about 9 to 200 ⁇ m.
  • the thickness of the barrier layer 3 is preferably about 85 ⁇ m or less, more preferably about 50 ⁇ m or less, still more preferably about 40 ⁇ m or less, and particularly preferably about 35 ⁇ m or less.
  • the thickness of the barrier layer 3 is preferably about 10 ⁇ m or more, more preferably about 20 ⁇ m or more, and more preferably about 25 ⁇ m or more.
  • the preferred range of the thickness of the barrier layer 3 is about 10 to 85 ⁇ m, about 10 to 50 ⁇ m, about 10 to 40 ⁇ m, about 10 to 35 ⁇ m, about 20 to 85 ⁇ m, about 20 to 50 ⁇ m, about 20 to 40 ⁇ m, and about 20 to. Examples thereof include about 35 ⁇ m, about 25 to 85 ⁇ m, about 25 to 50 ⁇ m, about 25 to 40 ⁇ m, and about 25 to 35 ⁇ m.
  • the barrier layer 3 is made of an aluminum alloy foil, the above range is particularly preferable.
  • the thickness of the stainless steel foil is preferably about 60 ⁇ m or less, more preferably about 50 ⁇ m or less, still more preferably about 40 ⁇ m or less, still more preferably about 30 ⁇ m. Below, it is particularly preferably about 25 ⁇ m or less.
  • the thickness of the stainless steel foil is preferably about 10 ⁇ m or more, more preferably about 15 ⁇ m or more.
  • the preferred range of the thickness of the stainless steel foil is about 10 to 60 ⁇ m, about 10 to 50 ⁇ m, about 10 to 40 ⁇ m, about 10 to 30 ⁇ m, about 10 to 25 ⁇ m, about 15 to 60 ⁇ m, about 15 to 50 ⁇ m, and about 15 to. Examples thereof include about 40 ⁇ m, about 15 to 30 ⁇ m, and about 15 to 25 ⁇ m.
  • the barrier layer 3 is a metal foil, it is preferable that a corrosion-resistant film is provided on at least the surface opposite to the base material layer in order to prevent dissolution and corrosion.
  • the barrier layer 3 may be provided with a corrosion resistant film on both sides.
  • the corrosion-resistant film is, for example, a hot water transformation treatment such as boehmite treatment, a chemical conversion treatment, an anodic oxidation treatment, a plating treatment such as nickel or chromium, and a corrosion prevention treatment for applying a coating agent on the surface of the barrier layer.
  • a hot water transformation treatment such as boehmite treatment
  • a chemical conversion treatment such as boehmite treatment
  • an anodic oxidation treatment such as anodic oxidation treatment
  • a plating treatment such as nickel or chromium
  • a corrosion prevention treatment for applying a coating agent on the surface of the barrier layer.
  • a thin film that makes the barrier layer provided with corrosion resistance for example, acid resistance, alkali resistance, etc.
  • the corrosion-resistant film means a film for improving the acid resistance of the barrier layer (acid-resistant film), a film for improving the alkali resistance of the barrier layer (alkali-resistant film), and the like.
  • the treatment for forming the corrosion-resistant film one type may be performed, or two or more types may be combined. Moreover, not only one layer but also multiple layers can be used.
  • the hydrothermal modification treatment and the anodic oxidation treatment are treatments in which the surface of the metal foil is dissolved by the treatment agent to form a metal compound having excellent corrosion resistance. In addition, these processes may be included in the definition of chemical conversion process.
  • the barrier layer 3 has a corrosion-resistant film
  • the barrier layer 3 includes the corrosion-resistant film.
  • the corrosion-resistant film is formed by preventing delamination between the barrier layer (for example, aluminum alloy foil) and the base material layer during molding of the exterior material for a power storage device, and by hydrogen fluoride generated by the reaction between the electrolyte and water. , Melting and corrosion of the surface of the barrier layer, especially when the barrier layer is an aluminum alloy foil, it prevents the aluminum oxide existing on the surface of the barrier layer from melting and corroding, and the adhesiveness (wetness) of the surface of the barrier layer. The effect of preventing the corrosion between the base material layer and the barrier layer at the time of heat sealing and the prevention of the corrosion between the base material layer and the barrier layer at the time of molding is shown.
  • the barrier layer for example, aluminum alloy foil
  • Various corrosion-resistant films formed by chemical conversion treatment are known, and mainly, at least one of phosphate, chromate, fluoride, triazinethiol compound, and rare earth oxide. Examples thereof include a corrosion-resistant film containing.
  • Examples of the chemical conversion treatment using phosphate and chromate include chromic acid chromate treatment, chromic acid chromate treatment, phosphoric acid-chromate treatment, and chromate treatment, and chromium used in these treatments.
  • Examples of the compound include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium bicarbonate, acetylacetate chromate, chromium chloride, chromium sulfate and the like.
  • examples of the phosphorus compound used in these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid and the like.
  • examples of the chromate treatment include etching chromate treatment, electrolytic chromate treatment, and coating type chromate treatment, and coating type chromate treatment is preferable.
  • At least the inner layer side surface of the barrier layer (for example, aluminum alloy foil) is first known as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activation method and the like. Degreasing is performed by the treatment method, and then metal phosphates such as Cr phosphate (chromium) salt, Ti (titanium) phosphate, Zr (zyroxide) salt, and Zn (zinc) phosphate are applied to the degreased surface.
  • metal phosphates such as Cr phosphate (chromium) salt, Ti (titanium) phosphate, Zr (zyroxide) salt, and Zn (zinc) phosphate are applied to the degreased surface.
  • This is a treatment in which a treatment liquid composed of a mixture is coated by a well-known coating method such as a roll coating method, a gravure printing method, or a dipping method, and dried.
  • a treatment liquid for example, various solvents such as water, alcohol-based solvent, hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, and ether-based solvent can be used, and water is preferable.
  • the resin component used at this time examples include polymers such as phenol-based resins and acrylic-based resins, and aminoated phenol polymers having repeating units represented by the following general formulas (1) to (4) can be used. Examples thereof include the chromate treatment used. In the amination phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. May be good.
  • the acrylic resin shall be a polyacrylic acid, an acrylic acid methacrylate copolymer, an acrylic acid maleic acid copolymer, an acrylic acid styrene copolymer, or a derivative of these sodium salts, ammonium salts, amine salts, etc. Is preferable.
  • polyacrylic acid means a polymer of acrylic acid.
  • the acrylic resin is preferably a copolymer of an acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride, and an ammonium salt or a sodium salt of a copolymer of an acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride.
  • it is preferably an amine salt. Only one type of acrylic resin may be used, or two or more types may be mixed and used.
  • X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 represent a hydroxy group, an alkyl group, or a hydroxyalkyl group, respectively, which are the same or different.
  • examples of the alkyl group represented by X, R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group.
  • Examples of the hydroxyalkyl groups represented by X, R 1 and R 2 include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group and 3-.
  • Alkyl groups can be mentioned.
  • the alkyl group and the hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different, respectively.
  • X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group.
  • the number average molecular weight of the amination phenol polymer having the repeating unit represented by the general formulas (1) to (4) is, for example, preferably about 5 to 1,000,000, and preferably about 1,000 to 20,000. More preferred.
  • the amination phenol polymer is produced, for example, by polycondensing a phenol compound or a naphthol compound with formaldehyde to produce a polymer composed of repeating units represented by the above general formula (1) or general formula (3), and then forming a formaldehyde. It is produced by introducing a functional group (-CH 2 NR 1 R 2 ) into the polymer obtained above using an amine (R 1 R 2 NH).
  • the amination phenol polymer is used alone or in combination of two or more.
  • the corrosion resistant film it is formed by a coating type corrosion prevention treatment in which a coating agent containing at least one selected from the group consisting of rare earth element oxide sol, anionic polymer, and cationic polymer is applied.
  • the thin film to be corroded is mentioned.
  • the coating agent may further contain phosphoric acid or phosphate, a cross-linking agent for cross-linking the polymer.
  • fine particles of the rare earth element oxide for example, particles having an average particle size of 100 nm or less
  • the rare earth element oxide examples include cerium oxide, yttrium oxide, neodium oxide, lanthanum oxide and the like, and cerium oxide is preferable from the viewpoint of further improving adhesion.
  • the rare earth element oxide contained in the corrosion-resistant film may be used alone or in combination of two or more.
  • various solvents such as water, alcohol-based solvent, hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, and ether-based solvent can be used, and water is preferable.
  • the cationic polymer examples include polyethyleneimine, an ionic polymer complex composed of polyethyleneimine and a polymer having a carboxylic acid, a primary amine graft acrylic resin obtained by graft-polymerizing a primary amine on an acrylic main skeleton, polyallylamine or a derivative thereof. , Amination phenol and the like are preferable.
  • the anionic polymer is preferably a poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the cross-linking agent is at least one selected from the group consisting of a compound having a functional group of any of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group and a silane coupling agent.
  • the phosphoric acid or phosphate is condensed phosphoric acid or condensed phosphate.
  • a film in which fine particles of metal oxides such as aluminum oxide, titanium oxide, cerium oxide, and tin oxide and barium sulfate are dispersed in phosphoric acid is applied to the surface of the barrier layer, and 150 Examples thereof include those formed by performing a baking treatment at a temperature of ° C. or higher.
  • the corrosion-resistant film may have a laminated structure in which at least one of a cationic polymer and an anionic polymer is further laminated, if necessary.
  • a cationic polymer and an anionic polymer include those described above.
  • composition of the corrosion-resistant film can be analyzed by using, for example, a time-of-flight secondary ion mass spectrometry method.
  • the amount of the corrosion-resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but for example, in the case of performing a coating type chromate treatment, a chromic acid compound per 1 m 2 of the surface of the barrier layer 3 Is, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of chromium, and the phosphorus compound is, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and an amination phenol polymer. Is preferably contained in a proportion of, for example, about 1.0 to 200 mg, preferably about 5.0 to 150 mg.
  • the thickness of the corrosion-resistant film is not particularly limited, but is preferably about 1 nm to 20 ⁇ m, more preferably 1 nm to 100 nm, from the viewpoint of the cohesive force of the film and the adhesion to the barrier layer and the heat-sealing resin layer. The degree, more preferably about 1 nm to 50 nm.
  • the thickness of the corrosion-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersion type X-ray spectroscopy or electron beam energy loss spectroscopy.
  • the time-of-flight secondary ion mass spectrometry analysis of the composition of the corrosion resistant coating using, for example, secondary ion consisting Ce and P and O (e.g., Ce 2 PO 4 +, CePO 4 - at least 1, such as species) or, for example, secondary ion of Cr and P and O (e.g., CrPO 2 +, CrPO 4 - peak derived from at least one), such as is detected.
  • secondary ion consisting Ce and P and O e.g., Ce 2 PO 4 +, CePO 4 - at least 1, such as species
  • secondary ion of Cr and P and O e.g., CrPO 2 +, CrPO 4 - peak derived from at least one
  • a solution containing a compound used for forming a corrosion-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, or the like, and then the temperature of the barrier layer is applied. It is carried out by heating so that the temperature is about 70 to 200 ° C.
  • the barrier layer may be subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like in advance. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the barrier layer.
  • an acid degreasing agent in which a fluorine-containing compound is dissolved in an inorganic acid for the degreasing treatment it is possible to form not only the degreasing effect of the metal foil but also the immobile metal fluoride. In such cases, only degreasing treatment may be performed.
  • the heat-sealing resin layer 4 corresponds to the innermost layer, and has a function of heat-sealing the heat-sealing resin layers with each other when assembling the power storage device to seal the power storage device element. It is a layer (sealant layer) that exerts.
  • a melting peak temperature of 130 ° C. or lower is observed in the heat-sealing resin layer 4.
  • the melting peak temperature is preferably about 100 ° C. or higher, more preferably about 110 ° C. or higher, still more preferably about 120 ° C. or higher.
  • Preferred ranges of the melting peak temperature include about 100 to 130 ° C., about 110 to 130 ° C., and about 120 to 130 ° C.
  • the number of melting peak temperatures may be one or plural. Further, if a melting peak temperature of 130 ° C.
  • a melting peak temperature of more than 130 ° C. may be further observed.
  • the melting peak temperatures observed in the heat-sealing resin layer 4 are all 130 ° C. or lower.
  • the melting peak temperature of the heat-sealing resin layer 4 is observed, but it is observed as in the first embodiment. Is preferable.
  • the method for measuring the melting peak temperature is as follows.
  • a heat-sealing resin layer is obtained from the exterior material for a power storage device and a measurement sample is obtained.
  • the melting peak temperature is measured in accordance with the provisions of JIS K7121: 2012 (Plastic transition temperature measurement method (Appendix 1 of JIS K7121: 1987)).
  • the measurement is performed using a differential scanning calorimeter (DSC, for example, a differential scanning calorimeter Q200 manufactured by TA Instruments).
  • the resin constituting the heat-bondable resin layer 4 is heat-sealable and contains a polyolefin skeleton in the first embodiment. Further, in the second embodiment, the resin constituting the heat-sealing resin layer 4 does not need to contain the polyolefin skeleton, but preferably contains the polyolefin skeleton. Examples of the resin containing a polyolefin skeleton include polyolefins and acid-modified polyolefins. The fact that the resin constituting the heat-sealing resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like.
  • a peak derived from maleic anhydride is detected.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the heat-sealing resin layer 4 is a layer composed of maleic anhydride-modified polyolefin, a peak derived from maleic anhydride is detected when measured by infrared spectroscopy.
  • the degree of acid denaturation is low, the peak may become small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene- ⁇ -olefin copolymers; homopolypropylene and block copolymers of polypropylene (for example, with propylene).
  • Polyolefins such as ethylene block copolymers) and polypropylene random copolymers (eg, propylene and ethylene random copolymers); propylene- ⁇ -olefin copolymers; ethylene-butene-propylene tarpolymers and the like.
  • polypropylene is preferable.
  • the polyolefin resin may be a block copolymer or a random copolymer. One type of these polyolefin resins may be used alone, or two or more types may be used in combination.
  • the polyolefin may be a cyclic polyolefin.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Be done.
  • cyclic monomer which is a constituent monomer of the cyclic polyolefin examples include cyclic alkenes such as norbornene; cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these, cyclic alkene is preferable, and norbornene is more preferable.
  • Acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component.
  • the acid-modified polyolefin the above-mentioned polyolefin, a copolymer obtained by copolymerizing the above-mentioned polyolefin with a polar molecule such as acrylic acid or methacrylic acid, or a polymer such as a crosslinked polyolefin can also be used.
  • the acid component used for acid modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.
  • the acid-modified polyolefin may be an acid-modified cyclic polyolefin.
  • the acid-modified cyclic polyolefin is a polymer obtained by copolymerizing a part of the monomers constituting the cyclic polyolefin in place of the acid component, or by block-polymerizing or graft-polymerizing the acid component with the cyclic polyolefin. be.
  • the acid component used for acid denaturation is the same as the acid component used for denaturation of the polyolefin.
  • Preferred acid-modified polyolefins include polyolefins modified with carboxylic acid or its anhydride, polypropylene modified with carboxylic acid or its anhydride, maleic anhydride-modified polyolefin, and maleic anhydride-modified polypropylene.
  • the heat-sealing resin layer 4 may be formed of one type of resin alone, or may be formed of a blended polymer in which two or more types of resins are combined. Further, the heat-sealing resin layer 4 may be formed of only one layer, but may be formed of two or more layers with the same or different resins.
  • the heat-sealing resin layer 4 may contain a lubricant or the like, if necessary.
  • a lubricant When the heat-sealing resin layer 4 contains a lubricant, the moldability of the exterior material for a power storage device can be improved.
  • the lubricant is not particularly limited, and a known lubricant can be used.
  • the lubricant may be used alone or in combination of two or more.
  • the lubricant is not particularly limited, but an amide-based lubricant is preferable. Specific examples of the lubricant include those exemplified in the base material layer 1. One type of lubricant may be used alone, or two or more types may be used in combination.
  • the amount of the lubricant is not particularly limited, but is preferably about 10 to 50 mg / m 2 from the viewpoint of improving the moldability of the exterior material for the power storage device. , More preferably about 15 to 40 mg / m 2.
  • the lubricant existing on the surface of the heat-sealing resin layer 4 may be one in which the lubricant contained in the resin constituting the heat-sealing resin layer 4 is exuded, or the lubricant contained in the heat-sealing resin layer 4 may be exuded.
  • the surface may be coated with a lubricant.
  • the thickness of the heat-sealing resin layer 4 is not particularly limited as long as the heat-sealing resin layers have a function of heat-sealing to seal the power storage device element, but is preferably about 100 ⁇ m or less, preferably about 100 ⁇ m or less. It is about 85 ⁇ m or less, more preferably about 15 to 85 ⁇ m.
  • the thickness of the heat-sealing resin layer 4 is preferably about 85 ⁇ m or less, more preferably about 15 to 45 ⁇ m, for example.
  • the thickness of the heat-sealing resin layer 4 is preferably about 20 ⁇ m or more, more preferably 35 to 85 ⁇ m. The degree can be mentioned.
  • the adhesive layer 5 is a layer provided between the barrier layer 3 (or a corrosion-resistant film) and the heat-sealing resin layer 4 in order to firmly bond them. ..
  • a melting peak is observed in the adhesive layer 5 at 135 ° C. or higher.
  • the melting peak temperature is preferably 140 ° C. or higher, more preferably 150 ° C. or higher.
  • the melting peak temperature is preferably 170 ° C. or lower.
  • the preferable temperature range of the melting peak temperature is preferably about 135 to 170 ° C., more preferably about 140 to 170 ° C., still more preferably about 150 to 170 ° C.
  • the number of melting peak temperatures may be one or plural. Further, if a melting peak temperature of 135 ° C.
  • a melting peak temperature of less than 135 ° C. may be further observed.
  • the melting peak temperatures observed in the adhesive layer 5 are all 135 ° C. or higher.
  • the exterior material for the power storage device according to the second embodiment it is not essential that the melting peak temperature of the adhesive layer 5 is observed, but it is observed as in the first embodiment. Is preferable.
  • the melting peak temperature is measured by the method described in the above (Measurement of melting peak temperature) column, except that an adhesive layer is obtained from the exterior material for a power storage device and a measurement sample is obtained.
  • the adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the heat-sealing resin layer 4.
  • the adhesive layer 5 contains a polyolefin skeleton.
  • the adhesive layer 5 does not need to contain the polyolefin skeleton, but preferably contains the polyolefin skeleton.
  • the resin forming the adhesive layer 5 include the polyolefins exemplified in the above-mentioned heat-sealing resin layer 4 and acid-modified polyolefins.
  • the adhesive layer 5 preferably contains an acid-modified polyolefin.
  • the acid-modifying component examples include dicarboxylic acids such as maleic acid, itaconic acid, succinic acid, and adipic acid, and anhydrides thereof, acrylic acid, and methacrylic acid. Maleic acid is most preferred.
  • the olefin component is preferably polypropylene-based resin, and the adhesive layer 5 most preferably contains maleic anhydride-modified polypropylene.
  • the resin constituting the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited.
  • the resin constituting the adhesive layer 5 comprises an acid-modified polyolefin, for example, when measuring the infrared spectroscopy at maleic anhydride-modified polyolefin, anhydride in the vicinity of a wave number of 1760 cm -1 and near the wave number 1780 cm -1 A peak derived from maleic anhydride is detected. However, if the degree of acid denaturation is low, the peak may become small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • the thickness of the adhesive layer 5 is preferably about 60 ⁇ m or less, about 50 ⁇ m or less, and about 45 ⁇ m or less.
  • the thickness of the adhesive layer 5 is preferably about 10 ⁇ m or more, about 20 ⁇ m or more, about 25 ⁇ m or more, and about 30 ⁇ m or more.
  • the thickness range of the adhesive layer 5 is preferably about 10 to 60 ⁇ m, about 10 to 50 ⁇ m, about 10 to 45 ⁇ m, about 20 to 60 ⁇ m, about 20 to 50 ⁇ m, about 20 to 45 ⁇ m, and about 25 to 60 ⁇ m. , About 25 to 50 ⁇ m, about 25 to 45 ⁇ m, about 30 to 60 ⁇ m, about 30 to 50 ⁇ m, and about 30 to 45 ⁇ m.
  • the adhesive layer 5 can be formed by, for example, extrusion molding of the heat-sealing resin layer 4 and the adhesive layer 5.
  • the exterior material for a power storage device of the present disclosure is above the base material layer 1 (base material layer 1), if necessary, for the purpose of improving at least one of designability, electrolytic solution resistance, scratch resistance, moldability, and the like.
  • the surface coating layer 6 may be provided on the side opposite to the barrier layer 3 of the above.
  • the surface coating layer 6 is a layer located on the outermost layer side of the exterior material for the power storage device when the power storage device is assembled using the exterior material for the power storage device.
  • the surface coating layer 6 can be formed of, for example, a resin such as polyvinylidene chloride, polyester, polyurethane, acrylic resin, or epoxy resin.
  • the resin forming the surface coating layer 6 is a curable resin
  • the resin may be either a one-component curable type or a two-component curable type, but is preferably a two-component curable type.
  • the two-component curable resin include two-component curable polyurethane, two-component curable polyester, and two-component curable epoxy resin. Of these, two-component curable polyurethane is preferable.
  • the two-component curable polyurethane examples include a polyurethane containing a first agent containing a polyol compound and a second agent containing an isocyanate compound.
  • a two-component curable polyurethane using a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol as a first agent and an aromatic or aliphatic polyisocyanate as a second agent can be mentioned.
  • the polyurethane include a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance, and a polyurethane containing the isocyanate compound.
  • polyurethane examples include a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance, and a polyurethane containing the polyol compound.
  • polyurethane examples include polyurethane obtained by reacting a polyurethane compound in which a polyol compound and an isocyanate compound are previously reacted with water such as in the air to cure the polyurethane.
  • the polyol compound it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit.
  • the second agent examples include aliphatic, alicyclic, aromatic, and aromatic aliphatic isocyanate compounds.
  • isocyanate-based compound examples include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalenediocyanate (NDI) and the like. Moreover, a polyfunctional isocyanate modified product from one kind or two or more kinds of these diisocyanates and the like can be mentioned. Further, a multimer (for example, a trimer) can be used as the polyisocyanate compound.
  • a multimer for example, a trimer
  • Examples of such a multimer include an adduct body, a biuret body, a nurate body and the like.
  • the aliphatic isocyanate-based compound refers to an isocyanate having an aliphatic group and no aromatic ring
  • the alicyclic isocyanate-based compound refers to an isocyanate having an alicyclic hydrocarbon group, which is an aromatic isocyanate-based compound.
  • the surface coating layer 6 has the above-mentioned lubricant or antistatic agent on at least one of the surface and the inside of the surface coating layer 6, depending on the functionality and the like to be provided on the surface coating layer 6 and the surface thereof. It may contain additives such as a blocking agent, a matting agent, a flame retardant, an antioxidant, a tackifier, and an antistatic agent. Examples of the additive include fine particles having an average particle size of about 0.5 nm to 5 ⁇ m. The average particle size of the additive shall be the median size measured by the laser diffraction / scattering type particle size distribution measuring device.
  • the additive may be either an inorganic substance or an organic substance.
  • the shape of the additive is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a scaly shape.
  • additives include talc, silica, graphite, kaolin, montmorillonite, mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodium oxide, and antimony oxide.
  • Titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, refractory nylon, acrylate resin examples thereof include crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel.
  • the additive may be used alone or in combination of two or more.
  • silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the additive may be subjected to various surface treatments such as an insulation treatment and a highly dispersible treatment on the surface.
  • the method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a resin for forming the surface coating layer 6.
  • a resin mixed with the additive may be applied.
  • the thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above-mentioned functions as the surface coating layer 6, and examples thereof include about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the method for manufacturing the exterior material for power storage device is not particularly limited as long as a laminated body in which each layer of the exterior material for power storage device of the present invention is laminated can be obtained, and at least the base material.
  • Examples thereof include a method including a step of laminating the layer 1, the barrier layer 3, and the heat-sealing resin layer 4 in this order. That is, in the method for producing an exterior material for a power storage device of the present invention, at least a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer are laminated in this order to form a laminate.
  • the heat-sealing resin layer has a melting peak temperature of 130 ° C.
  • the adhesive layer has a melting peak temperature of 135 ° C. or higher, and the heat-sealing resin layer has a melting peak temperature of 135 ° C. or higher. It has a polyolefin skeleton, and the adhesive layer has a polyolefin skeleton.
  • laminate A a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order
  • the laminated body A is formed by applying an adhesive used for forming the adhesive layer 2 on the base material layer 1 or, if necessary, on the barrier layer 3 whose surface has been chemically converted, by a gravure coating method. It can be carried out by a dry laminating method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a roll coating method.
  • the adhesive layer 5 and the heat-sealing resin layer 4 are laminated on the barrier layer 3 of the laminated body A.
  • a method of forming a laminated body in which layers 5 are laminated and laminating this with a heat-sealing resin layer 4 by a thermal laminating method A method of laminating the laminate A and the heat-sealing resin layer 4 via the adhesive layer 5 while pouring the molten adhesive layer 5 between the adhesive layer 4 (sandwich laminating method), (4).
  • An adhesive for forming the adhesive layer 5 is solution-coated on the barrier layer 3 of the laminated body A, and the adhesive is laminated by a method of drying, a method of baking, or the like, and the adhesive layer 5 is preliminarily made into a sheet. Examples thereof include a method of laminating the filmed heat-sealing resin layer 4.
  • the surface coating layer 6 is laminated on the surface of the base material layer 1 opposite to the barrier layer 3.
  • the surface coating layer 6 can be formed, for example, by applying the above resin that forms the surface coating layer 6 to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer 6.
  • the surface coating layer 6 / base material layer 1 / adhesive layer 2 / barrier layer 3 / adhesive layer 5 / heat-sealing resin layer 4 provided as needed are formed into this.
  • Laminates to be prepared in order are formed, but in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as needed, they may be further subjected to heat treatment.
  • each layer constituting the laminated body may be subjected to surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment, etc., if necessary, to improve processing suitability. ..
  • surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment, etc.
  • a corona treatment to the surface of the base material layer 1 opposite to the barrier layer 3, the printability of the ink on the surface of the base material layer 1 can be improved.
  • exterior materials for power storage devices of the present disclosure are used for packaging for sealing and accommodating power storage device elements such as positive electrodes, negative electrodes, and electrolytes. That is, a power storage device element having at least a positive electrode, a negative electrode, and an electrolyte can be housed in a package formed of the exterior material for a power storage device of the present disclosure to form a power storage device.
  • a power storage device element having at least a positive electrode, a negative electrode, and an electrolyte is provided with the exterior material for the power storage device of the present disclosure in a state in which metal terminals connected to each of the positive electrode and the negative electrode are projected outward.
  • the peripheral edge of the power storage device element is covered so that a flange portion (a region where the heat-sealing resin layers come into contact with each other) can be formed, and the heat-sealing resin layers of the flange portion are heat-sealed and sealed.
  • the heat-sealing resin portion of the exterior material for the power storage device of the present disclosure is inside (the surface in contact with the power storage device element). )
  • the heat-sealing resin layers of the two exterior materials for power storage devices may be overlapped with each other facing each other, and the peripheral edges of the overlapped exterior materials for power storage devices may be heat-sealed to form a package.
  • one exterior material for a power storage device may be folded back and overlapped, and the peripheral edge portion may be heat-sealed to form a package. In the case of folding and overlapping, as shown in the example shown in FIG.
  • the sides other than the folded side may be heat-sealed to form a package by a three-way seal, or the package may be folded so that a flange portion can be formed. It may be sealed on all sides.
  • a recess for accommodating the power storage device element may be formed by deep drawing molding or overhang molding. As shown in the example shown in FIG. 4, it is not necessary to provide a recess in one of the exterior materials for the power storage device and not in the exterior material for the other power storage device, and the other exterior material for the power storage device also has a recess. May be provided.
  • the exterior material for a power storage device of the present disclosure can be suitably used for a power storage device such as a battery (including a capacitor, a capacitor, etc.). Further, the exterior material for a power storage device of the present disclosure may be used for either a primary battery or a secondary battery, but is preferably used for a secondary battery.
  • the type of the secondary battery to which the exterior material for the power storage device of the present disclosure is applied is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, an all-solid-state battery, a lead storage battery, a nickel / hydrogen storage battery, and a nickel / hydrogen storage battery.
  • lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the exterior materials for power storage devices of the present disclosure.
  • Example 1-2 and Comparative Example 1-2 A stretched nylon (ONy) film (thickness 25 ⁇ m) was prepared as a base material layer. Further, as a barrier layer, an aluminum foil (JIS H4160: 1994 A8021HO (thickness 40 ⁇ m)) was prepared. Next, the base material layer and the barrier layer are adhered to each other by a dry laminating method using a two-component urethane adhesive (polyol compound and aromatic isocyanate compound), and an aging treatment is performed to carry out the base material layer.
  • a two-component urethane adhesive polyol compound and aromatic isocyanate compound
  • a laminate of (thickness 25 ⁇ m) / adhesive layer (thickness after curing is 3 ⁇ m) / barrier layer (thickness 40 ⁇ m) was prepared. Both sides of the aluminum foil are subjected to chemical conversion treatment.
  • the chemical conversion treatment of the aluminum foil is performed by applying a treatment liquid consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid to both sides of the aluminum foil by a roll coating method so that the amount of chromium applied is 10 mg / m 2 (dry mass). This was done by coating and baking.
  • the melting peak temperatures of the adhesive layer and the heat-sealing resin layer of Example 1-2 and Comparative Example 1-2 are as shown in Table 1. Moreover, these melting peak temperatures were measured by the following methods.
  • the seal strength of the exterior material for the power storage device was measured as follows.
  • an exterior material for a power storage device cut into strips having a width in the TD direction of 15 mm was prepared. Specifically, as shown in FIG. 5, first, the exterior material for each power storage device was cut into 60 mm (TD direction) ⁇ 200 mm (MD direction) (FIG. 5a). Next, the heat-sealing resin layers were made to face each other, and the exterior material for the power storage device was folded in half in the MD direction at the position of the crease P (middle in the MD direction) (FIG. 5b).
  • Heat-sealing resin layers were heat-sealed between the heat-sealing resin layers under the conditions of a seal width of 7 mm, a temperature of 120 ° C. or 190 ° C., and a surface pressure of 1.0 MPa for 3 seconds in the direction of MD about 10 mm from the crease P (FIG. 5c).
  • the shaded portion S is a heat-sealed portion.
  • a test piece was obtained by cutting in the direction of MD (cutting at the position of the alternate long and short dash line in FIG. 5d) so that the width in the direction of TD was 15 mm (FIG. 5e).
  • the test piece 13 was left in an environment of 25 ° C.
  • Martens hardness calculates the surface area A (mm 2) of the indenter at the maximum indentation depth of the Vickers indenter is obtained dividing the maximum load F (N) (F / A ) that in the surface area A (mm 2).
  • a picodenter HM-500 manufactured by Fisher Instruments Co., Ltd. was used as a measuring device. An exterior material for a power storage device was adhered to one side of a slide glass (76 mm ⁇ 26 mm ⁇ 1 mm) to which a double-sided adhesive tape was attached so that the heat-sealing resin layer side was opposite to the slide glass, and used as a measurement sample. Next, the surface hardness of the surface of the measurement sample on the heat-sealing resin layer side was measured.
  • the exterior material for the power storage device was cut into a size of 100 mm ⁇ 200 mm, and the heat-sealing resin layers were folded so as to face each other at the center position of the long side of the exterior material for the power storage device.
  • the short side was heat-sealed under the conditions of a temperature of 120 ° C., a surface pressure of 1.0 MPa, and a seal width of 7 mm for 3 seconds.
  • one long side is heat-sealed in the same manner, 2.0 g of water is added to the bag-shaped sample, and then the opening side (long side) is degassed from the inside air.
  • test sample was placed in an oven and allowed to stand in an environment of 105 ° C. for 8 hours to confirm whether or not the test sample was opened.
  • the results are shown in Table 1.
  • the internal pressure becomes about 120 kPa due to the increase in internal pressure due to the vaporization of water.
  • the heat-sealing resin layer was observed to have a melting peak temperature of 130 ° C. or lower, and the adhesive layer was observed to have a melting peak temperature of 135 ° C. or higher.
  • the resin constituting the layer and the adhesive layer each has a polyolefin skeleton.
  • the exterior material for the power storage device of Example 1-2 has a Martens hardness of 30.0 MPa or more, which is measured by pushing a Vickers indenter to a depth of 1 ⁇ m in the thickness direction from the surface on the heat-sealing resin layer side. Is.
  • the exterior material for a power storage device of Example 1-2 has high adhesion strength by heat-sealing the heat-sealing resin layers at a temperature lower than the conventional heat-sealing temperature (around 200 ° C.) (for example, about 120 ° C.). Even if the power storage device is formed and the power storage device is exposed to an environment of about 100 ° C., the exterior material for the power storage device is not opened.
  • Item 1 An exterior material for a power storage device composed of a laminate including a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order.
  • a melting peak temperature was observed below 130 ° C.
  • the adhesive layer a melting peak temperature was observed above 135 ° C.
  • the resin constituting the heat-sealing resin layer has a polyolefin skeleton and has a polyolefin skeleton.
  • the resin constituting the adhesive layer is an exterior material for a power storage device having a polyolefin skeleton.
  • An exterior material for a power storage device composed of a laminate including a base material layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer in this order. Based on the indentation method, the Vickers hardness measured by pushing the Vickers indenter to a depth of 1 ⁇ m in the thickness direction from the surface of the exterior material for the power storage device on the heat-sealing resin layer side at a measurement temperature of 25 ° C. Exterior material for power storage devices, which is 30.0 MPa or more. Item 3.
  • the exterior material for a power storage device according to Item 1 which is 25.0 MPa or more.
  • the exterior material for a power storage device is measured by heat-sealing the heat-sealing resin layers under the conditions of a temperature of 120 ° C. and a surface pressure of 1.0 MPa for 3 seconds, and peeling the heat-sealing resin layers from each other.
  • the exterior material for a power storage device according to any one of Items 1 to 3, wherein the heat seal strength is 35 N / 15 mm or more in the heat seal strength measurement.
  • Item 5 The exterior material for a power storage device is measured by heat-sealing the heat-sealing resin layers under the conditions of a temperature of 190 ° C. and a surface pressure of 1.0 MPa for 3 seconds, and peeling the heat-sealing resin layers from each other.
  • Item 4. The exterior material for a power storage device according to Item 4, wherein the heat seal strength is 80 N / 15 mm or more in the heat seal strength measurement.
  • Item 6. Item 2.
  • the exterior material for a power storage device contains polypropylene.
  • Item 7. Item 2. The exterior material for a power storage device according to any one of Items 1 to 6, wherein the resin constituting the adhesive layer contains acid-modified polypropylene.
  • Item 8. At least, it includes a step of laminating the base material layer, the barrier layer, the adhesive layer, and the heat-sealing resin layer in this order to obtain a laminate. In the heat-sealing resin layer, a melting peak temperature was observed below 130 ° C. In the adhesive layer, a melting peak temperature was observed above 135 ° C.
  • the resin constituting the heat-sealing resin layer has a polyolefin skeleton and has a polyolefin skeleton.
  • a method for manufacturing an exterior material for a power storage device which is 30.0 MPa or more.
  • Item 10 A power storage device in which a power storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for the power storage device according to any one of Items 1 to 7.
  • Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-sealing resin layer 5 Adhesive layer 6 Surface coating layer 10 Exterior material for power storage devices

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PCT/JP2021/014413 2020-04-03 2021-04-02 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス Ceased WO2021201294A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190997A1 (ja) * 2022-03-31 2023-10-05 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
US20230411741A1 (en) * 2022-06-08 2023-12-21 Resonac Packaging Corporation Packaging material for power storage device, packaging case for power storage device, and power storage device

Citations (4)

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