WO2017188445A1 - Matériau d'encapsulation de batterie et batterie - Google Patents

Matériau d'encapsulation de batterie et batterie Download PDF

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Publication number
WO2017188445A1
WO2017188445A1 PCT/JP2017/017026 JP2017017026W WO2017188445A1 WO 2017188445 A1 WO2017188445 A1 WO 2017188445A1 JP 2017017026 W JP2017017026 W JP 2017017026W WO 2017188445 A1 WO2017188445 A1 WO 2017188445A1
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WO
WIPO (PCT)
Prior art keywords
layer
packaging material
battery packaging
heat
battery
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Application number
PCT/JP2017/017026
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English (en)
Japanese (ja)
Inventor
純 景山
山下　力也
大佑 安田
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to JP2018514740A priority Critical patent/JP7020401B2/ja
Priority to CN201780025690.8A priority patent/CN109075270B/zh
Publication of WO2017188445A1 publication Critical patent/WO2017188445A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a battery packaging material and a battery.
  • the battery may generate a combustible gas and the pressure may increase.
  • the organic solvent used in the electrolytic solution may be decomposed to generate a combustible gas and cause an increase in pressure.
  • the battery may continuously increase the temperature in the battery due to charging due to overvoltage or discharging with an excessive current, thereby causing a runaway battery reaction.
  • such an increase in pressure or temperature in the battery may cause the battery packaging material to be cleaved and cause ignition due to ejection of combustible gas. Further, if the pressure or temperature rises continuously in the battery and the battery reaction runs out of control when the battery packaging material is excessively expanded, the battery may explode. For this reason, the packaging material for batteries is required to have high sealing performance that can suppress the opening of the battery even when exposed to high temperatures.
  • An object of the present invention is to provide a battery packaging material capable of effectively suppressing battery unsealing even when the battery is exposed to high temperatures.
  • a battery packaging material comprising a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order
  • the heat-fusible resin layers are opposed to each other. It is heat-sealed, and water is sealed with the battery packaging material.
  • T ° C. 100 ° C. or higher under vacuum
  • the temperature reaches T ° C. after reaching the opening test temperature T ° C.
  • the battery packaging material that is held and sealed for 10 minutes is designed not to be opened, and the melting peak temperature of the adhesive layer is 10 ° C. higher than the opening test temperature T ° C.
  • the battery can be effectively prevented from being opened even when exposed to high temperatures (for example, 100 ° C. or higher, 120 ° C. or higher, or 135 ° C. or higher under vacuum).
  • high temperatures for example, 100 ° C. or higher, 120 ° C. or higher, or 135 ° C. or higher under vacuum.
  • the present invention has been completed by further studies based on such knowledge.
  • water was used as a virtual electrolyte, and water was sealed with a battery packaging material, and the unsealing test was performed in view of ensuring the safety of the unsealing test and water instead of the electrolyte. This is because the opening performance can be evaluated even if it is used.
  • this invention provides the battery packaging material and battery of the aspect hung up below.
  • Item 1 A battery packaging material comprising a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, When the heat-fusible resin layers are heat-sealed in a state of facing each other, water is sealed with the battery packaging material, and the temperature is increased to 100 ° C. or higher opening test temperature T ° C. under vacuum. After the opening test temperature T ° C., the battery packaging material held at T ° C. and sealed for 10 minutes does not open, A battery packaging material, wherein a melting peak temperature of the adhesive layer is 10 ° C. or more higher than the opening test temperature T ° C. Item 2.
  • Item 2. The battery packaging material according to Item 1, wherein the adhesive layer is a cured product of a resin composition containing polyolefin.
  • Item 3. Item 3.
  • Packaging materials. Item 4.
  • Item 4. The battery packaging material according to any one of Items 1 to 3, wherein the adhesive layer has a thickness of 10 ⁇ m or less.
  • the battery packaging material according to any one of Items 1 to 4, wherein the heat-fusible resin layer includes at least one layer having a melting peak temperature equal to or higher than the opening test temperature T ° C. Item 6.
  • a seal width is set at a position of 20 mm in the length direction from the bent portion. 7 mm, pressure 1.0 MPa, seal temperature 190 ° C., seal time 3 seconds, heat sealed in 3 seconds, distance between gauge points 50 mm, T-peeling, and the seal strength when pulled at 300 mm / min Item 6.
  • a seal width is set at a position of 20 mm in the length direction from the bent portion. 7 mm, pressure 1.0 MPa, seal temperature 190 ° C., heat seal at seal time 3 seconds, fixed to a tensile tester in a state of T-peeling at a distance between gauge points of 50 mm and the opening test temperature T ° C., Item 7.
  • Item 8 A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is accommodated in a package formed of the battery packaging material according to any one of Items 1 to 7.
  • the present invention it is possible to provide a battery packaging material that can effectively prevent the battery from being opened even when the battery is exposed to high temperatures.
  • FIG. 1 It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram for demonstrating the method of the opening test of the packaging material for batteries in an Example. It is a graph which shows the relationship between the temperature at the time of the opening test at 100 degreeC in an Example, and time. It is a graph which shows the relationship between the temperature at the time of the opening test in 120 degreeC in an Example, and time. It is a graph which shows the relationship between the temperature at the time of the opening test at 135 degreeC in an Example, and time. It is a schematic diagram which shows the position which folds the sample after shaping
  • the battery packaging material of the present invention is a battery packaging material comprising a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, and the heat-fusible resin layers are Are sealed with the battery packaging material, and when the temperature is raised to 100 ° C. or higher at an opening test temperature T ° C. under vacuum, the opening test temperature T ° C. is reached. After reaching, the battery packaging material sealed at 10 ° C. for 10 minutes does not open, and the melting peak temperature of the adhesive layer is 10 ° C. or more higher than the opening test temperature T ° C. To do.
  • the battery packaging material of the present invention is a battery packaging material comprising a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order.
  • the peak temperature is H ° C. (110 ° C. or higher)
  • heat fusion is performed in a state where the heat-fusible resin layers are opposed to each other, and water is sealed with the battery packaging material.
  • the temperature is raised to the opening test temperature “H ° C.-10 ° C.” of 100 ° C. or higher, after reaching the above opening test temperature “H ° C.-10 ° C.”, the temperature is kept at “H ° C.-10 ° C.” for 10 minutes.
  • the sealed battery packaging material is not opened.
  • the aforementioned opening temperature T ° C. corresponds to the melting peak temperature “H ° C.-10 ° C.” of the adhesive layer.
  • the indication of “to” indicating a numerical range indicates that the numerical value is greater than or equal to the numerical value attached to the left side thereof and less than or equal to the numerical value attached to the right side thereof.
  • the notation "" means X or more and Y or less.
  • the battery packaging material has a laminate structure including at least a base material layer 1, a barrier layer 2, an adhesive layer 3, and a heat-fusible resin layer 4 in this order. Consists of the body.
  • the base material layer 1 is the outermost layer side
  • the heat-fusible resin layer 4 is the innermost layer. That is, at the time of battery assembly, the heat-fusible resin layers 4 positioned at the periphery of the battery element are thermally welded to seal the battery element, thereby sealing the battery element.
  • the battery packaging material of the present invention is provided with an adhesive layer 5 between the base material layer 1 and the barrier layer 2 as necessary for the purpose of enhancing the adhesion. May be.
  • the heat-fusible resin layers 4 are heat-sealed in a state of being opposed to each other, and the battery element containing water is sealed with the battery packaging material, and 100 ° C. under vacuum.
  • T ° C. opening test temperature
  • the opening test temperature T ° C. is a value set according to the use of the battery, and may be a high temperature of 100 ° C. or higher.
  • a set value for temperature abnormality in a vehicle or the like is generally set to a high temperature of 100 ° C. or higher.
  • the opening test temperature T ° C. is set to 100 ° C. or higher. Moreover, if it is not opened for 10 minutes after reaching the opening temperature T ° C. of 100 ° C. or higher, the battery can be detected and cooled during that time. In applications that are expected to be used at higher temperatures, the opening test temperature T ° C is preferably 120 ° C or higher, more preferably 135 ° C or higher.
  • the conditions for the unsealing test are as follows, and more specific methods are as described in the examples.
  • the battery packaging material is cut to prepare a sample having a short side of 90 mm and a long side of 150 mm.
  • each sample was molded using a molding die (female) having a diameter of 32 mm on the short side and 55 mm on the long side and a molding die (male) corresponding to this with a pressing pressure of 0.13 MPa and 3 mm.
  • Cold forming is performed at a depth, and a recess is formed in the central portion. At this time, the clearance between the female mold and the male mold is 0.3 mm.
  • the sample after molding is folded at the folding position P shown in FIG. 7 with the heat-fusible resin layers facing each other, and the three peripheral portions 10a (FIG.
  • the battery for unsealing test 10 is placed in the space between the two stainless steel plates 20, so that the distance w between the two stainless steel plates 20 is 7.0 mm. Adjust with the fixing spacer 21.
  • the pressure in the oven is set to 5000 Pa or less, and the temperature is raised to 5 ° C. ⁇ 2 ° C./min. Raise the temperature until As the temperature in the oven rises, the internal pressure of the unsealing test battery 10 rises and swells, resulting in a state as shown in FIG.
  • the determination that the opening test temperature T ° C. ⁇ 5 ° C. has been reached is made by measuring the environmental temperature in the oven.
  • the temperature sensor attached to the side of the battery for unsealing test is the time from when the unsealing test temperature T ° C is reached to when the battery packaging material peels off between the barrier layer and the heat-fusible resin layer and is unsealed. To confirm. Note that, at the moment when the battery 10 for unsealing test is opened, the internal water adheres to the temperature sensor, and the temperature is lowered by the heat of vaporization of the water. For this reason, the opening time can be measured by the temperature sensor.
  • the seal strength of the heat-sealed portion with the heat-fusible resin layers 4 facing each other is 40 N or more at the opening test temperature T ° C. preferable. Even when the battery is exposed to a high temperature, the unsealing test temperature T ° C. is 100 ° C., 120 ° C., and 135 ° C. Can be effectively suppressed.
  • the seal strength is preferably about 60 N or more.
  • the seal strength in the present invention was folded at a position of 100 mm long so that the heat-fusible resin layers of the battery packaging material having a width of 15 mm and a length of 200 mm face each other, as shown in FIG.
  • the position of 20 mm in the length direction from the bent part is heat-sealed between the heat-sealable resin layers with a seal width of 7 mm, a seal temperature of 190 ° C., a pressure of 1.0 MPa, and a seal time of 3 seconds.
  • the battery packaging material of the present invention As shown in FIG. 8, the battery packaging material having a width of 15 mm and a length of 200 mm is positioned at a length of 100 mm so that the heat-fusible resin layers face each other.
  • the position 20 mm in the length direction from the bent portion is heat-sealed at a seal temperature of 190 ° C., a pressure of 1.0 MPa, and a seal time of 3 seconds.
  • the displacement of the battery packaging material is about 4 mm or less when it is fixed to a testing machine and left at an opening test temperature T ° C. for 2 minutes and then pulled for 10 minutes with a force of 35 N.
  • the opening test temperature T ° C. Can be effectively suppressed.
  • the displacement is preferably about 3.0 mm or less.
  • the heat-sealed region is indicated by S. A more specific method is as described in the examples.
  • the thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but the viewpoint of effectively suppressing the opening of the battery even when the battery is exposed to high temperatures while reducing the thickness. Is preferably about 200 ⁇ m or less, more preferably about 60 to 160 ⁇ m.
  • the base material layer 1 is a layer located on the outermost layer side.
  • the material for forming the base material layer 1 is not particularly limited as long as it has insulating properties.
  • Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, polycarbonate, and a mixture or copolymer thereof. Is mentioned.
  • polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolymerized polyester mainly composed of ethylene terephthalate, and butylene terephthalate mainly composed of repeating units. And the like copolyester.
  • the copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)).
  • polyethylene terephthalate / isophthalate
  • polyethylene terephthalate / adipate
  • polyethylene terephthalate / sodium sulfoisophthalate
  • polyethylene terephthalate / sodium isophthalate
  • polyethylene terephthalate / phenyl-dicarboxylate
  • polyethylene terephthalate / decanedicarboxylate
  • polyester mainly composed of butylene terephthalate as a repeating unit
  • a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit hereinafter referred to as polybutylene (terephthalate / isophthalate).
  • polybutylene (terephthalate / adipate) polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like.
  • These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.
  • polyamides include aliphatic polyamides 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 Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, and polymetaxylylene azide Polyamide containing aromatics such as Pamide (MXD6); Alicyclic polyamides such as Polyaminomethylcyclohexyl Adipamide (PACM6); and Lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate are copolymerized Polyamide, co-weight Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like.
  • MXD6 Polya
  • polyamides may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.
  • the base material layer 1 may be formed of a uniaxial or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1. Moreover, the base material layer 1 may be formed by coating the above-mentioned raw material on the aluminum alloy foil layer 3.
  • the resin film forming the base layer 1 is preferably nylon or polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, and particularly preferably biaxially stretched nylon.
  • the base material layer 1 can be laminated (multi-layer structure) of at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery packaging. is there. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like.
  • the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films The body is preferred.
  • the base material layer 1 has a multilayer structure of a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film.
  • the base material layer 1 is preferably a laminate having biaxially stretched nylon and biaxially stretched polyester in this order from the aluminum alloy foil layer 3 side.
  • the thickness of each layer is preferably about 2 to 25 ⁇ m.
  • each resin film may be bonded via an adhesive or may be directly laminated without using an adhesive.
  • a method of bonding in a hot-melt state such as a co-extrusion method, a sandwich lamination method, or a thermal lamination method can be used.
  • the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive.
  • the adhesive mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, an electron beam curable type, an ultraviolet curable type, and the like.
  • Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 5.
  • the thickness of the adhesive can be the same as that of the adhesive layer 5.
  • a lubricant is preferably attached to the surface of the base material layer 1 from the viewpoint of improving the moldability of the battery packaging material.
  • an amide type lubricant is mentioned.
  • Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like.
  • Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like.
  • the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
  • methylolamide include methylol stearamide.
  • saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide.
  • unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc.
  • fatty acid ester amide include stearoamidoethyl stearate.
  • aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like.
  • 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 3 mg / m 2 or more, more preferably 4 to 15 mg / m 2 in a temperature 24 ° C. and relative humidity 50% environment. About m 2 , more preferably about 5 to 14 mg / m 2 is mentioned.
  • the thickness of the base layer 1 is preferably about 4 ⁇ m or more, more preferably 10 from the viewpoint of making the battery packaging material excellent in shape stability after molding while reducing the thickness of the battery packaging material. About 75 ⁇ m, more preferably about 10 to 50 ⁇ m.
  • the adhesive layer 5 is a layer provided between the base material layer 1 and the barrier layer 2 as necessary in order to firmly bond them.
  • the adhesive layer 5 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 2 together.
  • the adhesive used for forming the adhesive layer 5 may be a two-component curable adhesive or a one-component curable adhesive.
  • the bonding mechanism of the adhesive used for forming the adhesive layer 5 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
  • adhesive components that can be used to form the adhesive layer 5 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester; polyethers Polyurethane adhesives; epoxy resins; phenolic resins; polycarbonates; polyamide resins such as nylon 6, nylon 66, nylon 12, copolymer polyamides; polyolefins, carboxylic acid modified polyolefins, metal modified polyolefins, etc.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester
  • polyethers Polyurethane adhesives epoxy resins; phenolic resins; polycarbonates; polyamide resins such as nylon 6, nylon 66, nylon 12, copolymer polyamides; polyolefins,
  • Polyolefin resins polyvinyl acetate resins, cellulose adhesives, (meth) acrylic resins, polyimide resins, urea resins, melamine resins and other amino resins, chloroprene rubber, nitrile rubber, - Len rubbers such as butadiene rubber, silicone-based resins.
  • These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive is preferable.
  • the thickness of the adhesive layer 5 is not particularly limited as long as it exhibits a function as an adhesive layer, and for example, it is about 1 to 10 ⁇ m, preferably about 2 to 5 ⁇ m.
  • the barrier layer 2 is a layer having a function of preventing water vapor, oxygen, light, and the like from entering the battery, in addition to improving the strength of the battery packaging material.
  • the barrier layer 2 is preferably a metal layer, that is, a layer formed of metal. Specific examples of the metal constituting the barrier layer 2 include aluminum, stainless steel, and titanium, and preferably aluminum.
  • the barrier layer 2 can be formed by, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil.
  • the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like are more preferable.
  • the thickness of the barrier layer 2 is not particularly limited as long as it exhibits a barrier function such as water vapor, but is preferably about 100 ⁇ m or less, more preferably about 10 to 100 ⁇ m, from the viewpoint of reducing the thickness of the battery packaging material. More preferably, the thickness is about 10 to 80 ⁇ m.
  • the barrier layer 2 is preferably subjected to chemical conversion treatment on at least one surface, preferably both surfaces, for the purpose of stabilizing adhesion, preventing dissolution and corrosion, and the like.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer.
  • chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, potassium sulfate chromium; Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; an aminated phenol polymer having a repeating unit represented by the following general formulas (1) to (4) is used And chromate treatment.
  • the repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. Also good.
  • X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 are the same or different and each represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group.
  • 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, an isobutyl group, Examples thereof include straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as a tert-butyl group.
  • Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- Linear or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group is mentioned.
  • the alkyl group and hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having a repeating unit represented by the general formulas (1) to (4) is preferably about 500 to 1,000,000, for example, about 1,000 to 20,000. More preferred.
  • a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide or the like and fine particles of barium sulfate dispersed therein.
  • a method of forming an acid-resistant film on the surface of the barrier layer 2 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the acid resistant film.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.
  • At least the surface on the inner layer side of the aluminum alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method.
  • Treatment liquid (aqueous solution) mainly composed of a mixture of metal salts, or treatment liquid (aqueous solution) principally composed of a non-metallic phosphate and a mixture of these non-metallic salts, or acrylic resin Coating a treatment liquid (aqueous solution) consisting of a mixture with a water-based synthetic resin such as phenolic resin or urethane resin by a well-known coating method such as roll coating, gravure printing, or dipping.
  • the acid-resistant coating For example, when treated with a chromium phosphate salt treatment solution, it becomes an acid-resistant film made of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and treated with a zinc phosphate salt treatment solution. In this case, an acid-resistant film made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride or the like is obtained.
  • an acid-resistant film for example, at least the surface on the inner layer side of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid-resistant film can be formed by performing a degreasing process by a known processing method such as an activation method and then performing a known anodizing process on the degreasing surface.
  • acid-resistant films include phosphate-based and chromic acid-based films.
  • phosphate-based and chromic acid-based films examples include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate.
  • chromic acid system examples include chromium chromate.
  • an acid-resistant film by forming an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound, between the aluminum and the base material layer at the time of embossing molding
  • an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound
  • hydrogen fluoride generated by the reaction between electrolyte and moisture prevents dissolution and corrosion of the aluminum surface, especially the dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface This improves the wettability and prevents delamination between the base material layer and aluminum at the time of heat fusion.
  • embossed type it shows the effect of preventing delamination between the base material layer and aluminum at the time of press molding.
  • an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.
  • the acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is About 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
  • the anionic polymer is poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one 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 preferably condensed phosphoric acid or condensed phosphate.
  • the chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion processing may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds.
  • a chromate treatment a chemical conversion treatment combining a chromium compound, a phosphate compound, and an aminated phenol polymer are preferable.
  • chromium compounds chromic acid compounds are preferred.
  • the acid resistant film examples include those containing at least one of phosphate, chromate, fluoride, and triazine thiol.
  • An acid resistant film containing a cerium compound is also preferable.
  • cerium compound cerium oxide is preferable.
  • the acid resistant film examples include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film.
  • a phosphate film As an acid-resistant film, one of these may be used, or a plurality of combinations may be used.
  • a treatment solution comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed of a treatment liquid consisting of
  • the composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry.
  • time-of-flight secondary ion mass spectrometry for example, a peak derived from at least one of Ce + and Cr + is detected.
  • the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium.
  • the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contains at least one element selected from the group consisting of phosphorus, chromium and cerium. can do. Specifically, first, in the battery packaging material, the heat-fusible resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is put in an electric furnace, and organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, it confirms that these elements are contained using the X-ray photoelectron spectroscopy of the surface of aluminum alloy foil.
  • the amount of the acid-resistant film formed on the surface of the barrier layer 2 in the chemical conversion treatment is not particularly limited.
  • the chromium compound is chromium per 1 m 2 of the surface of the barrier layer 2.
  • About 0.5 to 50 mg in terms of conversion preferably about 1.0 to 40 mg, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and about 1.0 to 40 mg of aminated phenol polymer. It is desirable that it is contained in a proportion of about 200 mg, preferably about 5.0 to 150 mg.
  • the thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 ⁇ m, more preferably 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesion strength with the barrier layer 2 and the heat-sealing resin layer. About 1 to 50 nm is preferable.
  • the thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.
  • a solution containing a compound used for forming an acid-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, etc., and then the temperature of the barrier layer is 70. It is performed by heating to about 200 ° C.
  • the barrier layer may be previously 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. By performing the degreasing process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier layer.
  • the adhesive layer 3 firmly bonds the barrier layer 2 and the heat-fusible resin layer 4 and effectively opens the battery even when the battery is exposed to high temperatures. In order to suppress, it is a layer provided between these.
  • the melting peak temperature of the adhesive layer 3 is characterized by being 10 ° C. higher than the opening test temperature T ° C.
  • the adhesive layer 3 having a melting peak temperature that is 10 ° C. or more higher than the opening test temperature T ° C. (T ° C. + 10 ° C. or more) is provided. It can be set as the battery with high sealing performance which is not opened (it is not opened for 10 minutes or more). More specifically, the adhesion between the barrier layer 2 and the heat-fusible resin layer 4 in a high-temperature environment is improved by providing the adhesive layer 3 whose melting peak temperature is 10 ° C. higher than the opening test temperature T ° C.
  • the opening can be suppressed between the barrier layer 2 and the heat-fusible resin layer 4. Furthermore, even when the opening test temperature T ° C. is reached, it is possible to suppress the occurrence of opening due to cohesive failure in the adhesive layer 3. As a result, after reaching the opening test temperature T ° C., a battery with high sealing performance that does not open for 10 minutes can be obtained.
  • the melting peak temperature of the adhesive layer 3 is preferably an opening test temperature T ° C. + 20 ° C. or more and an opening test temperature T ° C. + 60 ° C. or less.
  • the melting peak temperature of the adhesive layer 3 is a value measured using a differential scanning calorimeter (DSC).
  • the melting peak temperature of the adhesive layer 3 can be measured for a resin (for example, a pellet) used for forming the adhesive layer 3.
  • the packaging material for batteries it can measure about the contact bonding layer 3 acquired from the packaging material for batteries.
  • IR measurement infrared absorption spectrum measurement
  • the adhesive layer 3 adhering to the surface on the barrier layer 2 side is scraped off with a scalpel or the like to obtain a sample of the adhesive layer 3.
  • a melting peak temperature is measured using DSC. Note that even when a trace amount of the barrier layer is present in the sample of the adhesive layer 3, the measured value of the melting peak temperature of the adhesive layer 3 is not affected.
  • the adhesive layer 3 is formed of a resin capable of bonding the barrier layer 2 and the heat-fusible resin layer 4.
  • the adhesive layer 3 is preferably a cured product of a resin composition containing polyolefin, and more preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent.
  • the acid-modified polyolefin has an advantage that it has excellent resistance to an electrolytic solution, excellent adhesion to the barrier layer 2 and the heat-fusible resin layer 4, and is a cured product using a curing agent. Thus, the mechanical strength can be increased.
  • the polyolefin includes an acid-modified polyolefin.
  • the polyolefin is preferably the same as the polyolefin exemplified in the heat-fusible resin layer 4 described later.
  • the acid-modified polyolefin preferably, the same carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4 described later can be exemplified.
  • the curing agent is not particularly limited as long as it can cure the acid-modified polyolefin.
  • the curing agent include an epoxy curing agent, a polyfunctional isocyanate curing agent, a carbodiimide curing agent, and an oxazoline curing agent.
  • the epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • the polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurating these, Examples thereof include mixtures and copolymers with other polymers.
  • the carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N ⁇ C ⁇ N—).
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd.
  • the curing agent may be composed of two or more kinds of compounds.
  • an oxazoline-based curing agent is preferable in terms of improving heat resistance
  • an epoxy-based curing agent is preferable in terms of improving adhesion.
  • the content of the curing agent in the resin composition forming the adhesive layer 3 is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.1 to 30% by mass. More preferably, it is in the range of 1 to 10% by mass.
  • the thickness of the adhesive layer 3 is not particularly limited as long as it functions as an adhesive layer, but the upper limit is preferably about 10 ⁇ m or less, more preferably about 5 ⁇ m or less, and the lower limit is preferably about 1 ⁇ m or more. Can be mentioned. A preferable range of the thickness of the adhesive layer 3 is about 1 to 10 ⁇ m and about 1 to 5 ⁇ m.
  • the adhesive layer 3 can be formed by applying the resin composition and curing it by heating or the like.
  • the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that heat-fuses the heat-fusible resin layers and seals the battery element when the battery is assembled.
  • the resin component used in the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-sealed, and examples thereof include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins. It is done.
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene And a random copolymer (eg, a random copolymer of propylene and ethylene); an ethylene-butene-propylene terpolymer; and the like.
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, and isoprene. It is done.
  • examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • Styrene can also be a constituent monomer.
  • the carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin with carboxylic acid.
  • Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by ⁇ , ⁇ with respect to the cyclic polyolefin.
  • the cyclic polyolefin to be modified with carboxylic acid is the same as described above.
  • the carboxylic acid used for modification is the same as that used for modification of the polyolefin.
  • carboxylic acid-modified polyolefin is preferable; carboxylic acid-modified polypropylene is more preferable.
  • the heat-fusible resin layer 4 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.
  • the heat-fusible resin layer 4 preferably includes at least one layer having a melting peak temperature equal to or higher than the above-described opening test temperature T ° C.
  • the heat-fusible resin layer 4 is made of polypropylene, and the melting peak of the polypropylene.
  • the aspect whose temperature is more than the above-mentioned opening test temperature T degreeC is preferable.
  • the heat-fusible resin layer 4 preferably includes a layer containing an acid-modified polyolefin located on the barrier layer 2 side and a layer containing a polyolefin located on the innermost layer side, and the acid-modified polyolefin located on the barrier layer 2 side. It is more preferable to include a layer composed of polyolefin and a layer composed of polyolefin located on the innermost layer side.
  • the melting peak temperature of the heat-sealing portion of the heat-fusible resin layer 4 can be lowered, and the heat of the heat-fusible resin layer 4 can be reduced.
  • the fusing property can be improved.
  • the layer on the barrier layer 2 side of the heat-fusible resin layer 4 is formed of acid-modified polypropylene, and the innermost layer is made of polypropylene. It is preferable that the melting peak temperature of the polypropylene is equal to or higher than the above-described opening test temperature T ° C.
  • the melting peak temperature of the heat-fusible resin layer 4 can be measured for a resin (for example, a pellet) used for forming the heat-fusible resin layer 4. Moreover, if the battery packaging material is formed, the heat-fusible resin layer 4 obtained from the battery packaging material can be measured. When the heat-fusible resin layer 4 is obtained from the battery or the battery packaging material and the melting peak temperature is measured, first, the barrier layer 2 and the adhesive layer 3 are physically peeled off without using a solvent or the like. . Next, it is confirmed by infrared absorption spectrum measurement (IR measurement) that the adhesive layer 3 is not attached to the surface of the heat-fusible resin layer 4 side, and the melting peak temperature is measured using DSC. Note that even when a small amount of the adhesive layer is present in the sample of the heat-fusible resin layer 4, the measured value of the melting peak temperature of the heat-fusible resin layer 4 is not affected.
  • IR measurement infrared absorption spectrum measurement
  • a lubricant is present on the surface of the heat-fusible resin layer 4.
  • the amount of the lubricant present on the surface of the heat-fusible resin layer 4 is not particularly limited, but from the viewpoint of a battery packaging material having higher moldability and excellent battery continuous productivity. Preferably, it is about 10 to 50 mg / m 2 , more preferably about 15 to 40 mg / m 2 .
  • the method for measuring the amount of lubricant present on the surface of the heat-fusible resin layer 4 is the same as the method for measuring the amount of lubricant present on the surface of the laminate.
  • the kind of lubricant which exists in the surface of the heat-fusible resin layer 4 what was illustrated in the above-mentioned base material layer 1 is mentioned.
  • the thickness of the heat-fusible resin layer 4 is not particularly limited as long as it functions as a heat-fusible resin layer, but is preferably about 20 to 150 ⁇ m, more preferably about 70 to 100 ⁇ m.
  • the thickness of each layer is preferably about 10 to 75 ⁇ m, more preferably about 35 to 50 ⁇ m.
  • the base material layer 1 (barrier layer of the base material layer 1) is optionally formed. If necessary, a surface coating layer (not shown) may be provided on the side opposite to (2).
  • a surface coating layer is a layer located in the outermost layer when a battery is assembled.
  • the surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • Examples of the additive include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific additives include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, 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, high Melting
  • money, aluminum, copper, nickel etc. are mentioned.
  • additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment.
  • the method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer on one surface of the base material layer 1.
  • the additive may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer is not particularly limited as long as it exhibits the above function as the surface coating layer, and for example, it is about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the production method of the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained.
  • An example of the method for producing the battery packaging material of the present invention is as follows. First, a laminate including the base material layer 1, the adhesive layer 5, and the barrier layer 2 in this order (hereinafter sometimes referred to as “laminate A”) is formed.
  • the laminate A is formed by applying an adhesive used for forming the adhesive layer 5 on the base layer 1 or the barrier layer 2 whose surface is subjected to a chemical conversion treatment, if necessary, a gravure coating method, After applying and drying by a coating method such as a roll coating method, the barrier layer 2 or the base material layer 1 can be laminated and the adhesive layer 5 can be cured by a dry laminating method.
  • the adhesive layer 3 and the heat-fusible resin layer 4 are laminated on the barrier layer 2 of the laminate A.
  • a method of laminating the adhesive layer 3 and the heat-fusible resin layer 4 on the barrier layer 2 of the laminate A by coextrusion (coextrusion laminating method) (2) separately, the adhesive layer 3 And a layered product of the heat-fusible resin layer 4 and a method of laminating the layered product on the barrier layer 2 of the layered product A by a thermal laminating method.
  • Adhering to the barrier layer 2 of the layered product A The adhesive for forming the layer 3 is laminated by an extrusion method, a solution-coated high temperature drying or baking method, and the heat-fusible resin layer 4 previously formed into a sheet on the adhesive layer 3 is thermally formed.
  • the surface coating layer is laminated on the surface of the base material layer 1 opposite to the barrier layer 2.
  • the surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 2 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited.
  • the barrier layer 2 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing (pouching, embossing), etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment may be performed.
  • the battery packaging material of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed using the battery packaging material of the present invention, with the metal terminals connected to each of the positive electrode and the negative electrode protruding outward.
  • a flange portion region where the heat-fusible resin layers are in contact with each other
  • heat-sealing the heat-fusible resin layers of the flange portion to seal the battery
  • the battery packaging material of the present invention is used such that the sealant portion is on the inner side (surface in contact with the battery element).
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited.
  • a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery , Nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors and the like are suitable applications for the battery packaging material of the present invention.
  • Example 1-4 A base material layer was prepared by bonding a polyethylene terephthalate film (thickness 12 ⁇ m) and a biaxially stretched nylon film (thickness 15 ⁇ m) with a two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m).
  • a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the barrier layer.
  • an aging treatment was performed to prepare a base material layer / adhesive layer / barrier layer laminate.
  • the chemical conversion treatment of the aluminum foil used as the barrier layer was performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium was 10 mg / m 2 (dry weight).
  • Comparative Example 1 In the same manner as in Example 1, a base material layer / adhesive layer / barrier layer laminate was produced. Next, a non-axially stretched polypropylene film (CPP, 80 ⁇ m) is laminated on the surface of the barrier layer by a dry laminating method using an adhesive (main agent: polyester polyol, curing agent: tolylene diisocyanate), and a battery packaging material is obtained. Obtained.
  • the melting peak temperature of the heat-fusible resin layer (CPP layer) is as shown in Table 1.
  • the CPP has a two-layer / three-layer structure (random PP layer / block PP layer / random PP layer).
  • the random PP layer has a melting peak temperature of 140 ° C. and the block PP layer has a melting peak temperature of 160 ° C. is there.
  • Example 2 a battery packaging material was obtained in the same manner as in Example 1 except that no adhesive layer was provided on the barrier layer.
  • each battery packaging material obtained above was cut to prepare samples each having a short side of 90 mm and a long side of 150 mm.
  • each sample was molded to 3 mm with a pressing pressure of 0.13 MPa using a molding die (female die) having a diameter of 32 mm short side ⁇ 55 mm long side and a corresponding molding die (male die).
  • Cold forming was performed at a depth, and a recess was formed in the central portion.
  • the clearance between the female mold and the male mold was set to 0.3 mm.
  • the molded sample is turned back with the heat-fusible resin layers facing each other at the turn-back position P shown in FIG. 7, and the edge portion 10a (see FIG.
  • the unsealing test battery 10 is placed in the space between the two stainless steel plates 20, and the distance w between the two stainless steel plates 21 is 7.0 mm.
  • the opening test temperature T ° C. is a set value in the test oven.
  • a battery 10 for opening test was prepared in the same manner as the opening test at 100 ° C.
  • the battery for unsealing test is put into an oven capable of decompression (vacuum drying oven AVO-310NS-D manufactured by AS ONE), and the pressure in the oven is set to 5000 Pa, and 5 ° C. ⁇ 2 ° C./min.
  • the temperature was raised to 135 ° C. ⁇ 5 ° C.
  • T ° C. 135 ° C. did not open, the temperature of 135 ° C. was maintained as it was.
  • each battery packaging material is 15 mm wide and 200 mm long and folded at a position of 100 mm in length so that the heat-fusible resin layers face each other, and from the bent portion to the length direction.
  • the 20 mm position was heat-sealed at a seal width of 7 mm, a seal temperature of 190 ° C., a pressure of 1.0 MPa, and a seal time of 3 seconds.
  • the heat-sealed region is indicated by S.
  • each battery packaging material is 15 mm wide and 200 mm long, and is folded from the bent portion at a position of 100 mm long so that the heat-fusible resin layers face each other.
  • Heat sealing was performed at a position of 20 mm in the direction with a pressure of 1.0 MPa, a seal width of 7 mm, a seal temperature of 190 ° C., and a seal time of 3 seconds.
  • the heat-sealed region is indicated by S.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

La présente invention concerne un matériau d'encapsulation de batterie qui peut supprimer efficacement le descellement d'une batterie, même lorsque la batterie est soumise à une température élevée. Le matériau d'encapsulation de batterie comprend un stratifié pourvu d'au moins une couche de matériau de base, une couche de barrière, une couche d'adhésion et une couche de résine thermofusible dans cet ordre, le matériau d'encapsulation de batterie étant caractérisé en ce que : lorsque les couches de résine thermofusible sont thermiquement fusionnées les unes aux autres tout en se faisant mutuellement face de façon à rendre le matériau d'encapsulation de batterie étanche à l'eau et lorsque la température est augmentée à une température de test de descellement T°C qui est de 100 °C ou plus dans un vide, le matériau d'encapsulation de batterie scellé n'est pas descellé pendant au moins 10 minutes tandis que la température est maintenue à T°C après que la température a atteint la température de test de descellement T°C ; et la température de pic de fusion de la couche d'adhésion est supérieure à la température de test de descellement T°C d'au moins 10 °C.
PCT/JP2017/017026 2016-04-28 2017-04-28 Matériau d'encapsulation de batterie et batterie WO2017188445A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111512463A (zh) * 2017-12-20 2020-08-07 大日本印刷株式会社 电池用包装材料和电池
JP2020161326A (ja) * 2019-03-26 2020-10-01 大日本印刷株式会社 蓄電デバイス用外装体及び蓄電デバイス
JPWO2021201294A1 (fr) * 2020-04-03 2021-10-07
WO2022210548A1 (fr) * 2021-04-02 2022-10-06 大日本印刷株式会社 Matériau extérieur pour dispositif de stockage d'énergie, son procédé de fabrication, et dispositif de stockage d'énergie

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CN111512463A (zh) * 2017-12-20 2020-08-07 大日本印刷株式会社 电池用包装材料和电池
JP2020161326A (ja) * 2019-03-26 2020-10-01 大日本印刷株式会社 蓄電デバイス用外装体及び蓄電デバイス
JPWO2021201294A1 (fr) * 2020-04-03 2021-10-07
WO2021201294A1 (fr) * 2020-04-03 2021-10-07 大日本印刷株式会社 Boîtier extérieur pour dispositifs de stockage d'électricité, procédé de fabrication dudit boîtier extérieur et dispositif de stockage d'électricité
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WO2022210548A1 (fr) * 2021-04-02 2022-10-06 大日本印刷株式会社 Matériau extérieur pour dispositif de stockage d'énergie, son procédé de fabrication, et dispositif de stockage d'énergie
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