WO2011078321A1 - 電気化学デバイス用の包装材および電気化学デバイス - Google Patents
電気化学デバイス用の包装材および電気化学デバイス Download PDFInfo
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- WO2011078321A1 WO2011078321A1 PCT/JP2010/073337 JP2010073337W WO2011078321A1 WO 2011078321 A1 WO2011078321 A1 WO 2011078321A1 JP 2010073337 W JP2010073337 W JP 2010073337W WO 2011078321 A1 WO2011078321 A1 WO 2011078321A1
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- thermocompression bonding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/80—Gaskets; Sealings
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/08—Housing; Encapsulation
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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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
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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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/121—Organic material
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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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
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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 of a single cell or a single battery
- H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
- H01M50/133—Thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/4911—Electric battery cell making including sealing
Definitions
- the present invention relates to a packaging material for an electrochemical device such as a battery and an electrochemical device having a simple configuration and excellent durability and heat resistance.
- lithium ion secondary batteries are frequently used in terms of energy density and output density.
- Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries are packaged with metal cans or laminate films.
- the metal can is excellent in terms of strength, since the outer wall of the container is hard, the degree of freedom of shape is small, and the shape and dimensions on the hardware side where the battery is used are determined by the shape of the battery.
- metal cans are disadvantageous in terms of weight.
- a laminate film is lighter than a metal can and is advantageous in terms of price.
- Patent Document 1 describes a battery packaged with an aluminum laminate film. As shown in FIG. 17, this battery 1 is formed by laminating and winding a positive electrode and a negative electrode through a separator to form a flat type, and a battery element to which an electrolytic solution is added is packaged with an aluminum laminate film. It was produced by sealing the periphery.
- the positive electrode lead electrode 2a and the negative electrode lead electrode 2b connected to the positive electrode and the negative electrode are, for example, drawn from one side of the battery 1 to the outside of the battery.
- the battery element is inserted from an unsealed opening, and finally the lead-out sides of the positive electrode lead electrode 2a and the negative electrode lead electrode 2b are sealed.
- a battery can be obtained.
- the aluminum laminate film used generally has a structure of exterior layer / adhesive layer / aluminum foil (metal layer) / adhesive layer / heat seal layer from the outside.
- the aluminum foil plays a role of protecting the battery contents by preventing the ingress of moisture, oxygen and light in addition to improving the strength of the exterior material.
- the exterior layer is made of polyolefin, polyamide, polyimide and polyester, specifically nylon (Ny), polyethylene terephthalate (PET), polyethylene (PE), polyethylene because of its beautiful appearance, toughness, heat resistance and flexibility. Naphthalate (PEN) is used.
- the inner heat seal layer has heat-sealing properties to enclose the battery element, and is made of polyethylene (PE), unstretched polyethylene (CPE), unstretched polypropylene (CPP), polyethylene terephthalate (PET), nylon Resins having a relatively low melting point such as (Ny), low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE) are used.
- PE polyethylene
- CPE unstretched polyethylene
- CPP unstretched polypropylene
- PET polyethylene terephthalate
- nylon Resins having a relatively low melting point such as (Ny), low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE) are used.
- the adhesive layer may not be used, acid-modified polyolefin, ionomer, ethylene vinyl acetate copolymer (EVA), ethylene acrylic acid copolymer, or the like having good adhesion to metal is used.
- the adhesive layer generally has a lower melting point than the heat seal layer, and these layers may themselves be used as the heat seal layer.
- the inner heat seal layer is in contact with the electrolytic solution, it is necessary to have durability against acids generated by hydrolysis of the electrolytic solution and the electrolyte over a long period of time. This is because when the heat seal layer is deteriorated, the electrolyte solution invades the aluminum foil, and further moisture permeation proceeds, and the deterioration of the electrolyte solution proceeds rapidly.
- JP 2008-262803 A JP 2001-30407 A JP 2001-52748 A
- non-aqueous electrolyte secondary batteries are increasingly used in various fields, and their use under harsh conditions that could not be considered in the past has begun to be studied.
- the laminate film exteriors proposed to date have limitations in terms of durability and heat resistance, and there is a problem that the application of secondary batteries such as lithium ion secondary batteries cannot be sufficiently expanded. Furthermore, since the film itself is flammable, there is a problem in terms of safety.
- the present invention provides a packaging material for an electrochemical device such as a battery, which can be used even under severe conditions such as high temperature and / or low temperature, and an electrochemical device using the packaging material. Objective.
- the present invention relates to the following matters.
- thermocompression bonding polyimide layer A packaging material for an electrochemical device, Formed using a laminate having a metal layer and a thermocompression bonding polyimide layer, A packaging material, wherein a hermetic packaging structure is formed by thermocompression bonding of the thermocompression bonding polyimide layer around the laminate.
- the packaging material is such that the laminate is overlaid so that the thermocompression bonding polyimide layer is on the inside, and the thermocompression bonding polyimide layer is thermocompression bonded around the laminate to form a sealed structure. 2.
- thermocompression bonding polyimide layer is formed of a material that can be thermocompression bonded in the range of 150 to 400 ° C.
- thermocompression bonding polyimide layer has a multilayer structure of thermocompression bonding polyimide and heat resistant polyimide.
- thermoplastic polyimide is a polyimide obtained from a combination comprising 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine.
- the packaging material according to any one of 1 to 6 above; An electrochemical device having an electrochemical device element sealed and accommodated inside the packaging material.
- a method for producing an electrochemical device comprising an electrochemical device element and a packaging material encapsulating the electrochemical device element, Preparing a laminate having a metal layer and a thermocompression bonding polyimide layer; Forming the packaging material by forming the hermetic packaging structure by fusing the thermocompression bonding polyimide layer of the laminate at the outer periphery so as to accommodate the electrochemical device element therein.
- a method for producing an electrochemical device comprising an electrochemical device element and a packaging material encapsulating the electrochemical device element, Preparing a laminate having a metal layer and a thermocompression bonding polyimide layer; Forming the packaging material by forming the hermetic packaging structure by fusing the thermocompression bonding polyimide layer of the laminate at the outer periphery so as to accommodate the electrochemical device element therein.
- the laminated body is overlaid so that the thermocompression bonding polyimide layer is inside, and the thermocompression bonding polyimide layer is thermocompression bonded around the laminated body to form a sealed packaging structure. 10.
- thermocompression bonding polyimide layer is subjected to thermocompression bonding by heating and pressing in a range of 150 to 400 ° C.
- a packaging material for electrochemical devices such as batteries that can be used under severe conditions such as high temperature and / or low temperature.
- a packaging material for an electrochemical device that is extremely excellent in heat resistance and durability can be obtained.
- the packaging material of this invention is formed from the laminated body 10 provided with the metal layer 11 and the thermocompression bonding polyimide layer 12 at least as shown in FIG.
- the material of the metal layer 11 is not particularly limited, and examples thereof include aluminum, stainless steel, and iron with Ni plating.
- Aluminum is preferable.
- the metal layer can be formed by vapor deposition or the like, but usually a metal foil is used.
- the thickness of the metal layer is not particularly limited, but is, for example, 1 to 1000 ⁇ m, preferably 8 to 100 ⁇ m, and more preferably 20 to 100 ⁇ m. For the purpose of shape retention, a thicker is preferable, for example, 200 to 500 ⁇ m.
- thermocompression bonding polyimide layer 12 is formed of polyimide as a whole, and at least the surface 15 which is the inner surface of the packaging material has thermocompression bonding. Therefore, the entire layer 12 may be formed of a single layer of thermocompression bonding polyimide, or has a laminated structure of two or more layers of thermocompression bonding polyimide and heat resistant polyimide (that is, polyimide that does not soften at the bonding temperature). Also good.
- FIG. 2 shows an example in which the thermocompression bonding polyimide layer 12 has a three-layer structure, in which the thermocompression bonding polyimide 12a is formed on both sides of the heat resistant polyimide 12b.
- the boundary between the layers may be clear, or the layer may be an inclined layer in which the composition is mixed.
- the thickness of the thermocompression bonding polyimide layer 12 is not particularly limited, but is, for example, 5 to 100 ⁇ m, preferably 12.5 to 50 ⁇ m.
- an exterior layer 13 may be provided outside the metal layer 11.
- a known material such as nylon described in the background art can be used, but a polyimide layer may be used.
- the exterior layer 13 may be formed of the same material as the thermocompression bonding polyimide layer 12.
- the exterior layer when the exterior layer is formed of a multi-layer polyimide, it may have a three-layer structure of thermocompression bonding polyimide / heat resistant polyimide / thermocompression bonding polyimide as in the layer 12 of FIG. 2, or thermocompression bonding from the metal layer side. It is also possible to have a two-layer structure of conductive polyimide / heat-resistant polyimide.
- thermocompression bonding polyimide layer 12 and / or the outer layer 13 and polyimide having excellent flame retardancy it is preferable to use polyimide as the material of the thermocompression bonding polyimide layer 12 and / or the outer layer 13 and polyimide having excellent flame retardancy.
- conventional exterior layer materials such as nylon also have a problem of melting due to heat applied when the inner layers (thermocompression-bonding polyimide layers) are joined together.
- thermocompression bonding polyimide layer 12 has a three-layer structure of thermocompression bonding polyimide / heat resistant polyimide / thermocompression bonding polyimide as shown in FIG. 2 and is laminated on both surfaces of the metal layer
- thermocompression bonding polyimide a layer
- thermocompression bonding polyimide a layer
- heat-resistant polyimide a layer composed of heat-resistant polyimide
- the heat-resistant polyimide (b layer) has a heat-resistant polyimide having at least one of the following characteristics, and having at least two of the following characteristics [1) and 2), 1) and 3), 2) and 3 ))], Particularly those having all of the following characteristics can be used.
- MD coefficient of linear expansion
- a combination comprising 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), p-phenylenediamine (PPD), and optionally 4,4-diaminodiphenyl ether (DADE).
- s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
- PPD p-phenylenediamine
- DADE 4,4-diaminodiphenyl ether
- the PPD / DADE (molar ratio) is preferably 100/0 to 85/15.
- a combination comprising 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride (PMDA), p-phenylenediamine and optionally 4,4-diaminodiphenyl ether.
- PMDA pyromellitic dianhydride
- BPDA / PMDA is preferably 0/100 to 90/10.
- PPD and DADE are used in combination, PPD / (DADE is preferably 90/10 to 10/90, for example.
- DADE / PPD is preferably 90/10 to 10/90.
- the combination of 1) above is preferable because it is particularly excellent in heat resistance.
- DADE 4,4-diaminodiphenyl ether
- diamine component capable of obtaining a heat-resistant polyimide
- m-phenylenediamine, 2,4-toluenediamine, 3,3′-diaminodiphenyl sulfide in addition to the diamine component shown above, as long as the target properties are not impaired.
- thermocompression bonding polyimide or thermocompression bonding polyimide (a layer)
- a known polyimide having a property capable of being thermocompression bonded under pressure to a metal foil such as a copper foil or an aluminum foil can be used.
- thermocompression bonding polyimide is preferably at or above the glass transition temperature of the thermocompression bonding polyimide, preferably 20 ° C. higher than the glass transition temperature, more preferably 30 ° C. higher than the glass transition temperature, particularly preferably 50 ° C. higher than the glass transition temperature. It is a polyimide having a thermocompression bonding property that can be bonded to a metal foil at a high temperature to 400 ° C. or lower.
- thermocompression bonding polyimide further has at least one of the following characteristics, and at least two of the following characteristics [a combination of 1) and 2), 1) and 3), 2) and 3)], [1), 2), 3), 1), 3), 4), 2), 3), 4), 1), 2), 4), etc.], especially What has all the following characteristics can be used.
- the thermocompression bonding polyimide (a layer) has a peel strength of 0.7 N / mm or more with a metal foil, and a peel strength retention rate of 90% or more, even 95% or more even after heat treatment at 150 ° C. for 168 hours. In particular, the polyimide should be 100% or more.
- thermocompression bonding between thermocompression polyimides or between thermocompression polyimide and metal at 150 to 400 ° C, preferably 250 to 370 ° C.
- the tensile elastic modulus is 100 to 700 kg / mm 2 .
- the linear expansion coefficient (50 to 200 ° C.) (MD) is 13 to 30 ⁇ 10 ⁇ 6 cm / cm / ° C.
- thermocompression bonding polyimide preferably has a thermocompression bonding between thermocompression bonding polyimides (a layer) and adhesion between the thermocompression bonding polyimide (a layer) and the lead electrode of the electrochemical device at 250 ° C. or higher.
- Thermocompression bonding polyimide (1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′ , 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 1,4-hydroquinone dibenzoate -An acid component containing at least one component selected from acid dianhydrides such as 3,3 ', 4,4'-tetrac
- the diamine component examples include 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-Diaminobenzophenone, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4 -(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4
- An acid component containing seeds preferably an acid component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of these acid components
- Examples of the diamine component include 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 4,4′-bis (3-aminophenoxy) biphenyl, bis [4 -(3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-amin
- thermocompression bonding polyimide As a diamine component capable of obtaining a thermocompression bonding polyimide, in addition to the diamine component shown above, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 3, as long as the characteristics of the present invention are not impaired.
- the synthesis of the polyimide precursor can be performed by a known method.
- an acid component such as an aromatic tetracarboxylic dianhydride and an diamine component are randomly polymerized or block polymerized in an organic solvent. Is achieved. May also be mixed with the reaction conditions was keep two or more polyimide precursors in which either of these two components is excessive, the respective polyimide precursor solution together.
- the polyimide precursor solution thus obtained can be used for the production of a self-supporting film as it is or after removing or adding a solvent if necessary.
- the polyimide precursor solution is heated to 150 to 250 ° C., or an imidizing agent is added and reacted at a temperature of 150 ° C. or less, particularly 15 to 50 ° C. to imide cyclization. Thereafter, the solvent is evaporated or precipitated in a poor solvent to obtain a powder. Thereafter, the powder can be dissolved in an organic solution to obtain an organic solvent solution of polyimide.
- organic solvent for the polyimide precursor solution examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like. These organic solvents may be used alone or in combination of two or more.
- the polyimide precursor solution may contain an imidization catalyst, an organic phosphorus-containing compound, fine particles such as inorganic fine particles and organic fine particles, if necessary.
- the imidization catalyst examples include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound.
- Cyclic compounds such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, etc.
- Benzimidazoles such as alkylimidazole and N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n- Substituted pyridines such as propylpyridine It can be used to apply.
- the amount of the imidization catalyst used is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
- a chemical imidizing agent in which a dehydrating ring-closing agent and an organic amine are combined is usually contained in the polyimide precursor solution.
- the dehydrating ring-closing agent include dicyclohexylcarbodiimide, and acid anhydrides such as acetic anhydride, propionic anhydride, valeric anhydride, benzoic anhydride, trifluoroacetic acid dianhydride, and the organic amines include picoline, quinoline, and the like. , Isoquinoline, pyridine and the like, but are not limited thereto.
- Any polyimide precursor solution can be cast on the support, and the self-supporting film can be peeled from the support, and then a self-supporting film that can be stretched in at least one direction in the second step can be formed.
- the viscosity of the polyimide precursor solution such as the type and concentration of various additives added to the solution as required, such as the type of polymer, the degree of polymerization, and the concentration, can be appropriately set.
- the concentration of the polyimide precursor in the polyimide precursor solution is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 15 to 20% by mass.
- the solution viscosity of the polyimide precursor solution is preferably 100 to 10,000 poise, preferably 400 to 5000 poise, and more preferably 1000 to 3000 poise.
- thermocompression bonding film for forming the thermocompression bonding polyimide layer 12 is preferably formed by (i) a heat-resistant polyimide layer (b layer) by a coextrusion-casting film forming method (also simply referred to as a multilayer extrusion method).
- thermocompression bonding polyimide layer (a layer) dope solution are laminated, dried and imidized to obtain a multilayer polyimide film, (ii) or the heat resistant polyimide layer (b layer) dope solution is supported
- a method of obtaining a multilayer polyimide film by applying a dope solution of a thermocompression bonding polyimide layer (a layer) on one side or both sides of a self-supporting film (gel film) that has been cast applied onto a body and dried, and then dried and imidized.
- a dope solution of a thermocompression bonding polyimide layer (a layer) on one side or both sides of a self-supporting film (gel film) that has been cast applied onto a body and dried, and then dried and imidized can be obtained by:
- the coextrusion method can be carried out by a known method, and for example, the method described in JP-A-3-180343 (JP-B-7-102661) can be used.
- thermocompression bonding polyimide film having thermocompression bonding on both surfaces is shown.
- a polyamic acid solution for heat-resistant polyimide (b layer) and a polyamic acid solution for thermocompression bonding polyimide (a layer) are formed by a three-layer coextrusion method, and the thickness of the heat-resistant polyimide (b layer) is 4 to 45 ⁇ m on both sides. Is supplied to a three-layer extrusion die so that the total thickness of the thermocompression bonding polyimide (layer a) is 3 to 10 ⁇ m, cast on a support, and this is on a support surface such as a stainless steel mirror surface or a belt surface. A self-supporting film that is semi-cured or dried at 100 to 200 ° C. can be obtained.
- the self-supporting film tends to cause defects such as a decrease in adhesiveness in the production of a polyimide film having thermocompression bonding.
- This semi-cured state or an earlier state means that it is in a self-supporting state by heating and / or chemical imidization.
- the obtained self-supporting film was measured at a temperature not higher than the temperature at which deterioration occurs at a temperature higher than the glass transition temperature (Tg) of the thermocompression bonding polyimide (a layer), preferably 250 to 420 ° C. (measured with a surface thermometer).
- Tg glass transition temperature
- thermocompression bonding polyimide a layer
- thermocompression bondable polyimide a layer
- the obtained self-supporting film preferably has about 20 to 60% by mass, particularly preferably 30 to 50% by mass of the solvent and water produced (particularly preferably, the loss on heating is preferably about 20 to 60% by mass. 30-50 mass%), when raising the temperature of the self-supporting film to the drying temperature, it is preferable to raise the temperature within a relatively short time, for example, a temperature rising rate of 10 ° C./min or more. Is preferred.
- a relatively short time for example, a temperature rising rate of 10 ° C./min or more. Is preferred.
- At least a pair of both end edges of the self-supporting film is continuously or intermittently fixed with a fixing device or the like that can be moved together with the self-supporting film.
- a fixing device or the like that can be moved together with the self-supporting film.
- the support film is dried and heat-treated, and the solvent is preferably removed from the self-support film so that the content of volatile substances composed of an organic solvent and product water in the finally obtained polyimide film is 1% by weight or less.
- the polyimide film having the thermocompression bonding on both sides is sufficiently removed by sufficiently imidizing the polymer constituting the film. It is possible to form a beam.
- the fixing device for the self-supporting film examples include, for example, a belt-like or chain-like one provided with a large number of pins or gripping tools at equal intervals, and the length of the solidified film supplied continuously or intermittently.
- a device that can be installed in a pair along both side edges in the direction and can fix the film while moving the film continuously or intermittently with the movement of the film is suitable.
- the solidified film fixing device can expand and contract the film being heat-treated in the width direction or the longitudinal direction at an appropriate elongation or contraction rate (particularly preferably an expansion ratio of about 0.5 to 5%). It may be a device.
- the polyimide film having thermocompression bonding on both sides produced in the above step is preferably at a temperature of 100 to 400 ° C. under low tension or no tension of preferably 4N or less, particularly preferably 3N or less.
- a polyimide film having thermocompression bonding on both sides having particularly excellent dimensional stability can be obtained.
- the manufactured polyimide film which has thermocompression bonding on both surfaces can be wound up in a roll shape by an appropriate known method.
- the loss on heating of the self-supporting film is a value obtained by drying the film to be measured at 420 ° C. for 20 minutes and calculating from the weight W1 before drying and the weight W2 after drying by the following formula.
- Loss on heating (mass%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100
- the imidization ratio of the self-supporting film can be obtained by a technique using a Karl Fischer moisture meter described in JP-A-9-316199.
- inorganic additives include particulate or flat inorganic fillers.
- organic additive include polyimide particles and thermosetting resin particles. The usage amount and shape (size, aspect ratio) are preferably selected according to the purpose of use.
- the heat treatment can be performed using various known devices such as a hot stove and an infrared heating furnace.
- thermocompression bonding polyimide film having a structure of thermocompression bonding polyimide (a layer) / heat resistant polyimide (b layer) / thermocompression bonding polyimide (a layer) is obtained.
- this double-sided thermocompression bonding polyimide film (hereinafter simply referred to as double-sided thermocompression bonding film) is laminated on both sides of a metal foil such as an aluminum foil.
- a heating device When laminating a metal foil and a thermocompression-bondable polyimide film, a heating device, a pressurizing device, or a heating and pressurizing device can be used, and the heating conditions and pressurizing conditions can be appropriately selected depending on the materials used. Although it will not specifically limit if it can laminate continuously or batchwise, it is preferable to carry out continuously using roll lamination, a double belt press, etc.
- thermocompression bonding film a long (200 to 2000 m long) metal foil, and a long double-sided thermocompression bonding film are stacked in this order, preferably introduced.
- Preheating is performed using a preheater such as a hot air supply device or an infrared heater so that preheating can be performed for about 2 to 120 seconds at a temperature of about 150 to 250 ° C., particularly higher than 150 ° C. and lower than 250 ° C.
- a pair of crimping rolls or a double belt press the temperature of the thermocompression bonding zone of the pair of crimping rolls or double belt press is 20 ° C.
- thermocompression bonding is performed under pressure in a temperature range of 30 ° C. or higher than the temperature, and further in a temperature range of 400 ° C., particularly in a temperature range of 50 ° C. or higher to the glass transition temperature to 400 ° C.
- it is subsequently cooled under pressure in a cooling zone.
- it is cooled to a temperature lower than the glass transition temperature of polyimide by 20 ° C. or more, further from 30 ° C.
- thermocompression bonding films are laminated on both sides of the metal foil, and as a result, a laminate having thermocompression-bonding polyimide layers on both sides of the metal layer is obtained.
- Preheating the polyimide film before thermocompression can prevent appearance defects due to foaming of the laminate after thermocompression due to moisture contained in the polyimide.
- the double belt press can perform high temperature heating and cooling under pressure, and is preferably a hydraulic type using a heat medium.
- the laminated body can be made to have a take-up speed of 1 m / min or more preferably by thermocompression-cooling under pressure using a double belt press, and the laminated body is long and has a width of about 400 mm.
- wide adhesive strength of about 500 mm or more and high adhesion strength peel strength between metal foil and polyimide film is 0.7 N / mm or more, and peel strength retention is 90% even after heat treatment at 150 ° C. for 168 hours.
- peel strength retention is 90% even after heat treatment at 150 ° C. for 168 hours.
- a protective material that is, two protective materials
- a protective material may be interposed between both sides of the outermost layer and the belt, and may be laminated by bonding under pressure and thermocompression-cooling.
- any material can be used as long as it is non-thermocompressible and has good surface smoothness with respect to the thermocompression bonding polyimide layer 12 and the metal layer 11 during the production of the laminate.
- copper foils, stainless steel foils, aluminum foils, high heat-resistant polyimide films (for example, Ube Industries, Upilex S, Toray DuPont Kapton H) and the like having a thickness of about 5 to 125 ⁇ m are preferable.
- Upilex S manufactured by Ube Industries, Ltd. is preferable.
- thermocompression bonding polyimide film of ⁇ thermocompression bonding PI (a layer) / heat resistance PI (b layer) / thermocompression bonding PI (a layer) ⁇ is formed, and ⁇ thermocompression bonding PI (a Layer) / heat resistance PI (b layer) / thermocompression bonding PI (a layer) ⁇ / metal layer / ⁇ thermocompression bonding PI (a layer) / heat resistance PI (b layer) / thermocompression bonding PI (a layer) ⁇
- the production of the laminate having the structure was described.
- thermocompression-bonding PI (a layer) / heat-resistant PI (b-layer) ⁇ two-layer structure film (one-side thermocompression bonding polyimide film), ⁇ thermocompression-bonding PI (a layer) single layer ⁇ structure film Therefore, a laminate having the following structure can also be manufactured by combining them.
- thermocompression bonding polyimide film one-side thermocompression bonding polyimide film
- thermocompression-bonding PI a layer
- thermocompression bonding polyimide layer can be directly formed on a metal foil that becomes a metal layer in the laminate. That is, imidization can be carried out by casting or applying the polyimide precursor solution prepared as described above on a metal foil, followed by heat treatment.
- the heat treatment conditions for imidization the same heat treatment conditions as those for producing the aforementioned film may be employed.
- thermocompression bonding polyimide layer can be composed of a single layer of thermocompression bonding polyimide or can be composed of multiple layers.
- the manufacturing method in the case of constituting with multiple layers can be prepared by, for example, applying the polyimide precursor solution on the metal foil instead of casting the polyimide precursor solution on the support.
- ⁇ thermocompression bonding PI (a layer) / heat resistance PI (b layer) / thermocompression bonding PI (a layer) ⁇ / metal layer structure by casting and applying the same by multilayer extrusion method Can be produced.
- the polyimide precursor solution can be cast on both surfaces of the metal foil.
- the form of the packaging material of the present invention (the shape in which the electrochemical device element is encapsulated) is not particularly limited as long as the thermocompression bonding polyimide layer is fused at the outer peripheral portion to form a hermetic packaging structure. Are possible.
- the packaging material has a bag shape
- a lithium ion secondary battery will be described as an example.
- the laminate 10 is prepared first, and as shown in FIG. 4 (b), it is folded back so that the thermocompression bonding polyimide layer 12 is inside.
- the folded state is shown in (b-1) plan view and (b-2) sectional view.
- thermocompression bonding the surface of the thermocompression bonding polyimide layer may be pressed while being heated to a temperature at which thermocompression bonding can be performed.
- pressing is performed using a thermocompression bonding jig having a suitable shape. Can be implemented.
- FIG. 5 shows that three sides around the folded laminate 10 are thermocompression bonded to form thermocompression bonding portions 21 on the three sides, and a bag shape is formed from the laminate.
- the surface of the thermocompression bonding polyimide layer may be pressed while being heated to a temperature at which thermocompression bonding can be performed.
- pressing is performed using a thermocompression bonding jig having a suitable shape. Can be implemented.
- a spacer 22 having a non-thermocompression bonding property to the thermocompression bonding polyimide layer 12 such as a protective material is used so that the laminates overlap each other on the three peripheral sides, and the rest By pressing and heating the whole while sandwiching the spacer 22 in the center including one side (left side in the figure), the three surrounding sides where the laminate is overlapped are heat-sealed. Thereafter, by removing the spacer 22, a bag with three sides sealed as shown in (b) is formed.
- the battery element 31 is connected to the lead electrodes 32a and 32b from the opening 34, as shown in FIG.
- the opening 34 is thermocompression-bonded as shown in FIG. 7C
- the thermocompression-bonding polyimide layer is thermocompression-bonded and the battery element 31 is enclosed. Sealed.
- the lithium ion secondary battery 35 provided with the battery element 31 and the packaging material 33 is completed.
- the packaging material has a hermetic bag structure formed by thermocompression bonding of a thermocompression bonding polyimide layer around the laminate. In the portion where the thermocompression bonding portion and the lead electrode intersect, the thermocompression bonding polyimide layer is in close contact with the lead electrode, and in the other thermocompression bonding portion, the thermocompression bonding polyimide layers are bonded (in close contact).
- the battery element includes known battery components such as a positive electrode, a negative electrode, an electrolytic solution or a solid electrolyte, and a separator.
- the folded side is also thermocompression bonded, but the folded side 37 does not have to be thermocompression bonded as shown in FIG.
- the folded side 37 instead of folding a single laminate as shown in FIG. 4, prepare two laminates and stack them so that the thermocompression-bonding polyimide layers face each other, and then thermocompression bond the surroundings. May be.
- a pillow shape as shown in FIG.
- a pair of opposite sides of one rectangular laminate 10 are combined to form a thermocompression bonding portion 23 to form a cylindrical shape, and then the upper and lower openings 34a in the drawing. , 34b are sequentially thermocompression bonded to form the thermocompression bonding portions 24 and 25, respectively, so that a sealed bag structure can be produced.
- the lead electrode 32a and the lead electrode 32b can be taken out from different sides.
- the packaging material of the present invention may have a tray-type structure.
- a lower tray 41 formed by pressing the laminated body 10 with a press or the like and an upper tray 42 (a laminated body not formed in this example) are prepared.
- a flange portion 43 is provided around the lower tray 41 so as to facilitate thermocompression bonding, and a thermocompression bonding polyimide layer is provided on the side where the upper tray and the lower tray overlap.
- the upper tray is overlapped and the periphery is thermocompression bonded, so that the periphery as shown in FIG.
- the battery 35 is completed.
- a tray-like molded body such as the lower tray 41 may be used for the upper tray.
- the tray-structured packaging material can be formed without using a press molding method.
- a thermocompression bonding polyimide film 51 is prepared.
- the polyimide film may be formed of a single layer of thermocompression-bonding polyimide.
- the film is cut to create a large number of frame-like sheets 52 as shown in FIG.
- a sheet 53 that is substantially the same as or larger than the outer shape of the frame-shaped sheet 52 is produced from a laminate having a metal layer and a thermocompression bonding polyimide layer.
- a plurality of frame-like sheets 52 are stacked on the thermocompression bonding polyimide layer surface of the sheet 53 and thermocompression bonded, whereby the tray 54 shown in FIG. 13B is manufactured. be able to.
- the battery element is housed in the tray, and the sheet 53b made from the laminate having the metal layer and the thermocompression-bonding polyimide layer is replaced with the thermocompression-bonding polyimide layer.
- a lithium ion secondary battery housed in a packaging material whose end is sealed with a thermocompression bonding portion of thermocompression bonding polyimide is completed by overlapping and thermocompression bonding.
- the sheet 53b is used as the upper lid, but a battery element can be accommodated by using a tray equivalent to the tray 54 as the upper lid.
- the tray 54 may be formed with a metal frame between the frame-like sheets 52.
- the width of the metal frame 55 is preferably the same as or smaller than the frame-shaped sheet 52 (the inner opening is large).
- a plurality of the frame-like sheets 56 having only three sides shown in FIG. 15 and the two sheets 53 are used to form a box-like container whose one side surface is opened in advance to store the battery elements. Then, the open surface can be sealed by thermocompression.
- FIG. 16 shows an example of a multi-tray type packaging material. 12 to 15, one tray is formed.
- the multi-frame sheet 58 having a plurality of openings 59 corresponding to one tray is used.
- a film having a structure of ⁇ thermocompression bonding PI (a layer) / heat resistant PI (b layer) / thermocompression bonding PI (a layer) ⁇ is cut and formed.
- a multi-tray 60 shown in FIG. 16B can be manufactured by stacking a plurality of multi-frame sheets 58 on a sheet 53 (same as described above) and thermocompression bonding.
- a battery element is put in each battery storage portion 61 of the multi-tray 60 and another sheet 53 is thermocompression bonded as an upper lid to complete a lithium ion secondary battery in which a plurality of batteries are stored. .
- the lead electrodes are pulled out to the front side for the batteries stored in the tray in the front row, and the back electrodes are set in the rear side for the batteries stored in the tray in the rear row. It can be pulled out. Further, the lead electrode can be pulled out in any direction by changing the shape of the sheet serving as the upper lid. For example, in the sheet 62 and the sheet 63 shown in FIGS. 16C and 16D, the lead electrode can be pulled out to the near side even with the batteries stored in the trays in the back row.
- a sheet serving as the upper lid may be thermocompression bonded after the batteries stored in the multi-tray are connected in series and / or in parallel.
- thermocompression bonding between the thermocompression bonding polyimide and the thermocompression bonding polyimide can be performed at a temperature excellent in adhesion under pressure, for example, a temperature range in which the thermocompression bonding polyimide and the metal foil are bonded together, preferably a glass transition.
- the temperature is 20 ° C. higher than the temperature, more preferably 30 ° C. higher than the glass transition temperature, particularly preferably 50 ° C. to 400 ° C. or lower.
- thermocompression bonding polyimide and the lead electrode for example, the lead electrode 32a and / or the lead electrode 32b
- other heat melting polyimides are used.
- An adhesive resin, a thermocompression bonding resin, a thermosetting resin, or the like may be used.
- the packaging material of the present invention is applicable not only to lithium ion secondary batteries (including lithium polymer ion secondary batteries) but also to various electrochemical devices.
- Electrochemical devices to which the present invention is applied include, in addition to lithium ion secondary batteries, manganese dry batteries, alkaline manganese dry batteries, nickel-based primary batteries, oxyride batteries, silver oxide batteries, mercury batteries, air zinc batteries, lithium batteries, Alternatively, a primary battery such as a seawater battery, a secondary battery such as a lead storage battery, a nickel-hydrogen storage battery, a nickel-cadmium storage battery, or a sodium-sulfur battery, an electric double layer capacitor, a dye-sensitized solar cell, and the like can be given.
- lithium ion secondary batteries including lithium polymer ion secondary batteries
- electricity A double layer capacitor is preferred.
- the electrochemical device element means a portion obtained by removing the packaging material and the extraction electrode from the electrochemical device.
- a battery or a capacitor it means a power generation element or a power storage element involved in an electrochemical reaction such as discharge and / or power storage.
- a battery a known battery such as at least a positive electrode, a negative electrode, an electrolyte or a solid electrolyte, a separator, etc. Constituent elements are included.
- the packaging material structure of the present invention can be applied not only to electrochemical devices but also to other electronic and electrical components.
- thermocompression multilayer polyimide film Using a film-forming device equipped with a three-layer extrusion die (multimanifold die), the polyamic acid solution for heat-resistant polyimide and the polyamic acid solution for thermocompression bonding polyimide produced above are made of metal from the three-layer extrusion die.
- the film was cast on a support, dried continuously with hot air at 140 ° C., and then peeled to form a self-supporting film. After peeling this self-supporting film from the support, the temperature is gradually raised from 150 ° C. to 450 ° C. in a heating furnace to remove the solvent and imidize, and wind the long three-layer polyimide film on a roll. It was.
- the properties of the obtained three-layer polyimide film (layer structure: thermocompression bonding polyimide (a layer) / heat resistant polyimide (b layer) / thermocompression bonding polyimide (a layer)) were evaluated.
- thermocompression multilayer polyimide film Thickness configuration: 4 ⁇ m / 17 ⁇ m / 4 ⁇ m (total 25 ⁇ m) -Glass transition temperature of thermocompression bonding polyimide (a layer): 240 ° C -Glass transition temperature of heat-resistant polyimide (b layer): A clear temperature could not be confirmed at 300 ° C or higher.
- thermocompression-bonding multilayer polyimide film / metal (aluminum foil) / thermocompression-bonding multilayer polyimide film
- Three layers of the thermocompression-bonding multilayer polyimide film, aluminum foil, and the thermocompression-bonding multilayer polyimide film are stacked in this order, preheated without applying pressure at 230 ° C. for 30 seconds immediately before hot pressing, and then hot pressed (heating temperature: 330). C., pressure: 2.3 MPa, pressure bonding time 5 minutes), cooled and taken out to produce a laminate.
- a laminate having a metal layer and a thermocompression bonding polyimide layer has excellent mechanical strength even at high and low temperatures, and, as is well known, has excellent heat resistance, flame retardancy, and durability. Therefore, it is suitable as a packaging material for electrochemical devices such as batteries used under harsh conditions.
- the laminate is bent using the laminate, and the product name Upilex S (manufactured by Ube Industries, thickness 25 ⁇ m) is used as a spacer at the non-joined portion. (Heating temperature: 330 ° C., pressure: 2.3 MPa, pressure bonding time 5 minutes). After the hot pressing, the spacer was taken out, and a bag was produced in which one piece was opened and three pieces were joined by thermocompression bonding. The bag body is excellent in heat resistance and flame retardancy.
- Upilex S manufactured by Ube Industries, thickness 25 ⁇ m
- Glass transition temperature (Tg) of polyimide film determined from a peak value of tan ⁇ by a dynamic viscoelasticity method (tensile method, frequency 6.28 rad / sec, temperature rising rate 10 ° C./min).
- Linear expansion coefficient of polyimide film (50 to 200 ° C.) An average linear expansion coefficient of 20 to 200 ° C. was measured by a TMA method (tensile method, heating rate 5 ° C./min).
- Mechanical properties and tensile strength of polyimide film Measured according to ASTM D882 (crosshead speed 50 mm / min).
- Elongation rate Measured according to ASTM D882 (crosshead speed 50 mm / min).
- -Tensile elastic modulus Measured according to ASTM D882 (crosshead speed 5 mm / min).
- the packaging material of the present invention is useful for electrochemical devices such as batteries.
Abstract
Description
金属層と熱圧着性ポリイミド層を有する積層体を用いて形成され、
前記積層体の周囲において、前記熱圧着性ポリイミド層が熱圧着されることで密閉包装構造が形成されていることを特徴とする包装材。
前記包装材の内部に密封されて収納された電気化学デバイス要素と
を有する電気化学デバイス。
金属層と熱圧着性ポリイミド層を有する積層体を用意する工程と、
電気化学デバイス要素を内部に収納するように、前記積層体の前記熱圧着性ポリイミド層を外周部で融着して密閉包装構造を形成することで、前記包装材を形成する工程と
を有することを特徴とする電気化学デバイスの製造方法。
本発明の包装材は、図1に示すように少なくとも金属層11と熱圧着性ポリイミド層12とを備える積層体10から形成されている。
次に、本発明の包装材に使用される積層体の製造方法を説明する。
1)単独のポリイミドフィルムとして、ガラス転移温度が300℃以上、好ましくはガラス転移温度が330℃以上、さらに好ましくは確認不可能であるもの。
2)単独のポリイミドフィルムとして、線膨張係数(50~200℃)(MD)が、耐熱性樹脂基板に積層する金属箔の熱膨張係数に近いこと。
3)単独のポリイミドフィルムとして、引張弾性率(MD、ASTM-D882)は300kg/mm2以上、好ましくは500kg/mm2以上、さらに700kg/mm2以上であるもの。
(1)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物及び1,4-ヒドロキノンジベンゾエート-3,3’,4,4’-テトラカルボン酸二無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分としてp-フェニレンジアミン、4,4’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、m-トリジン及び4,4’-ジアミノベンズアニリドより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
1)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)と、p-フェニレンジアミン(PPD)と、必要により4,4-ジアミノジフェニルエーテル(DADE)を含む組み合わせ。この場合、PPD/DADE(モル比)は100/0~85/15であることが好ましい。
2)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物及びピロメリット酸二無水物(PMDA)と、p-フェニレンジアミンと必要により4,4-ジアミノジフェニルエーテルを含む組み合わせ。この場合、BPDA/PMDAは0/100~90/10であることが好ましい。PPDとDADEを併用する場合、PPD/(DADEは、例えば90/10~10/90が好ましい。
3)ピロメリット酸二無水物と、p-フェニレンジアミン及び4,4-ジアミノジフェニルエーテルの組み合わせ。この場合、DADE/PPDは90/10~10/90であることが好ましい。
4)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物とp-フェニレンジアミンとを主成分(合計100モル%中の50モル%以上)として得られるものを挙げることができる。
1)熱圧着性ポリイミド(a層)は、金属箔とのピール強度が0.7N/mm以上で、150℃で168時間加熱処理後でもピール強度の保持率が90%以上、さらに95%以上、特に100%以上であるポリイミドであること。
2)ガラス転移温度が130~330℃であること、または熱圧着ポリイミド同士或いは熱圧着ポリイミドと金属とが150~400℃、好ましくは250~370℃で熱圧着が可能な物。
3)引張弾性率が100~700Kg/mm2であること。
4)線膨張係数(50~200℃)(MD)が13~30×10-6cm/cm/℃であること。
(1)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2,3,3’,4’-ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、ビス(3,4-ジカルボキシフェニル)スルフィド二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、ビス(3,4-ジカルボキシフェニル)メタン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物及び1,4-ヒドロキノンジベンゾエート-3,3’,4,4’-テトラカルボン酸二無水物などの酸二無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分としては、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、3,3’-ジアミノベンゾフェノン、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]ケトン、ビス[4-(4-アミノフェノキシ)フェニル]ケトン、ビス[4-(3-アミノフェノキシ)フェニル]スルフィド、ビス[4-(4-アミノフェノキシ)フェニル]スルフィド、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパンなどのジアミンより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
(1)3,3’,4,4’-ビフェニルテトラカルボン酸二無水物及び2,3,3’,4’-ビフェニルテトラカルボン酸二無水物の酸二無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分としては、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン4,4’-ビス(3-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパンなどのジアミンより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
また、上記の自己支持性フィルムのイミド化率は、特開平9-316199記載のカールフィッシャー水分計を用いる手法で求めることができる。
-{熱圧着性PI(a層)/耐熱性PI(b層)/熱圧着性PI(a層)}/金属層/{熱圧着性PI(a層)/耐熱性PI(b層)}、
-{熱圧着性PI(a層)/耐熱性PI(b層)/熱圧着性PI(a層)}/金属層、
-{熱圧着性PI(a層)単層}/金属層/{熱圧着性PI(a層)/耐熱性PI(b層)}、
-{熱圧着性PI(a層)単層}/金属層
-{熱圧着性PI(a層)単層}/金属層/{熱圧着性PI(a層)/耐熱性PI(b層)/熱圧着性PI(a層)}。
本発明の包装材の形態(電気化学デバイス要素を封入した状態の形状)は、外周部で熱圧着性ポリイミド層が融着されて密閉包装構造が形成されていれば、特に限定はなく、種々の形状が可能である。
最後に、積層体の代表的製造例とその特性を示す。
N,N-ジメチルアセトアミド中でパラフェニレンジアミン(PPD)と3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)とを1000:998のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加え、50℃で3時間反応させた。得られたポリアミック酸溶液の25℃における溶液粘度は、約1680ポイズであった。
N,N-ジメチルアセトアミド中で1,3-ビス(4-アミノフェノキシ)ベンゼン(TPE-R)と2,3,3’,4’-ビフェニルテトラカルボン酸二無水物(a-BPDA)および3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)とを1000:200:800のモル比で加え、モノマー濃度が18%になるように、またトリフェニルホスフェートをモノマー重量に対して0.5重量%加え、40℃で3時間反応させた。得られたポリアミック酸溶液の25℃における溶液粘度は、約1680ポイズであった。
三層押出し成形用ダイス(マルチマニホールド型ダイス)を設けた製膜装置を使用し、上記で製造した耐熱性ポリイミド用ポリアミック酸溶液および熱圧着性ポリイミド用ポリアミック酸溶液を三層押出ダイスから金属製支持体上に流延し、140℃の熱風で連続的に乾燥した後、剥離して自己支持性フィルムを形成した。この自己支持性フィルムを支持体から剥離した後加熱炉で150℃から450℃まで徐々に昇温して溶媒の除去、イミド化を行って、長尺状の三層ポリイミドフィルムをロールに巻き取った。得られた三層ポリイミドフィルム(層構成:熱圧着性ポリイミド(a層)/耐熱性ポリイミド(b層)/熱圧着性ポリイミド(a層))の特性を評価した。
・厚み構成:4μm/17μm/4μm(合計25μm)
・熱圧着性ポリイミド(a層)のガラス転移温度:240℃
・耐熱性ポリイミド(b層)のガラス転移温度:300℃以上で明確な温度は確認できなかった。
・線膨張係数(50~200℃):MD19ppm/℃,TD17ppm/℃
・機械的特性(試験方法:ASTM・D882)
1)引張強度:MD,TD 520MPa
2)伸び率:MD,TD 100%
3)引張弾性率:MD,TD 7100MPa
・電気的特性(試験方法:ASTM・D149)
1)絶縁破壊電圧:7.2kV
上記熱圧着性多層ポリイミドフィルム、アルミ箔、上記熱圧着性多層ポリイミドフィルムの順に3枚重ね合わせて熱プレス直前に230℃ 30秒間圧力をかけない状態で予熱し、その後熱プレス(加熱温度:330℃、圧力:2.3MPa、圧着時間5分)を行い、冷却して取り出して、積層体を製造した。
図4~図6に示す説明と同様にして、上記積層体を用いて積層体を折り曲げて、非接合部分にスペーサとして商品名ユーピレックスS(宇部興産社製、厚み25μm)を用いて、熱プレス(加熱温度:330℃、圧力:2.3MPa、圧着時間5分)を行った。熱プレス後は、スペーサーを取り出し、1片が開口し、3片が熱圧着により接合した袋体を製造した。袋体は耐熱性と、難燃性に優れている。
1)ポリイミドフィルムのガラス転移温度(Tg):動的粘弾性法により、tanδのピーク値から求めた(引張り法、周波数6.28rad/秒、昇温速度10℃/分)。
2)ポリイミドフィルムの線膨張係数(50~200℃):TMA法により、20~200℃平均線膨張係数を測定した(引張り法、昇温速度5℃/分)。
3)ポリイミドフィルムの機械的特性
・引張強度:ASTM・D882に準拠して測定した(クロスヘッド速度50mm/分)。
・伸び率:ASTM・D882に準拠して測定した(クロスヘッド速度50mm/分)。
・引張弾性率:ASTM・D882に準拠して測定した(クロスヘッド速度5mm/分)。
11 金属層
12 熱圧着性ポリイミド層
12a 熱圧着性ポリイミド
12b 耐熱性ポリイミド
13 外装層
15 包装材の内面となる面
21 熱融着部
22 スペーサー
23、24、25 熱融着部
31 電池要素
32a、32b リード電極
33 包装材
34、34a、34b 開口部
35 リチウムイオン二次電池
41 下側トレー
42 上側トレー
43 フランジ部分
51 熱圧着性ポリイミドフィルム
52 枠状シート
53、53b シート
54 トレー
55 金属枠
56 枠状シート
58 マルチ枠シート
59 開口
60 マルチトレー
61 電池収納部
62 シート(上側フタ)
63 シート(上側フタ)
Claims (12)
- 電気化学デバイス用の包装材であって、
金属層と熱圧着性ポリイミド層を有する積層体を用いて形成され、
前記積層体の周囲において、前記熱圧着性ポリイミド層が熱圧着されることで密閉包装構造が形成されていることを特徴とする包装材。 - 前記包装材は、前記熱圧着性ポリイミド層が内側になるように前記積層体が重ね合わされ、前記積層体の周囲において前記熱圧着性ポリイミド層が熱圧着されて密閉構造が形成されていることを特徴とする請求項1記載の包装材。
- 前記密閉構造が、密閉袋構造または密閉トレー構造であることを特徴とする請求項2記載の包装材。
- 前記熱圧着性ポリイミド層は、150~400℃の範囲で熱圧着可能な材料で形成されていることを特徴とする請求項1~3のいずれかに記載の包装材。
- 前記熱圧着性ポリイミド層は、熱圧着性ポリイミドと耐熱性ポリイミドの多層構造を有することを特徴とする請求項1~4のいずれかに記載の包装材。
- 前記耐熱性ポリイミドが、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物と、p-フェニレンジアミンとを含む組み合わせから得られるポリイミドであることを特徴とする請求項5記載の包装材。
- 請求項1~6のいずれかに記載の包装材と、
前記包装材の内部に密封されて収納された電気化学デバイス要素と
を有する電気化学デバイス。 - リチウムイオン二次電池である請求項7記載の電気化学デバイス。
- 電気化学デバイス要素、および前記電気化学デバイス要素を封入している包装材を備える電気化学デバイスの製造方法であって、
金属層と熱圧着性ポリイミド層を有する積層体を用意する工程と、
電気化学デバイス要素を内部に収納するように、前記積層体の前記熱圧着性ポリイミド層を外周部で融着して密閉包装構造を形成することで、前記包装材を形成する工程と
を有することを特徴とする電気化学デバイスの製造方法。 - 前記包装材は、前記熱圧着性ポリイミド層が内側になるように前記積層体が重ね合わされ、前記積層体の周囲において前記熱圧着性ポリイミド層が熱圧着されて密閉包装構造が形成されることを特徴とする請求項9記載の電気化学デバイスの製造方法。
- 前記密閉包装構造が、密閉袋構造または密閉トレー構造となるように、前記包装材を形成することを特徴とする請求項10記載の電気化学デバイスの製造方法。
- 前記熱圧着性ポリイミド層を、150~400℃の範囲で加熱加圧して熱圧着することを特徴とする請求項9~11のいずれかに記載の電気化学デバイスの製造方法。
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JP2009185101A (ja) * | 2008-02-01 | 2009-08-20 | Ube Ind Ltd | ポリイミドフィルムおよびポリイミドフィルムの製造方法 |
JP2009266392A (ja) * | 2008-04-22 | 2009-11-12 | Hitachi Maxell Ltd | リチウム一次電池 |
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WO2015003725A1 (en) | 2013-07-09 | 2015-01-15 | Friedrich-Schiller-Universität Jena | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
US10103384B2 (en) | 2013-07-09 | 2018-10-16 | Evonik Degussa Gmbh | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
WO2016111182A1 (ja) * | 2015-01-06 | 2016-07-14 | 凸版印刷株式会社 | 蓄電デバイス用外装材 |
US10290837B2 (en) | 2015-01-06 | 2019-05-14 | Toppan Printing Co., Ltd. | Packaging material for power storage device |
Also Published As
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JP2011138636A (ja) | 2011-07-14 |
US20120258354A1 (en) | 2012-10-11 |
KR20120110133A (ko) | 2012-10-09 |
JP5573151B2 (ja) | 2014-08-20 |
CN102804446A (zh) | 2012-11-28 |
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