WO2013141293A1 - リチウムイオン電池用外装材 - Google Patents
リチウムイオン電池用外装材 Download PDFInfo
- Publication number
- WO2013141293A1 WO2013141293A1 PCT/JP2013/058055 JP2013058055W WO2013141293A1 WO 2013141293 A1 WO2013141293 A1 WO 2013141293A1 JP 2013058055 W JP2013058055 W JP 2013058055W WO 2013141293 A1 WO2013141293 A1 WO 2013141293A1
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- WIPO (PCT)
- Prior art keywords
- layer
- resin film
- sample
- stress value
- exterior material
- Prior art date
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Images
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- B32B2307/73—Hydrophobic
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
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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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
-
- 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 packaging material for a lithium ion battery.
- This application claims priority based on Japanese Patent Application No. 2012-063713 filed in Japan on March 21, 2012, the contents of which are incorporated herein by reference.
- lithium salt such as LiPF 6 or LiBF 4 is used as the electrolyte of the lithium ion battery.
- these lithium salts generate hydrofluoric acid by hydrolysis.
- the hydrofluoric acid may cause corrosion of the metal surface of the battery member and decrease of the laminate strength between the respective layers of the exterior material made of the multilayer film. Therefore, in the exterior material made of a multilayer film, an aluminum foil layer is provided inside, and moisture is prevented from entering the battery from the surface of the exterior material.
- a packaging material in which a heat-resistant base material layer / first adhesive layer / aluminum foil layer / corrosion prevention treatment layer for preventing corrosion due to hydrofluoric acid / second adhesive layer / sealant layer is sequentially laminated is known. .
- the lithium ion battery in which the exterior material is used is called an aluminum laminate type lithium ion battery.
- a recess is formed in a part of an exterior material by cold molding, and battery contents (a positive electrode, a separator, a negative electrode, an electrolytic solution, etc.) are accommodated in the recess.
- battery contents a positive electrode, a separator, a negative electrode, an electrolytic solution, etc.
- An embossed type lithium ion battery in which the remaining part of the exterior material is folded and the edge part is sealed by heat sealing is known.
- a lithium ion battery has been manufactured in which a recess is formed in both of the two exterior materials to be bonded together and can accommodate more battery contents.
- biaxially stretched polyamide films having excellent moldability are widely used for the base material layer.
- a laminated film in which a biaxially stretched polyester film is laminated on the outer surface of the biaxially stretched polyamide film is also used for the base material layer (for example, Patent Document 1).
- Patent Document 2 a film whose elongation in each of the four directions of 0 °, 45 °, 90 °, and 135 ° is 80% or more with respect to the MD direction (flow direction).
- the base material layer in which the biaxially stretched polyamide film or the laminated film of the biaxially stretched polyester film and the biaxially stretched polyamide film is used as the base material layer, sufficient moldability is obtained depending on the humidity environment in which the molding is performed. There may not be. Also, when a film having an elongation rate in four directions (an increase rate with respect to the length of the original base material layer when the base material layer is stretched) of 80% or more is used for the base material layer, molding is performed. Sufficient moldability may not be obtained depending on the humidity environment.
- An object of the present invention is to provide a packaging material for a lithium ion battery that can provide excellent moldability regardless of the humidity environment.
- An exterior material for a lithium ion battery includes a base layer made of a resin film, and a first adhesive layer, a metal foil layer, and a corrosion prevention treatment layer that are sequentially laminated on one surface of the base layer. , A second adhesive layer, and a sealant layer, the resin film,
- the water absorption in the test specified in JIS K 7209: 2000 is 0.1% or more and 3% or less, and in the following tensile test, the resin film sample is compared to the length of the sample before the tensile test.
- the stress value in the MD direction of the sample and the stress value in the TD direction of the sample are both 110 MPa or less, and the stress value in the MD direction of the sample and the stress value in the TD direction of the sample In at least one of the above, it is 70 MPa or more.
- Tensile test After storing the sample for 24 hours in an environment of 23 ° C. and 40% RH, the sample was pulled under the conditions of 23 ° C. and 40% RH under conditions of a width of the sample of 6 mm, a distance between gauge points of 35 mm, and a pulling speed of 300 mm / min. A test is performed, and a stress value is measured when the sample is stretched by 10% with respect to the length of the sample before the test (displacement amount: 3.5 mm).
- the stress value in the MD direction of the sample and Both of the stress values in the TD direction of the samples are preferably 70 MPa or more and 110 MPa or less.
- the resin film is preferably a polyethylene terephthalate film having a thickness of 10 to 40 ⁇ m.
- the said resin film contains 2 to 30 mass% of thermoplastic polyester elastomers.
- the exterior material for a lithium ion battery of the present invention has excellent moldability regardless of the humidity environment.
- an exterior material 1 for a lithium ion battery according to the present embodiment has a first adhesive layer 12 and a metal foil layer on one surface of a base material layer 11. 13 is a laminate in which the corrosion prevention treatment layer 14, the second adhesive layer 15, and the sealant layer 16 are sequentially laminated.
- the base material layer 11 is the outermost layer
- the sealant layer 16 is the innermost layer. That is, the exterior material 1 is used by arranging the base material layer 11 on the outer side (outer surface) of the battery and the sealant layer 16 on the inner side (inner surface) of the battery.
- the base material layer 11 provides heat resistance in a sealing process when manufacturing a lithium ion battery, and plays a role of suppressing generation of pinholes that may occur during processing and distribution.
- the base material layer 11 has a water absorption rate of 0.1% or more and 3% or less in the test specified in JIS K 7209: 2000, and in the following tensile test, 10% of the original length before the tensile test.
- the stress value in the MD direction and the stress value in the TD direction are both 110 MPa or less, and the stress value in the MD direction and the stress value in the TD direction are at least 70 MPa or more (hereinafter referred to as “resin film”). (A) ")). Since the base material layer 11 is made of the resin film (A), excellent formability can be obtained regardless of the humidity environment, and the exterior material 1 having excellent resistance to the electrolytic solution of the base material layer 11 can be obtained.
- the reason why the effect can be obtained when the base material layer 11 is made of the resin film (A) is considered as follows.
- the moldability during cold molding may differ between exterior materials, and in some cases, sufficient moldability may not be obtained.
- the present inventor examined this problem it was found that the humidity environment during storage and molding of the exterior material greatly affects the moldability of the exterior material.
- the resin film forming the base material layer needs to contain a certain amount of moisture in order that the exterior material has excellent moldability.
- injection and sealing of an electrolytic solution are performed in a dry room in order to avoid a reaction between electrolyte and moisture.
- the humidity environment at the time of storage and molding processing of the exterior material before injecting the electrolytic solution is not strictly controlled and is in various conditions.
- conventional exterior materials when the humidity during storage or molding is high, excellent moldability can be obtained by containing sufficient water in the base material layer, but when the humidity during storage or molding is low It is thought that the amount of water in the base material layer was insufficient, the film characteristics were greatly changed, and the moldability was lowered.
- the exterior material of the present invention has a stress value when the resin film (A) forming the base layer is stretched by 10% with respect to the length of the resin film (A) before the tensile test.
- the stress value in the MD direction of the resin film (A) and the stress value in the TD direction of the resin film (A) are both 110 MPa or less, and the stress value in the MD direction of the resin film (A) and the resin film (A)
- the stress value in the TD direction is at least 70 MPa or more on the other hand, so that excellent moldability is achieved.
- the resin film (A) has a water absorption rate of 0.1% or more, so that a sufficient amount of moisture is secured in the film, and a water absorption rate of 3% or less allows the moisture content in the film to be a humidity environment. It is hard to change by. Therefore, the film characteristics of the resin film (A) are unlikely to change depending on the humidity environment. From these things, it is thought that the exterior material of this invention shows the outstanding moldability irrespective of humidity environment.
- the water absorption rate of the resin film (A) is preferably 0.5% or more from the viewpoint that the flexibility of the resin film (A) is enhanced and the moldability of the exterior material 1 is more excellent. Further, the water absorption rate of the resin film (A) is preferably 2% or less from the viewpoint that the moldability of the exterior material 1 is difficult to change depending on the humidity environment.
- the stress value in the MD direction of the resin film (A) and the resin film (A) are preferably 70 MPa or more and 110 MPa or less. Thereby, more excellent moldability can be obtained regardless of the humidity environment. Further, in the stress value in the MD direction of the resin film (A) and the stress value in the TD direction of the resin film (A), the resin film (A) is 10 with respect to the length of the resin film (A) before the tensile test.
- the lower limit of the stress value when% stretched is preferably 80 MPa.
- the upper limit of the stress value is preferably 100 MPa. If the said stress value is more than a lower limit (80 Mpa), it will become the exterior material 1 which has the more excellent moldability. When the stress value is equal to or lower than the upper limit (100 MPa), the exterior material 1 having more excellent moldability is obtained.
- the resin film (A) is preferably a nylon film or a polyethylene terephthalate (PET) film from the viewpoint of excellent puncture strength and impact strength. Moreover, as a resin film (A), a PET film is more preferable from the point that a water absorption is low, the change of the film characteristic by a humidity environment is smaller, and it is excellent in electrolyte solution resistance. Furthermore, the resin film (A) may be any of a uniaxially stretched film, a biaxially stretched film, and an unstretched film, but is preferably a biaxially stretched film. The resin film (A) may be a single layer film or a multilayer film, but a single layer film is preferred from the viewpoint of cost.
- PET polyethylene terephthalate
- the resin film (A) is a multilayer film
- the stress value in the TD direction of the resin film (A) are both 110 MPa or less
- the stress value in the MD direction of the resin film (A) and the stress value in the TD direction of the resin film (A) are A multilayer film satisfying at least one of 70 MPa or more
- a multilayer film contains the single base material obtained by a multilayer coextrusion manufacturing method.
- thermoplastic polyester elastomer is contained in the resin film (A) from the viewpoint of obtaining better moldability.
- a PET film containing a thermoplastic polyester elastomer is preferable.
- the thermoplastic polyester elastomer is a polyester elastomer having a hard segment and a soft segment.
- the hard segment include crystalline polyesters such as polybutylene terephthalate, polybutylene naphthalate, and polyethylene terephthalate. Of these, polybutylene terephthalate is preferable.
- the soft segment include polyoxyalkylene glycols such as polytetramethylene glycol; polyesters such as polycaprolactone and polybutylene adipate. Of these, polytetramethylene glycol is preferable.
- the ratio (mass ratio) of the soft segment to the hard segment in the thermoplastic polyester elastomer is preferably 1.0 to 4.0, more preferably 1.2 to 3.0, and still more preferably 1.5 to 2.3. . If the said ratio is more than a lower limit (1.0), crystallinity can be maintained and a water absorption can be made low. If the ratio is not more than the upper limit (4.0), flexibility can be maintained.
- the content of the thermoplastic polyester elastomer in the resin film (A) is preferably 2% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass. If content of a thermoplastic polyester elastomer is more than a lower limit (2 mass%), a resin film (A) will become soft and it will be excellent in a moldability. If content of a thermoplastic polyester elastomer is below an upper limit (30 mass%), the hardness of a resin film (A) will be hold
- the thickness of the base material layer 11 is preferably 10 to 40 ⁇ m, and more preferably 20 to 35 ⁇ m. If the thickness of the base material layer 11 is not less than the lower limit (10 ⁇ m), the moldability is excellent. If the thickness of the base material layer 11 is equal to or less than the upper limit (40 ⁇ m), the shrinkage force of the base material layer 11 at the location stretched by the molding process is not so great, and the shape of the exterior material after the molding process can be maintained. .
- the first adhesive layer 12 is a layer that bonds the base material layer 11 and the metal foil layer 13 together.
- the adhesive constituting the first adhesive layer 12 is a two-component curable type in which a bifunctional or higher functional aromatic or aliphatic isocyanate compound is allowed to act as a curing agent on a main component such as polyester polyol, polyether polyol, and acrylic polyol.
- the urethane adhesive is preferable.
- the urethane-based adhesive is aged at 40 ° C. for 4 days or more after coating, whereby the reaction of the hydroxyl group of the main agent and the isocyanate group of the curing agent proceeds to enable strong adhesion.
- the thickness of the first adhesive layer 12 is such that the adhesive strength, workability, etc., or followability (even if the member provided with the first adhesive layer 12 is deformed / stretched, the member does not peel off) In order to reliably form the first adhesive layer 12 thereon, the thickness is preferably 1 to 10 ⁇ m, more preferably 3 to 7 ⁇ m.
- Metal foil layer 13 As the metal foil layer 13, various metal foils such as aluminum and stainless steel can be used, and aluminum foil is preferable from the viewpoint of workability such as moisture resistance and spreadability and cost. A general soft aluminum foil can be used as the aluminum foil. Among these, an aluminum foil containing iron is preferable from the viewpoint of excellent pinhole resistance and extensibility during molding.
- the content of iron in the aluminum foil containing iron (100% by mass) is preferably 0.1 to 9.0% by mass, and more preferably 0.5 to 2.0% by mass. If the iron content is not less than the lower limit (0.1% by mass), the exterior material 1 is excellent in pinhole resistance and spreadability. If the iron content is not more than the upper limit (9.0% by mass), the exterior material 1 is excellent in flexibility.
- the thickness of the metal foil layer 13 is preferably 9 to 200 ⁇ m, more preferably 15 to 100 ⁇ m, from the viewpoint of barrier properties, pinhole resistance, and workability.
- the corrosion prevention treatment layer 14 serves to suppress corrosion of the metal foil layer 13 due to the electrolytic solution or hydrofluoric acid generated by the reaction between the electrolytic solution and moisture. Further, it plays a role of increasing the adhesion between the metal foil layer 13 and the second adhesive layer 15.
- a coating film formed by a coating type or immersion type acid resistant corrosion prevention treatment agent is preferable. The said coating film is excellent in the corrosion prevention effect with respect to the acid of the metal foil layer 13.
- FIG. since the adhesive force of the metal foil layer 13 and the 2nd contact bonding layer 15 is strengthened by an anchor effect, the outstanding tolerance with respect to contents, such as electrolyte solution, is acquired.
- the coating film examples include coating films, chromates, phosphates, fluorides, and various types of heat formed by a ceriazol treatment using a corrosion prevention treatment agent composed of cerium oxide, phosphate, and various thermosetting resins.
- examples thereof include a coating film formed by a chromate treatment with a corrosion preventing treatment agent comprising a curable resin.
- the corrosion prevention treatment layer 14 is not limited to the coating film as long as the corrosion resistance of the metal foil layer 13 is sufficiently obtained.
- a coating film formed by phosphate treatment, boehmite treatment, or the like may be used.
- the corrosion prevention treatment layer 14 may be a single layer or a plurality of layers.
- an additive such as a silane coupling agent may be added to the corrosion prevention treatment layer 14.
- the thickness of the corrosion prevention treatment layer 14 is preferably 10 nm to 5 ⁇ m, and more preferably 20 nm to 500 nm, from the viewpoint of the corrosion prevention function and the function as an anchor.
- the second adhesive layer 15 is a layer that bonds the metal foil layer 13 on which the corrosion prevention treatment layer 14 is formed and the sealant layer 16.
- the packaging material 1 is roughly divided into a thermal laminate configuration and a dry laminate configuration depending on the adhesive component forming the second adhesive layer 15.
- an adhesive component for forming the second adhesive layer 15 in the thermal laminate configuration an acid-modified polyolefin resin obtained by graft-modifying a polyolefin resin with an acid such as maleic anhydride is preferable.
- the acid-modified polyolefin resin has a nonpolar sealant layer 16 formed of a polyolefin resin film and the like, and a polar corrosion prevention because a polar group is introduced into part of the nonpolar polyolefin resin. It can be firmly adhered to both the treatment layer 14.
- a polar corrosion prevention because a polar group is introduced into part of the nonpolar polyolefin resin. It can be firmly adhered to both the treatment layer 14.
- resistance to contents such as an electrolytic solution is improved, and even if hydrofluoric acid is generated inside the battery, the corrosion prevention treatment layer 14 and the sealant due to the deterioration of the second adhesive layer 15 are used. It is easy to prevent a decrease in adhesion with the layer 16.
- the acid-modified polyolefin resin used for the second adhesive layer 15 may be one type or two or more types.
- polyolefin resin used for the acid-modified polyolefin resin examples include low density, medium density, and high density polyethylene; ethylene- ⁇ olefin copolymer; homo, block or random polypropylene; propylene- ⁇ olefin copolymer. Can be mentioned. Further, a copolymer obtained by copolymerizing a polar molecule such as acrylic acid or methacrylic acid with the above-described compound, a polymer such as a crosslinked polyolefin, and the like can also be used.
- the acid that modifies the polyolefin-based resin examples include carboxylic acid, epoxy compound, acid anhydride and the like, and maleic anhydride is preferable.
- a polyolefin resin is anhydrous maleic from the viewpoint that it is easy to maintain the adhesive force between the sealant layer 16 and the metal foil layer 13 even when the electrolytic solution penetrates.
- a maleic anhydride-modified polyolefin resin graft-modified with an acid is preferable, and a maleic anhydride-modified polypropylene is particularly preferable.
- the modification rate of maleic anhydride-modified polypropylene with maleic anhydride is preferably 0.1 to 20% by mass, preferably 0.3 to 5% by mass. % Is more preferable.
- the second adhesive layer 15 having a heat laminate configuration contains a styrene-based or olefin-based elastomer.
- a styrene-based or olefin-based elastomer As a result, cracks in the second adhesive layer 15 due to cold forming during cold forming and whitening of the exterior material can be easily suppressed, and adhesion between the corrosion prevention treatment layer 14 and the sealant layer 16 can be improved by improving wettability.
- the improvement of the film forming property of the second adhesive layer 15 due to the reduction of the directivity can be expected.
- These elastomers are preferably dispersed and compatible with each other in the order of nanometers (nanometer size) in an acid-modified polyolefin resin.
- the second adhesive layer 15 having a thermal laminate configuration can be formed by extruding the adhesive component with an extrusion device.
- the melt flow rate (MFR) of the adhesive component of the second adhesive layer 15 having a thermal laminate configuration is preferably 4 to 30 g / 10 min under the conditions of 230 ° C. and 2.16 kgf.
- the thickness of the second adhesive layer 15 having a heat laminate configuration is preferably 2 to 50 ⁇ m.
- Examples of the adhesive component of the second adhesive layer 15 having a dry laminate configuration include a two-component curable polyurethane adhesive similar to the compound mentioned in the first adhesive layer 12. Since the second adhesive layer 15 having a dry laminate configuration has a bondable portion such as an ester group or a urethane group that can be hydrolyzed, the second adhesive layer 15 having a thermal laminate configuration is used for applications that require higher reliability. Layer 15 is preferred.
- the sealant layer 16 is a layer that imparts sealing properties by heat sealing in the exterior material 1.
- the sealant layer 16 include a polyolefin resin or a resin film made of an acid-modified polyolefin resin obtained by graft-modifying an acid such as maleic anhydride to a polyolefin resin.
- the polyolefin resin include low density, medium density, and high density polyethylene; ethylene- ⁇ olefin copolymer; homo, block, or random polypropylene; propylene- ⁇ olefin copolymer. These polyolefin resin may be used individually by 1 type, and may use 2 or more types together.
- the acid-modified polyolefin resin include the same compounds as those exemplified in the second adhesive layer 15.
- the sealant layer 16 may be a single layer film or a multilayer film, and may be selected according to a required function. For example, in terms of imparting moisture resistance, a multilayer film in which a resin such as an ethylene-cycloolefin copolymer or polymethylpentene is interposed can be used.
- the sealant layer 16 may be blended with various additives such as a flame retardant, slip agent, anti-blocking agent, antioxidant, light stabilizer, and tackifier.
- the thickness of the sealant layer 16 is preferably 10 to 100 ⁇ m, and more preferably 20 to 60 ⁇ m.
- the exterior material 1 may be an exterior material in which the sealant layer 16 is laminated on the second adhesive layer 15 by dry lamination, but from the viewpoint of improving adhesiveness, the second adhesive layer 15 is made of an acid-modified polyolefin resin, The sealant layer 16 is preferably laminated on the second adhesive layer 15 by sandwich lamination.
- the manufacturing method of the exterior material 1 is demonstrated.
- the manufacturing method of the exterior material 1 is not limited to the following method.
- Examples of the manufacturing method of the packaging material 1 include a method having the following steps (1) to (3).
- a corrosion prevention treatment agent is applied to one surface of the metal foil layer 13 and dried to form a corrosion prevention treatment layer 14.
- the anti-corrosion treatment agent include the above-described anti-corrosion treatment agent for ceriazole treatment, anti-corrosion treatment agent for chromate treatment, and the like.
- the coating method of the corrosion inhibitor is not particularly limited, and various methods such as gravure coating, reverse coating, roll coating, and bar coating can be employed.
- Step (2) Resin film for forming base material layer 11 by a method such as dry lamination using an adhesive for forming first adhesive layer 12 on the surface opposite to the surface on which corrosion prevention treatment layer 14 is formed in metal foil layer 13 Bond (A).
- an aging treatment may be performed in the range of room temperature to 100 ° C. in order to promote adhesion.
- the exterior material 1 is obtained by the steps (1) to (3) described above.
- the manufacturing method of the exterior material 1 is not limited to the method of sequentially performing the steps (1) to (3).
- step (1) may be performed after performing step (2).
- the lithium ion battery in which the exterior material of the present invention is used can be manufactured by a known method except that the exterior material of the present invention is used. For example, it is obtained as follows. A recess is formed in a part of the exterior material of the present invention by cold molding, and a positive electrode, a separator, and a negative electrode are placed inside the recess, and another sealant layer of the present invention is placed so that the sealant layers face each other. Overlap and heat seal the three sides of the outer edge of the overlaid exterior material. Thereafter, in a vacuum state, an electrolyte is injected from one side of the remaining exterior material, and one side of the remaining exterior material is overlapped, heat sealed, and sealed to obtain a lithium ion battery.
- the lithium ion battery in which the exterior material of the present invention is used is not limited to the lithium ion battery manufactured by the above method.
- Base material layer 11 Base material A-1: Biaxially stretched PET film (containing 8% by mass of thermoplastic polyester elastomer, thickness 25 ⁇ m).
- Base material A-2 Biaxially stretched PET film (containing 16% by mass of thermoplastic polyester elastomer, thickness 25 ⁇ m).
- Base material A-3 Biaxially stretched PET film (containing 1% by weight of thermoplastic polyester elastomer, thickness 25 ⁇ m).
- Base material A-4 Biaxially stretched nylon 6 film (thickness 25 ⁇ m).
- the base material A-4 when the width of the sample of the base material A-4 is 15 mm, the distance between the gauge points is 50 mm, and the tensile speed is 100 mm / second, the elongation rate in the TD direction of the resin film ( The ratio of increase relative to the length of the original base material when the base material was stretched was 75% (the base material A-4 was extended to 175%).
- Adhesive B-1 Urethane adhesive (trade name “A525 / A50”, manufactured by Mitsui Chemicals Polyurethanes).
- Metal foil layer 13 Metal foil C-1: Soft aluminum foil 8079 (Toyo Aluminum Co., Ltd., thickness 40 ⁇ m).
- Treatment agent D-1 Treatment agent for coating ceriazole treatment mainly comprising cerium oxide, phosphoric acid, and acrylic resin.
- Adhesive resin E-1 Polypropylene resin graft-modified with maleic anhydride (trade name “Admer”, manufactured by Mitsui Chemicals, Inc.).
- Film F-1 A film obtained by corona-treating the inner surface of an unstretched polypropylene film (thickness: 40 ⁇ m).
- the treatment agent D-1 was applied to one surface of the metal foil C-1 to be the metal foil layer 13 and dried to form a corrosion prevention treatment layer.
- any one of the substrates A-1 to A-4 is bonded to the opposite surface of the metal foil layer 13 to the anticorrosion treatment layer 14 by a dry laminating method using an adhesive B-1, and the first adhesion is performed.
- the base material layer 11 was laminated via the layer 12. Thereafter, the exterior material was aged at 60 ° C. for 6 days.
- a second adhesive layer 15 is formed by extruding the adhesive resin E-1 with an extrusion device on the surface of the obtained laminate on the anticorrosion treatment layer 14, and the film F-1 is laminated to sandwich lamination.
- the sealant layer 16 was formed.
- the obtained laminate, 160 ° C. was created exterior material by heat pressing at 4kg / cm 2, 2m / min conditions.
- Stress value H-1 The stress value in the MD direction of the resin film and the stress value in the resin film TD direction are both 70 MPa or more and 110 MPa or less.
- Stress value H-2 One of the stress value in the MD direction of the resin film and the stress value in the TD direction of the resin film is 70 MPa or more and 110 MPa or less, and the other stress value is 70 MPa or less.
- Stress value H-3 At least one of the stress value in the MD direction of the resin film and the stress value in the TD direction of the resin film is greater than 110 MPa.
- a mold having a shape of 100 mm ⁇ 150 mm, a punch corner R (RCP) of 1.5 mm, a punch shoulder R (RP) of 0.75 mm, and a die shoulder R (RD) of 0.75 mm was used. Evaluation was performed according to the following criteria. “Excellent”: It is possible to perform deep drawing with a molding depth of 7 mm or more without causing breakage and cracks in the exterior material. “Good”: Deep drawing with a molding depth of 5 mm or more and less than 7 mm can be performed without causing breakage or cracks in the exterior material. “Bad”: When deep drawing with a molding depth of less than 5 mm is performed, fractures and cracks occur in the exterior material.
- Example 1 and 2 and Comparative Examples 1 and 2 The exterior material which has the base material layer structure shown in Table 1 with the said preparation method was created. Table 1 shows the evaluation results of the electrolytic solution resistance and moldability.
- the base material is a resin film in which both the stress value in the MD direction and the stress value in the TD direction of the resin film are 110 MPa or less, and the stress value in the MD direction of the resin film and the stress value in the TD direction of the resin film are at least 70 MPa or more.
- the exterior materials of Examples 1 and 2 used for the layers showed excellent moldability without being affected by the storage environment and the molding processing environment.
- the stress value in the MD direction of the resin film and the stress value in the TD direction of the resin film are both 70 MPa or more and 110 MPa or less.
- Example 1 using the resin film as the base material layer particularly excellent moldability was exhibited.
- the exterior materials of Examples 1 and 2 were excellent in the electrolyte solution resistance of the base material layer.
- the water absorption of the resin film is 0.1% or more and 3% or less, but when the resin film is stretched 10% with respect to the length of the resin film before the tensile test, the resin film in the MD direction.
- the exterior material of Comparative Example 1 in which at least one of the stress value and the stress value in the TD direction of the resin film is greater than 110 MPa did not provide sufficient moldability in any environment of 40% RH and dew point temperature of ⁇ 35 ° C. . Further, when the resin film is stretched by 10% with respect to the length of the resin film before the tensile test, the stress value in the MD direction of the resin film and the stress value in the TD direction of the resin film are both 70 MPa or more and 110 MPa or less.
- the exterior material of Comparative Example 2 having a water absorption rate of more than 3% has an elongation in the TD direction (an increase rate relative to the original substrate when the substrate is stretched) of less than 80%, 40% Excellent moldability was exhibited in an RH humidity environment.
- the exterior material of Comparative Example 2 did not have sufficient moldability. This is because, in the exterior material of Comparative Example 2, the water absorption rate of the resin film is 4%, so that the amount of water in the film tends to change, and the base material layer is used in a low humidity environment with a dew point temperature of ⁇ 35 ° C. It is thought that this is because the moisture in the resin film to be formed is insufficient due to evaporation and the film characteristics are changed.
- SYMBOLS 1 Exterior material for lithium ion batteries, 11 ... Base material layer, 12 ... 1st adhesion layer, 13 ... Metal foil layer, 14 ... Corrosion prevention processing layer, 15 ... 1st 2 adhesive layers, 16 ... sealant layer.
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Abstract
Description
本願は、2012年3月21日に、日本に出願された特願2012-063713号に基づき優先権を主張し、その内容をここに援用する。
そこで、多層フィルムからなる外装材では内部にアルミニウム箔層が設けられ、外装材表面から電池内に水分が浸入することを抑制している。例えば、耐熱性を有する基材層/第1接着層/アルミニウム箔層/フッ酸による腐食を防止する腐食防止処理層/第2接着層/シーラント層が順次積層された外装材が知られている。前記外装材が使用されたリチウムイオン電池は、アルミラミネートタイプのリチウムイオン電池と呼ばれる。
そこで、基材層には、優れた成型性を有する二軸延伸ポリアミドフィルムが広く用いられている。また、二軸延伸ポリアミドフィルムは耐電解液性が充分でないため、二軸延伸ポリアミドフィルムの外面に二軸延伸ポリエステルフィルムが積層された積層フィルムを基材層に用いることも行われている(例えば、特許文献1)。
また、基材層に、MD方向(流れ方向)に対して0°、45°、90°、135°の4方向の伸び率がいずれも80%以上であるフィルムを用いることも提案されている(特許文献2)。
また、4方向の伸び率(基材層を延伸した際における、もとの基材層の長さに対する増加割合)がいずれも80%以上のフィルムを基材層に用いる場合も、成型を行う湿度環境によって充分な成型性が得られないことがある。
JIS K 7209:2000で規定された試験における吸水率が0.1%以上3%以下であり、下記引張試験において、前記樹脂フィルムの試料が、前記引張試験前の前記試料の長さに対して、10%延伸された時に、前記試料のMD方向における応力値及び前記試料のTD方向における応力値が共に110MPa以下であり、かつ前記試料のMD方向における応力値及び前記試料のTD方向における応力値の少なくとも一方において70MPa以上である。
(引張試験)
23℃、40%RHの環境下で前記試料を24時間保管した後、23℃、40%RHの環境下、前記試料の幅6mm、標点間距離35mm、引張速度300mm/分の条件で引張試験を行い、前記試料が、試験前の前記試料の長さに対して、10%延伸された時(変位量3.5mm)の応力値を測定する。
また、本発明の一態様においては、前記樹脂フィルムは、厚さ10~40μmのポリエチレンテレフタレートフィルムであることが好ましい。
また、本発明の一態様においては、前記樹脂フィルムは、熱可塑性ポリエステルエラストマーが2質量%以上30質量%以下含有されていることが好ましい。
本実施形態のリチウムイオン電池用外装材1(以下、「外装材1」という。)は、図1に示すように、基材層11の一方の面に、第1接着層12、金属箔層13、腐食防止処理層14、第2接着層15及びシーラント層16が順次積層された積層体である。外装材1は、基材層11が最外層、シーラント層16が最内層である。すなわち、外装材1は、基材層11を電池の外部側(外面)、シーラント層16を電池の内部側(内面)に配置して使用される。
基材層11は、リチウムイオン電池を製造する際のシール工程における耐熱性を付与し、加工や流通の際に起こり得るピンホールの発生を抑制する役割を果たす。
基材層11は、JIS K 7209:2000で規定された試験における吸水率が0.1%以上3%以下で、下記引張試験において、前記引張試験前のもとの長さに対して10%延伸された時に、MD方向における応力値及びTD方向における応力値が共に110MPa以下で、かつMD方向における応力値及びTD方向における応力値が少なくとも一方で70MPa以上である樹脂フィルム(以下、「樹脂フィルム(A)」という。)からなる層である。基材層11が樹脂フィルム(A)からなることで、湿度環境に関わらず優れた成型性が得られ、また基材層11の耐電解液性にも優れた外装材1となる。
23℃、40%RHの環境下で前記樹脂フィルム(A)の試料を24時間保管した後、23℃、40%RHの環境下、前記樹脂フィルム(A)の試料の試料幅が6mmであり、標点間距離が35mmであり、引張速度が300mm/分である条件で引張試験を行い、前記樹脂フィルム(A)の試料が、前記引張試験前の前記試料の長さに対して10%延伸された時(変位量3.5mm)の応力値を測定する。
従来の外装材では、同じ外装材であっても冷間成型する際の成型性が外装材間で異なることがあり、場合によっては充分な成型性が得られないことがあった。この問題について本発明者が検討したところ、外装材の保管時や成型時における湿度環境が外装材の成型性に大きく影響していることが判明した。具体的には、外装材が優れた成型性を有するには、基材層を形成する樹脂フィルムが一定の水分を含んだ状態であることが必要であることが判明した。一般にリチウムイオン電池は電解質と水分の反応を避けるため、ドライルームにて電解液の注入と封止が行われる。しかし、電解液を注入する前の外装材の保管時や成型加工時における湿度環境は厳密に管理されておらず、様々な条件となっている。従来の外装材では、保管時や成型加工時における湿度が高い場合は基材層が充分な水を含むことで優れた成型性が得られるが、保管時や成型加工時の湿度が低い場合は基材層中の水分量が不足し、フィルム特性が大きく変化して成型性が低下していたと考えられる。
これに対し、本発明の外装材は、基材層を形成する樹脂フィルム(A)が前記引張試験前の前記樹脂フィルム(A)の長さに対して10%延伸された時の応力値が前記条件(樹脂フィルム(A)のMD方向における応力値及び樹脂フィルム(A)のTD方向における応力値が共に110MPa以下で、かつ樹脂フィルム(A)のMD方向における応力値及び樹脂フィルム(A)のTD方向における応力値が少なくとも一方で70MPa以上であること)を満たすことで、優れた成型性を有している。さらに、樹脂フィルム(A)は、吸水率が0.1%以上であることでフィルム中に水分が充分に確保され、かつ吸水率が3%以下であることでフィルム中の水分量が湿度環境によって変化し難い。そのため、樹脂フィルム(A)のフィルム特性は湿度環境によって変化し難い。これらのことから、本発明の外装材は湿度環境に関わらず優れた成型性を示すと考えられる。
また、樹脂フィルム(A)のMD方向における応力値及び樹脂フィルム(A)のTD方向における応力値において、樹脂フィルム(A)が、引張試験前の樹脂フィルム(A)の長さに対して10%延伸された時の応力値の下限値は、80MPaが好ましい。また、前記応力値の上限値は、100MPaが好ましい。
前記応力値が下限値(80MPa)以上であれば、より優れた成型性を有する外装材1となる。前記応力値が上限値(100MPa)以下であれば、より優れた成型性を有する外装材1となる。
樹脂フィルム(A)は、単層フィルムでも多層フィルムでもよいが、コスト面で有利な点から、単層フィルムが好ましい。樹脂フィルム(A)が多層フィルムの場合、前記吸水率及び前記樹脂フィルムが、前記引張試験前の前記樹脂フィルムの長さに対して10%延伸された時の応力値の条件(樹脂フィルム(A)のMD方向における応力値及び樹脂フィルム(A)のTD方向における応力値が共に110MPa以下で、かつ樹脂フィルム(A)のMD方向における応力値及び樹脂フィルム(A)のTD方向における応力値が少なくとも一方で70MPa以上であること)を満たす多層フィルムを用いればよい。なお、多層フィルムは、多層共押出し製法によって得られる単一基材を含む。
熱可塑性ポリエステルエラストマーは、ハードセグメントとソフトセグメントを有するポリエステルエラストマーである。
ハードセグメントとしては、例えば、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリエチレンテレフタレート等の結晶性ポリエステルが挙げられる。なかでも、ポリブチレンテレフタレートが好ましい。
ソフトセグメントとしては、例えば、ポリテトラメチレングリコール等のポリオキシアルキレングリコール類;ポリカプロラクトン、ポリブチレンアジペート等のポリエステル等が挙げられる。なかでも、ポリテトラメチレングリコールが好ましい。
第1接着層12は、基材層11と金属箔層13とを接着する層である。
第1接着層12を構成する接着剤としては、ポリエステルポリオール、ポリエーテルポリオール、アクリルポリオール等の主剤に、硬化剤として2官能以上の芳香族系又は脂肪族系イソシアネート化合物を作用させる2液硬化型のウレタン系接着剤が好ましい。
前記ウレタン系接着剤は、塗工後、例えば40℃で4日以上のエージングを行うことで、主剤の水酸基と硬化剤のイソシアネート基の反応が進行して強固な接着が可能となる。
第1接着層12の厚さは、接着強度、加工性などの点において、或いは、追随性を得るため(第1接着層12が設けられる部材が変形・伸縮したとしても、剥離することなく部材上に第1接着層12を確実に形成するため)には、1~10μmが好ましく、3~7μmがより好ましい。
金属箔層13としては、アルミニウム、ステンレス鋼等の各種金属箔を使用することができ、防湿性、延展性等の加工性、コストの面から、アルミニウム箔が好ましい。アルミニウム箔としては、一般の軟質アルミニウム箔を用いることができる。なかでも、耐ピンホール性、及び成型時の延展性に優れる点から、鉄を含むアルミニウム箔が好ましい。
鉄を含むアルミニウム箔(100質量%)中の鉄の含有量は、0.1~9.0質量%が好ましく、0.5~2.0質量%がより好ましい。鉄の含有量が下限値(0.1質量%)以上であれば、外装材1は耐ピンホール性、延展性に優れる。鉄の含有量が上限値(9.0質量%)以下であれば、外装材1は柔軟性に優れる。
金属箔層13の厚さは、バリア性、耐ピンホール性、加工性の点から、9~200μmが好ましく、15~100μmがより好ましい。
腐食防止処理層14は、電解液や、電解液と水分との反応により発生するフッ酸による金属箔層13の腐食を抑制する役割を果たす。また、金属箔層13と第2接着層15との密着力を高める役割を果たす。
腐食防止処理層14としては、塗布型、又は浸漬型の耐酸性の腐食防止処理剤によって形成された塗膜が好ましい。前記塗膜は、金属箔層13の酸に対する腐食防止効果に優れる。また、アンカー効果によって金属箔層13と第2接着層15との密着力をより強固にするので、電解液等の内容物に対して優れた耐性が得られる。
なお、腐食防止処理層14は、金属箔層13の耐食性が充分に得られる塗膜であれば、前記塗膜には限定されない。例えば、リン酸塩処理、ベーマイト処理等によって形成された塗膜であってもよい。
腐食防止処理層14の厚さは、腐食防止機能、及びアンカーとしての機能の点から、10nm~5μmが好ましく、20nm~500nmがより好ましい。
第2接着層15は、腐食防止処理層14が形成された金属箔層13とシーラント層16とを接着する層である。外装材1は、第2接着層15を形成する接着成分によって、熱ラミネート構成とドライラミネート構成に大きく分けられる。
熱ラミネート構成における第2接着層15を形成する接着成分としては、ポリオレフィン系樹脂を無水マレイン酸等の酸でグラフト変性した酸変性ポリオレフィン系樹脂が好ましい。酸変性ポリオレフィン系樹脂は、無極性であるポリオレフィン系樹脂の一部に極性基が導入されていることから、ポリオレフィン系樹脂フィルム等で形成された無極性のシーラント層16と、極性を有する腐食防止処理層14との両方に強固に密着することができる。また、酸変性ポリオレフィン系樹脂を使用することで、電解液等の内容物に対する耐性が向上し、電池内部でフッ酸が発生しても第2接着層15の劣化による腐食防止処理層14とシーラント層16との密着力の低下を防止しやすい。
第2接着層15に使用する酸変性ポリオレフィン系樹脂は、1種であってもよく、2種以上であってもよい。
前記ポリオレフィン系樹脂を変性する酸としては、カルボン酸、エポキシ化合物、酸無水物等が挙げられ、無水マレイン酸が好ましい。
無水マレイン酸変性ポリプロピレンの無水マレイン酸による変性率(無水マレイン酸変性ポリプロピレンの総質量に対する無水マレイン酸に由来する部分の質量)は、0.1~20質量%が好ましく、0.3~5質量%がより好ましい。
熱ラミネート構成を有する第2接着層15の接着成分のメルトフローレート(MFR)は、230℃、2.16kgfの条件において4~30g/10分が好ましい。
熱ラミネート構成を有する第2接着層15の厚さは、2~50μmが好ましい。
ドライラミネート構成を有する第2接着層15は、エステル基やウレタン基等の加水分解され得る結合部を有しているので、より高い信頼性が求められる用途には熱ラミネート構成を有する第2接着層15が好ましい。
シーラント層16は、外装材1においてヒートシールによる封止性を付与する層である。
シーラント層16としては、ポリオレフィン系樹脂、又はポリオレフィン系樹脂に無水マレイン酸等の酸をグラフト変性させた酸変性ポリオレフィン系樹脂からなる樹脂フィルムが挙げられる。
前記ポリオレフィン系樹脂としては、例えば、低密度、中密度、高密度のポリエチレン;エチレン-αオレフィン共重合体;ホモ、ブロック、又はランダムポリプロピレン;プロピレン-αオレフィン共重合体等が挙げられる。これらポリオレフィン系樹脂は、1種を単独で使用してもよく、2種以上を併用してもよい。
酸変性ポリオレフィン系樹脂としては、例えば、第2接着層15で挙げた化合物と同じ化合物が挙げられる。
また、シーラント層16は、難燃剤、スリップ剤、アンチブロッキング剤、酸化防止剤、光安定剤、粘着付与剤等の各種添加剤が配合されてもよい。
シーラント層16の厚さは、10~100μmが好ましく、20~60μmがより好ましい。
以下、外装材1の製造方法について説明する。ただし、外装材1の製造方法は以下の方法に限定されない。
外装材1の製造方法としては、例えば、下記工程(1)~(3)を有する方法が挙げられる。
(1)金属箔層13上に、腐食防止処理層14を形成する工程。
(2)金属箔層13における腐食防止処理層14が形成された面と反対の面に、第1接着層12を介して基材層11を貼り合わせる工程。
(3)金属箔層13の腐食防止処理層14が形成された面に、第2接着層15を介してシーラント層16を貼り合わせる工程。
金属箔層13の一方の面に、腐食防止処理剤を塗布、乾燥して腐食防止処理層14を形成する。腐食防止処理剤としては、例えば、前記したセリアゾール処理用の腐食防止処理剤、クロメート処理用の腐食防止処理剤等が挙げられる。
腐食防止処理剤の塗布方法は特に限定されず、グラビアコート、リバースコート、ロールコート、バーコート等、各種方法を採用できる。
金属箔層13における腐食防止処理層14が形成された面と反対の面に、第1接着層12を形成する接着剤を用いて、ドライラミネーション等の手法で基材層11を形成する樹脂フィルム(A)を貼り合わせる。
工程(2)では、接着性の促進のため、室温~100℃の範囲でエージング(養生)処理を行ってもよい。
熱ラミネート構成の場合は、例えば、基材層11、第1接着層12、金属箔層13及び腐食防止処理層14がこの順に積層された積層体の腐食防止処理層14が形成された面に、押出ラミネート法によって第2接着層15が形成され、シーラント層16を形成するフィルムを貼り合わせる。シーラント層16の第2接着層上への積層は、サンドイッチラミネーションにより行うことが好ましい。
ドライラミネート構成の場合は、例えば、前述の接着剤が使用され、前記積層体の腐食防止処理層14が形成された面に、ドライラミネーション、ノンソルベントラミネーション、ウエットラミネーション等の手法で、第2接着層15を介してシーラント層16を形成するフィルムを積層する。
なお、外装材1の製造方法は、前記工程(1)~(3)を順次実施する方法に限定されない。例えば、工程(2)を行ってから工程(1)を行ってもよい。
なお、本発明の外装材が使用されたリチウムイオン電池は、前記方法で製造されたリチウムイオン電池に限定されない。
[使用材料]
本実施例で使用した材料を以下に示す。
(基材層11)
基材A-1:二軸延伸PETフィルム(熱可塑性ポリエステルエラストマー8質量%含有、厚み25μm)。
基材A-2:二軸延伸PETフィルム(熱可塑性ポリエステルエラストマー16質量%含有、厚み25μm)。
基材A-3:二軸延伸PETフィルム(熱可塑性ポリエステルエラストマー1質量%含有、厚み25μm)。
基材A-4:二軸延伸ナイロン6フィルム(厚み25μm)。
基材A-4について、基材A-4の試料の幅が15mmであり、標点間距離が50mmであり、引張速度が100mm/秒である場合において、樹脂フィルムのTD方向における伸び率(基材を延伸した際における、もとの基材の長さに対する増加割合)を測定したところ、75%であった(基材A-4は、175%まで伸びた)。
接着剤B-1:ウレタン系接着剤(商品名「A525/A50」、三井化学ポリウレタン社製)。
金属箔C-1:軟質アルミニウム箔8079材(東洋アルミニウム社製、厚さ40μm)。
処理剤D-1:酸化セリウム、リン酸、アクリル系樹脂を主体として有する塗布型セリアゾール処理用の処理剤。
接着樹脂E-1:無水マレイン酸でグラフト変性したポリプロピレン系樹脂(商品名「アドマー」、三井化学社製)。
フィルムF-1:無延伸ポリプロピレンフィルム(厚さ40μm)の内面となる面がコロナ処理されたフィルム。
金属箔層13となる金属箔C-1の一方の面に処理剤D-1を塗布、乾燥させて腐食防止処理層14を形成した。次に、金属箔層13における腐食防止処理層14の反対面に、接着剤B-1を用いたドライラミネート法により、基材A-1~A-4のいずれかを貼り合せ、第1接着層12を介して基材層11を積層した。その後、60℃、6日間の外装材のエージングを行った。次に、得られた積層体の腐食防止処理層14上の面に、押出し装置にて接着樹脂E-1を押出して第2接着層15を形成し、フィルムF-1を貼り合わせてサンドイッチラミネーションすることでシーラント層16を形成した。その後、得られた積層体に対し、160℃、4kg/cm2、2m/分の条件で加熱圧着することで外装材を作成した。
基材層11に使用された各フィルムについては、JIS K 7209:2000に準拠した試験により、吸水率を測定し、以下の基準で分類した。
吸水率G-1:吸水率が0.1%以上3%以下である。
吸水率G-2:吸水率が3%より大きい。
基材層11に使用した各樹脂フィルムについては、23℃、40%RHの環境下で24時間保管した後に、23℃、40%RHの環境下で引張試験(基材層試料の幅6mm、標点間距離35mm、引張速度300mm/分。)を行った。樹脂フィルムのMD方向(流れ方向)と樹脂フィルムのTD方向(垂直方向)のそれぞれにおいて、樹脂フィルムが、引張試験前の樹脂フィルムの長さに対して10%延伸された時(変位量3.5mm)の応力値を測定して、以下の基準で分類した。
応力値H-1:樹脂フィルムのMD方向における応力値、及び樹脂フィルムTD方向における応力値が、共に70MPa以上110MPa以下である。
応力値H-2:樹脂フィルムのMD方向における応力値、及び樹脂フィルムのTD方向における応力値のうち一方の応力値が70MPa以上110MPa以下であり、他方の応力値が70MPa以下である。
応力値H-3:樹脂フィルムのMD方向における応力値、及び樹脂フィルムのTD方向における応力値の少なくとも一方の応力値が110MPaより大きい。
各例で得られた外装材の基材層表面に電解液を数滴滴下し、25℃、65%RHの環境下で24時間放置し、電解液を拭き取り、基材層表面の変質を目視にて確認した。評価は、以下の基準に従って行った。
「優」:基材層表面の変質が観察されない。
「良」:基材層表面における変質範囲が電解液接触面積の10%以下である。
「不良」:基材層表面における変質範囲が電解液接触面積の10%を超える。
各例で得られた外装材を、150mm×190mmのブランク形状(平面形状)に切り取り、23℃、40%RHの環境下で24時間保管した後、23℃、40%RHの環境下で成型深さを変化させながら冷間成型し、成型性を評価した。また、保管環境(24時間)と成型加工環境が露点温度-35℃(温度23℃)である以外は上記と同様の条件で、成型性も評価した。
パンチとしては、形状が100mm×150mm、パンチコーナーR(RCP)が1.5mm、パンチ肩R(RP)が0.75mm、ダイ肩R(RD)が0.75mmの金型を使用した。評価は、以下の基準に従って行った。
「優」:外装材に破断、クラックを生じさせずに、成型深さ7mm以上の深絞り成型をすることが可能である。
「良」:外装材に破断、クラックを生じさせずに、成型深さ5mm以上7mm未満の深絞り成型をすることが可能である。
「不良」:成型深さ5mm未満の深絞り成型をした際に、外装材に破断、クラックが生じる。
前記作成方法により、表1に示す基材層構成を有する外装材を作成した。
耐電解液性及び成型性の評価結果を表1に示す。
一方、樹脂フィルムの吸水率が0.1%以上3%以下であるが、樹脂フィルムが、引張試験前の樹脂フィルムの長さに対して10%延伸された際に、樹脂フィルムのMD方向における応力値及び樹脂フィルムのTD方向における応力値少なくとも一方が、110MPaより大きい比較例1の外装材は、40%RH及び露点温度-35℃のいずれの環境下でも充分な成型性が得られなかった。
また、樹脂フィルムが、引張試験前の樹脂フィルムの長さに対して10%延伸された際に、樹脂フィルムのMD方向における応力値及び樹脂フィルムのTD方向における応力値が共に70MPa以上110MPa以下であるが、吸水率が3%より大きい比較例2の外装材は、TD方向における伸び率(基材を延伸した際におけるもとの基材に対する増加割合)が80%未満であるものの、40%RHの湿度環境下では優れた成型性を示した。しかし、露点温度-35℃の湿度環境下では、比較例2の外装材は充分な成型性が得られなかった。これは、比較例2の外装材においては、樹脂フィルムの吸水率が4%であるためにフィルム中の水分量が変化しやすくなり、露点温度-35℃の湿度の低い環境では基材層を形成する樹脂フィルム中の水分が蒸発して不足し、フィルムの特性が変化したためであると考えられる。
Claims (4)
- リチウムイオン電池用外装材であって、
樹脂フィルムからなる基材層と、前記基材層の一方の面に、順次積層された第1接着層、金属箔層、腐食防止処理層、第2接着層、及びシーラント層を備え、
前記樹脂フィルムが、
JIS K 7209:2000で規定された試験における吸水率が0.1%以上3%以下であり、
下記引張試験において、前記樹脂フィルムの試料が、前記引張試験前の前記試料の長さに対して、10%延伸された時に、前記試料のMD方向における応力値及び前記試料のTD方向における応力値が共に110MPa以下であり、かつ前記試料のMD方向における応力値及び前記試料のTD方向における応力値の少なくとも一方において70MPa以上であることを特徴とするリチウムイオン電池用外装材。
(引張試験)
23℃、40%RHの環境下で前記試料を24時間保管した後、23℃、40%RHの環境下、前記試料の幅6mm、標点間距離35mm、引張速度300mm/分の条件で引張試験を行い、前記試料が、前記引張試験前の前記試料の長さに対して、10%延伸された時(変位量3.5mm)の応力値を測定する。 - 前記樹脂フィルムの前記引張試験により、前記試料が、前記引張試験前の前記試料の長さに対して10%延伸された時に、前記試料のMD方向における応力値及び前記試料のTD方向における応力値が共に70MPa以上110MPa以下である請求項1に記載のリチウムイオン電池用外装材。
- 前記樹脂フィルムが厚さ10~40μmのポリエチレンテレフタレートフィルムである請求項1又は2に記載のリチウムイオン電池用外装材。
- 前記樹脂フィルムに熱可塑性ポリエステルエラストマーが2質量%以上30質量%以下含有されている請求項1~3のいずれか一項に記載のリチウムイオン電池用外装材。
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US10135038B2 (en) | 2018-11-20 |
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