WO2023048242A1 - 封止フィルム、電極リード線部材および電池 - Google Patents
封止フィルム、電極リード線部材および電池 Download PDFInfo
- Publication number
- WO2023048242A1 WO2023048242A1 PCT/JP2022/035403 JP2022035403W WO2023048242A1 WO 2023048242 A1 WO2023048242 A1 WO 2023048242A1 JP 2022035403 W JP2022035403 W JP 2022035403W WO 2023048242 A1 WO2023048242 A1 WO 2023048242A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sealing film
- adhesive layer
- layer
- hydrogen
- lead wire
- Prior art date
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 164
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 122
- 239000011347 resin Substances 0.000 claims abstract description 122
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 55
- 239000012790 adhesive layer Substances 0.000 claims description 176
- 239000010410 layer Substances 0.000 claims description 157
- 229920000098 polyolefin Polymers 0.000 claims description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000000463 material Substances 0.000 description 84
- 238000002844 melting Methods 0.000 description 52
- 230000008018 melting Effects 0.000 description 52
- 239000004743 Polypropylene Substances 0.000 description 48
- 229920001155 polypropylene Polymers 0.000 description 48
- -1 polypropylene Polymers 0.000 description 39
- 229920002292 Nylon 6 Polymers 0.000 description 37
- 239000000853 adhesive Substances 0.000 description 35
- 230000001070 adhesive effect Effects 0.000 description 35
- 125000004429 atom Chemical group 0.000 description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 18
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- 239000000470 constituent Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 229920005604 random copolymer Polymers 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000002335 surface treatment layer Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920005606 polypropylene copolymer Polymers 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920005678 polyethylene based resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920005673 polypropylene based resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01M50/184—Sealing members characterised by their shape or structure
-
- 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
- H01M50/188—Sealing members characterised by the disposition of the sealing members the sealing members being arranged between the lid and terminal
-
- 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
- H01M50/19—Sealing members characterised by the material
- H01M50/193—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/197—Sealing members characterised by the material having a layered structure
-
- 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 sealing film, an electrode lead wire member and a battery.
- This application claims priority based on Japanese Patent Application No. 2021-155742 filed in Japan on September 24, 2021, the contents of which are incorporated herein.
- the battery includes, for example, a battery main body, a container for housing the battery main body, and electrode lead wires connected to the battery main body.
- the storage container is produced using a battery exterior laminate having excellent waterproof and light shielding properties.
- the battery exterior laminate is, for example, a laminate obtained by laminating a substrate layer made of polyamide or the like and an aluminum foil.
- the electrode lead wire is sealed in the housing container with a portion including one end drawn out from the housing container.
- the film for sealing described in Patent Document 1 suppresses a decrease in adhesive strength of the film by adding an inorganic filler such as heavy calcium carbonate.
- hydrogen fluoride generated in the electrolyte may react with calcium carbonate or the like in the film to generate water. Therefore, it is feared that the generated water reacts with the components in the electrolytic solution to generate hydrogen fluoride, and the hydrogen fluoride reduces the bonding strength between the sealing film and the electrode lead wire.
- An object of the present invention is to provide a sealing film, an electrode lead wire member, and a battery that can suppress a decrease in adhesive strength due to hydrogen fluoride.
- the present invention includes the following aspects.
- thermoplastic resin layers are provided, and the plurality of thermoplastic resin layers are a first thermoplastic resin layer that is a first adhesive layer that adheres to the electrode lead wire, and a first thermoplastic resin layer that adheres to the container. a second thermoplastic resin layer that is a second adhesive layer, and a third thermoplastic resin layer that is a base layer provided between the first adhesive layer and the second adhesive layer. , the sealing film according to [1], wherein the hydrogen-bonding resin is contained in at least one of the first to third thermoplastic resin layers.
- An electrode lead wire member comprising the sealing film according to any one of [1] to [9] and the electrode lead wire extending in one direction. A portion of the sealing film may be adhered to the electrode lead wire.
- a battery comprising the electrode lead wire member according to [10]. The battery includes a battery body, a container that houses the battery body, and the electrode lead wire member. A part of the sealing film is adhered to the electrode lead wire, and the sealing film is Other parts may be adhered to the container.
- the present invention it is possible to provide a sealing film, an electrode lead wire member, and a battery that can suppress a decrease in adhesive strength due to hydrogen fluoride.
- FIG. 4 is an enlarged cross-sectional view taken along line II in FIG. 3;
- FIG. It is a cross-sectional enlarged view which shows the sealing film of other embodiment.
- FIG. 1 A sealing film, an electrode lead wire member, and a battery according to an embodiment will be described below with reference to FIGS. 1 to 4.
- FIG. 1 the dimensions and ratios of constituent elements may differ from the actual ones.
- FIG. 1 is an enlarged cross-sectional view showing a sealing film 1 of an embodiment.
- FIG. 2 is a perspective view showing the electrode lead wire member 10 of the embodiment.
- the electrode lead wire member 10 includes an electrode lead wire 11 made of a conductor such as a metal, and a pair of sealing films 1 intersecting the electrode lead wire 11 and adhered at the center thereof.
- the sealing film 1 includes a first adhesive layer 2 , a second adhesive layer 3 and a base layer 4 .
- the first adhesive layer 2 is a layer that is fused (adhered) to the electrode lead wire 11 (see FIG. 2) by heating and pressing.
- the surface of the first adhesive layer 2 is one surface 1 a of the sealing film 1 .
- the first adhesive layer 2 is a thermoplastic resin layer containing a thermoplastic resin.
- the first adhesive layer 2 is an example of the "first thermoplastic resin layer”.
- the first adhesive layer 2 mainly contains, for example, acid-modified polyolefin.
- the fact that the first adhesive layer 2 “mainly contains acid-modified polyolefin” means that the content of the acid-modified polyolefin is the highest among the resins constituting the first adhesive layer 2 .
- the first adhesive layer 2 preferably contains 50% by mass or more of the acid-modified polyolefin with respect to the total amount of the first adhesive layer 2 .
- the first adhesive layer 2 preferably contains more than 50% by mass, more preferably 80% by mass or more, of the acid-modified polyolefin with respect to the total amount of the first adhesive layer 2 .
- polyolefins constituting the first adhesive layer 2 examples include polypropylene, polyethylene, poly-1-butene, and polyisobutylene. Among them, polypropylene is preferable as the polyolefin constituting the first adhesive layer 2 because of its excellent flexibility.
- polypropylene may be abbreviated as "PP”.
- the polyolefin may be a copolymer of propylene and ethylene (propylene-ethylene copolymer).
- a copolymer of propylene and ethylene may be a block copolymer or a random copolymer, but a random copolymer is preferred.
- Polyolefins may be copolymers of propylene and olefinic monomers. Olefinic monomers include 1-butene, isobutylene, 1-hexene and the like.
- An acid-modified polyolefin is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative of an unsaturated carboxylic acid.
- Acid-modified polyolefins have acid functional groups such as carboxy groups and carboxylic acid anhydride groups in their molecular structures.
- Acid-modified polyolefins are obtained by graft polymerizing unsaturated carboxylic acids or unsaturated carboxylic acid derivatives onto polyolefins, or by copolymerizing acid functional group-containing monomers with olefins. That is, in the acid-modified polyolefin, the repeating unit having an acid group may be contained in the side chain or may be contained in the main chain.
- unsaturated carboxylic acids include acrylic acid and methacrylic acid.
- Derivatives of unsaturated carboxylic acids include unsaturated carboxylic acid esters such as ethyl acrylate and acid anhydrides of unsaturated carboxylic acids such as maleic anhydride.
- acid-modified polyolefin can enhance the adhesion of the first adhesive layer 2 to the electrode lead wire 11 (see FIG. 2).
- Polyolefins and acid-modified polyolefins are thermoplastic resins.
- acid-modified polypropylene As the acid-modified polyolefin, acid-modified polypropylene (acid-modified PP) is preferable because it has excellent heat resistance.
- Acid-modified PP is, for example, a polymer obtained by graft-copolymerizing polypropylene or a propylene-ethylene copolymer with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative.
- the acid-modified PP contains an ionomer obtained by neutralizing the carboxy acid groups of an acid-modified polypropylene polymer or an acid-modified propylene-ethylene copolymer with a metal hydroxide, alkoxide, lower fatty acid salt, or the like.
- the acid group of acid-modified PP is preferably a maleic anhydride group. That is, maleic anhydride-modified PP is preferable as the acid-modified PP.
- the first adhesive layer 2 may not contain a hydrogen-bonding resin (described later). In this case, in the first adhesive layer 2, it is possible to increase the ratio of materials having excellent adhesive strength. Thereby, the adhesive strength between the first adhesive layer 2 and the electrode lead wire 11 is improved.
- the melting point of the resin (or resin composition) forming the first adhesive layer 2 is preferably 110° C. or higher and 150° C. or lower.
- the melting point of the resin constituting the first adhesive layer 2 is 110° C. or higher, the first adhesive layer 2 is less likely to become excessively thin during thermocompression bonding, and it is easy to secure adhesive strength.
- the melting point of the resin constituting the first adhesive layer 2 is 150° C. or less, the resin easily flows during thermocompression bonding. easy to seal.
- the "melting point of the resin constituting the first adhesive layer 2" is the melting point of the polymer alloy constituting the first adhesive layer 2. means melting point.
- optional components other than polyolefin include known additives such as stabilizers, antistatic agents, and colorants.
- the thickness of the first adhesive layer 2 can be, for example, 5 or more and 90 or less, where the total thickness of the sealing film 1 is 100. That is, the thickness of the first adhesive layer 2 can be 5% or more and 90% or less of the total thickness of the sealing film 1 .
- the thickness of the first adhesive layer 2 is preferably 25 or more and 70 or less when the entire thickness of the sealing film 1 is 100.
- the thickness ratio of the layers when the total thickness of the encapsulating film 1 is 100 is referred to as the "thickness ratio".
- the thickness ratio of the first adhesive layer 2 is 5 or more (preferably 25 or more), sufficient adhesive strength between the first adhesive layer 2 and the electrode lead wire 11 can be ensured.
- the thickness ratio of the first adhesive layer 2 is 90 or less (preferably 70 or less), sufficient thickness can be imparted to the second adhesive layer 3 and the base material layer 4 . Therefore, it is possible to increase the adhesive strength between the second adhesive layer 3 and the container without lowering the electrolytic solution resistance of the sealing film 1 .
- electrolytic solution resistance is resistance to the electrolyte solution.
- the second adhesive layer 3 is, for example, a layer that is fused (bonded) to the container by heating and pressurization. The storage container will be described later.
- the surface of the second adhesive layer 3 is the other surface 1 b of the sealing film 1 .
- the second adhesive layer 3 is a thermoplastic resin layer containing a thermoplastic resin.
- the second adhesive layer 3 is an example of a "second thermoplastic resin layer”.
- the second adhesive layer 3 mainly contains polyolefin, for example.
- the fact that the second adhesive layer 3 “mainly contains polyolefin” means that the content of polyolefin is the highest among the resins constituting the second adhesive layer 3 .
- the second adhesive layer 3 contains 50% by mass or more, preferably more than 50% by mass, more preferably 80% by mass or more of polyolefin with respect to the total amount of the second adhesive layer 3 .
- Polyolefins constituting the second adhesive layer 3 include polypropylene (PP), polyethylene, poly-1-butene, and polyisobutylene. Among them, PP is preferable as the polyolefin constituting the second adhesive layer 3 because of its excellent flexibility.
- the polyolefin may be a copolymer of propylene and ethylene (propylene-ethylene copolymer).
- a copolymer of propylene and ethylene may be a block copolymer or a random copolymer, but a random copolymer is preferred.
- Polyolefins may be copolymers (eg, random copolymers) of propylene and olefinic monomers. Olefinic monomers include 1-butene, isobutylene, 1-hexene and the like.
- the polyolefin that constitutes the second adhesive layer 3 may be an acid-modified polyolefin.
- acid-modified polyolefin acid-modified PP is preferable because of its excellent heat resistance.
- the acid-modified PP the acid-modified PP exemplified as the material of the first adhesive layer 2 is preferably used.
- the acid-modified PP a polymer obtained by acid-modifying a random copolymer of propylene and ethylene is preferable because of its excellent flexibility. The use of acid-modified polyolefin can enhance the adhesion of the second adhesive layer 3 to the container.
- the second adhesive layer 3 may contain both acid-modified PP and acid-modified polyethylene.
- the melting point of the second adhesive layer 3 can be lowered, and the heating temperature when fusing the second adhesive layer 3 can be lowered. Therefore, deterioration of the first adhesive layer 2 can be suppressed.
- the second adhesive layer 3 may not contain a hydrogen-bonding resin (described later). In this case, in the second adhesive layer 3, it is possible to increase the ratio of materials having excellent adhesive strength. Thereby, the adhesive strength between the second adhesive layer 3 and the container is improved.
- the melting point of the resin (or resin composition) forming the second adhesive layer 3 is preferably 110°C or higher and 150°C or lower.
- the melting point of the resin constituting the second adhesive layer 3 is 110° C. or higher, the second adhesive layer 3 is less likely to become excessively thin during thermocompression bonding, and it is easy to ensure adhesive strength. If the melting point of the resin forming the second adhesive layer 3 is 150° C. or lower, the resin will easily flow during the thermocompression bonding, so that the container and the electrode lead wire 11 can be easily sealed.
- the "melting point of the resin constituting the second adhesive layer 3" is the melting point of the polymer alloy constituting the second adhesive layer 3. means melting point.
- optional components other than the acid-modified polyolefin include known additives such as stabilizers, antistatic agents, and colorants.
- the thickness (thickness ratio) of the second adhesive layer 3 can be, for example, 5 or more and 90 or less, with the total thickness of the sealing film 1 being 100. That is, the thickness of the second adhesive layer 3 can be 5% or more and 90% or less of the total thickness of the sealing film 1 .
- the thickness ratio of the second adhesive layer 3 is preferably 5 or more and 50 or less.
- the thickness ratio of the second adhesive layer 3 is 5 or more, sufficient adhesive strength can be secured between the second adhesive layer 3 and the container.
- the thickness ratio of the second adhesive layer 3 is 90 or less (preferably 50 or less), sufficient thickness can be imparted to the first adhesive layer 2 and the base material layer 4 . Therefore, it is possible to increase the adhesive strength between the first adhesive layer 2 and the electrode lead wire 11 without lowering the electrolytic solution resistance of the sealing film 1 .
- the base material layer 4 is interposed between the first adhesive layer 2 and the second adhesive layer 3 .
- the base material layer 4 is a thermoplastic resin layer containing a thermoplastic resin.
- the base material layer 4 is an example of the "third thermoplastic resin layer”.
- the base material layer 4 mainly contains polyolefin, for example.
- the fact that the base material layer 4 “mainly contains polyolefin” means that the content of polyolefin is the highest among the resins constituting the base material layer 4 .
- the base material layer 4 contains 50% by mass or more of polyolefin with respect to the total amount of the base material layer 4, preferably more than 50% by mass, and more preferably 80% by mass or more.
- Polyolefins that constitute the base material layer 4 include polypropylene (PP), polyethylene, poly-1-butene, and polyisobutylene. Among them, PP is preferable because of its excellent flexibility.
- the polyolefin constituting the base material layer 4 may be a homopolymer of one olefin or a copolymer of two or more olefins. Homopolymers include homopolymers of propylene only (homo PP). Copolymers include copolymers of propylene and olefinic monomers (ethylene, 1-butene, isobutylene, 1-hexene, etc.), such as propylene-ethylene copolymers. As the polyolefin constituting the base material layer 4, each polymer exemplified as the polyolefin constituting the first adhesive layer 2 can be exemplified.
- ICP impact copolymer
- ICP has a phase-separated structure having a first phase and a second phase, for example, a sea-island structure.
- the sea-island structure is a structure in which a plurality of second phases corresponding to "islands" are dispersed in a first phase corresponding to "sea”.
- the first phase is composed of, for example, homopolymers of olefinic monomers such as propylene and ethylene.
- the second phase is composed of a polymer different from the homopolymer that constitutes the first phase.
- the second phase comprises, for example, a polymer of olefinic monomers such as propylene, ethylene, such as ethylene propylene rubber (EPR).
- the second phase is composed of, for example, a main phase and a surface layer covering the surface of the main phase.
- the main phase is composed of polyethylene, for example.
- the surface layer is made of EPR, for example.
- An ICP in which the homopolymer constituting the first phase is homoPP is called a polypropylene ICP or a polypropylene dispersion.
- An ICP in which the homopolymer constituting the first phase is homoPP is a so-called block PP.
- ICPs are also called heterophasic copolymers or block copolymers.
- the base material layer 4 contains a hydrogen-bonding resin.
- the base material layer 4 may contain, for example, a mixture of hydrogen-bonding resin and polyolefin.
- the hydrogen-bonding resin is preferably a thermoplastic resin.
- a hydrogen-bonding resin is a resin that contains a hydrogen-bondable structure in its molecule.
- a hydrogen bond is, for example, a non-covalent bond in which a hydrogen atom covalently bonded to an atom with high electronegativity (negative atom) forms a nearby lone pair of electrons such as nitrogen, oxygen, sulfur, and fluorine. It is an attractive interaction. Since the electronegativity of the negative atoms is greater than that of the hydrogen atoms, a partial positive charge is produced on the hydrogen atoms and a partial negative charge is produced on the negative atoms.
- the electronegativity of negative atoms (Pauling's electronegativity) is preferably 3.0 or more.
- the electronegativity (Pauling's electronegativity) of the atom to which the hydrogen atom bonded to the negative atom forms a hydrogen bond is preferably 3.0 or more.
- the structure capable of hydrogen bonding may be an atom group such as an amide bond, a urethane bond, or a diketone, or a functional group such as an amino group, a carbonyl group, a hydroxyl group, a thiol group, a carboxy group, a sulfonic acid group, or a phosphoric acid group.
- an amide bond atom group and a urethane bond atom group are preferable.
- the amide bond atom group (CO—NH) includes carbon and oxygen constituting “CO” and nitrogen and hydrogen constituting “NH” as constituents.
- Hydrogen fluoride is formed by a covalent bond between fluorine, which is an electronegative atom, and hydrogen.
- amide bond atomic group CO-NH
- hydrogen Pauling electronegativity 2.1
- nitrogen Pauling electronegativity 3.0
- a hydrogen bond may be formed between the hydrogen atom of the amide bond atom group (CO—NH) and the fluorine lone electron pair of hydrogen fluoride. That is, as shown in formula (2), a hydrogen bond indicated by " may be formed between H and F indicated by "NH...FH".
- hydrogen atoms contained in hydrogen-bondable structures may be covalently bonded to atoms with high electronegativity (for example, atoms with Pauling electronegativity of 3.0 or higher).
- Hydrogen-bonding resins having amide bond atoms include polyamide-based resins.
- a polyamide-based resin has an amide bond atomic group (CO—NH) as a repeating unit in its molecule.
- Polyamide resins include aliphatic polyamide resins such as nylon resins. Examples of nylon resins include nylon 6, nylon 11, nylon 12, nylon 610, and nylon 612 represented by the following formula (3), and nylon 66, nylon 6/66, and nylon 66/12 represented by the following formula (4). , and blends of at least two of these, and the like.
- An aromatic polyamide resin can also be used as the polyamide-based resin.
- Aromatic polyamide resins include poly-p-phenylene terephthalamide, poly-p-phenylene isophthalamide, poly-m-phenylene isophthalamide, and nylon MXD6 represented by the following formula (5). Blends of at least two of these may be used.
- the urethane bond atom group (NH-COO) contains nitrogen and hydrogen that constitute "NH” and carbon and oxygen that constitute “COO” as constituent elements.
- urethane bond atom group (NH-COO)
- hydrogen (Pauling electronegativity 2.1) is covalently bonded to nitrogen (Pauling electronegativity 3.0). Therefore, a hydrogen bond may be formed between the hydrogen atom of the urethane bond atom group (NH—COO) and the lone electron pair of fluorine in hydrogen fluoride. That is, a hydrogen bond indicated by "" may be formed between H and F indicated by "NH...FH".
- Polyurethane-based resins are examples of hydrogen-bonding resins having urethane-bonded atomic groups.
- a polyurethane resin has a urethane bond atom group (NH—COO) as a repeating unit in its molecule.
- Examples of polyurethane-based resins include polyether-based polyurethane resins, polyester-based polyurethane resins, and polycarbonate-based polyurethane resins.
- the polyurethane-based resin may be a urethane-based elastomer.
- a urethane-based elastomer has, for example, a hard segment and a soft segment.
- the hard segment is composed of polyurethane.
- the soft segment is composed of polycarbonate-based polyols, ether-based polyols, caprolactone-based polyesters, adipate-based polyesters, and the like.
- the addition amount (content rate) of the hydrogen bonding resin in the entire sealing film 1 is preferably 0.2% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and 1.0% by mass or more. % by mass or more and 10 mass % or less is more preferable.
- the amount of the hydrogen-bonding resin added to the entire sealing film 1 is 0.2% by mass or more, the effect of reducing the influence of hydrogen fluoride on the electrode lead wires 11 can be enhanced. If the amount of hydrogen-bonding resin added to the entire encapsulating film 1 is 30% by mass or less, functional deterioration of the layer containing the hydrogen-bonding resin (base material layer 4 in this embodiment) can be suppressed. For example, deterioration of heat resistance, mechanical strength, etc. of the base material layer 4 can be suppressed.
- the layer containing the hydrogen-bonding resin is at least one of the first adhesive layer 2 and the second adhesive layer 3, the amount of the hydrogen-bonding resin added to the entire sealing film 1 is 30% by mass or less. Then, deterioration of adhesiveness, mechanical strength, etc. of the adhesive layer can be suppressed.
- the addition amount of the hydrogen bonding resin in the base material layer 4 is, for example, 0.5% by mass or more and 60% by mass or less (preferably 1.0% by mass or more and 40% by mass or less, more preferably 2.0% by mass or more and 20% by mass or more. mass% or less).
- the layer containing the hydrogen-bonding resin may contain not only the hydrogen-bonding resin and polyolefin, but also other resin materials.
- the layer containing the hydrogen-bonding resin (the substrate layer 4 in this embodiment) may be composed only of the hydrogen-bonding resin.
- the thickness (thickness ratio) of the base material layer 4 is preferably 5 or more and 70 or less, with the total thickness of the sealing film 1 being 100. That is, the thickness of the base material layer 4 is preferably 5% or more and 70% or less of the total thickness of the sealing film 1 .
- the thickness ratio of the base material layer 4 is 5 or more, the resin does not flow excessively, and the necessary fluidity is easily exhibited during pressure bonding.
- the thickness ratio of the base material layer 4 is 5 or more (preferably 25 or more), there is an advantage that the electrolytic solution resistance and heat resistance of the sealing film 1 can be improved.
- the thickness ratio of the base material layer 4 is 70 or less, the fluidity of the resin during thermocompression bonding can be suppressed within an appropriate range.
- the thickness ratio of the base material layer 4 is 70 or less, the first adhesive layer 2 and the second adhesive layer 3 can be given a sufficient thickness, so the adhesive strength between the first adhesive layer 2 and the electrode lead wire 11 can be increased. , and the adhesive strength between the second adhesive layer 3 and the container can be increased.
- the melting point of the resin (or resin composition) forming the base material layer 4 is preferably 150°C or higher and 170°C or lower.
- the melting point of the resin constituting the base material layer 4 is 150° C. or higher, it is easy to ensure the electrolytic solution resistance of the sealing film 1 . Moreover, heat resistance can be imparted to the sealing film 1 .
- the sealing film 1 can be given flexibility. Therefore, gaps are less likely to occur between the electrode lead wires 11 and the container, and the sealing film 1 .
- the melting point M4 of the resin forming the base material layer 4 is higher than the melting point M2 of the resin forming the first adhesive layer 2 or the melting point M3 of the resin forming the second adhesive layer 3. That is, melting point M4 is higher than melting point M2 or melting point M3.
- the melting point M4 is preferably higher than both the melting point M2 and the melting point M3. In other words, the melting point M4 is preferably higher than at least one of the melting points M2 and M3.
- the melting point M4 When the melting point M4 is higher than the melting point M2, the fluidity of the resin does not become too low, and the fluidity of the resin during thermocompression bonding can be kept within an appropriate range. In addition, it becomes easier to ensure the electrolytic solution resistance of the sealing film 1 without lowering the adhesive strength between the first adhesive layer 2 and the electrode lead wire 11 .
- the melting point M4 is higher than the melting point M3, the fluidity of the resin does not become too low, and the fluidity of the resin during thermocompression bonding can be kept within an appropriate range. Moreover, it becomes easy to ensure the electrolyte solution resistance of the sealing film 1, without reducing the adhesive strength of the 2nd contact bonding layer 3 and a container.
- the melting point M4 When the melting point M4 is higher than the melting point M2 or the melting point M3, there is an advantage that the sealing film 1 can be easily imparted with heat resistance.
- the hydrogen-bonding resin of the substrate layer 4 has low compatibility with other resins that constitute the substrate layer 4, uneven mixing (uneven mixing) and poor appearance due to undissolved residue may occur. .
- all of the materials other than the hydrogen-bonding resin may be acid-modified polyolefin. 10 mass % or more is preferable.
- adding a hydrogen-bonding resin to the first adhesive layer 2 it is desirable to add acid-modified polyolefin to the first adhesive layer 2 .
- it is desirable to add acid-modified polyolefin to the second adhesive layer 3 it is desirable to add acid-modified polyolefin to the second adhesive layer 3 .
- the electrode lead wire member 10 has electrode lead wires 11 and a pair of sealing films 1 .
- the electrode lead wire 11 in this example has a strip shape with a constant thickness having both flat sides and extends linearly.
- the sealing films 1 of this example have rectangular shapes with the same dimensions, and are arranged so that the central portions thereof are orthogonal to the electrode lead wires 11 .
- the electrode lead wire member of the present invention is not limited to this shape, and can be appropriately modified as necessary.
- a pair of sealing films 1 are arranged with the first adhesive layers 2 facing each other.
- a pair of sealing films 1 sandwich an electrode lead wire 11 .
- the pair of sealing films 1 are in contact with regions corresponding to one surface and the other surface of the electrode lead wire 11, respectively. Therefore, the pair of sealing films 1 are in contact with the entire circumference of the electrode lead wire 11 as a whole.
- the electrode lead wire 11 has a lead wire body 111 and a surface treatment layer 112 .
- the electrode lead wire 11 extends linearly in one direction.
- the electrode lead wire 11 is made of metal.
- the electrode lead wire 11 has conductivity.
- the electrode lead wire 11 is electrically connected to a lithium ion battery 30 (see FIG. 3).
- the electrode lead wire 11 conducts electricity between the lithium ion battery 30 and an external device.
- Known metals such as aluminum, copper, nickel, iron, gold, platinum, and various alloys can be used as the material of the lead wire main body 111 .
- aluminum and copper are preferable because they have excellent conductivity and are advantageous in terms of cost.
- the surface of the lead wire body 111 may be nickel-plated.
- the nickel plating of the lead wire body 111 may be formed by electroplating using a Watts bath containing nickel sulfate, nickel chloride, boric acid, or the like as a main component.
- Nickel plating of the lead wire body 111 is preferably performed using a nickel sulfamate plating bath containing nickel sulfamate and boric acid as main components.
- the plating film formed by this method has excellent flexibility and is less likely to crack.
- the lead wire body 111 is preferably an aluminum plate or a nickel-plated copper plate.
- the surface treatment layer 112 is formed on the surface of the lead wire main body 111 .
- the surface treatment layer 112 has corrosion resistance. "Corrosion resistance” refers to the property of being resistant to corrosion by the electrolyte inside the battery.
- an acid-resistant coating made of phosphate, chromate, fluoride, triazinethiol compound, or the like can be used.
- the acid-resistant coating can be formed by subjecting the lead wire body 111 to a chemical conversion treatment.
- the electrode lead wire may not have the surface treatment layer formed thereon.
- the sealing film 1 contains a hydrogen-bonding resin. Therefore, when hydrogen fluoride is contained in the electrolytic solution, at least part of this hydrogen fluoride is captured by the sealing film 1 through hydrogen bonding with the hydrogen-bonding resin. Therefore, the influence of hydrogen fluoride on the electrode lead wire 11 can be reduced, and deterioration of the electrode lead wire 11 can be suppressed. Therefore, a decrease in adhesive strength of the sealing film 1 to the electrode lead wire 11 can be suppressed.
- the sealing film 1 includes a first adhesive layer 2, a base material layer 4, and a second adhesive layer 3, which are laminated in order. Therefore, different properties can be imparted to each layer by selecting the constituent materials. Therefore, the base material layer 4 can enhance the resistance to the electrolytic solution and the heat resistance, and the adhesive layers 2 and 3 can enhance the adhesion to the electrode lead wire 11 and the container.
- the hydrogen-bonding resin is contained only in the base material layer 4, it is possible to increase the ratio of materials excellent in adhesive strength in the adhesive layers 2 and 3. can enhance sexuality.
- the electrode lead wire member 10 is provided with the sealing film 1, it is possible to suppress a decrease in the adhesive strength between the sealing film 1 and the electrode lead wire 11.
- FIG. 3 is a schematic perspective view showing the battery 100 of the embodiment.
- the battery 100 has the above-described electrode lead wire member 10, container 20, and lithium ion battery 30 (battery main body).
- a battery main body 30 of this example has a flat rectangular parallelepiped shape, and a pair of electrode lead wire members 10 are connected to one end in the longitudinal direction so as to be parallel to each other.
- the storage container 20 of this example has a flat rectangular parallelepiped shape corresponding to the battery main body 30 .
- the battery of the present invention is not limited to this shape, and can be appropriately modified as necessary.
- the container 20 has a container body 21 and a lid 22 .
- the container main body 21 is obtained by drawing a laminate for battery exterior.
- the container main body 21 has a molded portion 21a that forms a concave portion that accommodates the lithium ion battery 30 .
- the battery exterior laminate will be described later.
- the lid 22 is composed of a laminate for battery exterior, and has a plane view area equivalent to that of the container body 21 .
- the storage container 20 is formed by stacking a container body 21 and a lid 22 and heat-sealing a peripheral edge portion 25 .
- FIG. 4 is a cross-sectional view taken along line II in FIG.
- the battery exterior laminate which is the constituent material of the container body 21 and the lid 22, includes a first film substrate 201, a second film substrate 202, a metal foil 203, and a sealant layer 204 in this order. It is a laminate laminated with
- the resin that constitutes the first film substrate 201 and the second film substrate 202 polyamide, polyethylene terephthalate (PET), phenolic resin, polypropylene, and the like are suitable.
- PET polyethylene terephthalate
- metal foil 203 aluminum foil, stainless steel foil, copper foil, iron foil, or the like can be used.
- the sealant layer 204 is heat-sealed in contact with the second adhesive layer 3 of the sealing film 1 .
- a resin that can be fused with the sealing film 1 is selected as the resin that forms the sealant layer 204 .
- the resin forming the sealant layer 204 include polypropylene-based resins and polyethylene-based resins.
- the polypropylene-based resin a homopolymer of polypropylene, a copolymer of propylene and ethylene, or the like can be used.
- Low-density polyethylene, linear low-density polyethylene, or the like can be used as the polyethylene-based resin.
- the electrode lead wire member 10 is pulled out of the container 20 from the lithium ion battery 30 inside the container 20 (inside the molded portion 21a).
- the electrode lead wire 11 is fused to the sealant layer 204 of the container 20 via the sealing film 1 .
- the electrode lead wire member 10 since the electrode lead wire member 10 has the above-described sealing film 1, the deterioration of the electrode lead wire 11 due to hydrogen fluoride is suppressed, and the adhesion strength between the sealing film 1 and the electrode lead wire 11 is reduced. can be suppressed. Therefore, a highly reliable battery 100 can be realized.
- the sealing film 1 shown in FIG. 1 includes a first adhesive layer 2 (first thermoplastic resin layer), a second adhesive layer 3 (second thermoplastic resin layer), and a substrate layer 4 (third Of the plastic resin layers), only the substrate layer 4 contains a hydrogen-bonding resin, but the sealing film is not limited to the structure shown in FIG.
- the hydrogen-bonding resin should be contained in at least one of the first to third thermoplastic resin layers.
- the hydrogen-bonding resin may be contained in any thermoplastic resin layer.
- only the first adhesive layer 2 may contain the hydrogen bonding resin, or only the second adhesive layer 3 may contain the hydrogen bonding resin. It may contain a flexible resin.
- the hydrogen-bonding resin may be contained in only two of the first adhesive layer 2, the second adhesive layer 3, and the base material layer 4.
- the first adhesive layer 2 and the second adhesive layer 3 may contain a hydrogen-bonding resin
- the first adhesive layer 2 and the substrate layer 4 may contain a hydrogen-bonding resin
- the second adhesive layer 3 and the substrate layer 4 may contain a hydrogen-bonding resin.
- the hydrogen-bonding resin may be contained in all of the first adhesive layer 2, the second adhesive layer 3, and the base material layer 4.
- the amount of the hydrogen-bonding resin added the amount exemplified in the sealing film 1 shown in FIG. 1 can be adopted.
- At least one of the first to third thermoplastic resin layers of the sealing film contains a hydrogen-bonding resin. At least part of the hydrogen is trapped in the sealing film by hydrogen bonding with the hydrogen-bonding resin. Therefore, a decrease in adhesive strength of the sealing film to the electrode lead wire can be suppressed.
- thermoplastic resin layer contains a hydrogen-bonding resin includes the case where the thermoplastic resin layer is composed only of a hydrogen-bonding resin.
- Hydrogen-bonding resins are not limited to homopolymers of monomers containing structures capable of hydrogen bonding, and may be copolymers of monomers containing structures capable of hydrogen bonding and monomers not containing structures capable of hydrogen bonding. good.
- the sealing film 1 shown in FIG. 1 includes a first adhesive layer 2, a second adhesive layer 3, and a base material layer 4, but the sealing film of the embodiment is not limited to this structure.
- FIG. 5 is a schematic cross-sectional view showing a sealing film of another embodiment.
- the sealing film 401 shown in FIG. 5 has a two-layer structure including a first adhesive layer 102 (first thermoplastic resin layer) and a second adhesive layer 103 (second thermoplastic resin layer). there is The same reference numerals are given to the same components as those of the sealing film 1 shown in FIG. 1, and the description thereof is omitted.
- the constituent material of the first adhesive layer 102 may be the material exemplified as the constituent material of the first adhesive layer 2 in the sealing film 1 shown in FIG.
- the constituent material of the second adhesive layer 103 may be the material exemplified as the constituent material of the second adhesive layer 3 in the sealing film 1 shown in FIG.
- a hydrogen-bonding resin is added to one or both of the first adhesive layer 102 and the second adhesive layer 103 .
- the amount of the hydrogen-bonding resin added the amount exemplified for the sealing film 1 shown in FIG. 1 can be adopted.
- the sealing film 401 contains a hydrogen-bonding resin, it is possible to suppress a decrease in adhesive strength to the electrode lead wire 11 .
- FIG. 6 is a schematic cross-sectional view showing a sealing film of still another embodiment.
- a sealing film 501 shown in FIG. 6 has a single-layer structure. The same reference numerals are given to the same components as those of the sealing film 1 shown in FIG. 1, and the description thereof is omitted.
- the sealing film 501 is composed of one thermoplastic resin layer.
- the constituent material of the sealing film 501 may be the material exemplified as the constituent material of the first adhesive layer 2 or the second adhesive layer 3 in the sealing film 1 shown in FIG.
- a hydrogen-bonding resin is added to the sealing film 501 . As for the amount of the hydrogen-bonding resin added, the amount exemplified for the sealing film 1 shown in FIG. 1 can be adopted.
- the sealing film 501 contains a hydrogen-bonding resin, it is possible to suppress a decrease in adhesive strength to the electrode lead wire 11 .
- the first adhesive layer and the second adhesive layer may contain a resin other than polyolefin.
- the sealing film may contain layers other than the first adhesive layer, the base material layer and the second adhesive layer.
- a sealing film formed of only the substrate layer was produced as follows.
- a sealing film was obtained by heating and melting a resin that is a raw material of the base material layer to form a film.
- This sealing film was formed in a belt shape (width 15 mm, thickness 100 ⁇ m).
- the sealing film (base material layer) is composed of a mixture of maleic anhydride-modified polypropylene (melting point 140°C) and nylon 6 (melting point 225°C).
- Maleic anhydride-modified polypropylene is a polymer obtained by graft polymerizing maleic anhydride to a random copolymer of propylene and ethylene.
- Nylon 6 is a hydrogen bonding resin because it contains amide bonding atoms. The amount of nylon 6 added to the entire sealing film is 0.2% by mass.
- a sealing film in which a first adhesive layer, a substrate layer, and a second adhesive layer were laminated in this order was produced as follows.
- a laminate was obtained by separately heating and melting the resins used as raw materials for each layer and performing simultaneous multilayer film formation using an extruder capable of simultaneous multilayer extrusion molding. This laminate was formed into a belt shape (width 15 mm, thickness 100 ⁇ m).
- first adhesive layer maleic anhydride-modified polypropylene (melting point 140°C)
- Base layer mixture of polypropylene ICP (melting point 161°C) and nylon 6 (melting point 225°C)
- Second adhesive layer random copolymer of propylene and ethylene (melting point 140°C)
- the maleic anhydride-modified polypropylene is the same as the maleic anhydride-modified polypropylene used in Example 1.
- Polypropylene ICP has a structure (sea-island structure) in which the second phase is dispersed in the first phase.
- the first phase consists of homo PP.
- the second phase contains ethylene propylene rubber and polyethylene.
- the thickness of the first adhesive layer is 10 ⁇ m.
- the thickness of the base layer is 50 ⁇ m.
- the thickness of the second adhesive layer is 40 ⁇ m.
- the amount of nylon 6 added to the entire sealing film was 0.2% by mass.
- the amount of nylon 6 added to the base material layer is 0.4% by mass.
- the amount of nylon 6 added to the entire sealing film was 1% by mass.
- the amount of nylon 6 added to the base material layer was 2% by mass.
- Example 5 the amount of nylon 6 added to the entire sealing film was 5% by mass.
- the amount of nylon 6 added to the base material layer was 10% by mass.
- the amount of nylon 6 added to the entire sealing film was 10% by mass.
- the amount of nylon 6 added to the base material layer was 20% by mass.
- Example 7 the amount of nylon 6 added to the entire sealing film was 20% by mass. The amount of nylon 6 added to the base material layer was 40% by mass. In Example 8, the amount of nylon 6 added to the entire sealing film was 30% by mass. The amount of nylon 6 added to the base material layer was 60% by mass.
- Example 3 A sealing film in which a first adhesive layer, a substrate layer, and a second adhesive layer were laminated in this order was produced as follows.
- the constituent materials of the first adhesive layer, the base material layer, and the second adhesive layer are as follows.
- First adhesive layer mixture of maleic anhydride-modified polypropylene (melting point 140 ° C.) and nylon 6
- Base layer mixture of polypropylene ICP (melting point 161 ° C.) and nylon 6
- Second adhesive layer random co-polymer of propylene and ethylene Mixture of Polymer (Melting Point 140° C.) and Nylon 6
- the amount of nylon 6 added to the entire sealing film was 1% by mass.
- the amount of nylon 6 added to each of the first adhesive layer, base layer, and second adhesive layer was 1% by mass. Other conditions are the same as in Example 2.
- the amount of nylon 6 added to the entire sealing film was 30% by mass.
- the amount of nylon 6 added to each of the first adhesive layer, the substrate layer, and the second adhesive layer was 30% by mass. Other conditions are the same as in Example 2.
- Example 10 A sealing film in which the first adhesive layer and the second adhesive layer are laminated was produced as follows.
- the constituent materials of the first adhesive layer and the second adhesive layer are as follows.
- First adhesive layer mixture of maleic anhydride-modified polypropylene (melting point 140°C) and nylon 6
- Second adhesive layer mixture of random copolymer of propylene and ethylene (melting point 140°C) and nylon 6
- First adhesive layer is 20 ⁇ m thick.
- the thickness of the second adhesive layer is 80 ⁇ m.
- the amount of nylon 6 added to the entire sealing film is 30% by mass.
- the amount of nylon 6 added to the first adhesive layer and the second adhesive layer was 30% by mass, respectively.
- Other conditions are the same as in Example 3.
- Examples 11 to 15 As in Examples 2 and 4 to 8, a sealing film in which a first adhesive layer, a base layer, and a second adhesive layer were laminated in this order was produced as follows.
- a laminate was obtained by separately heating and melting the resins used as raw materials for each layer and performing simultaneous multilayer film formation using an extruder capable of simultaneous multilayer extrusion molding. This laminate was formed into a belt shape (width 15 mm, thickness 100 ⁇ m).
- first adhesive layer maleic anhydride-modified polypropylene (melting point 140°C)
- Base layer mixture of polypropylene ICP (melting point 161°C) and nylon MXD6 (melting point 240°C)
- Second adhesive layer random copolymer of propylene and ethylene (melting point 140°C)
- the maleic anhydride-modified polypropylene is the same as the maleic anhydride-modified polypropylene used in Example 1.
- Polypropylene ICP has a structure (sea-island structure) in which the second phase is dispersed in the first phase.
- the first phase consists of homo PP.
- the second phase contains ethylene propylene rubber and polyethylene.
- Nylon MXD6 is a hydrogen bonding resin because it contains amide bonding atoms.
- the thickness of the first adhesive layer is 25 ⁇ m.
- the thickness of the base layer is 50 ⁇ m.
- the thickness of the second adhesive layer is 25 ⁇ m.
- the amount of nylon MXD6 added to the entire sealing film is 0.5% by mass.
- the amount of nylon MXD6 added to the base material layer was 1.0% by mass.
- the amount of nylon MXD6 added to the entire sealing film is 0.8% by mass.
- the amount of nylon MXD6 added to the base material layer was 1.5% by mass.
- Example 13 the amount of nylon MXD6 added to the entire sealing film is 1.0% by weight.
- the amount of nylon MXD6 added to the base material layer was 2.0% by mass.
- the amount of nylon MXD6 added to the entire sealing film is 1.3% by weight.
- the amount of nylon MXD6 added to the base material layer was 2.5% by mass.
- the amount of nylon MXD6 added to the entire sealing film is 2.0% by weight.
- Example 1 A sealing film was produced in the same manner as in Example 2, except that nylon 6 was not added to the base layer. The amount of nylon 6 added to the entire sealing film is 0% by mass.
- a sealing film was produced in the same manner as in Example 2, except that the amount of nylon 6 added to the substrate layer was 80% by mass. The amount of nylon 6 added to the entire sealing film is 40% by mass.
- Electrode lead wire having a lead wire body and a surface treatment layer formed on the surface of the lead wire body was produced.
- ⁇ Test 1 Measurement of adhesive strength to electrode lead wire (non-immersion)>
- the adhesive strength of the sealing films to the electrode lead wires was measured as follows. This test is a test under "non-immersion" conditions because the sample for measurement is not immersed in the electrolytic solution (described later). A sealing film and an electrode lead wire were overlapped and adhered by heat sealing to obtain a sample for measurement. The heat sealing conditions were 180° C., 0.5 MPa, and 10 seconds. The 180-degree peel strength (adhesive strength) of this measurement sample was measured using a tester (a desktop precision universal tester manufactured by Shimadzu Corporation: Autograph AGS-500NX) as follows.
- Table 1 shows the measurement results of the sealing films of Examples 1 to 10, Comparative Example 1, and Reference Examples 1 to 3.
- Table 2 shows the measurement results for the sealing films of Examples 11 to 15.
- ⁇ Test 2 Measurement of adhesive strength to electrode lead wire (after immersion)>
- the adhesive strength of the sealing films to the electrode lead wires was measured as follows. This test is a test under the condition of "after immersion” because the measurement is performed after the sample for measurement is immersed in the electrolytic solution.
- a sample for measurement prepared in the same manner as in Test 1 was placed in this packaging bag and immersed in the electrolytic solution. After storing the packaging bag containing the sample for measurement in an oven at 85° C. for 7 days, the 180° peel strength (adhesive strength) was measured in the same manner as in Test 1.
- Table 1 shows the measurement results of the sealing films of Examples 1 to 10, Comparative Example 1, and Reference Examples 1 to 3.
- Table 2 shows the measurement results for the sealing films of Examples 11 to 15.
- the mechanical strength of the sealing films of Examples 1 to 15, Comparative Example 1, and Reference Examples 1 to 3 was measured as follows. Using each sealing film, a type 5 dumbbell-shaped test piece specified in JIS K7127 was produced. This test piece was subjected to a tensile test according to JIS K7127 using a desktop precision universal testing machine Autograph AGS-X manufactured by Shimadzu Corporation. The chuck-to-chuck distance was 80 mm. The test speed (tensile speed) was 500 mm/min. The test environment was a temperature of 23° C. and a humidity of 50% RH. When the tensile strength (breaking strength) at the time of cutting was 25 MPa or more, it was judged as "good”. When the breaking strength was less than 25 MPa, it was determined as "low”. Table 1 shows the measurement results of the sealing films of Examples 1 to 10, Comparative Example 1, and Reference Examples 1 to 3. Table 2 shows the measurement results for the sealing films of Examples 11 to 15.
- Tables 1 and 2 show the product of the added amount [mass%] of the hydrogen-bonding resin (nylon 6 or nylon MXD6) in each layer and the thickness [ ⁇ m] of the layer (added amount of hydrogen-bonding resin ⁇ Thickness) [mass % ⁇ m] and hydrogen-bonding resin added amount [mass %] of the entire sealing film are also shown.
- the sealing film, the electrode lead wire member and the battery of the present invention it is possible to suppress the reduction in adhesive strength due to hydrogen fluoride, so the present invention can be applied industrially.
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Abstract
Description
本願は、2021年9月24日に、日本に出願された特願2021-155742号に基づき優先権を主張し、その内容をここに援用する。
封止用のフィルムは、電極リード線と収容容器とを接着することにより、外部から収容容器内部へ水が浸入するのを抑制する。
[4] 前記水素結合性樹脂は、前記第1の熱可塑性樹脂層に含まれる、[2]または[3]に記載の封止フィルム。
[5] 前記水素結合性樹脂は、前記第3の熱可塑性樹脂層に含まれる、[2]~[4]のうちいずれか1つに記載の封止フィルム。
[6] 前記第1の熱可塑性樹脂層は、前記酸変性ポリオレフィンを50質量%以上含む、[3]記載の封止フィルム。
[7] 前記第3の熱可塑性樹脂層は、酸変性ポリオレフィンを10質量%以上含む、[2]~[6]のうちいずれか1つに記載の封止フィルム。
[8] 前記封止フィルム全体における前記水素結合性樹脂の添加量は、0.2質量%以上30質量%以下である、[1]~[7]のうちいずれか1つに記載の封止フィルム。
[9] 前記水素結合性樹脂は、ポリアミド系樹脂である、[1]~[8]のうちいずれか1つに記載の封止フィルム。
[11] [10]に記載の電極リード線部材を備える電池。前記電池は、電池本体と、前記電池本体を収容する収容容器と、前記電極リード線部材とを備え、前記封止フィルムの一部が前記電極リード線に接着されるとともに、前記封止フィルムの他の部分が前記収容容器に接着されていてもよい。
図1は、実施形態の封止フィルム1を示す断面拡大図である。図2は、実施形態の電極リード線部材10を示す斜視図である。
図1に示すように、封止フィルム1は、第1接着層2と、第2接着層3と、基材層4とを備える。
第1接着層2は、加熱・加圧によって電極リード線11(図2参照)に融着(接着)する層である。第1接着層2の表面は、封止フィルム1の一方の表面1aである。第1接着層2は、熱可塑性樹脂を含む熱可塑性樹脂層である。第1接着層2は「第1の熱可塑性樹脂層」の一例である。
不飽和カルボン酸の誘導体としては、アクリル酸エチルなどの不飽和カルボン酸エステル、無水マレイン酸などの不飽和カルボン酸の酸無水物が挙げられる。
酸変性ポリオレフィンの使用により、電極リード線11(図2参照)に対する第1接着層2の接着性を高めることができる。
ポリオレフィンおよび酸変性ポリオレフィンは、熱可塑性樹脂である。
第1接着層2を構成する樹脂の融点が110℃以上であると、熱圧着時に第1接着層2が過度に薄くなりにくく、接着強度を確保しやすい。第1接着層2を構成する樹脂の融点が150℃以下であると、熱圧着時に樹脂が流動しやすくなるため、電極リード線11の周囲に樹脂が十分に回り込み、電極リード線11の全周を封止しやすい。
第2接着層3は、例えば、加熱・加圧によって収容容器と融着(接着)する層である。収容容器については後述する。第2接着層3の表面は、封止フィルム1の他方の表面1bである。第2接着層3は、熱可塑性樹脂を含む熱可塑性樹脂層である。第2接着層3は「第2の熱可塑性樹脂層」の一例である。
ポリオレフィンは、プロピレンとエチレンとの共重合体(プロピレン-エチレン共重合体)でもよい。プロピレンとエチレンとの共重合体は、ブロック共重合体でもよくランダム共重合体でもよいが、ランダム共重合体が好ましい。ポリオレフィンは、プロピレンとオレフィン系モノマーとの共重合体(例えば、ランダム共重合体)であってもよい。オレフィン系モノマーとしては、1-ブテン、イソブチレン、1-ヘキセン等が挙げられる。
基材層4は、第1接着層2と第2接着層3との間に介在して設けられている。基材層4は、熱可塑性樹脂を含む熱可塑性樹脂層である。基材層4は「第3の熱可塑性樹脂層」の一例である。
基材層4を構成するポリオレフィンとしては、第1接着層2を構成するポリオレフィンとして例示した各重合体を例示することができる。
フッ化水素は、陰性原子であるフッ素と、水素とが共有結合して形成されている。フッ素の電気陰性度(ポーリングの電気陰性度)は4.0であり、水素の電気陰性度(ポーリングの電気陰性度)は2.1である。そのため、アミド結合原子群の酸素(ポーリングの電気陰性度3.5)の孤立電子対と、フッ化水素の水素原子との間には、水素結合が形成される可能性がある。すなわち、式(1)に示すように、「C=O・・・H-F」に示すOとHとの間に「・・・」で示す水素結合が形成される可能性がある。
ポリアミド系樹脂としては、芳香族ポリアミド樹脂も使用できる。芳香族ポリアミド樹脂としては、ポリ-p-フェニレンテレフタルアミド、ポリ-p-フェニレンイソフタルアミド、ポリ-m-フェニレンイソフタルアミド、下記の式(5)に示すナイロンMXD6などがある。これらのうち少なくとも2つのブレンド物を使用してもよい。
図2に示すように、電極リード線部材10は、電極リード線11と、一対の封止フィルム1とを有する。この例の電極リード線11は平坦な両面を有する一定厚さの帯状をなし、直線的に延びている。この例の封止フィルム1は互いに同寸法の矩形状をなし、電極リード線11に対して中央部を直交させて配置されている。ただし、本発明の電極リード線部材はこの形状に限定はされず、必要に応じて適宜変形が可能である。
一対の封止フィルム1は、第1接着層2が向かい合って配置される。一対の封止フィルム1は、電極リード線11を挟持する。一対の封止フィルム1は、それぞれ電極リード線11の一方の面および他方の面に相当する領域に接する。そのため、一対の封止フィルム1は、全体として電極リード線11の全周に接している。
図3は、実施形態の電池100を示す概略斜視図である。図3に示すように、電池100は、上述した電極リード線部材10と、収容容器20と、リチウムイオン電池30(電池本体)とを有する。この例の電池本体30は偏平な直方体状をなし、その長手方向の一端に互いに平行になるように一対の電極リード線部材10が接続されている。この例の収容容器20は電池本体30に対応して偏平な直方体状をなしている。ただし、本発明の電池はこの形状に限定されることはなく、必要に応じて適宜変形が可能である。
図5は、他の実施形態の封止フィルムを示す概略断面図である。図5に示す封止フィルム401は、第1接着層102(第1の熱可塑性樹脂層)と、第2接着層103(第2の熱可塑性樹脂層)とを備えた2層構造とされている。図1に示す封止フィルム1と共通の構成については同じ符号を付して説明を省略する。
封止フィルム501には、水素結合性樹脂が添加される。水素結合性樹脂の添加量は、図1に示す封止フィルム1において例示された添加量を採用できる。
(実施例1)
基材層のみで形成された封止フィルムを、次のようにして作製した。基材層の原料となる樹脂を加熱溶融し、製膜を行うことで封止フィルムを得た。この封止フィルムを帯状(幅15mm、厚さ100μm)に形成した。
第1接着層、基材層、および第2接着層がこの順に積層された封止フィルムを、次のようにして作製した。各層の原料となる樹脂をそれぞれ別々に加熱溶融し、同時多層押出成形が可能な押出機を用いて同時多層製膜を行うことで積層体(封止フィルム)を得た。この積層体を帯状(幅15mm、厚さ100μm)に形成した。
第1接着層:無水マレイン酸変性ポリプロピレン(融点140℃)
基材層:ポリプロピレンICP(融点161℃)とナイロン6(融点225℃)との混合物
第2接着層:プロピレンとエチレンとのランダム共重合体(融点140℃)
ポリプロピレンICPは、第1相のなかに第2相が分散する構造(海島構造)を有する。第1相は、ホモPPで構成される。第2相は、エチレンプロピレンラバーとポリエチレンとを含む。
実施例2では、封止フィルム全体におけるナイロン6の添加量は0.2質量%である。基材層におけるナイロン6の添加量は0.4質量%である。
実施例4では、封止フィルム全体におけるナイロン6の添加量は1質量%である。基材層におけるナイロン6の添加量は2質量%である。
実施例5では、封止フィルム全体におけるナイロン6の添加量は5質量%である。基材層におけるナイロン6の添加量は10質量%である。
実施例6では、封止フィルム全体におけるナイロン6の添加量は10質量%である。基材層におけるナイロン6の添加量は20質量%である。
実施例7では、封止フィルム全体におけるナイロン6の添加量は20質量%である。基材層におけるナイロン6の添加量は40質量%である。
実施例8では、封止フィルム全体におけるナイロン6の添加量は30質量%である。基材層におけるナイロン6の添加量は60質量%である。
第1接着層、基材層、および第2接着層がこの順に積層された封止フィルムを、次のようにして作製した。第1接着層、基材層、および第2接着層の構成材料は以下のとおりである。
第1接着層:無水マレイン酸変性ポリプロピレン(融点140℃)とナイロン6との混合物
基材層:ポリプロピレンICP(融点161℃)とナイロン6との混合物
第2接着層:プロピレンとエチレンとのランダム共重合体(融点140℃)とナイロン6との混合物
実施例3では、封止フィルム全体におけるナイロン6の添加量は1質量%である。第1接着層、基材層、および第2接着層におけるナイロン6の添加量はそれぞれ1質量%である。その他の条件は実施例2と同様である。
実施例9では、封止フィルム全体におけるナイロン6の添加量は30質量%である。第1接着層、基材層、および第2接着層におけるナイロン6の添加量はそれぞれ30質量%である。その他の条件は実施例2と同様である。
第1接着層と第2接着層とが積層された封止フィルムを、次のようにして作製した。第1接着層および第2接着層の構成材料は以下のとおりである。
第1接着層:無水マレイン酸変性ポリプロピレン(融点140℃)とナイロン6との混合物
第2接着層:プロピレンとエチレンとのランダム共重合体(融点140℃)とナイロン6との混合物
第1接着層の厚さは20μmである。第2接着層の厚さは80μmである。封止フィルム全体におけるナイロン6の添加量は30質量%である。第1接着層および第2接着層におけるナイロン6の添加量はそれぞれ30質量%である。その他の条件は実施例3と同様である。
実施例2,4~8と同様に、第1接着層、基材層、および第2接着層がこの順に積層された封止フィルムを、次のようにして作製した。各層の原料となる樹脂をそれぞれ別々に加熱溶融し、同時多層押出成形が可能な押出機を用いて同時多層製膜を行うことで積層体(封止フィルム)を得た。この積層体を帯状(幅15mm、厚さ100μm)に形成した。
第1接着層:無水マレイン酸変性ポリプロピレン(融点140℃)
基材層:ポリプロピレンICP(融点161℃)とナイロンMXD6(融点240℃)との混合物
第2接着層:プロピレンとエチレンとのランダム共重合体(融点140℃)
ポリプロピレンICPは、第1相のなかに第2相が分散する構造(海島構造)を有する。第1相は、ホモPPで構成される。第2相は、エチレンプロピレンラバーとポリエチレンとを含む。
ナイロンMXD6は、アミド結合原子群を含むため、水素結合性樹脂である。
実施例11では、封止フィルム全体におけるナイロンMXD6の添加量は0.5質量%である。基材層におけるナイロンMXD6の添加量は1.0質量%である。
実施例12では、封止フィルム全体におけるナイロンMXD6の添加量は0.8質量%である。基材層におけるナイロンMXD6の添加量は1.5質量%である。
実施例13では、封止フィルム全体におけるナイロンMXD6の添加量は1.0質量%である。基材層におけるナイロンMXD6の添加量は2.0質量%である。
実施例14では、封止フィルム全体におけるナイロンMXD6の添加量は1.3質量%である。基材層におけるナイロンMXD6の添加量は2.5質量%である。
実施例15では、封止フィルム全体におけるナイロンMXD6の添加量は2.0質量%である。基材層におけるナイロンMXD6の添加量は4.0質量%である。
基材層にナイロン6を添加しないこと以外は実施例2と同様にして封止フィルムを作製した。封止フィルム全体におけるナイロン6の添加量は0質量%である。
基材層におけるナイロン6の添加量を0.1質量%としたこと以外は実施例1と同様にして封止フィルムを作製した。封止フィルム全体におけるナイロン6の添加量は0.1質量%である。
基材層におけるナイロン6の添加量を0.2質量%としたこと以外は実施例2と同様にして封止フィルムを作製した。封止フィルム全体におけるナイロン6の添加量は0.1質量%である。
基材層におけるナイロン6の添加量を80質量%としたこと以外は実施例2と同様にして封止フィルムを作製した。封止フィルム全体におけるナイロン6の添加量は40質量%である。
リード線本体と、リード線本体の表面に形成された表面処理層とを有する電極リード線を作製した。リード線本体としては、幅45mm×長さ52mmの矩形状のニッケルめっき銅箔を用いた。
実施例1~15、比較例1、および参考例1~3の封止フィルムについて、電極リード線に対する封止フィルムの接着強度を次のようにして測定した。この試験は、測定用検体を電解液に浸漬(後述)しないため、「非浸漬」条件の試験である。
封止フィルムと電極リード線とを重ね合わせ、ヒートシールにより接着して測定用検体を得た。ヒートシールの条件は、180℃、0.5MPa、10秒間とした。
この測定用検体について、試験機(株式会社島津製作所製の卓上形精密万能試験機:オートグラフAGS-500NX)を用いて、180度剥離強度(接着強度)を次のようにして測定した。
封止フィルムの端部と、電極リード線の端部とを試験機の把持部で把持し、180度剥離となるように、封止フィルムを電極リード線から剥離させた。剥離速度は50mm/minとした。
実施例1~10、比較例1、および参考例1~3の封止フィルムについての測定結果を表1に示す。実施例11~15の封止フィルムについての測定結果を表2に示す。
実施例1~15、比較例1、および参考例1~3の封止フィルムについて、電極リード線に対する封止フィルムの接着強度を次のようにして測定した。この試験は、測定用検体を電解液に浸漬した後に測定を行うため、「浸漬後」条件の試験である。電池外装用積層体を用いて包装袋を作製し、その中に、LiPF6を1.6mol/リットル含む電解液(DMC:EMC:EC(体積基準)=4:3:3)を入れた。電解液には、純水を0.2質量%(2000ppm)添加した。
この包装袋に、前述の試験1と同様にして作製した測定用検体を入れ、電解液に浸漬させた。測定用検体を入れた包装袋を85℃のオーブンに7日間保管した後、試験1と同様にして180度剥離強度(接着強度)を測定した。
実施例1~15、比較例1、および参考例1~3の封止フィルムについて、封止フィルムの機械的強度を次のようにして測定した。
各封止フィルムを用いて、JIS K7127に規定されたタイプ5のダンベル状の試験片を作製した。この試験片について、JIS K7127に従い、島津製作所社製の卓上形精密万能試験機オートグラフAGS-Xを用いて引張試験を行った。チャック間距離は80mmとした。試験速度(引張速度)は500mm/minとした。試験環境は、温度23℃、湿度50%RHとした。
切断時の引張強度(破断強度)が25MPa以上となった場合を「良」と判定した。破断強度が25MPa未満となった場合を「低」と判定した。実施例1~10、比較例1、および参考例1~3の封止フィルムについての測定結果を表1に示す。実施例11~15の封止フィルムについての測定結果を表2に示す。
これに対し、水素結合性樹脂を含まない比較例1では、電解液に浸漬させた後の接着強度が低くなった。水素結合性樹脂の添加量が低い参考例1,2では、電解液に浸漬させた後の接着強度が低くなった。水素結合性樹脂の添加量が多い参考例3では、機械的強度が低くなった。
2…第1接着層(第1の熱可塑性樹脂層)
3…第2接着層(第2の熱可塑性樹脂層)
4…基材層(第3の熱可塑性樹脂層)
10…電極リード線部材
11…電極リード線
20…収容容器
21…容器本体
22…蓋
30…リチウムイオン電池
100…電池
102…第1接着層(第1の熱可塑性樹脂層)
103…第2接着層(第2の熱可塑性樹脂層)
111…リード線本体
112…表面処理層
201…第1フィルム基材
202…第2フィルム基材
203…金属層
204…シーラント層
Claims (11)
- 電池本体と電気的に接続される電極リード線と、前記電池本体を収容する収容容器との間を封止する封止フィルムであって、
1または複数の熱可塑性樹脂層を備え、
少なくとも1つの前記熱可塑性樹脂層は、分子中に水素結合可能な構造を有する水素結合性樹脂を含む、封止フィルム。 - 前記熱可塑性樹脂層は、複数設けられ、
複数の前記熱可塑性樹脂層は、
前記電極リード線に接着する第1接着層である第1の熱可塑性樹脂層と、
前記収容容器に接着する第2接着層である第2の熱可塑性樹脂層と、
前記第1接着層と前記第2接着層との間に設けられた基材層である第3の熱可塑性樹脂層とを含み、
前記水素結合性樹脂は、前記第1~第3の熱可塑性樹脂層のうち少なくとも1つに含まれる、請求項1記載の封止フィルム。 - 前記第1の熱可塑性樹脂層は、酸変性ポリオレフィンを含む、請求項2記載の封止フィルム。
- 前記水素結合性樹脂は、前記第1の熱可塑性樹脂層に含まれる、請求項2または3に記載の封止フィルム。
- 前記水素結合性樹脂は、前記第3の熱可塑性樹脂層に含まれる、請求項2~4のうちいずれか1項に記載の封止フィルム。
- 前記第1の熱可塑性樹脂層は、前記酸変性ポリオレフィンを50質量%以上含む、請求項3記載の封止フィルム。
- 前記第3の熱可塑性樹脂層は、酸変性ポリオレフィンを10質量%以上含む、請求項2~6のうちいずれか1項に記載の封止フィルム。
- 前記封止フィルム全体における前記水素結合性樹脂の添加量は、0.2質量%以上30質量%以下である、請求項1~7のうちいずれか1項に記載の封止フィルム。
- 前記水素結合性樹脂は、ポリアミド系樹脂である、請求項1~8のうちいずれか1項に記載の封止フィルム。
- 請求項1~9のうちいずれか1項に記載の封止フィルムと、
一方向に延在する前記電極リード線とを備える電極リード線部材。 - 電池本体と、前記電池本体を収容する収容容器と、請求項10に記載の電極リード線部材を備える電池。
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JP2011151030A (ja) * | 2011-02-07 | 2011-08-04 | Dainippon Printing Co Ltd | 電池ケース用シートおよび電池装置 |
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JP2007242548A (ja) * | 2006-03-10 | 2007-09-20 | Nec Lamilion Energy Ltd | フィルム外装電気デバイスの製造方法、ヒータおよびフィルム外装電気デバイス |
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JP2011151030A (ja) * | 2011-02-07 | 2011-08-04 | Dainippon Printing Co Ltd | 電池ケース用シートおよび電池装置 |
JP6055300B2 (ja) | 2012-12-18 | 2016-12-27 | 大倉工業株式会社 | フッ化水素による接着強度の低下が防止できるリード端子接着用テープ |
JP2016184546A (ja) * | 2015-03-26 | 2016-10-20 | 大日本印刷株式会社 | 金属端子用接着性フィルム |
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