CN112687996A - 电池用包装材料 - Google Patents
电池用包装材料 Download PDFInfo
- Publication number
- CN112687996A CN112687996A CN202011578143.2A CN202011578143A CN112687996A CN 112687996 A CN112687996 A CN 112687996A CN 202011578143 A CN202011578143 A CN 202011578143A CN 112687996 A CN112687996 A CN 112687996A
- Authority
- CN
- China
- Prior art keywords
- layer
- packaging material
- battery
- laminate
- metal layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 122
- 229910052751 metal Inorganic materials 0.000 claims abstract description 113
- 239000002184 metal Substances 0.000 claims abstract description 113
- 239000000463 material Substances 0.000 claims abstract description 70
- 238000007789 sealing Methods 0.000 claims abstract description 67
- 239000003792 electrolyte Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920006284 nylon film Polymers 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229920002799 BoPET Polymers 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 267
- 239000002585 base Substances 0.000 description 67
- 239000012790 adhesive layer Substances 0.000 description 48
- -1 polyethylene terephthalate Polymers 0.000 description 39
- 238000000034 method Methods 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 27
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 229920000098 polyolefin Polymers 0.000 description 23
- 239000000565 sealant Substances 0.000 description 21
- 239000011247 coating layer Substances 0.000 description 19
- 238000011282 treatment Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000004381 surface treatment Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 12
- 239000006224 matting agent Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000003475 lamination Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000009820 dry lamination Methods 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910021563 chromium fluoride Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- RSYUFYQTACJFML-DZGCQCFKSA-N afzelechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C=C1 RSYUFYQTACJFML-DZGCQCFKSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- OOUMMVQQCICTGF-UHFFFAOYSA-K chromium(3+);dihydrogen phosphate Chemical compound [Cr+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O OOUMMVQQCICTGF-UHFFFAOYSA-K 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
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Abstract
本发明提供一种电池用包装材料，其包括至少依次叠层有基材层、金属层和密封层的叠层体，总厚度薄，成型性和刺破强度优异。该电池用包装材料包括至少依次叠层有基材层、金属层和密封层的叠层体，上述叠层体的总厚度处于50～80μm的范围，上述基材层和上述金属层的厚度之和相对于上述叠层体的总厚度的比率处于0.380～0.630的范围。
Description
本案是申请日为2015年9月25日、申请号为201580051722.2(PCT/JP2015/ 077209)、发明名称为电池用包装材料的分案申请。
技术领域
本发明涉及厚度薄、成型性和刺破强度优异的电池用包装材料。
背景技术
以往，开发了各种各样类型的电池，在所有电池中，用于封装电极和电解质等的电池元件的包装材料成为不可欠缺的部件。以往，作为电池用包装大多使用金属制的包装材料，但是，近年来，伴随着电动汽车、混合动力电动汽车、个人电脑、照相机、便携电话等的高性能化，对电池不仅要求多种多样的形状，还要求薄型化和轻质化。但是，以往大多使用的金属制的电池用包装材料存在如下的缺点：难以追随形状的多样化，并且在轻质化方面也存在限度。
为此，作为容易加工成多种多样的形状且能够实现薄型化和轻质化的电池用包装材料，提出了依次叠层有基材层/粘接层/金属层/密封层的膜状的叠层体(例如，参照专利文献1)。这样的膜状的电池用包装材料形成为使密封层彼此对置并将周缘部通过热封进行热熔接，由此能够封装电池元件。
用于笔记本型PC、智能手机等的移动机器(便携机器)的锂电池特别要求薄型、轻质，一般使用100μm左右的厚度非常薄的电池用包装材料。近年来，对移动制品要求更加薄型化、轻质化、锂电池的大容量化等，随之，对电池用包装材料要求进一步薄型化。
但是，如果简单地使基材层、金属箔层、密封层的各层均等地变薄来将电池用包装材料薄型化，则基材层、金属层变得过薄，在成型时针孔的发生概率变高。另一方面，如果为了抑制针孔的发生，使成型深度变浅，则导致与锂电池的大容量化逆行这样的严重的问题。另外，如果基材层变薄，则导致刺破强度的降低，由于来自外部的冲击导致锂电池的破裂，如果使密封层薄膜化，则产生密封物性、绝缘性、耐电解液性受损的问题。
现有技术文献
专利文献
专利文献1：日本特开2008－287971号公报
发明内容
发明所要解决的课题
本发明的主要目的在于提供一种包括至少依次叠层有基材层、金属层和密封层的叠层体、总厚度薄、成型性和刺破强度优异的电池用包装材料。
用于解决课题的方法
本发明的发明人为了解决上述课题进行了深入研究。其结果发现，在包括至少依次叠层有基材层、金属层和密封层的叠层体的电池用包装材料中，不是简单地使各层均等地变薄，而是控制电池用包装材料的总厚度中各层或多个层的组合的厚度所占的比，由此，第一、能够使成型性、第二、能够使刺破性、第三、能够使密封物性、绝缘性、耐电解液性停留在作为电池用包装材料能够接受的物性值的范围。本发明是基于这些见解，进一步重复研究而完成的。
即，本发明提供如下所述的方式的电池用包装材料和电池。
项1.一种电池用包装材料，其包括至少依次叠层有基材层、金属层和密封层的叠层体，
上述叠层体的总厚度处于50～80μm的范围，
上述基材层和上述金属层的厚度之和相对于上述叠层体的总厚度的比率处于0.380～0.630的范围。
项2.如项1所述的电池用包装材料，其中，上述密封层的厚度相对于上述叠层体的总厚度的比率处于0.300～0.570的范围。
项3.如项1或2所述的电池用包装材料，其中，
上述基材层的厚度处于9～25μm的范围，
上述金属层的厚度处于15～30μm的范围，
上述密封层的厚度处于22～35μm的范围。
项4.如项1～3中任一项所述的电池用包装材料，其中，上述基材层为双轴拉伸尼龙膜或双轴拉伸PET膜。
项5.如项1～4中任一项所述的电池用包装材料，其中，上述金属层由铝箔形成。
项6.一种至少具备正极、负极和电解质的电池元件收纳于项1～5中任一项所述的电池用包装材料内的电池。
项7.一种电池的制造方法，其包括利用电池用包装材料收纳至少具备正极、负极和电解质的电池元件的工序，
上述电池用包装材料包括至少依次叠层有基材层、金属层和密封层的叠层体，
上述叠层体的总厚度处于50～80μm的范围，
上述基材层和上述金属层的厚度之和相对于上述叠层体的总厚度的比率处于0.380～0.630的范围。
项8.一种叠层体作为电池用包装材料的使用，其中，
该叠层体包括至少依次叠层有基材层、金属层和密封层的叠层体，
上述叠层体的总厚度处于50～80μm的范围，
上述基材层和上述金属层的厚度之和相对于上述叠层体的总厚度的比率处于0.380～0.630的范围。
发明的效果
根据本发明，构成电池用包装材料的叠层体的总厚度和该叠层体中所含的基材层和金属层的厚度之和的比率设定于特定的范围，因此，即使电池用包装材料的总厚度非常薄，也能够提供成型性和刺破强度优异的电池用包装材料。另外，本发明中，通过控制电池用包装材料的总厚度中各层或多个层的组合的厚度所占的比，也能够有效地提高密封物性、绝缘性、耐电解液性等的各项物性。
附图说明
图1是表示本发明的电池用包装材料的剖面结构的一例的图。
图2是表示本发明的电池用包装材料的剖面结构的一例的图。
具体实施方式
本发明的电池用包装材料的特征在于，包括至少依次叠层有基材层、金属层和密封层的叠层体，叠层体的总厚度处于50～80μm的范围，并且基材层和金属层的厚度之和相对于叠层体的总厚度的比率处于0.380～0.630的范围。以下，对本发明的电池用包装材料进行详细阐述。
1.电池用包装材料的叠层结构
如图1所示，电池用包装材料包括至少依次叠层有基材层1、金属层3和密封层4的叠层体。本发明的电池用包装材料中，基材层1形成为最外层，密封层4形成为最内层。即，在组装电池时，通过将位于电池元件的边缘的密封层4彼此热熔接来密封电池元件，封装电池元件。
另外，如图1所示，本发明的电池用包装材料中，在基材层1和金属层3之间，以提高它们的粘接性为目的，也可以根据需要设置粘接层2。另外，如图2所示，在金属层3和密封层4之间，以提高它们的粘接性为目的，也可以根据需要设置粘接层5。
2.构成电池用包装材料的层的厚度
构成本发明的电池用包装材料的叠层体的总厚度处于50～80μm的范围。电池用包装材料中，总厚度为80μm以下是非常薄的，如果是通常的设计，则非常容易发生成型时的针孔，刺破强度也变小。相对于此，本发明的电池用包装材料中，通过将叠层体的厚度设定于50～80μm的范围，并且将基材层和金属层的厚度之和相对于叠层体的总厚度的比率设定于0.380～0.630的范围，形成成型性和刺破强度优异的电池用包装材料。需要说明的是，在本发明中，构成电池用包装材料的叠层体的总厚度是在电池用包装材料的中央部分中使用厚度计(microgauge)测定的值。
另外，在本发明中，通过将电池用包装材料的总厚度中各层或多个层的组合的厚度所占的比设定于后述的范围，能够有效地提高后述的密封物性、绝缘性、耐电解液性等的各项物性。
从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且更好地实现如上所述的各项物性等的观点考虑，作为叠层体的进一步优选的总厚度，可以列举54～76μm的范围。
从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且更好地实现如上所述的各项物性等的观点考虑，作为后述的基材层1和金属层3的厚度之和相对于叠层体的上述总厚度的比率([基材层1+金属层3]/总厚度)，进一步优选处于0.400～0.625的范围。
另外，从同样的观点考虑，后述的密封层4的厚度相对于叠层体的总厚度的比率(密封层4/总厚度)优选处于0.300～0.570的范围，进一步优选处于0.310～0.550的范围。
从同样的观点考虑，基材层1的厚度相对于金属层3的厚度的比率(基材层1/金属层3)优选处于0.450～1.700的范围，进一步优选处于0.480～1.500的范围。
从同样的观点考虑，基材层1的厚度相对于基材层1和金属层3的厚度之和的比率(基材层1/基材层1和金属层3)优选处于0.324～0.444的范围，进一步优选处于0.324～0.380的范围。
从同样的观点考虑，密封层4的厚度相对于基材层1和金属层3的厚度之和的比率(密封层4/基材层1和金属层3)优选处于0.489～1.458的范围，进一步优选处于0.533～1.400的范围。
另外，从同样的观点考虑，特别优选基材层1的厚度处于9～25μm的范围、金属层3的厚度处于15～30μm的范围、密封层4的厚度处于22～35μm的范围。
3.电池用包装材料的物性
(成型性)
本发明的电池用包装材料通过将叠层体的总厚度设定于上述的范围并且将基材层和金属层的厚度之和相对于叠层体的总厚度的比设定于上述的范围，即使厚度非常薄，也具备优异的成型性。具体而言，即使在以成型深度6mm、0.1MPa的按压压力(面压)按压并冷轧成型这样的严酷条件进行成型的情况下，成型后的电池用包装材料中的金属层的针孔和裂痕也被有效地抑制。此外，关于成型性的评价，更具体而言，能够通过实施例所述的方法来进行。
(刺破强度)
本发明的电池用包装材料通过将叠层体的总厚度设定于上述的范围并且将基材层和金属层的厚度之和相对于叠层体的总厚度的比设定于上述的范围，即使厚度非常薄，也具备优异的刺破强度。更具体而言，例如，在根据JIS 1707：1997的规定，对于电池用包装材料，将直径1.0mm、前端形状半径0.5mm的半圆形的针以每分钟50±5mm的速度插刺，测定直至针贯通的最大应力时，能够使最大应力为10N以上，优选为12～15N。此外，关于刺破强度的评价，更具体而言，能够通过实施例所述的方法来进行。
(柔性)
本发明的电池用包装材料通过将叠层体的总厚度设定于上述的范围并且将基材层和金属层的厚度之和相对于叠层体的总厚度的比设定于上述的范围，即使厚度非常薄，也具有优异的柔性(折弯的容易程度)。更具体而言，例如，能够使通过东洋精机株式会社制的LOOP STIFFNESS TESTER测定的环刚度值(测定条件：样品宽度15mm、环圆周100mm、压碎剩余距离15mm)优选为5.0g～15.0g的范围，更优选为5.5～12.0g的范围。此外，关于柔性的评价，更具体而言，能够通过实施例所述的方法来进行。
(绝缘性)
本发明的电池用包装材料通过将叠层体的总厚度、以及基材层和金属层的厚度之和相对于该叠层体的总厚度的比设定于上述特定的范围，进一步将密封层的厚度相对于叠层体的总厚度的比率设定于上述的范围，从而，即使厚度非常薄，也具备优异的绝缘性。具体而言，例如，能够使如下测得的电阻值成为1MΩ以上，优选为1～10MΩ，该电阻值为，以铝端子(tab)夹入的方式将密封层彼此热封，在两侧的基材层的表面分别连接测试仪的端子，在测试仪之间施加DC25V的电压15秒时的电阻值。此外，关于绝缘性的评价，更具体而言，能够通过实施例所述的方法来进行。
(密封强度)
本发明的电池用包装材料通过将叠层体的总厚度、以及基材层和金属层的厚度之和相对于该叠层体的总厚度的比设定于上述特定的范围，进一步将密封层的厚度相对于叠层体的总厚度的比率设定于上述的范围，从而，即使厚度非常薄，也具备优异的密封强度。具体而言，例如，在将电池用包装材料的密封层彼此以密封温度190℃、面压1.0MPa、密封时间3.0秒进行热封，将密封部用牵引机以300mm/分钟的速度牵引，测定密封强度时，能够使密封强度为40N/15mm以上，优选为60～75N/15mm。此外，关于密封强度的评价，更具体而言，能够通过实施例所述的方法来进行。
(耐电解液性)
本发明的电池用包装材料通过将叠层体的总厚度、和基材层和金属层的厚度之和相对于该叠层体的总厚度的比设定于上述特定的范围，进一步将密封层的厚度相对于叠层体的总厚度的比率设定于上述的范围，从而，即使厚度非常薄，也具备优异的耐电解液性。具体而言，例如，将电池用包装材料以在密封层侧形成凹部的方式成型，在该凹部填充电解液(含有1M的LiPF6、碳酸亚乙酯、碳酸二乙酯和碳酸二甲酯(容量比1：1：1)的混合液)，将另1片电池用包装材料以密封层彼此对置的方式从凹部之上重叠，将周缘部热封，将其在85℃保存1天之后，开封，目视观察金属层和密封层之间有无脱层，此时，没有发生脱层。此外，关于耐电解液性的评价，更具体而言，能够通过实施例所述的方法来进行。
本发明为了通过将构成电池用包装材料的叠层体的总厚度设定于上述的范围，并且将基材层和金属层的厚度之和相对于叠层体的总厚度的比设定于上述的范围，使总厚度非常薄地形成为上述的范围，并且，更好地实现如上所述的各项物性等，调整构成电池用包装材料的基材层1、根据需要设置的粘接层2、金属层3、根据需要设置的粘接层5、密封层4的组成、物性、厚度等即可。以下，对本发明的电池用包装材料的物性和构成电池用包装材料的各层进行详细阐述。
4.形成电池用包装材料的各层的组成
[基材层1]
在本发明的电池用包装材料中，基材层1为形成最外层的层。关于形成基材层1的原材料，以具备绝缘性为限度，没有特别限制。作为形成基材层1的原材料，例如，可以列举聚酯树脂、聚酰胺树脂、环氧树脂、丙烯酸树脂、氟树脂、聚氨酯树脂、硅树脂、酚醛树脂以及这些的混合物或共聚物等的树脂膜。这些之中，可以优选列举聚酯树脂、聚酰胺树脂，更优选列举双轴拉伸聚酯树脂、双轴拉伸聚酰胺树脂。作为聚酯树脂，具体而言，可以列举聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、共聚聚酯、聚碳酸酯等。另外，作为聚酰胺树脂，具体而言，可以列举尼龙6、尼龙6,6、尼龙6与尼龙6,6的共聚物、尼龙6,10、聚己二酰间苯二甲胺(MXD6)等。
基材层1也可以由1层树脂膜形成，但为了使耐针孔性和绝缘性提高，也可以由2层以上的树脂膜形成。在由多层树脂膜形成基材层1的情况下，2个以上的树脂膜经由粘接剂或粘接性树脂等粘接成分叠层即可，关于所使用的粘接成分的种类和量等，与后述的粘接层2或粘接层5的情况相同。此外，作为叠层2层以上的树脂膜的方法，没有特别限制，能够采用公知方法，例如可以列举干式层压法、夹层层压法等，优选列举干式层压法。通过干式层压法叠层时，作为粘接层优选使用聚氨酯系粘接剂。此时，作为粘接层的厚度，例如，可以列举2～5μm左右。
作为基材层1的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，可以列举以上所例示的厚度。
[粘接层2]
在本发明的电池用包装材料中，粘接层2是为了使基材层1与金属层3牢固地粘接而根据需要设置于它们之间的层。
粘接层2由能够将基材层1与金属层3粘接的粘接剂形成。粘接层2的形成中所使用的粘接剂可以为双液固化型粘接剂或单液固化型粘接剂。另外，对于粘接层2的形成中所使用的粘接剂的粘接机制也没有特别限制，可以为化学反应型、溶剂挥发型、热熔接型、热压型等的任一种。
作为粘接层2的形成中能够使用的粘接成分，具体而言，可以列举聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、聚碳酸酯、共聚聚酯等的聚酯系树脂；聚醚系粘接剂；聚氨酯系粘接剂；环氧系树脂；酚醛树脂系树脂；尼龙6、尼龙66、尼龙12、共聚聚酰胺等的聚酰胺系树脂；聚烯烃、羧酸改性聚烯烃、金属改性聚烯烃等的聚烯烃系树脂、聚乙酸乙烯酯系树脂；纤维素系粘接剂；(甲基)丙烯酸系树脂；聚酰亚胺系树脂；尿素树脂、三聚氰胺树脂等的氨基树脂；氯丁二烯橡胶、丁腈橡胶、苯乙烯－丁二烯橡胶等的橡胶；有机硅系树脂等。这些粘接成分可以单独使用1种，或者也可以组合2种以上使用。这些粘接成分之中，优选列举为聚氨酯系粘接剂。
作为粘接层2的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，优选列举3～4μm左右。
[金属层3]
在电池用包装材料中，金属层3除了用于提高电池用包装材料的强度以外，还是作为用于防止水蒸气、氧、光等侵入电池内部的阻隔层而发挥功能的层。作为构成金属层3的金属，具体而言，可以列举铝、不锈钢、钛等，优选列举铝。金属层3能够通过金属箔或金属蒸镀等形成，优选由金属箔形成，更优选由铝箔形成。从在电池用包装材料的制造时防止在金属层3发生褶皱和针孔的观点考虑，例如，更优选由退火处理后的铝(JIS A8021P-O、JISA8079P-O)等软质铝箔形成。
作为金属层3的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，可以列举以上所例示的厚度。
另外，为了粘接的稳定化、防止溶解、腐蚀等，金属层3优选对至少一个面、优选对两个面进行化学法表面处理。这里，化学法表面处理是指在金属层的表面形成耐酸性皮膜的处理。作为化学法表面处理，例如，可以列举使用硝酸铬、氟化铬、硫酸铬、乙酸铬、草酸铬、磷酸二氢铬、铬酸乙酰乙酸酯、氯化铬、硫酸铬钾等的铬酸化合物的铬酸铬酸盐处理；使用磷酸钠、磷酸钾、磷酸铵、多磷酸等的磷酸化合物的磷酸铬酸盐处理；使用具有下述通式(1)～(4)所示的重复单元的氨基化酚聚合物的铬酸盐处理等。其中，在该氨基化酚聚合物中，下述通式(1)～(4)所示的重复单元可以单独含有1种，也可以任意组合2种以上。
通式(1)～(4)中，X表示氢原子、羟基、烷基、羟基烷基、烯丙基或苄基。另外，R1和R2分别相同或不同地，表示羟基、烷基或羟基烷基。通式(1)～(4)中，作为X、R1和R2所示的烷基，例如，可以列举甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等碳原子数1～4的直链或支链状烷基。另外，作为X、R1和R2所示的羟基烷基，例如，可以列举羟基甲基、1-羟基乙基、2-羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、1-羟基丁基、2-羟基丁基、3-羟基丁基、4-羟基丁基等的取代有1个羟基的碳原子数1～4的直链或支链状烷基。通式(1)～(4)中，X、R1和R2所示的烷基和羟基烷基分别可以相同也可以不同。通式(1)～(4)中，X优选为氢原子、羟基或羟基烷基。具有通式(1)～(4)所示的重复单元的氨基化酚聚合物的数均分子量例如优选为500～100万，更优选为1000～2万左右。
另外，作为对金属层3赋予耐腐蚀性的化学法表面处理方法，可以列举如下方法：将在磷酸中分散有氧化铝、氧化钛、氧化铈、氧化锡等金属氧化物、硫酸钡的微粒的物质进行涂敷，在150℃以上进行烧制处理，由此，在金属层3的表面形成耐腐蚀处理层。另外，在耐腐蚀处理层之上，可以进一步形成用交联剂将阳离子性聚合物交联得到的树脂层。这里，作为阳离子性聚合物，例如，可以列举聚乙烯亚胺、由聚乙烯亚胺和具有羧酸的聚合物构成的离子高分子配位化合物、在丙烯酸主骨架接枝聚合有伯胺的伯胺接枝丙烯酸树脂、聚烯丙胺或其衍生物、氨基苯酚等。作为这些阳离子性聚合物，可以仅使用1种，也可以组合2种以上使用。另外，作为交联剂，例如，可以列举具有选自异氰酸酯基、环氧丙基、羧基和噁唑啉基中的至少1种官能团的化合物、硅烷偶联剂等。作为这些交联剂，可以仅使用1种，也可以组合2种以上使用。
化学法表面处理可以仅进行1种化学法表面处理，也可以组合进行2种以上的化学法表面处理。另外，这些化学法表面处理可以单独使用1种化合物进行，或者也可以组合使用2种以上的化合物进行。化学法表面处理之中，优选铬酸铬酸盐处理、或者组合铬酸化合物、磷酸化合物和氨基化酚聚合物的铬酸盐处理等。
化学法表面处理中，关于在金属层3的表面所形成的耐酸性皮膜的量，没有特别限制，例如，进行上述的铬酸盐处理时，优选以相对于金属层3的表面每1m2，铬酸化合物以铬换算为约0.5mg～约50mg、优选为约1.0mg～约40mg、磷化合物以磷换算为约0.5mg～约50mg、优选为约1.0mg～约40mg和氨基化酚聚合物为约1mg～约200mg、优选为约5.0mg～150mg的比例含有。
化学法表面处理通过以下方法进行：将含有用于形成耐酸性皮膜的化合物的溶液通过棒涂法、辊涂法、凹版涂布法、浸渍法等涂布在金属层3的表面之后，进行加热使得金属层3的温度成为70℃～200℃左右。另外，在对金属层3实施化学法表面处理之前，可以预先通过碱浸渍法、电解清洗法、酸清洗法、电解酸清洗法等对金属层3进行脱脂处理。通过这样进行脱脂处理，能够更高效地进行金属层3的表面的化学法表面处理。
[密封层4]
本发明的电池用包装材料中，密封层4是相当于最内层、在组装电池时密封层彼此热熔接而密封电池元件的层。
关于密封层4中使用的树脂成分，以能够热熔接为限度，没有特别限制，例如，可以列举聚烯烃、环状聚烯烃、羧酸改性聚烯烃、羧酸改性环状聚烯烃。
作为上述聚烯烃，具体而言，可以列举低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线性低密度聚乙烯等的聚乙烯；均聚丙烯、聚丙烯的嵌段共聚物(例如，丙烯与乙烯的嵌段共聚物)、聚丙烯的无规共聚物(例如，丙烯与乙烯的无规共聚物)等的聚丙烯；乙烯－丁烯－丙烯的三元共聚物等。这些聚烯烃之中，可以优选列举聚乙烯和聚丙烯。
上述环状聚烯烃为烯烃和环状单体的共聚物，作为上述环状聚烯烃的构成单体的烯烃，例如，可以列举乙烯、丙烯、4-甲基-1-戊烯、苯乙烯、丁二烯、异戊二烯等。另外，作为上述环状聚烯烃的构成单体的环状单体，例如，可以列举降冰片烯等的环状烯烃；具体而言，可以列举环戊二烯、二环戊二烯、环己二烯、降冰片二烯等的环状二烯等。这些聚烯烃之中，可以优选列举环状烯烃，更优选列举降冰片烯。
上述羧酸改性聚烯烃是指用羧酸将上述聚烯烃通过嵌段聚合或接枝聚合改性得到的聚合物。作为改性中所使用的羧酸，例如，可以列举马来酸、丙烯酸、衣康酸、巴豆酸、马来酸酐、衣康酸酐等。
上述羧酸改性环状聚烯烃是指将构成环状聚烯烃的单体的一部分替代为α,β-不饱和羧酸或其酸酐进行共聚、或者对环状聚烯烃嵌段共聚或接枝共聚α,β-不饱和羧酸或其酸酐得到的聚合物。关于要被羧酸改性的环状聚烯烃，与上述同样。另外，作为改性中所使用的羧酸，与上述酸改性环状烯烃共聚物的改性中所使用的羧酸相同。
这些树脂成分之中，可以优选列举羧酸改性聚烯烃；更优选列举羧酸改性聚丙烯。
密封层4可以由1种树脂成分单独形成，或者也可以由组合2种以上的树脂成分的共混聚合物形成。另外，密封层4可以仅以1层形成，也可以由相同或不同的树脂成分以2层以上形成。
作为密封层4的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，可以列举以上所例示的厚度。此外，密封层4以2层以上形成时，该厚度是指密封层4的总厚度。
[粘接层5]
本发明的电池用包装材料中，粘接层5是为了使金属层3与密封层4牢固地粘接而根据需要设置于它们之间的层。
粘接层5由能够将金属层3与上述密封层4粘接的粘接剂成分形成。粘接层5的形成中所使用的粘接剂可以为双液固化型粘接剂或单液固化型粘接剂。另外，对于粘接层5的形成中所使用的粘接剂成分的粘接机制也没有特别限制，例如可以为化学反应型、溶剂挥发型、热熔接型、热压型等。
作为粘接层5的形成中能够使用的粘接剂成分的具体例，可以列举聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、聚碳酸酯、共聚聚酯等的聚酯系树脂；聚醚系粘接剂；聚氨酯系粘接剂；环氧系树脂；酚醛树脂系树脂；尼龙6、尼龙66、尼龙12、共聚聚酰胺等的聚酰胺系树脂；聚烯烃、羧酸改性聚烯烃、金属改性聚烯烃等的聚烯烃系树脂、聚乙酸乙烯酯系树脂；纤维素系粘接剂；(甲基)丙烯酸系树脂；聚酰亚胺系树脂；尿素树脂、三聚氰胺树脂等的氨基树脂；氯丁二烯橡胶、丁腈橡胶、苯乙烯－丁二烯橡胶等的橡胶；有机硅系树脂等。这些粘接剂成分可以单独使用1种，或者也可以组合2种以上使用。
作为粘接层5的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，优选列举2～5μm左右。
[涂敷层]
本发明的电池用包装材料中，以设计性、耐电解液性、耐摩擦性、成型性的提高等为目的，也可以根据需要在基材层1之上(基材层1的与金属层3相反一侧)设置涂敷层(未图示)。在组装电池时，涂敷层是位于最外层的层。
涂敷层例如能够由聚偏氯乙烯、聚酯树脂、聚氨酯树脂、丙烯酸树脂、环氧树脂等形成。这些之中，优选涂敷层由双液固化型树脂形成。作为形成涂敷层的双液固化型树脂，例如，可以列举双液固化型聚氨酯树脂、双液固化型聚酯树脂、双液固化型环氧树脂等。另外，也可以在涂敷层中配合消光剂。
作为消光剂，例如，可以列举粒径为0.5nm～5μm左右的微粒。关于消光剂的材质，没有特别限制，例如，可以列举金属、金属氧化物、无机物、有机物等。另外，关于消光剂的形状，也没有特别限制，例如，可以列举球状、纤维状、板状、无定形、空心球状等。作为消光剂，具体而言，可以列举滑石、二氧化硅、石墨、高岭土、蒙脱土(モンモリロイド)、蒙脱石、合成云母、水滑石、硅胶、沸石、氢氧化铝、氢氧化镁、氧化锌、氧化镁、氧化铝、氧化钕、氧化锑、氧化钛、氧化铈、硫酸钙、硫酸钡、碳酸钙、硅酸钙、碳酸锂、苯甲酸钙、草酸钙、硬脂酸镁、氧化铝、炭黑、碳纳米管类、高熔点尼龙、交联丙烯酸、交联苯乙烯、交联聚乙烯、苯代三聚氰二胺、金、铝、铜、镍等。这些消光剂可以单独使用1种，另外，也可以组合使用2种以上。这些消光剂中，从分散稳定性和成本等观点考虑，可以优选列举二氧化硅、硫酸钡、氧化钛。另外，对于消光剂，也可以对表面实施绝缘处理、高分散性处理等各种表面处理。
作为形成涂敷层的方法，没有特别限制，例如，可以列举将形成涂敷层的双液固化型树脂涂布在基材层1的一个表面上的方法。在配合消光剂的情况下，在双液固化型树脂中添加消光剂并混合后，涂布即可。
作为涂敷层的厚度，从使作为电池用包装材料的总厚度非常薄地形成为上述的范围并且能够更良好地实现如上所述的各项物性等的观点考虑，优选列举1～4μm左右。
5.电池用包装材料的制造方法
关于本发明的电池用包装材料的制造方法，以能够得到叠层有规定组成的各层的叠层体为限度，没有特别限制，例如，可以例示以下的方法。
首先，形成依次叠层有基材层1、粘接层2、金属层3的叠层体(以下，有时也记为“叠层体A”)。关于叠层体A的形成，具体而言，能够通过以下的干式层压法来进行：在基材层1上或根据需要对表面进行过化学法表面处理的金属层3上，将用于形成粘接层2的粘接剂通过挤出法、凹版涂布法、辊涂法等的涂布方法涂布、干燥之后，叠层该金属层3或基材层1并使粘接层2固化。
接着，在叠层体A的金属层3上叠层密封层4。在金属层3上直接叠层密封层4时，在叠层体A的金属层3上通过凹版涂布法、辊涂法等的方法涂布构成密封层4的树脂成分即可。另外，在金属层3和密封层4之间设置粘接层5时，例如，可以列举：(1)在叠层体A的金属层3上通过将粘接层5和密封层4共挤出来叠层的方法(共挤出层压法)；(2)另外形成叠层有粘接层5和密封层4的叠层体，将其在叠层体A的金属层3上通过热层压法叠层的方法；(3)在叠层体A的金属层3上将用于形成粘接层5的粘接剂通过挤出法或溶液涂敷，在高温干燥并进而进行烧制的方法等叠层，在该粘接层5上通过热层压法叠层预先制膜为片状的密封层4的方法；(4)边使熔融的粘接层5流入到叠层体A的金属层3与预先制膜为片状的密封层4之间、边经由粘接层5贴合叠层体A与密封层4的方法(夹层层压法)等。
在设置涂敷层的情况下，在基材层1的与金属层3相反一侧的表面叠层涂敷层。涂敷层例如能够通过将形成涂敷层的上述的树脂涂布在基材层1的表面来形成。此外，在基材层1的表面叠层金属层3的工序和在基材层1的表面叠层涂敷层的工序的顺序没有特别限制。例如，也可以在基材层1的表面形成涂敷层后，在基材层1的与涂敷层相反一侧的表面形成金属层3。
如上所述操作，形成包括基材层1/粘接层2/根据需要对表面进行了化学法表面处理的金属层3/根据需要设置的粘接层5/密封层4/根据需要设置的涂敷层的叠层体，为了使粘接层2和根据需要设置的粘接层5的粘接性牢固，也可以进一步进行热辊接触式、热风式、近或远红外线式等的加热处理。作为这样的加热处理的条件，例如，可以列举在150～250℃进行1～5分钟。
在本发明的电池用包装材料中，对于构成叠层体的各层，为了使制膜性、叠层化加工、最终制品2次加工(包装化、压花成型)适应性等提高或稳定化，可以根据需要实施电晕放电处理、喷砂处理、氧化处理、臭氧处理等的表面活性化处理。
6.电池用包装材料的用途
本发明的电池用包装材料可以作为用于密封并收纳正极、负极、电解质等的电池元件的包装材料使用。
具体而言，将至少具备正极、负极和电解质的电池元件，以能够在与上述正极和负极分别连接的金属端子向外侧突出的状态下，在电池元件的边缘形成凸缘部(密封层彼此接触的区域)的方式，用本发明的电池用包装材料进行包覆，并将上述凸缘部的密封层彼此热封，进行密封，由此，提供使用了电池用包装材料的电池。此外，在使用本发明的电池用包装材料收纳电池元件时，以本发明的电池用包装材料的密封部分成为内侧(与电池元件接触的面)的方式使用。
本发明的电池用包装材料可以用于一次电池、二次电池的任一种，优选为二次电池。关于适用本发明的电池用包装材料的二次电池的种类，没有特别限制，例如，可以列举锂离子电池、锂离子聚合物电池、铅蓄电池、镍·氢蓄电池、镍·镉蓄电池、镍·铁蓄电池、镍·锌蓄电池、氧化银·锌蓄电池、金属空气电池、多价阳离子电池、电容器(condenser)、电容器(capacitor)等。这些二次电池之中，作为本发明的电池用包装材料的合适的适用对象，可以列举锂离子电池和锂离子聚合物电池。
实施例
以下，例示实施例和比较例，详细说明本发明。但是，本发明不限定于实施例。
实施例1－26和比较例1－4
＜电池用包装材料的制造＞
对于依次叠层有基材层1/粘接层2/金属层3的叠层体，通过挤出层压法叠层密封层4，由此，制造包括依次叠层有基材层1/粘接层2/金属层3/密封层4的电池用包装材料。此外，实施例4、10－13、24－26的电池用包装材料中，在基材层1的与金属层的相反一侧设置有涂敷层。电池用包装材料的具体的制造条件如下所示。
首先，制作依次叠层有基材层1/粘接层2/金属层3的叠层体。具体而言，在基材层1的一个面形成包括聚酯系的主剂和异氰酸酯系固化剂的双液型聚氨酯粘接剂的粘接层2，使其为3μm，与金属层3的化学法表面处理面进行加压加热贴合(夹层层压)，制作依次叠层有基材层1/粘接层2/金属层3的叠层体。
作为基材层1使用具有表1所述的厚度的双轴拉伸尼龙膜，作为金属层3，使用包括表1所述的由铝箔构成的金属层2，铝箔分别通过辊涂法在金属层的两面分别以10mg/m2涂布含有酚醛树脂、氟化铬化合物(三价)和磷酸的处理液，以皮膜温度成为180℃以上的条件烧制20秒，由此进行化学法表面处理。
另外，单独通过共挤出层压法形成密封层4，使其成为表1所述的厚度和结构。密封层4设为将构成金属层侧的树脂层和构成最内层侧的树脂层共挤出。表1中的PPA为用不饱和羧酸接枝改性得到的不饱和羧酸接枝改性无规聚丙烯，PP是聚丙烯(无规共聚物)。如上所述操作，在包括基材层1/粘接层2/金属层3的叠层体的金属层表面形成表1所述的厚度和结构的密封层，由此，得到包括依次叠层有基材层1/粘接层2/金属层3/密封层4的叠层体的实施例1－26和比较例1－4的电池用包装材料。
[表1]
＜叠层体的总厚度的测定＞
将上述所得到的电池用包装材料裁断，制作120×80mm的长条片，作为试验片，在该试验片的中央部分，使用千分表(Mitutoyo公司制的547-401)测定叠层体的总厚度。在表1中表示结果。
＜成型性的评价＞
将上述得到的各电池用包装材料裁断，制作120×80mm的长条片，将其作为试验样品。使用包括30×50mm的矩形状的阳模和与该阳模的间隙为0.5mm的阴模的直模，以热粘接性树脂层侧位于阳模侧的方式在阴模上载置上述试验样品，分别以成型深度成为5.5mm的方式以0.1MPa的按压压力(面压)挤压该试验样品，进行冷轧成型(牵引1段成型)。确认成型得到的电池用包装材料中有无金属层的针孔和裂纹的发生，计算针孔和裂纹的发生率(％)。关于针孔和裂纹的发生率，将在进行了上述成型后至少一个部位确认到针孔或裂纹的样品判断为成型不良品，将对30个试验样品以上述条件成型时发生的成型不良品的比例，作为针孔和裂纹的发生率求出。在表2中表示结果。
＜刺破强度的评价＞
根据JIS 1707：1997的规定，对于上述所得到的各电池用包装材料，将直径1.0mm、前端形状半径0.5mm的半圆形的针以每分钟50±5mm速度插刺，测定直至针贯通的最大应力。各个试验片的数量设为5个，求出最大应力的平均值。关于评价基准，将为12N以上的情况记为○、将低于12N的情况记为×。在表2中表示结果。
＜绝缘性的评价＞
将上述所得到的各电池用包装材料切成宽度40mm、长度100mm的大小，得到试验片。接着，以使短边彼此对置的方式折叠该试验片，以试验片的密封层表面相互对置的方式配置。接着，在相互对置的密封层的表面之间插入厚度100μm、宽度5mm的铝制的电极端子。接着，在该状态下，在与电池用包装材料的长度方向正交的方向，用包括上下共7mm宽度的平板状热板的热封机将密封层彼此热封。接着，使电池用包装材料的夹有铝端子的部分为中央，在两侧的基材层的表面分别连接测试仪的端子。接着，在测试仪之间施加DC25V的电压15秒，测定其间的电阻值。关于绝缘性的评价基准，将电阻值为1MΩ以上的情况记为○，将低于1MΩ的情况记为×。在表2中表示结果。
＜密封强度的评价＞
将上述所得到的各电池用包装材料裁断成60mm(MD方向)×120mm(TD方向)的长条片。将各长条片在TD方向折半，将对置的二边以7mm宽度热封，制作在一个方向具有开口的袋。接着，将所得到的袋的开口部以7mm宽度、密封温度190℃、面压1.0MPa、密封时间3.0秒进行热封。接着，将开口部的热封部切成15mm宽度的长条状，将其用牵引机(岛津制作所制、AGS－50D(商品名))以300mm/分钟的速度牵引，测定密封强度。单位为N/15mm宽度。关于密封强度的评价基准，将密封强度为60N/15mm以上的情况记为○，将低于60N/15mm的情况记为×。在表2中表示结果。
＜柔性的评价＞
通过上述所得到的各电池用包装材料的环刚度值评价电池用包装材料的柔性(折弯的容易程度)。利用东洋精机株式会社制的LOOP STIFFNESSTESTER测定环刚度值(测定条件：样品宽度15mm、环圆周100mm、压碎剩余距离15mm)。测定以N＝5进行，求其平均值。关于评价基准，将环刚度值为5.5g～12.0g的情况记为○，将低于5.0g的情况和15.0g以上的情况记为×。在表2中表示结果。
＜耐电解液性的评价＞
将上述所得到的各电池用包装材料裁断为80mm×150mm后，用35mm×50mm的口径的成型模具(阴模)和与其对应的成型模具(阳模)以0.4MPa冷轧成型为3.0mm的深度，在其中心部分形成凹部。在该凹部填充3g上述的电解液(含有1M的LiPF6、碳酸亚乙酯、碳酸二乙酯和碳酸二甲酯(容量比1：1：1)的混合液)，再将1片电池用包装材料以密封层彼此对置的方式从凹部之上重叠，将周缘部热封。热封的条件设为以190℃、面压1.0MPa进行3秒。将其在85℃保存1天之后，开封，目视确认金属层和密封层之间有无脱层。在表2中表示结果。
＜经济性·通用性的评价＞
构成上述所得到的电池用包装材料的基材层和金属层的厚度下限值在商品目录中记载，根据是否为通常能够购入的厚度，评价经济性·通用性。关于评价基准，将经济性·通用性高的情况记为○，将稍低的情况记为△，将低的情况记为×。在表2中表示结果。
[表2]
符号说明
1 基材层
2 粘接层
3 金属层
4 密封层
5 粘接层
Claims (8)
1.一种电池用包装材料，其特征在于：
包括至少依次叠层有基材层、金属层和密封层的叠层体，
所述叠层体的总厚度处于50～80μm的范围，
所述基材层和所述金属层的厚度之和相对于所述叠层体的总厚度的比率处于0.380～0.630的范围。
2.如权利要求1所述的电池用包装材料，其特征在于：
所述密封层的厚度相对于所述叠层体的总厚度的比率处于0.300～0.570的范围。
3.如权利要求1或2所述的电池用包装材料，其特征在于：
所述基材层的厚度处于9～25μm的范围，
所述金属层的厚度处于15～30μm的范围，
所述密封层的厚度处于22～35μm的范围。
4.如权利要求1～3中任一项所述的电池用包装材料，其特征在于：
所述基材层为双轴拉伸尼龙膜或双轴拉伸PET膜。
5.如权利要求1～4中任一项所述的电池用包装材料，其特征在于：
所述金属层由铝箔形成。
6.一种电池，其特征在于：
至少具备正极、负极和电解质的电池元件收纳于权利要求1～5中任一项所述的电池用包装材料内。
7.一种电池的制造方法，其特征在于：
包括利用电池用包装材料收纳至少具备正极、负极和电解质的电池元件的工序，
所述电池用包装材料包括至少依次叠层有基材层、金属层和密封层的叠层体，
所述叠层体的总厚度处于50～80μm的范围，
所述基材层和所述金属层的厚度之和相对于所述叠层体的总厚度的比率处于0.380～0.630的范围。
8.一种叠层体作为电池包装用材料的使用，其特征在于：
该叠层体包括至少依次叠层有基材层、金属层和密封层的叠层体，
所述叠层体的总厚度处于50～80μm的范围，
所述基材层和所述金属层的厚度之和相对于所述叠层体的总厚度的比率处于0.380～0.630的范围。
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