CN108780855A - 电化学电池用包装材料 - Google Patents
电化学电池用包装材料 Download PDFInfo
- Publication number
- CN108780855A CN108780855A CN201780019133.5A CN201780019133A CN108780855A CN 108780855 A CN108780855 A CN 108780855A CN 201780019133 A CN201780019133 A CN 201780019133A CN 108780855 A CN108780855 A CN 108780855A
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- CN
- China
- Prior art keywords
- acid
- layer
- packaging material
- substrate
- electrochemical cells
- Prior art date
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- Granted
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- 239000005022 packaging material Substances 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 121
- 239000012528 membrane Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- -1 phosphorus compound Chemical class 0.000 claims abstract description 46
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 24
- 239000004840 adhesive resin Substances 0.000 claims abstract description 23
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003475 lamination Methods 0.000 claims abstract description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 239000003792 electrolyte Substances 0.000 abstract description 32
- 230000004888 barrier function Effects 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 160
- 239000003795 chemical substances by application Substances 0.000 description 42
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 33
- 229910001416 lithium ion Inorganic materials 0.000 description 33
- 239000002904 solvent Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- 229920001155 polypropylene Polymers 0.000 description 23
- 239000004743 Polypropylene Substances 0.000 description 22
- 229910001868 water Inorganic materials 0.000 description 20
- 239000005030 aluminium foil Substances 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 210000000981 epithelium Anatomy 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- 238000007789 sealing Methods 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000004103 aminoalkyl group Chemical group 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003755 zirconium compounds Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 2
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- UEUMIMKGIUYUGH-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] UEUMIMKGIUYUGH-UHFFFAOYSA-H 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
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- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
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- 238000001883 metal evaporation Methods 0.000 description 1
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- 239000002480 mineral oil Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
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- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
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- ZYPJORZNHDXKSD-UHFFFAOYSA-N oxotitanium;sulfuric acid Chemical compound [Ti]=O.OS(O)(=O)=O ZYPJORZNHDXKSD-UHFFFAOYSA-N 0.000 description 1
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- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
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- DTEMQJHXKZCSMQ-UHFFFAOYSA-J phosphonato phosphate;zirconium(4+) Chemical compound [Zr+4].[O-]P([O-])(=O)OP([O-])([O-])=O DTEMQJHXKZCSMQ-UHFFFAOYSA-J 0.000 description 1
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 1
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- JAJWGJBVLPIOOH-IZYKLYLVSA-M sodium taurocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS([O-])(=O)=O)C)[C@@]2(C)[C@@H](O)C1 JAJWGJBVLPIOOH-IZYKLYLVSA-M 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- RIAJLMJRHLGNMZ-UHFFFAOYSA-N triazanium;trioxomolybdenum;phosphate Chemical compound [NH4+].[NH4+].[NH4+].O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.[O-]P([O-])([O-])=O RIAJLMJRHLGNMZ-UHFFFAOYSA-N 0.000 description 1
- KAHROJAJXYSFOD-UHFFFAOYSA-J triazanium;zirconium(4+);tricarbonate;hydroxide Chemical compound [NH4+].[NH4+].[NH4+].[OH-].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KAHROJAJXYSFOD-UHFFFAOYSA-J 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical class [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/78—Cases; Housings; Encapsulations; Mountings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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Abstract
本发明提供一种具有能够防止短路的绝缘性、以及优异的耐电解液性和水蒸气阻隔性的电化学电池用包装材料。本发明的电化学电池用包装材料是依次叠层有金属层、粘接性树脂层和热粘接性树脂层的电化学电池用包装材料,其特征在于,在上述金属层与上述粘接性树脂层之间具有基底皮膜层,上述基底皮膜层至少含有:平均粒径在1nm以上500nm以下的范围内的锆氧化物(A)、选自每1分子中具有4个以上膦酸基的磷化合物中的1种或2种以上的含磷化合物(B)和酸改性聚烯烃树脂(C)。
Description
技术领域
本发明涉及电化学电池用包装材料,特别涉及具有能够防止短路的绝缘性、以及优异的对于电解液的耐久性和水蒸气阻隔性的电化学电池用包装材料。
背景技术
锂离子电池也称为锂二次电池,包含液态、凝胶态或高分子聚合物态的电解液和正极及负极活性物质。锂离子电池包括由正极集电材料/正极活性物质层/电解液层/负极活性物质层/负极集电材料构成的锂离子电池本体、以及包装它们的外装体,外装体由多层膜所构成的电化学电池用包装材料(以后也简称为包装材料)形成。
图4是表示现有电化学电池用包装材料的层构成的截面图,如图4所示,现有电化学电池用包装材料210至少依次叠层基材层211、金属层212和热粘接性树脂层215而构成。
由该包装材料形成的电池用外装体有2种类型,一种是将包装材料加工成袋状并将电池本体收纳在内部的袋型,另一种是对包装材料进行加压加工以形成凹部并将电池本体收纳在凹部内部的压纹型。任意类型的电池用外装体均在内部收纳电池本体,将热粘接性树脂层215彼此重叠并进行热封,由此将电池本体收纳在电池用外装体内部。
图5是现有的压纹型锂离子电池221的立体图,图6是表示图5的锂离子电池221的B-B′的截面结构的图。如图5和图6所示,利用外装体220中的热粘接性树脂层215夹入从锂离子电池本体222向外装体220外部延伸的金属端子224,将外装体周缘部220a热封(以下将被热封的部分记作热封部220a),将锂离子电池本体222收纳在外装体220的内部。
另一方面,由于锂离子电池221的长期使用或急速充电,锂离子电池本体222会放热,与锂离子电池本体222接触的热粘接性树脂层215的一部分熔融,填充在外装体220内部的电解液浸透金属层212,有时在锂离子电池本体222与金属层212之间发生短路。并且,在将外装体周缘部220a热封时,锂离子电池本体222所包括的隔膜的一部分、或者从电极剥离的电极活性物质进入热封部220a的情况下,隔膜的一部分或从电极剥离的电极活性物质与金属层212接触,有时会引起短路。另外,在金属端子224存在毛边的状态下利用外装体220的热粘接性树脂层215夹入从锂离子电池本体222向外装体220外部延伸的金属端子224、并将外装体周缘部220a热封的情况下,有时也会在金属端子224与金属层212之间发生短路。
在现有技术中,为了解决这些问题,提出了在金属层212与热粘接性树脂层215之间存在有聚对苯二甲酸乙二醇酯等耐热性优异的耐热性树脂层的包装材料。另外,在专利文献1中,提出了利用以聚烯烃多元醇和多官能异氰酸酯固化剂为必须成分的粘接剂组合物,将作为金属层212的一种形态的铝箔层与作为热粘接性树脂层215的一种形态的热塑性树脂膜粘接而成的包装材料。
现有技术文献
专利文献
专利文献1:日本特开2005-63685号公报
发明内容
发明要解决的技术问题
但是,在金属层212与热粘接性树脂层215之间存在耐热性树脂层的情况下,必须在这些层间存在用于将金属层212与耐热性树脂层粘接的粘接剂层。并且,在设置粘接剂层的情况下,水蒸气从粘接剂层的端面透过至外装体220内部,与电解液反应,可能会生成氟化氢气体。并且,在专利文献1所记载的包装材料中也同样,水蒸气从上述的由粘接剂组合物构成的层的端面透过至外装体220内部,与电解液反应,可能会生成氟化氢气体。因此,包装材料也需求水蒸气阻隔性优异。
另外,包装材料还需求即使在包装材料与电解液接触时金属层212与热粘接性树脂层215之间的密合性也优异,即需求对电解液的耐久性(以后也称为耐电解液性)优异。
因此,本发明鉴于上述问题,其目的在于提供一种具有能够防止短路的绝缘性、以及优异的耐电解液性和水蒸气阻隔性的电化学电池用包装材料。
用于解决技术问题的技术方案
本发明如下所述。
(1)一种电化学电池用包装材料,其特征在于:
依次叠层有金属层、粘接性树脂层和热粘接性树脂层,
在上述金属层与上述粘接性树脂层之间具有基底皮膜层,
上述基底皮膜层至少含有平均粒径在1nm以上500nm以下的范围内的锆氧化物(A)、选自每1分子中具有4个以上膦酸基的磷化合物中的1种或2种以上的含磷化合物(B)和酸改性聚烯烃树脂(C)。
(2)如上述(1)所述的电化学电池用包装材料,其中,相对于上述基底皮膜层的全部固态成分,上述锆氧化物(A)的含量在3质量%以上54质量%以下的范围内。
(3)如上述(1)或(2)所述的电化学电池用包装材料,其中,相对于上述基底皮膜层的全部固态成分,上述酸改性聚烯烃树脂(C)的含量在24质量%以上96质量%以下的范围内。
发明效果
通过本发明,能够提供一种具有能够防止短路的绝缘性、以及优异的耐电解液性和水蒸气阻隔性的电化学电池用包装材料。
附图说明
图1是表示本发明电化学电池用包装材料的层构成的一例的截面图。
图2是表示具有使用本发明电化学电池用包装材料形成的外装体的锂离子电池的一例的立体图。
图3是表示图2中的锂离子电池的A-A′的截面结构的图。
图4是表示现有电化学电池用包装材料的层构成的截面图。
图5是表示具有使用现有电化学电池用包装材料形成的外装体的锂离子电池的立体图。
图6是表示图5中的锂离子电池的B-B′的截面结构的图。
具体实施方式
以下,参照附图对本发明的电化学电池用包装材料进行详细说明。其中,对于与现有例的图4~图6通用的部分省略说明。
图1是表示作为本发明实施方式的一例的电化学电池用包装材料的层构成的截面图。如图1所示,本实施方式所涉及的电化学电池用包装材料110通过基材层111、金属层112、粘接性树脂层114、热粘接性树脂层115依次叠层而构成,在金属层112与粘接性树脂层114之间,例如在粘接性树脂层114侧的金属层112表面形成有基底皮膜层113。另外,本发明的电化学电池用包装材料110除了上述各层以外,可以还包括1层或2层以上的不同的层。不同的层可以配置于上述各层间、与金属层112侧相反一侧的基材层111的表面上、与粘接性树脂层114相反一侧的热粘接性树脂层115的表面上等的一部分或全部。
图2是具有使用本发明电化学电池用包装材料110形成的袋型外装体120的锂离子电池121的立体图,图3是表示图2中的锂离子电池121的A-A′截面结构的图。如图2和图3所示,在外装体120夹入有金属端子124的状态下,包括该夹入部分在内的周缘部被热封,将包含电解液的锂离子电池本体122收纳在外装体120内部。
在此,在金属层112表面形成的基底皮膜层113具有作为绝缘层的功能,即使在粘接性树脂层114和热粘接性树脂层115的一部分因锂离子电池本体122的放热而熔融的情况下,基底皮膜层113也不会熔融。因此,即使在电解液从粘接性树脂层114和热粘接性树脂层115的发生了熔融的部位浸透至基底皮膜层113的情况下,电解液也会被基底皮膜层113阻隔,金属层112与锂离子电池本体122不导通。由此,能够防止锂离子电池121中发生短路。
另外,在热封部120a中,即使在金属端子124所产生的毛边在热封时进入粘接性树脂层114和热粘接性树脂层115的情况下,在本发明中,也能够防止金属端子124与金属层112导通而发生短路。并且,由于基底皮膜层113本身的水蒸气透过性低,因而电化学电池用包装材料110的水蒸气阻隔性也优异。另外,在本发明中,基底皮膜层113与粘接性树脂层114的粘接性长期不发生变化,基底皮膜层113与粘接性树脂层114之间具有高的层压强度。并且,基底皮膜层113与粘接性树脂层114的粘接对于电解液也是稳定的,因电解液的影响造成的、基底皮膜层113与粘接性树脂层114之间的层压强度的降低也少。
另外,虽然图中没有表示,但也可以在基材层111侧的金属层112表面形成基底皮膜层113。这样,通过在基材层111侧的金属层112表面形成基底皮膜层113,在将多个锂离子电池121排列成组件状使用时,即使部分锂离子电池121放电,也能够确保相邻接的锂离子电池121的绝缘性。
以下,对基底皮膜层113进行详细说明。其中,本发明可以在包括其要旨的范围任意变更,并不仅限于下述实施方式。
[基底皮膜层]
基底皮膜层113至少含有平均粒径在1nm以上500nm以下的范围内的锆氧化物(A)、选自每1分子中具有4个以上膦酸基的磷化合物中的1种或2种以上的含磷化合物(B)和酸改性聚烯烃树脂(C)。
以下对基底皮膜层113的构成要素和基底皮膜层113的形成方法进行详细说明。
基底皮膜层113是由基底皮膜形成剂形成的皮膜,该基底皮膜形成剂至少含有平均粒径在1nm以上500nm以下的范围内的锆氧化物(A)、选自每1分子中具有4个以上膦酸基的磷化合物中的1种或2种以上的含磷化合物(B)和酸改性聚烯烃树脂(C)。其形成方法包括:使基底皮膜形成剂与金属层112的表面接触的工序(接触工序);和对接触了基底皮膜形成剂的金属层112不进行水洗而将其干燥的工序(干燥工序)。其中,基底皮膜层113的形成方法中,可以在接触工序之前包括预先对金属层112进行脱脂或酸清洗等的前处理工序。
(锆氧化物)
作为锆氧化物(A),可以列举平均粒径在1nm以上500nm以下的范围内的锆的氧化物。具体可以列举氧化锆(IV)(ZrO2)。
其中,基底皮膜层113可以含有氢氧化锆(IV)(Zr(OH)2)。
锆氧化物(A)优选以其固体颗粒分散在水性溶剂中的状态(例如溶胶等状态)使用。该分散溶液与锆氧化物(A)的固体颗粒本身相比,具有更容易操作、基底皮膜形成剂的制造变得更容易的优点。
上述分散溶液可以通过公知的方法制造。
水性溶剂是指含有50质量%以上的水的溶剂。作为水性溶剂所含的除水以外的溶剂,可以列举:己烷、戊烷等烷烃系溶剂;苯、甲苯等芳香族系溶剂;乙醇、1-丁醇、乙基溶纤剂等醇系溶剂;四氢呋喃、二噁烷等醚系溶剂;乙酸乙酯、乙酸丁氧基乙酯等酯系溶剂;二甲基甲酰胺、N-甲基吡咯烷酮等酰胺系溶剂;二甲亚砜等砜系溶剂;六甲基磷酸三酰胺等磷酸酰胺系溶剂等。这些除水以外的溶剂可以单独使用,也可以将2种以上组合使用。
基底皮膜层113中的锆氧化物(A)的含量没有特别限定,优选相对于基底皮膜层113的全部固态成分(干燥状态的皮膜质量)在1质量%以上60质量%以下的范围内。其中,从电化学电池用包装材料110的耐电解液性更优异的观点考虑,更优选为3质量%以上;从电化学电池用包装材料110的水蒸气阻隔性更优异的观点考虑,更优选为54质量%以下。
基底皮膜层113中的锆氧化物(A)的平均粒径在1nm以上500nm以下的范围内。其中,从电化学电池用包装材料110的耐电解液性更优异的观点考虑,优选在5nm以上200nm以下的范围内,更优选在10nm以上100nm以下的范围内。
关于基底皮膜层113中的锆氧化物(A)的平均粒径,例如可以通过利用具备能量分散型X射线分析装置(EDS)的扫描型电子显微镜(SEM)、场发射型扫描电子显微镜(FE-SEM)、透射型电子显微镜(TEM)或场发射型透射电子显微镜(FE-TEM)观察基底皮膜层113的表面或截面而求得。具体而言,在使用FE-SEM观察的基底皮膜层113的视场范围内,通过EDS分析特定具有Zr和O的颗粒,之后,测定从特定的颗粒中随机选取的10个颗粒的直径(在具有长径和短径时意指长径),算出测得的各颗粒直径的平均,由此求出锆氧化物(A)的平均粒径。
(含磷化合物)
作为含磷化合物(B),只要是每1分子中具有4个以上膦酸基(-P(=O)(OH)2)的磷化合物即可,具体可以列举肌醇六磷酸及其盐(铵盐、钠盐、钙盐、镁盐、锂盐等)、乙二胺四亚甲基膦酸及其盐(铵盐、钠盐、钙盐、镁盐、锂盐等)等。这些磷化合物可以单独使用,也可以将2种以上组合使用。
基底皮膜层113中的含磷化合物(B)的含量没有特别限定,从基底皮膜层113与粘接性树脂层114之间的初始密合性和电化学电池用包装材料110的耐电解液性的观点考虑,含磷化合物(B)中的磷原子的摩尔量的总和(P)相对于锆氧化物(A)中的锆原子的摩尔量的总和(Zr)的比例(P/Zr)优选在0.01以上5.0以下的范围内,更优选在0.1以上2.0以下的范围内。
(酸改性聚烯烃树脂)
作为酸改性聚烯烃树脂(C),能够应用公知的酸改性聚烯烃树脂。
酸改性聚烯烃树脂(C)为水溶性和水分散性(乳液、分散液)均可。并且,只要不损害基底皮膜形成剂的稳定性,酸改性聚烯烃树脂(C)可以为阳离子性、非离子性和阴离子性的任一种。
作为酸改性聚烯烃树脂(C),可以列举利用不饱和羧酸或其酸酐将聚烯烃改性而得到的酸改性聚烯烃树脂,该聚烯烃可以为:聚丙烯;聚乙烯;丙烯、乙烯与α-烯烃的共聚物等。还可以进一步使少量的其他烯属不饱和单体与这些酸改性聚烯烃树脂共聚。作为使酸改性聚烯烃树脂(C)溶解于水中或分散于水中的方法,可以列举利用氨或胺类将酸改性聚烯烃树脂(C)所含的羧基中和的方法。
作为不饱和羧酸或其酸酐,可以应用公知的物质。具体可以例示丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、衣康酸酐、富马酸、巴豆酸等,还可以例示不饱和二羧酸的半酯、半酰胺等。其中,优选丙烯酸、甲基丙烯酸、马来酸、马来酸酐,更优选丙烯酸、马来酸酐。不饱和羧酸或其酸酐只要与聚烯烃共聚即可,其形态没有特别限定,例如可以列举无规共聚、嵌段共聚、接枝共聚(接枝改性)等。其中,在聚烯烃中导入了不饱和羧酸的酸酐的情况下,在树脂的干燥状态下,形成相邻接的羧基发生脱水环化的酸酐结构,但通过树脂在水中分散,有时酸酐结构的一部分或全部水解而形成羧基或其盐的结构。
上述的酸改性聚烯烃树脂(C)可以单独使用,也可以将2种以上组合使用。
基底皮膜层113中的酸改性聚烯烃树脂(C)的含量没有特别限定,相对于基底皮膜层113的全部固态成分(干燥状态的皮膜质量),优选在5质量%以上98质量%以下的范围内。其中,从电化学电池用包装材料110的水蒸气阻隔性更优异的观点考虑,更优选为24质量%以上;从电化学电池用包装材料110的耐电解液性更优异的观点考虑,更优选为96质量%以下。
(其他)
基底皮膜层113和基底皮膜形成剂还可以含有除了上述的锆氧化物(A)、含磷化合物(B)和酸改性聚烯烃树脂(C)以外的成分。
例如,从与金属层112的表面接触时的操作性的观点考虑,基底皮膜形成剂可以根据需要含有各种溶剂。作为溶剂,例如可以列举:水;己烷、戊烷等烷烃系溶剂;苯、甲苯等芳香族系溶剂;乙醇、1-丁醇、乙基溶纤剂等醇系溶剂;四氢呋喃、二噁烷等醚系溶剂;乙酸乙酯、乙酸丁氧基乙酯等酯系溶剂;二甲基甲酰胺、N-甲基吡咯烷酮等酰胺系溶剂;二甲亚砜等砜系溶剂;六甲基磷酸三酰胺等磷酸酰胺系溶剂等。其中,可以使用1种溶剂,也可以将2种以上的溶剂组合使用。
除此之外,在不损害本发明的要旨和由该基底皮膜形成剂形成的基底皮膜层113的性能的范围内,基底皮膜形成剂还可以含有树脂、表面活性剂、消泡剂、流平剂、交联剂、增塑剂、防菌剂、防霉剂、着色剂等添加剂。
作为消泡剂,例如可以使用矿物油系消泡剂、脂肪酸系消泡剂、有机硅系消泡剂等。
作为流平剂,例如可以使用非离子性或阳离子性的表面活性剂、聚乙炔二醇的聚环氧乙烷或聚环氧丙烷的加成物、乙炔二醇化合物等公知的化合物。
另外,作为交联剂,只要是与锆氧化物(A)和/或酸改性聚烯烃树脂(C)键合而形成牢固的基底皮膜层113的物质即可,没有特别限定,例如可以列举三聚氰胺树脂、封端异氰酸酯、环氧化合物、胺、多元醇、多元酚、多元羧酸、羟基羧酸、磷酸或磷酸化合物(不包括含磷化合物(B))、多价金属化合物等。在使用交联剂的情况下,为了促进交联,可以进一步使用合适的固化催化剂。
作为三聚氰胺树脂,可以使用公知的三聚氰胺树脂。具体可以例示:下式(1)所示的完全烷基化型的三聚氰胺树脂、式(1)中的(ROCH2)2N-基的至少1个被式(2)所示的基团取代的羟甲基型的三聚氰胺树脂、式(1)中的(ROCH2)2N-基的至少1个被式(3)所示的基团取代的亚氨基型的三聚氰胺树脂、或者式(1)中的(ROCH2)2N-基的至少1个被式(4)所示的基团取代的羟甲基/亚氨基型的三聚氰胺树脂。
作为封端异氰酸酯,可以使用使公知的异氰酸酯中的异氰酸酯基与封端化剂反应而得到的封端异氰酸酯。作为异氰酸酯,具体可以例示萘二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、二甲苯二异氰酸酯(XDI)、六亚甲基二异氰酸酯(HMDI)、四甲基二甲苯二异氰酸酯(TMXDI)、二环己基甲烷二异氰酸酯(H12MDI)、氢化二苯基甲烷二异氰酸酯(氢化MDI)、二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)等有机多异氰酸酯、或者它们的缩二脲化物、异氰脲酸酯化物、碳化二亚胺改性体或它们的混合物等。
作为封端化剂,例如可以列举:苯酚、丁基苯酚、氯苯酚、苯基苯酚等酚类;甲乙酮肟、环己酮肟、丙酮肟等肟类;咪唑、2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑等咪唑类;亚硫酸氢钠等亚硫酸氢盐。这些之中,从容易以较低温度且在短时间内解离的观点出发,优选使用亚硫酸氢钠。亚硫酸氢钠等亚硫酸氢盐还兼备作为亲水基导入剂的功能。
另外,封端异氰酸酯可以以乳液的形态使用。上述乳液例如可以通过使用非离子性表面活性剂使封端异氰酸酯在水中乳化而获得。
其中,作为封端异氰酸酯,可以使用以下的(i)~(iii)所示的、具有水溶性或水分散性的封端异氰酸酯。
(i)具有磺酸基或其盐的封端异氰酸酯,其通过使牛磺酸钠等具有磺酸基或其盐和含活泼氢的基团(例如羟基、伯氨基)的化合物与多异氰酸酯反应而得到生成物,之后,使所得到的生成物中残存的异氰酸酯基与封端化剂反应而得到。
(ii)具有聚亚烷基二醇链的封端异氰酸酯,其通过使聚乙二醇等聚亚烷基二醇与多异氰酸酯反应而得到聚氨酯预聚物,之后,使所得到的聚氨酯预聚物所具有的末端异氰酸酯基与封端化剂反应而得到。
(iii)具有季铵基的封端异氰酸酯,其通过使N-甲基二乙醇胺等具有叔氨基和含活泼氢的基团的化合物与多异氰酸酯反应而得到生成物,之后,使所得到的生成物中残存的异氰酸酯基与封端化剂反应,再利用季铵化剂将所得到的生成物中的叔氨基季铵化而得到。
其中,作为上述季铵化剂,可以例示卤代烷或硫酸二乙酯等。
作为环氧化合物,可以使用公知的环氧化合物。具体可以例示山梨糖醇多缩水甘油醚、聚甘油多缩水甘油醚、季戊四醇多缩水甘油醚、二甘油多缩水甘油醚、甘油多缩水甘油醚、三羟甲基丙烷多缩水甘油醚、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚等。
胺意指氨(NH3)中的至少1个氢原子分别独立地被烷基、氨基烷基、N-氨基烷基-氨基烷基、N-[N-(氨基烷基)氨基烷基]氨基烷基或羟基烷基取代的化合物,可以使用公知的胺。具体可以例示乙二胺、二乙三胺、三乙四胺、四乙五胺、五乙六胺、己二胺、单乙醇胺、二乙醇胺、三乙醇胺等。
多元醇意指具有2个以上羟基的化合物,可以使用公知的多元醇。具体可以例示乙二醇、聚乙二醇、丙二醇、聚丙二醇、甘油、聚甘油、季戊四醇、聚季戊四醇等。
多元酚意指具有2个以上酚羟基的芳香族化合物,可以使用公知的多元酚。具体可以例示六羟基苯、邻苯三酚、1,2,4-三羟基苯、均苯三酚、邻苯二酚、间苯二酚、对苯二酚、5-甲基邻苯三酚、2-甲基间苯二酚、5-甲基间苯二酚、2,5-二甲基间苯二酚、3-甲基邻苯二酚、4-甲基邻苯二酚、甲基对苯二酚、2,6-二甲基对苯二酚、5-甲氧基间苯二酚、3-甲氧基邻苯二酚、甲氧基对苯二酚、2,5-二羟基-1,4-苯醌等。
多元羧酸意指具有2个以上羧基的化合物,可以使用公知的多元羧酸。具体可以例示草酸、丙二酸、琥珀酸、戊二酸、己二酸、富马酸、马来酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、丙烯三羧酸、1,2,3-丙三羧酸、1,2,3,4-丁四羧酸等。
羟基羧酸意指具有羟基和羧基的化合物,可以使用公知的羟基羧酸。具体可以例示羟基乙酸、乳酸、丙醇二酸、甘油酸、2-羟基丁酸、3-羟基丁酸、γ-羟基丁酸、苹果酸、酒石酸、柠苹酸、柠檬酸、异柠檬酸、亮氨酸、甲羟戊酸、泛解酸、蓖麻油酸、反蓖麻油酸、羟基二十四烷酸、奎尼酸、莽草酸、水杨酸、杂酚油酸(creosotic acid)、香草酸、焦儿茶酸、间苯二酚羧酸、原儿茶酸、龙胆酸、苔色酸、没食子酸、扁桃酸、二苯乙醇酸、苯基乳酸、邻羟苯丙酸、香豆酸、伞形酸、咖啡酸、阿魏酸、芥子酸等。
作为磷酸或磷酸化合物,可以使用公知的无机磷酸类、磷酸酯类等。作为无机磷酸类,例如可以列举:磷酸(正磷酸)及其盐;偏磷酸、聚磷酸、过磷酸等缩合磷酸及其盐等。作为磷酸酯类,例如可以列举:磷酸单甲酯、磷酸二甲酯、磷酸乙酯、磷酸二乙酯、磷酸单丁酯、磷酸二丁酯、磷酸淀粉酯、葡萄糖一磷酸和葡萄糖六磷酸以及它们的盐等。其中,作为盐,例如可以列举:铵盐;锂盐、钠盐等碱金属盐;钙盐、镁盐等碱土金属盐等。
多价金属化合物意指含有能够形成2价以上的离子的金属原子的化合物。
作为多价金属化合物,可以使用公知的含有选自Mg、Al、Zr、Ti、W、Mo和V中的1种或2种以上金属原子的无机化合物等。具体可以例示:双(乙酰丙酮)镁二水合物(II)、苯甲酸镁、甲酸镁、草酸镁、钨酸镁、偏铌酸镁、钼酸镁、焦磷酸镁、硝酸镁、硫酸镁、碳酸镁、氢氧化镁、氟化镁、磷酸铵镁、磷酸氢镁、氧化镁等的镁盐等;单乙酰丙酮双(乙酰丙酮)铝、硝酸铝、硫酸铝、硫酸钾铝、硫酸钠铝、硫酸铵铝、磷酸铝、碳酸铝、氧化铝、氢氧化铝、氧化铝、氟化铝、乙酸铝、苯甲酸铝、柠檬酸铝、葡糖酸铝、草酸铝、酒石酸铝、乳酸铝等的铝盐等;四(乙酰丙酮)锆(IV)、硅酸锆、碳酸氧锆、六氟锆(IV)酸铵、六氟锆(IV)酸钾、碱式碳酸锆、碳酸锆铵、碳酸氧锆铵、硝酸锆、硝酸氧锆、硫酸锆(IV)、硫酸氧锆、六氟锆酸、磷酸氧锆、焦磷酸锆、磷酸二氢氧锆、氟化锆、乙酸氧锆等的锆盐等;二草酸氧钛二铵、二草酸氧钛二钾、硫酸氧钛、碱式磷酸钛、溴化钛(IV)、偏钛酸、偏钛酸锌(II)、钛酸铝(III)、偏钛酸钾、偏钛酸钴(II)、钛酸锆、偏钛酸铁(III)、偏钛酸铜(II)、钛酸钠、一缩二亚钛酸钕(III)、偏钛酸钡、偏钛酸铋(III)、偏钛酸镁、钛酸镁、偏钛酸锰(II)、一缩二亚钛酸镧(III)、偏钛酸锂、六氟钛(IV)酸铵、六氟钛(IV)酸钾、硫酸钛(III)、硫酸钛(IV)、氯化钛、硝酸钛、硫酸氧钛、氟化钛(IV)、六氟钛酸、乳酸钛、过氧钛酸、乙酰丙酮钛等的钛盐等或钛酸盐等;氯化钨(VI)、氧化钨酸铁(III)、二氧化钨、三氧化钨、偏钨酸、偏钨酸铵、偏钨酸钠、仲钨酸、仲钨酸铵、仲钨酸钠、钨酸锌(II)、钨酸钾、钨酸钙、钨酸钴(II)、钨酸铜(II)、钨酸镍、钨酸钡、钨酸镁、钨酸锰(II)、钨酸锂、磷钨酸、磷钨酸铵、磷钨酸钠等的钨盐等或钨酸盐等;氧化钼(IV)、氧化钼(VI)、钼酸锌(II)、钼酸钾、钼酸钙、钼酸钴(II)、钼酸镍(II)、钼酸钡、钼酸铋(III)、钼酸镁、钼酸锂、仲钼酸锂、磷钼酸、磷钼酸铵、磷钼酸钠、钼酸、钼酸铵、仲钼酸铵、钼酸钠等的钼盐等或钼酸盐等;氧化钒、四钒酸铁(III)、草酸氧钒、五氧化钒、偏钒酸、焦钒酸钠、钒酸钠、偏钒酸铵、偏钒酸钠、偏钒酸钾、三氧化钒、二氧化钒、硫酸氧钒、乙酰丙酮氧钒、乙酰丙酮钒、磷钒钼酸等的钒盐等或钒酸盐等。
上述各种交联剂可以单独使用,也可以将2种或3种以上组合使用。
作为增塑剂,例如可以列举2,2,4-三甲基-1,3-戊二醇单异丁酸酯、二乙二醇单丁醚乙酸酯、乙二醇单丁醚、二丙二醇正丁基醚、二乙二醇二丁基醚、二丙二醇单丙基醚等。
基底皮膜形成剂的pH优选在3以上11以下的范围内,更优选在6以上10以下的范围内。pH在上述范围内时,电化学电池用包装材料110的耐电解液性更优异。
(基底皮膜形成剂的制造)
基底皮膜形成剂的制造方法没有特别限定。例如,可以将锆氧化物(A)或其分散溶液、含磷化合物(B)、酸改性聚烯烃树脂(C)和根据需要的添加剂和/或溶剂混合,适当地调节pH,由此能够制造基底皮膜形成剂。
[基底皮膜层的制造方法]
基底皮膜层113是由上述的基底皮膜形成剂形成的皮膜。该皮膜的制造方法包括:使基底皮膜形成剂与金属层112的表面接触的工序(接触工序);和在该接触工序之后,对接触了基底皮膜形成剂的金属层112的表面不进行水洗而使其干燥的工序(干燥工序)。并且,上述皮膜的制造方法还可以在接触工序之前具有预先对金属层112的表面进行脱脂或酸洗等的前处理工序。
(接触工序)
关于基底皮膜形成剂与金属层112的表面的接触方法,只要能够使基底皮膜形成剂与金属层112的表面接触即可,没有特别限定,例如可以列举喷涂法、浸涂法、辊涂法、帘涂法、旋涂法、棒涂法以及它们的组合等。
基底皮膜形成剂的接触条件没有特别限定,例如,基底皮膜形成剂或金属层112的温度优选在10℃以上90℃以下的范围内,更优选在20℃以上60℃以下的范围内。温度在60℃以下时,能够抑制能源的浪费,因而从经济的观点考虑更为优选。另外,接触时间可以适当设定。(干燥工序)
在干燥工序中,在接触工序后,对于接触了基底皮膜形成剂的金属层112的表面,不进行水洗而是进行干燥。通过该工序能够形成基底皮膜层113。作为干燥条件,优选金属层112的最高到达温度(PMT)在50℃以上250℃以下的范围内。最高到达温度在50℃以上时,溶剂从基底皮膜形成剂中的蒸发能够在更短的时间内进行,因而优选。另外,最高到达温度在250℃以下时,不存在能源的浪费,从经济的观点考虑优选。
干燥方法没有特别限定,可以列举利用间歇式干燥炉、连续式热风循环型干燥炉、传送式热风干燥炉或IH加热器的电磁感应加热炉等的干燥方法。干燥方法中设定的风量和风速等可以任意设定。
(基底皮膜层)
基底皮膜层113能够由上述的制造方法获得。
基底皮膜层113的皮膜量没有特别限定,优选在100mg/m2以上5000mg/m2以下的范围内。通过使基底皮膜层113的皮膜量在该范围内,能够提高基底皮膜层113与粘接性树脂层114之间的初始密合性、以及电化学电池用包装材料110的耐电解液性和绝缘性。对于这些特性而言,更优选的皮膜量在200mg/m2以上3000mg/m2以下的范围内,特别优选的皮膜量在400mg/m2以上2000mg/m2以下的范围内。
基底皮膜层113中存在锆氧化物(A)能够通过利用薄膜X射线衍射法对所得到的具有基底皮膜层113的金属层112进行分析来确认。具体而言,利用薄膜X射线衍射法,对具有基底皮膜层113的金属层进行分析(PANalytical制的Xpert-MPD、广角法、管电压电流:45kV-40mA、扫描速度:0.025°/秒),根据所得到的衍射图案确认基底皮膜层113中的锆氧化物(A)的存在。
另外,基底皮膜层113中存在含磷化合物(B)可以用溶剂(例如氯仿、DMSO等)萃取基底皮膜层113的成分,通过31P-NMR测定进行确认。
另外,基底皮膜层113中存在酸改性聚烯烃树脂(C)可以通过IR测定确认。
如上所述操作得到的基底皮膜层113设置在金属层112与粘接性树脂层114之间,能够提高两者的密合性,并且能够提高金属层112的耐腐蚀性。另外,在金属层112与粘接性树脂层114之间形成有上述基底皮膜层113的本发明的电化学电池用包装材料具有优异的耐电解液性。
以下,对本实施方式所涉及的电化学电池用包装材料110的基底皮膜层113以外的各种层进行详细说明。
[粘接性树脂层]
粘接性树脂层114是配置在基底皮膜层113与热粘接性树脂层115之间的层。
粘接性树脂层114例如含有酸改性聚烯烃树脂。作为酸改性聚烯烃树脂,优选酸改性聚丙烯。作为酸改性聚烯烃树脂,例如可以列举利用不饱和羧酸或其酸酐对聚烯烃进行了酸改性的树脂。其中,酸改性聚烯烃树脂的种类优选对应于热粘接性树脂层115所使用的树脂种类适当选择使用。
粘接性树脂层114的厚度没有特别限定。
另外,粘接性树脂层114的形成方法没有特别限定,能够采用公知的方法,例如可以列举挤出成型法、分散法等。
其中,粘接性树脂层114中可以根据需要添加5%以上的丁烯成分、乙烯-丙烯-丁烯共聚物、非晶质的乙烯-丙烯共聚物、丙烯-α-烯烃共聚物等。
[热粘接性树脂层]
热粘接性树脂层115例如含有聚烯烃。作为聚烯烃,优选聚丙烯。
聚丙烯中可以含有来自丙烯以外的其他α-烯烃(例如乙烯)的重复单元,作为这样的聚丙烯,可以列举无规聚丙烯、嵌段聚丙烯等各种类型的物质。
作为聚丙烯以外的聚烯烃,例如可以列举线型低密度聚乙烯、中密度聚乙烯、线型低密度聚乙烯和中密度聚乙烯的掺混树脂等。其中,中密度聚乙烯是密度在930kg/m3以上且低于942kg/m3的聚乙烯。另外,线型低密度聚乙烯是将乙烯与少量α-烯烃聚合而成的聚合物。
热粘接性树脂层115的厚度没有特别限定。
另外,热粘接性树脂层115的形成方法没有特别限定,可以采用公知的方法,例如可以列举挤出成型法、分散法等。
其中,热粘接性树脂层115可以为单层也可以为多层。在热粘接性树脂层115为多层的情况下,各层可以是含有相同的聚烯烃的层,也可以是含有不同的聚烯烃的层。
[金属层]
金属层112是用于提高电化学电池用包装材料110的强度、并且防止水蒸气从外部经由基材层111侵入锂离子电池121内部的层。
作为构成金属层112的金属,具体可以列举铝、不锈钢、钛等,优选为铝。
金属层112可以是金属箔,也可以是通过金属蒸镀等形成的层,优选为金属箔,更优选为铝箔。从防止在制造包装材料时金属层112出现褶皱或针孔的观点考虑,更加优选使用例如经过退火处理的铝(JIS A8021P-O、JIS A8079P-O)等软质铝箔。
金属层112的厚度只要能够发挥作为水蒸气等的阻隔层的功能即可,没有特别限定,例如可以设定为10μm~50μm左右,优选设定为10μm~40μm左右。
作为金属层112的铝箔,例如可以列举纯铝箔、含铁的铝箔等。[基材层]
基材层111是位于电化学电池用包装材料110的最外层侧的层。关于形成基材层111的原料,只要是绝缘体即可,没有特别限定。
作为形成基材层111的原料,例如可以列举聚酯、聚酰胺、环氧树脂、丙烯酸树脂、含氟树脂、聚氨酯树脂、含硅树脂、酚醛树脂、聚醚酰亚胺、聚酰亚胺以及它们的混合物或共聚物。
作为聚酯,只要是分子内具有酯键(-COO-)的聚合物即可,没有特别限定,例如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。
作为聚酰胺,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。
另外,使用了这些原料的基材层111可以通过在金属层112的表面上涂覆含有这些原料的处理剂而形成。
基材层111可以是含有上述原料的树脂膜、或者将其单轴或双轴拉伸的树脂膜。其中,从通过取向结晶化来提高耐热性的观点考虑,优选基材层111为经过双轴拉伸的树脂膜。其中,在基材层111为上述树脂膜的情况下,通过在金属层112的表面上粘接或粘贴基材层111,由此能够将基材层111配置在金属层112上。
另外,为了提高耐针孔性以及将电化学电池用包装材料110作为电池的外装体使用时外装体的绝缘性,基材层111可以为不同材质的膜叠层而成的叠层体。
另外,在图2和图3中对锂离子电池121进行了说明,但也可以利用由电化学电池用包装材料110形成的外装体120包装除锂离子电池本体122以外的电化学电池本体,制作除锂离子电池121以外的电化学电池。
例如,电化学电池除了包括锂离子电池以外,还包括镍氢电池、镍镉电池、锂金属一次电池或二次电池、锂聚合物电池等化学电池、双电荷层电容器、锂离子电容器等电容器、电解电容器。在此,所谓电化学电池本体包括电池(蓄电部)、和与电池内的正极以及负极连接的电极端子等产生电能的电器设备元件的全部,其中,电池包括封入电化学电池用包装材料前的由正极活性物质和正极集电材料构成的正极、由负极活性物质和负极集电材料构成的负极、以及填充在正极和负极之间的电解液。
但是,本发明并不限定于上述的实施方式,能够进行各种变更,将不同的实施方式中分别公开的技术手段适当组合而得到的实施方式也包括在本发明的技术范围内。
实施例
以下,通过实施例和比较例对本发明进行更为详尽的说明。本发明并不受以下实施例的限定。
[1.带有基底皮膜层的铝箔的制作]
在作为溶剂的水中添加表1所示的各成分并混合之后,使用氨或乙酸调节pH,准备表1所示的各基底皮膜形成剂。其中,表1中的“pH”是各基底皮膜形成剂的pH。
之后,利用使用SUS金属棒的棒涂法在铝箔(厚度40μm)的单面涂布表1所示的各基底皮膜形成剂。之后,将涂布了各基底皮膜形成剂的铝箔在180℃干燥1分钟,由此,制作在铝箔的表面形成有表2所示的各基底皮膜层的带有基底皮膜层的铝箔。
其中,表2中的“浓度(%)”一栏表示基底皮膜层的各成分相对于全部固态成分的含量(质量%),为了能够形成规定的基底皮膜层,适当地调节表1所示的各基底皮膜形成剂中的锆化合物(a)、含磷化合物(b)和水溶性或水分散性的树脂(c)的浓度。并且,在表2中表示含磷化合物(b)中的磷原子的摩尔量的总和(P)相对于锆化合物(a)中的锆原子的摩尔量的总和(Zr)的比例(P/Zr)、以及各基底皮膜层的皮膜量(g/m2)。
<锆化合物(a)>
表1中(a)成分一栏中记载的各符号所对应的锆化合物的种类如下所示。其中,以下所示的a1~a3的氧化锆溶胶的平均粒径是使用大塚电子株式会社制的动态光散射光度计(DLC-6500)测得的值。
a1:氧化锆(IV)溶胶(固态成分20质量%、平均粒径30nm)
a2:氧化锆(IV)溶胶(固态成分15质量%、平均粒径250nm)
a3:氧化锆(IV)溶胶(固态成分25质量%、平均粒径1μm)
a4:乙酸锆(固态成分20质量%)
a5:碳酸锆铵(固态成分31质量%)
<含磷化合物(b)>
表1中(b)成分一栏中记载的各符号所对应的含磷化合物的种类如下所示。
b1:肌醇六磷酸[C6H18O24P6]
b2:乙二胺四亚甲基膦酸[C6H20N2O12P4]
b3:磷酸铵[(NH4)3PO4]
b4:羟基亚乙基二膦酸[C2H8O7P2]
<水溶性或水分散性的树脂(c)>
表1中(c)成分一栏中记载的各符号所对应的水溶性树脂或水分散性树脂的种类、以及这些溶液的制造方法如下所示。
(c1:酸改性聚丙烯树脂)
对等规结构的均聚丙烯树脂(MFR=0.1g/10分钟-170℃·2160g)一边供给氮气,一边在常压下以360℃进行80分钟的热降解。将所得到的聚丙烯树脂1000质量份在氮气中加热升温至180℃使其熔融,之后,加入马来酸酐125质量份进行混合。在该混合物中滴加溶解了过氧化二异丙苯6.3质量份的二甲苯125质量份,以180℃搅拌3小时使其反应。之后,在减压下蒸馏除去二甲苯,将所得到的反应物注入丙酮中,使树脂固化并回收。将该树脂切细之后,加工成粒料状。利用丙酮将经过加工的树脂清洗2次后,进行减压干燥,得到酸改性聚丙烯树脂。接着,以300rpm对上述酸改性聚丙烯树脂150.0质量份、异丙醇60.0质量份、四氢呋喃340.0质量份、二甲基氨基乙醇30.0质量份和蒸馏水420.0质量份进行搅拌,保持看不到树脂沉淀的状态(悬浮状态)。加热10分钟后,再以150℃搅拌60分钟,之后自然冷却。在冷却至80℃的上述搅拌物中追加投入四氢呋喃120.0质量份、二甲基氨基乙醇20.0质量份和蒸馏水100.0质量份,之后,一边以300rpm进行搅拌一边再次进行加热(再升温),以140℃搅拌60分钟。接着,冷却至80℃后,利用真空泵减压蒸馏除去异丙醇、四氢呋喃和水。之后,冷却至35℃后,在残渣(酸改性聚丙烯树脂)中加水,将酸改性聚丙烯树脂的浓度调节为20质量%。利用180目的不锈钢制过滤器对分散有酸改性聚丙烯树脂的水性分散体进行加压过滤,得到酸改性聚丙烯树脂的水性乳液。
(c2:丙烯酸树脂)
在室温下,使异丙醇210质量份、N-羟甲基丙烯酰胺120质量份和丙烯酰胺30质量份混合在离子交换水390质量份中,使其溶解。在该混合物中加入过硫酸钾1.5质量份、亚硫酸氢钠0.06质量份和无水乙酸钠1.5质量份,使其溶解。将该溶解物在氮气氛下用30分钟升温至65℃,在65℃反应3小时。将反应生成物冷却至室温后,进行过滤并回收滤液。作为滤液回收的丙烯酸树脂的水溶液的不挥发成分浓度为20质量%、粘度为2.86dPa·s、pH=5.6。
(c3:弹性体)
作为弹性体,使用具有羧基和羟甲基的丙烯腈丁二烯苯乙烯橡胶的水分散体(固态成分浓度:47%、pH:8、粘度:45mPa·s、Tg:18℃、比重:1.01)。
(c4:环氧树脂)
在氮气氛下将环氧当量为188的双酚A型环氧树脂(双酚-A-二缩水甘油醚)6150质量份、双酚A1400质量份、十二烷基苯酚335质量份、对甲酚470质量份和二甲苯441质量份加热至125℃,反应10分钟。接着,将反应物加热至130℃后,在反应物中添加N,N’-二甲基苄胺23质量份。保持该温度直至环氧当量达到880。接着,在反应物中进一步添加聚醚(BYKChemie公司生产、商品名:K-2000)90质量份,之后,将混合物保存在100℃。30分钟后,在混合物中添加丁基醇211质量份和异丁醇1210质量份。
将二乙三胺与甲基异丁基酮混合后,以130℃~150℃进行加热回流除去生成水,另外得到酮亚胺。
将所得到的酮亚胺467质量份和甲基乙醇胺450质量份添加到上述的含有丁基醇和异丁醇等的混合物中,调节至100℃。30分钟后,将温度升至105℃,进一步在混合物中添加N,N’-二甲基氨基丙胺80质量份。在添加N,N’-二甲基氨基丙胺后75分钟之后,在混合物中依次添加丙二醇化合物(BASF公司生产、商品名:Plastilit 3060)903质量份和丙二醇苯基醚725质量份,制作含氨基的环氧树脂。接着,配合含氨基的环氧树脂87.5质量份和10%乙酸13质量份,得到混合物之后,对去离子水193.5质量份一边进行剧烈搅拌,一边大约用15分钟将上述混合物滴加到上述去离子水中,得到环氧树脂的乳液。
[2.基底皮膜层的表面SEM观察]
对于制得的上述带有基底皮膜层的铝箔的基底皮膜层1和基底皮膜层3,利用FE-SEM(株式会社日立高新技术制、S-4700TypeII型)进行表面观察,确认基底皮膜层1和基底皮膜层3中的氧化锆的粒径(具有长径和短径时意指长径)在500nm以下。即,没有确认到超过500nm的氧化锆。其中,表面观察以加速电压2kV、倍率5000倍对随机选择的十几处视野(1cm见方)进行。
[3.电化学电池用包装材料]
对于上述的带有基底皮膜层的铝箔,在基底皮膜层的上表面熔融挤出酸改性聚丙烯(厚度20μm),并且从其上方熔融挤出聚丙烯(厚度15μm),得到由铝箔层/基底皮膜层/酸改性聚丙烯层/聚丙烯层构成的电化学电池用包装材料。
[4.浸渍电解液后的层压强度的评价(耐电解液性)]
将电化学电池用包装材料切断,制作15mm×250mm的试验片,将该试验片在添加有离子交换水1000ppm的85℃的电解液(制品名:LBG-00015(KISHIDA CHEMICAL Co.,Ltd.生产)、电解质:1M-LiPF6、溶剂:碳酸亚乙酯/碳酸二乙酯/碳酸二甲酯=1/1/1(体积比))中浸渍2周。之后,利用拉伸试验机(岛津制作所制、AGS-50D(商品名))将铝箔与酸改性聚丙烯层之间以夹具间距离50mm、拉伸速度300mm/分钟向180°方向剥离,同时测定剥离时的强度。该测定结果以等级1~4评价。将评价结果示于表3。等级3以上为合格。
等级4:层压强度在10N/15mm以上。
等级3:层压强度在6N/15mm以上且低于10N/15mm的范围内。
等级2:层压强度在3N/15mm以上且低于6N/15mm的范围内。
等级1:由酸改性聚丙烯层和聚丙烯层构成的层压膜已经剥离、或者层压强度低于3N/15mm。
[5.水蒸气阻隔性的评价]
将电化学电池用包装材料切断,制作120×120mm的试验片,并将该试验片对折。将对折而重叠的60mm的边缘部分的一侧以3mm的宽度热封。另外,将通过对折120mm的边缘彼此重叠的部分以10mm的宽度热封,之后,从经过热封的部分中裁切7mm宽度的量,制作另一侧的60mm的边缘部分开口的由120×53mm的外部尺寸构成的袋。接着,在干燥房间(露点-50℃)中,在上述袋中注入3g的电解液溶剂〔碳酸亚乙酯/碳酸二乙酯/碳酸二甲酯=1/1/1(容积比)〕之后,将开口部以10mm的宽度热封,制作水蒸气阻隔性评价样品。将该水蒸气阻隔性评价样品在65℃、90%RH的恒温恒湿槽中静置336小时,利用卡尔费歇尔法测定电解液溶剂中增加的水分浓度(质量ppm)。该测定结果以下述等级1~3评价。其中,120mm的边缘彼此重叠的部分的热封条件为190℃、2.0MPa、3.0秒,60mm的边缘部分的热封条件为190℃、1.0MPa、3.0秒。将评价结果示于表3。等级2以上为合格。
等级3:增加水分浓度在150质量ppm以下。
等级2:增加水分浓度在超过150质量ppm且在200质量ppm以下的范围内。
等级1:增加水分浓度超过200质量ppm。
[6.绝缘性的评价]
将电化学电池用包装材料裁切成40mm×120mm的试验片,之后,用铝片(30mm×100mm)和电化学电池用包装材料的聚丙烯层侧的面夹住金属引线(内径为25.4μm),由热封棒以1.0MPa、190℃持续按压。此时,引线因热封棒的按压侵入酸改性聚丙烯层和聚丙烯层,测定铝片与电化学电池用包装材料的铝箔层之间绝缘性下降的时间。其中,绝缘性下降的时间意指:在开始热封的同时在铝片与电化学电池用包装材料的铝箔层之间持续施加100V的电压,电阻值达到200MΩ以下所需要的时间(达到时间:秒),以下述等级1~4评价。将评价结果示于表3。等级3以上为合格。
等级4:达到时间在60秒以上。
等级3:达到时间在30秒以上且低于60秒的范围内。
等级2:达到时间在5秒以上且低于30秒的范围内。
等级1:达到时间低于5秒。
[表1]
表1
[表2]
表2
[表3]
表3
如表3所示,判明了实施例1~7的电化学电池用包装材料具有优异的耐电解液性和水蒸气阻隔性,并且具有充分的绝缘性。
符号说明
110、210:电化学电池用包装材料;111、211:基材层;112、212:金属层;113:基底皮膜层;114:粘接性树脂层;115、215:热粘接性树脂层;120、220:外装体;121、221:锂离子电池;122、222:锂离子电池本体;124、224:金属端子。
Claims (3)
1.一种电化学电池用包装材料,其特征在于:
其为依次叠层有金属层、粘接性树脂层和热粘接性树脂层的电化学电池用包装材料,
在所述金属层与所述粘接性树脂层之间具有基底皮膜层,
所述基底皮膜层至少含有平均粒径在1nm以上500nm以下的范围内的锆氧化物(A)、选自每1分子中具有4个以上膦酸基的磷化合物中的1种或2种以上的含磷化合物(B)和酸改性聚烯烃树脂(C)。
2.如权利要求1所述的电化学电池用包装材料,其特征在于:
相对于所述基底皮膜层的全部固态成分,所述锆氧化物(A)的含量在3质量%以上54质量%以下的范围内。
3.如权利要求1或2所述的电化学电池用包装材料,其特征在于:
相对于所述基底皮膜层的全部固态成分,所述酸改性聚烯烃树脂(C)的含量在24质量%以上96质量%以下的范围内。
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