CN102729541A - Aluminum foil laminated sheet for secondary battery packing material and secondary battery packaging material - Google Patents
Aluminum foil laminated sheet for secondary battery packing material and secondary battery packaging material Download PDFInfo
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- CN102729541A CN102729541A CN2012100874622A CN201210087462A CN102729541A CN 102729541 A CN102729541 A CN 102729541A CN 2012100874622 A CN2012100874622 A CN 2012100874622A CN 201210087462 A CN201210087462 A CN 201210087462A CN 102729541 A CN102729541 A CN 102729541A
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- China
- Prior art keywords
- aluminium foil
- laminated
- layer
- secondary cell
- secondary battery
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 32
- 239000011888 foil Substances 0.000 title abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 8
- 239000005022 packaging material Substances 0.000 title abstract description 5
- 238000012856 packing Methods 0.000 title 1
- -1 polypropylene Polymers 0.000 claims abstract description 55
- 239000004743 Polypropylene Substances 0.000 claims abstract description 45
- 229920001155 polypropylene Polymers 0.000 claims abstract description 45
- 229920000098 polyolefin Polymers 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 238000012545 processing Methods 0.000 claims abstract description 18
- 239000005030 aluminium foil Substances 0.000 claims description 116
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 239000004677 Nylon Substances 0.000 claims description 8
- 230000009545 invasion Effects 0.000 claims description 8
- 229920001778 nylon Polymers 0.000 claims description 8
- 229920006267 polyester film Polymers 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 35
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012611 container material Substances 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 238000007788 roughening Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 59
- 238000000465 moulding Methods 0.000 description 24
- 239000002648 laminated material Substances 0.000 description 23
- 230000006978 adaptation Effects 0.000 description 20
- 238000007654 immersion Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 210000000981 epithelium Anatomy 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-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
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000011282 treatment Methods 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an aluminum foil laminated sheet applied for a secondary battery container or packaging material and having the advantages of vibration resistance, fitness, excellent electrolyte resistance and forming excellence. The invention further comprises a secondary battery packaging material using the aluminum foil laminated sheet. The aluminum foil laminated sheet for the secondary battery packaging material is characterized by sequentially comprising a laminated aluminum foil (A), an improved polyolefin layer (B) and a polypropylene screen (C) which is not stretched. A roughening processing operation is performed on at least one A surface on the B side. Then a continuous spongy gap is formed from the uttermost surface of the roughened surface along the thickness direction. The resin on the B layer penetrates into the gap with the maximum penetration depth being over 1-7 mu m.
Description
Technical field
The present invention relates to the laminated material that uses in the secondary cell exterior material, more particularly, relate to excellent aluminium foil laminated of adaptation, electrolyte resistance property as the exterior material of secondary cell and the secondary cell exterior material that uses it.
Background technology
With the environmental protection kinematic mounting is background, and the importing of electric automobile, PHEV, electric motor car with two wheels etc. obtains promoting.In these, utilizing of lithium rechargeable battery is developed.
In the lithium rechargeable battery, be used to keep the shape of battery, the exterior material of protection, maintenance battery functi on plays an important role.Lithium rechargeable battery uses with the laminated material of aluminium foil as barrier material with the exterior material trend.
As to the require performance of lithium ion battery exterior material with laminated, it is minimum to enumerate (1) moisture-vapor transmission, (2) bag, after electrolyte is injected in inside; Even as time passes, electrolyte inside can not leaked yet, (3) electrolyte resistance excellent; Constituent material can not peeled off as time passes, and extrusion forming can be carried out in (4), and aluminium foil can not produce pin hole, crackle after the moulding; (5) after the moulding; Constituent material can not crack, and the aluminium foil when making battery in lead and the laminated material can conducting, and (6) have the hear resistance etc. of the high temperature of about 110 ℃ of temporary transient tolerances.
As the laminated that satisfies these requirements; Disclosed secondary cell container uses laminated material to handle the laminated material that aluminium foil/second adhesive phase/the diaphragm seal lamination forms for outer dress resin molding/first adhesive phase/chemical conversion in the patent documentation 1; It is characterized in that; Chemical conversion is handled and is carried out through chromium compound, and second adhesive phase is for containing the polyester-polyurethane class of epoxy (epoxy).
Disclosed secondary cell container uses laminated material to handle the laminated material that aluminium foil/prime coat/the diaphragm seal lamination forms for outer dress resin molding/adhesive phase/chemical conversion in the patent documentation 2; It is characterized in that; Chemical conversion is handled and to be carried out through chromium compound, and prime coat contains and is selected from least a in epoxy resin, melmac, polyurethane resin, the carboxyl modified polypropylene resin.
Disclosed secondary cell container uses laminated material for stack gradually the laminated material of the laminated body formation that forms through biaxially oriented polyester film layer/biaxial stretch-formed nylon rete/metal foil layer/Thermoadhesive resin bed in the patent documentation 3; It is characterized in that; Metal foil layer is an aluminium foil; Handle to form epithelium through chromate, the Thermoadhesive resin bed uses any one the individual layer in for example polyethylene, polypropylene, the sour modified polypropene etc., or the two or more composite bed that suitably cascades.
Propose the secondary cell container in the patent documentation 4 and used laminated material; And practicability; This secondary cell container uses laminated material to be laminated material that heat-resistant resin rete/metal foil layer/the thermoplastic resin film lamination forms; It is characterized in that the impact strength of heat-resistant resin rete is more than the 30000J/m, metal foil layer has been implemented the primary coat of silane coupler, titanium coupling agent etc. and has been handled; Chemical conversions such as chromate processing are handled, and thermoplastic resin film is the unstretching film of polypropylene, maleic acid modified polypropene, ethylene acrylate copolymer or ionomer resin etc.
In the patent documentation 5; As the useful multilayer film of taking in for food, commodity, secondary cell etc.; Proposed following multilayer film, this multilayer film is the multilayer film that comprises crystallinity acrylic polymer layer/acid-modified polyolefin resin layer/aluminium foil/aramid layer/polyester based resin layer, it is characterized in that; Aluminium foil has been implemented non-chromium chemical conversion tunicle and has been handled, and the degree of crystallinity of crystallinity acrylic polymer is more than 60% under the temperature of the fusing point of acid-modified polyolefin resin.
Disclosed laminated body in the patent documentation 6, in the packaging material for polymer cell that comprises outermost layer/barrier layer/innermost layer, comprising the barrier layer surface roughness is that Ra is that 0.2 μ m is above, Rmax is the above aluminium foils of 1.0 μ m.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2003-288865 communique
[patent documentation 2] TOHKEMY 2003-288866 communique
[patent documentation 3] TOHKEMY 2002-56824 communique
[patent documentation 4] TOHKEMY 2005-22336 communique
[patent documentation 5] TOHKEMY 2009-61670 communique
[patent documentation 6] TOHKEMY 2001-35455 communique.
Summary of the invention
But; When the lithium ion battery of lift-launch on electric automobile, PHEV, electric motor car with two wheels uses these laminated materials with exterior material; Adaptation, the electrolyte resistance property of aluminium foil and diaphragm seal are insufficient; There are the problem that liquid leaks or electrolyte disperses that produces electrolysis in aluminium foil and diaphragm seal owing to the vibration in the road traveling is prone to peel off.
Problem of the present invention is; Provide adaptation, the electrolyte resistance property of aluminium foil and diaphragm seal further to improve; Even the vibration in the road traveling, aluminium foil and diaphragm seal can not peeled off yet, the aluminium foil laminated that the secondary cell exterior material that electrolyte inside can not leaked yet, dispersed is used.
The inventor furthers investigate in order to solve above-mentioned problem; The result has invented; Stack gradually aluminium foil (A), improved polyalkene layer (B), un-stretched polypropylene film (C); The side surface of B at least of A is carried out the asperities processing, has from the surface spongy space continuous on thickness direction, and B layer resin is that the degree of depth of 1～7 μ m invades the aluminium foil laminated that secondary cell in this space is adorned usefulness outward with maximum depth of invasion.Further can know; Carried out the asperities processing through forming with the B side surface of A only; Formation from the surface on thickness direction with 1/10 the continuous spongiform space of the degree of depth of the thickness of 1 μ m～A, B layer resin invades in this space, to be that 1 μ m is above use the aluminium foil laminated as the secondary cell exterior material of characteristic to maximum depth of invasion; Mouldability further improves
According to the present invention; Use the secondary cell exterior material of aluminium foil laminated of the present invention; Adaptation, electrolyte resistance property excellence, even carry on electric automobile, PHEV, electric motor car with two wheels etc., aluminium foil and diaphragm seal also can not peeled off owing to the vibration in the road traveling; The leakage or the electrolyte that can not produce electrolyte inside disperse, thereby can improve the reliability of secondary cell tremendously.
Description of drawings
[Fig. 1] be aluminium foil of the present invention (A) the surface one the example scanning electron microscope photo (5000 times of multiplying powers).
[Fig. 2] is for observing the scanning electron microscope photo (5000 times of multiplying powers) of aluminium foil (A) and the state at the interface of improved polyalkene layer (B) behind an example of the present invention range upon range of.
Symbol description
1. improved polyalkene layer (B)
2. aluminium foil (A)
3. maximum depth of invasion.
The specific embodiment
Below the present invention is specified.
The laminated that secondary cell exterior material of the present invention uses the aluminium foil laminated to cascade as aluminium foil (A), improved polyalkene layer (B), un-stretched polypropylene film (C).A has and prevents that moisture from invading the function of inside battery from the outside.C has the secondary cell exterior material is stressed to merge sealing (heat bonding) with the C of laminated, is shaped to the function of exterior material.A and C can not be directly bonding, and B and A or have cohesive with C have A and the bonding securely function of C.
The asperities processing is carried out on the surface of the side of B at least of the aluminium foil among the present invention (A), has from the most surperficial spongiform space continuous on thickness direction.As spongiform space, be the zone of 1 μ m～10 μ m continuously to depth capacity from the surface preferably, the asperities processing is more than the 1 μ m through the depth capacity that makes the sponge state, becomes abundant with the closing force of B layer resin.Even the degree of depth of sponge state surpasses 10 μ m; Closing force does not improve yet; Be processed into the intensity that aluminium foil can not be born in spongiform gap by asperitiesization, be prone to break when therefore being shaped to the secondary cell exterior material, the steam barrier property is prone to variation owing to the generation of pin hole.
Breaking when preventing the moulding of aluminium foil keeps intensity, carried out the aluminium foil of asperities processing with the two sides and compared, if the aluminium foil that uses the surface of B side only to be carried out the asperities processing, then be difficult for breaking during moulding, and mouldability improves.At this moment, be preferably formed from the B side surface that carried out the asperities processing 1/10 the continuous spongiform space of the degree of depth on thickness direction with the thickness of 1 μ m～aluminium foil.Through making spongiform space is below 1/10 of thickness of aluminium foil, is difficult for during moulding breaking, and can obtain excellent mouldability.Be difficult for producing the pin hole that causes steam barrier property variation during moulding as a result, the performance steam barrier that aluminium foil had.
Above-mentioned spongiform space forms from the surface continuously, is not to be made up of separate emptying aperture.The improved polyalkene layer resin of B from the range upon range of interface of A, be that the surface of aluminium foil enters into this spongiform space with fusion or soft state, thereby the closing force of B and A improves, A and C are bonding securely.
Aluminium foil among the present invention (A) can use the aluminium foil that has formed spongiform space through the asperities processing.As the method for the asperities processing in the spongiform space that forms aluminium foil (A), can enumerate etch processes.Carried out the representational example on the surface of asperities processing, every 1cm for from surface observation the time
2Have 1 * 10
8～1 * 10
10The long limit of individual ellipse is the spongiform surface (with reference to Fig. 1) of the sized opening of 0.1～5 μ m.
For the aluminium foil among the present invention (A); The high-purity aluminium foil of Cu that will contain Si, the 200～3000ppm of Fe, the 200～2000ppm of 200～1000ppm; In the electrolyte that in hydrochloric acid, contains sulfuric acid, phosphoric acid, nitric acid etc., utilize alternating current, with 0.1～1A/cm
2Current density, the processing time about 1～10 minute carry out etching.In addition, through the liquid bath temperature is controlled at 30～70 ℃, can control the degree of depth of sponge state.In addition, contact with electrolyte, can make only simultaneously by the aluminium foil of asperitiesization through the one side that only makes aluminium foil.As the object lesson of A, can use known cathode foil for aluminum electrolytic capacitors.Static capacity is 99.9 μ F/cm
2The time, the surface area of aluminium foil is big and closing force improves, so more preferably.
Through having spongiform space, improved polyalkene layer (B) resin is immersed in this spongiform space, and B and A are bonding securely, as a result A and C bonding securely (with reference to Fig. 2).
If the opening size on the surface of aluminium foil is 0.1 μ m～5 μ m, then B layer resin is prone to enter into the space and more preferably.If the every 1cm of opening on the surface of aluminium foil
2More than 1 * 10
8Individual, then the closing force of A and C improves and more preferably.If less than 1 * 10
10Individual, then the mechanical strength of the part that is formed with the space of A is maintained, and the cohesion that suppresses aluminium foil self destroys, and can improve peel strength, so more preferably.
Among the present invention, B layer resin invades in the above-mentioned space, and maximum depth of invasion is that 1～7 μ m is important.Maximum depth of invasion can through after cross section in the evaluation method stated to the interface of A after range upon range of and B observe with scanning electron microscope and estimate.Maximum immersion depth refers to the length that improved polyalkene layer (B) resin is invaded at depth direction from the surface opening of aluminium foil.If maximum immersion depth is less than 1 μ m, then closing force is insufficient.More preferably maximum immersion depth is more than the 2 μ m.In addition, if maximum immersion depth surpasses 7 μ m, the air that then is in the spongiform space is extruded by part, in the improved polyalkene layer, produces bubble, is that basic point is because the influence of electrolyte is prone to the phenomenon of generation closing force reduction with this part when producing bubble.Particularly in the present invention, abundant for the closing force that makes B and A, being necessary to make maximum depth of invasion is more than the 1 μ m.
The thickness of aluminium foil is preferably 10～100 μ m.Be that 10 μ m are when above; Aluminium foil is difficult for because (
) processed in the deep-draw when being shaped to the secondary cell exterior material breaks; Be that 100 μ m are when following; Intensity degree as the toughness of laminated is suitable; Easy to operate, mouldability is also excellent, so preferred.The thickness of 20～50 μ m more preferably.
From keep the intensity of aluminium foil, can not produce during moulding breaking, the angle of pin hole considers that preferably it is more than the 10 μ m that thickness by aluminium foil deducts the value that the depth capacity that forms the zone in above-mentioned spongy space obtains.
In addition, invade the angle consideration of the performance degradation of secondary cell inside, secondary cell from preventing moisture, more preferably the steam permeability of A (JIS K7129:2008) is 0.05g/m
224 hours (40 ℃ * 90%RH) below.
Un-stretched polypropylene film (C) can use known sealing to use polypropylene screen.
If unstretching film is then compared heat-sealing temperature and reduced with stretched film, be prone to come the moulding secondary cell to use container, so preferred through heat-sealing.This be because, under the situation about stretching, polypropylene molecule is prone to twine mutually during sealing.
Thickness for C; If thickness is more than the 25 μ m, the sealing intensity that then is used for the exterior material of moulding secondary cell improves, and sealing is difficult for peeling off; Be difficult for producing leak of liquid; If thickness is below the 100 μ m, then the un-stretched polypropylene film of this thickness is prone on market, obtain, so thickness 25～100 μ m more preferably.
Among the present invention, between aluminium foil (A) and un-stretched polypropylene film (C), improved polyalkene layer (B) is set.
Wherein, Improved polyalkene refers to the polyolefin with functional group's composition; And as improved polyalkene; Use imports amino, carboxyl, hydroxyl, maleic anhydride base, siloyl group, acrylic, acrylate-based etc. and aluminium and has the improved polyalkene that the functional group of associativity forms in polyolefin such as polyethylene, polypropylene, the known improved polyalkenes such as olefin copolymer that will obtain as comonomer polymerizations such as alkene such as the ethene of principal monomer, propylene and acrylic acid, vinyl acetate, methyl propenoic acid glycidyl base ester, methyl acrylates.Particularly to have combined the fusing point of functional group be 110～130 ℃ graft modification polyethylene and the fusing point graft modification polypropylene that is 140～170 ℃ from considering preferred with the angle of the adaptation of aluminium foil in grafting.The graft copolymer that they form for the polyethylene that constitutes main skeleton or polyacrylic all or part of and unsaturated carboxylic acid or its acid anhydride-grafted copolymerization.
Improved polyalkene further is preferably graft modification polypropylene from considering with the angle of the adaptation of the un-stretched polypropylene of C layer.
The polypropylene that constitutes the main skeleton of graft modification polypropylene is the homopolymers of propylene or comprises propylene and the block copolymer of other monomer or random copolymer.As other monomer; Can enumerate for example ethene, 1-butylene, isobutene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 3-Methyl-1-pentene, 2-Methyl-1-pentene, 1-heptene etc., in polypropylene, can contain the combination more than a kind or 2 kinds in them.The content of the monomer of other in the polypropylene is generally below the 10 weight %.Wherein, consider, be preferably Noblen, ethylene, propylene block copolymer, ethylene, propylene random copolymer from the cost aspect.As in order to form modified polypropene with the unsaturated carboxylic acid of polypropylene grafted copolymerization or its acid anhydrides (below be called " grafted monomers "); Can enumerate for example unsaturated monocarboxylic such as acrylic acid, methacrylic acid; Unsaturated dicarboxylics such as maleic acid, fumaric acid, itaconic acid, citraconic acid, pi-allyl butanedioic acid, mesaconic acid, glutaconate, Na Dike acid (
), methyl Na Dike acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, pi-allyl succinyl oxide, glutaconic anhydride, carbic anhydride, methyl carbic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride etc.Graft modification polypropylene can contain the independent combination more than a kind or 2 kinds in these grafted monomers.Wherein, consider, be preferably maleic acid, maleic anhydride, Na Dike acid, carbic anhydride from cost aspect and rerum natura aspect.The content of the grafted monomers in this modified polypropene is considered with the cohesive of aluminium foil and with the angle of the excellent adhesive composition of the cohesive of un-stretched polypropylene film from obtaining, and is 0.1～10 weight %, is preferably 0.5～5 weight %.
Improved polyalkene closes with two reef knots of aluminium foil (A) and un-stretched polypropylene film (C) easily, through the improved polyalkene layer, and the vibration during owing to the traveling of automobile etc. and degree reduction that A and C are prone to peel off.
The thickness of improved polyalkene layer is 10 μ m when above, and A and C are difficult for peeling off, if thickness is below the 50 μ m, then the improved polyalkene layer is difficult for owing to vibrate and breaks, so the thickness of improved polyalkene layer 10 μ m～50 μ m more preferably.
The improved polyalkene layer can use modified polyolefin resin, is arranged between A and the C through utilizing extrusion coated layered manner.In addition, also can the improved polyalkene layer be arranged on the C in advance and form.
Manufacturing approach to laminated of the present invention does not limit especially, can form through following method.
Can be for aluminium foil (A) and un-stretched polypropylene film (C), use above-mentioned improved polyalkene is melt extruded the layer (B) that forms as the interlayer between A and the C, carry out range upon range of and make the A/B/C stack membrane.Perhaps, also can the film that comprise above-mentioned improved polyalkene (B) be arranged on the un-stretched polypropylene film (C) in advance, A and B/C laminated body is range upon range of, obtain the A/B/C stack membrane thus.And, the preferred pressing of under fusing point～temperature range higher 20 ℃ of B, condition, pressurizeing then at 0.1～1.0MPa than the fusing point of B.
More than the fusing point of B, pressurize pressing because the resin of B is immersed in the spongy space of aluminium foil, and closing force improves and preferred.When more than than the high 20 ℃ temperature of the fusing point of B, pressurizeing pressing; The modified polyolefin resin lowering viscousity can deeper be immersed in the spongy space of aluminium foil, but because its reaction; The air in spongy space is extruded; In the resin of B, be prone to produce bubble, when producing bubble with this part be basic point because the influence of electrolyte is prone to produce the phenomenon of closing force reduction, so under at the most than the high 20 ℃ temperature of the fusing point of B, add hot pressing.
Likewise, through the pressing of more than 0.1MPa, pressurizeing, the resin of B is immersed in the spongy space of aluminium foil, and closing force improves, so preferred.If more than 1.0MPa, pressurize pressing, then in the spongy space of part, clamp-on a large amount of B layer resins, because this reaction is prone to produce bubble, the pressing of preferably below 1.0 MPa, pressurizeing equally.
The secondary cell exterior material is through at the aluminium foil laminated of the opposite one side of the one side with pasting the un-stretched polypropylene film of aluminium foil laminated of the present invention nylon membrane for example, and the laminated material that range upon range of above that PETG film forms is made.In addition, also can nylon membrane, PETG film individual course be stacked on the aluminium foil laminated of the present invention.Cut out 2 from these laminated materials so that un-stretched polypropylene film (C) for inboard mode carry out overlapping, to its three limit through heat-sealing with the sticking bag of making of heat between the un-stretched polypropylene film, can make thus.In addition, laminated material is cut out 1, one end is bent, heat-sealing and above-mentioned likewise that heat between the un-stretched polypropylene film is sticking is passed through on the both sides of side, can make the exterior material of bag shape thus so that un-stretched polypropylene film (C) is inboard mode.
In addition; The secondary cell exterior material also can be made as follows; Cut out 2 laminated material sheets from above-mentioned laminated material so that the PETG film be the mode in the outside through mould with 1 laminated material deep-draw moulding, with the moulding material of the deep-draw forming part that is provided with the generating key element that is used to take in secondary cell and another sheet laminated material in un-stretched polypropylene film (C) side superimposed; Carry out the fusion adhesion through heat-sealing, can make exterior material thus.
[embodiment]
Below through embodiment the present invention is specified, but the present invention is not limited only to these embodiment.And each characteristic value is measured through following method.
(1) film, aluminum foil thickness
Use electronic gauge (the system K-312A of ア Application リ ッ Co., Ltd. type) to press the thickness of measuring thickness, aluminium foil with the 30g pin.
(2) thickness of the improved polyalkene layer (B) between A and the C
Small pieces (2mm * 2mm) be embedded in the epoxy resin (trade name " エ Port マ ウ Application ト " of リ Off ァ イ Application テ ッ Network (strain) system) with the A/B/C laminated; Use slicer to be cut into 50nm thickness, observe with 500 times multiplying power through transmissive optical microscope (the ニ コ of Co., Ltd. Application イ Application ス Star Le メ Application ト カ Application パ ニ ー system " エ Network リ プ ス E100 ") and try to achieve together with embeding resin.
(3) adaptation
Laminated is peeled off about 5cm between B layer and C layer; Be installed on the upper and lower scroll chuck of cupping machine (テ Application シ ロ Application); Under the condition that crosshead speed (
) 50mm/ minute, width 15mm, the long 15cm of sample, T type are peeled off, try to achieve dhering strength (N/15mm), adaptation is estimated (according to JIS-K6854-3:1999) according to following benchmark.And measure and carry out with 5 sample numbers, estimate with its mean value.
More than the A:15N/15mm, and all assess sample is the above situation of 15N/15mm
A～B: mean value is more than the 15N/15mm, but 1 above assess sample is less than the situation of 15N/15mm
More than the B:10N/15mm and less than 15N/15mm
C: less than 10N/15mm
(4) electrolyte resistance property
Electrolyte resistance property affirmation as laminated is estimated; The laminated that is cut into width 15mm, the long 15cm of sample impregnated in the solution that adding hexafluorophosphoric acid lithium salts (concentration 1mol/L) forms in ethylene carbonate/dimethyl carbonate/diethyl carbonate=1/1/1 (weight ratio); After preserving for 1 week under 85 ℃ of atmosphere; Peel off about 5cm; Use cupping machine (テ Application シ ロ Application), under the condition that crosshead speed 50mm/ minute, T type are peeled off, try to achieve dhering strength (N/15mm), carry out the evaluation (according to JIS-K6854-2) of electrolyte resistance property according to following benchmark.
A: more than 15N/15mm, and all assess sample is the above situation of 15N/15mm
A～B: mean value is more than the 15N/15mm, but 1 above assess sample is less than the situation of 15N/15mm
More than the B:10N/15mm and less than 15N/15mm
C: less than 10N/15mm
(5) outward appearance of laminated
Sheet with A/B/C after range upon range of is cut into the size of 10cm * 10cm, looks observation from the sidelong glance of un-stretched polypropylene sheet, according to following benchmark the generation situation of bubble is estimated.
A: number of bubbles is 0～1 a/sheet
B: number of bubbles is 2～20 a/sheet
C: number of bubbles is more than 21/sheet
(6) observational technique of the sponge state of aluminium foil
On the surface of aluminium foil, be coated with Pt; In addition; The cross section that utilizes ion milling (
) to expose aluminium foil; On machined surface, be coated with Pt; Through system electric field radioactive SEM (FE-SEM) S-4800 of Hitachi, carry out the surface and the cross-section of aluminium foil with the 2.0kV accelerating potential.With 5000 times multiplying powers to the formation situation in spongy space, estimate from the formation scope on surface.
(7) immersion depth of B layer resin
Through with above-mentioned (6) identical method; Cross section to the thickness direction of the near interface of the A layer/B layer of laminated is observed with FE-SEM, and the maximum immersion depth of the B layer resin when observing with the width 25 μ m of 5000 times multiplying powers in the visual field is measured shown in the solid line double-head arrow of Fig. 2.Promptly; In the FE-SEM cross-section photograph in the interface of the A layer of (Fig. 2) and B layer; Be present in position (Fig. 2 dotted portion) near the interface of B layer side as 0 μ m, until invading the degree of depth near the position (chain-dotted line of Fig. 2) of A layer side (Fig. 2 3) as maximum immersion depth (μ m).And B layer resin is immersed in the position of A layer side, and through the contrast in the space of the contrast of the B layer resin in the FE-SEM photo and A layer is compared, the immersion part of identification B layer resin is partly judged with non-immersion.This mensuration is carried out in 3 the mensuration visual field for mutual different widths direction, calculates its maximum.
(8) fusing point of improved polyalkene
The fusing point of improved polyalkene utilizes differential scanning type calorimeter (DSC), tries to achieve through the fusing point test according to JIS-K7121:1987.
(9) mouldability
(registration mark) ON is last with ユ ニ チ カ (strain) system nylon membrane " エ Application Block レ system " that solid shape divides thickness 3.5 μ m to be coated on 25 μ m with ロ ッ Network ペ イ Application ト (strain) system adhesive ロ ッ Network ボ Application De JRU-80/H-5; Behind the heat drying, fit with the aluminium foil side of dry laminate method and aluminium foil laminated.With nylon membrane is that protruding side is carried out the deep-draw moulding.As the moulding size is the size (shape of the recess of mould: bight R, end R, flange R are 3mm) of 30mm * 50mm; The deep-draw degree of depth when making moulding plays 1 millimeter 1 millimeter ground by 4mm deepens to carry out moulding, estimates through the maximum deep-draw degree of depth that laminated material is not damaged.
A: when deep-draw degree of depth 6mm, do not produce and break.
A～B: the pin hole of under transmitted light, confirming to have point-like during deep-draw degree of depth 6mm.
B: produce during deep-draw degree of depth 6mm and break.
C: produce below the deep-draw degree of depth 5mm and break.
(10) container evaluation
(registration mark) ON is last with ユ ニ チ カ (strain) system nylon membrane " エ Application Block レ system " that solid shape divides thickness 3.5 μ m to be coated on 25 μ m with ロ ッ Network ペ イ Application ト (strain) system adhesive ロ ッ Network ボ Application De JRU-80/H-5; Behind the heat drying, fit with the aluminium foil side of dry laminate method and aluminium foil laminated.With nylon membrane is that protruding side is carried out the deep-draw moulding.As the moulding size is the size (shape of the recess of mould: bight R, end R, flange R are 3mm) of 30mm * 50mm, and the deep-draw degree of depth when making moulding is that 4mm implements moulding.Laminated material after 2 moulding is overlapping with the mode of the inboard of polypropylene screen side formation container, implement tripartite sealing down with impulse sealer for 210 ℃ in the heat seal temperature.Then, in ethylene carbonate/dimethyl carbonate/diethyl carbonate=1/1/1 (weight ratio), inject hexafluorophosphoric acid lithium salts (concentration 1mol/L) 5ml, implement residue one side's sealing, make container.This container was preserved 120 hours under 60 ℃ condition, observed the outward appearance after preserving.
A: the bad problem that no liquid is leaked.
A～B: no liquid is leaked, but finds variable color in the liquid after preserving.
B: no liquid is leaked, but under transmitted light, confirms to have the pin hole of point-like.
C: have bad problems such as leak of liquid.
[embodiment 1]
Carried out the aluminium foil (A) (Showa Denko K. K's system cathode foil for aluminum electrolytic capacitors 1085) of asperities processing and the un-stretched polypropylene film (C) (" パ イ レ Application " film-CT P 1146 of Toyo Boseki K.K's system) of thickness 70 μ m for the both side surface of thickness 30 μ m; The polypropylene that to extrude with 30 μ m thickness is used for the B layer between A and the C as the improved polyalkene (B) (143 ℃ of Mitsubishi chemical Co., Ltd's graft modification polypropylene " モ デ ィ ッ Network " P553A, fusing points) of main component; Carry out range upon range of after; Aluminium foil laminated of the present invention is made in the pressing of under 145 ℃, the condition of 0.2MPa, pressurizeing.In addition, make container.Characteristic is as shown in table 1.
[embodiment 2]
Among the embodiment 1; As improved polyalkene (B); Mitsubishi chemical Co., Ltd is made graft modification polypropylene " モ デ ィ ッ Network " P502 (168 ℃ of fusing points) as the B layer, and in addition the pressing of under 170 ℃ condition, pressurizeing likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 3]
Among the embodiment 1; As improved polyalkene (B); Mitsubishi chemical Co., Ltd is made graft modification low density polyethylene (LDPE) " モ デ ィ ッ Network " L502 (110 ℃ of fusing points) as the B layer; In addition the pressing of under 120 ℃ condition, pressurizeing likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 4]
Among the embodiment 1; As improved polyalkene (B); Mitsubishi chemical Co., Ltd is made graft modification wire low density polyethylene (LDPE) " モ デ ィ ッ Network " M502 (124 ℃ of fusing points) to extrude; In addition the pressing of under 125 ℃ condition, pressurizeing likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 5]
Among the embodiment 1; As improved polyalkene (B); Mitsubishi chemical Co., Ltd is made graft modification high density polyethylene (HDPE) " モ デ ィ ッ Network " H503 (128 ℃ of fusing points) extrude, in addition the pressing of under 130 ℃ condition, pressurizeing likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 6]
Among the embodiment 1; As improved polyalkene (B); Sumitomo Chemical Co is made ethylene methacrylic acid methyl terpolymer " ア Network リ Off ト " WD301 (100 ℃ of fusing points) extrude, making the pressurization pressing-in temp is 110 ℃, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.Though result's adaptation is good, electrolyte resistance property is weaker.In addition, make container.Characteristic is as shown in table 1.
[embodiment 7]
Among the embodiment 1, making the pressurization pressing-in temp is 165 ℃, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.Though the adaptation no problem is found the generation of bubble in appearance, possibly be that electrolyte resistance property is also weaker therefrom.In addition, make container.Characteristic is as shown in table 1.
[embodiment 8]
Among the embodiment 1, making moulding pressure is 0.07MPa, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.Characteristic is as shown in table 1.Because moulding pressure is low, immersion depth is little, be 1.2 μ m, and adaptation, electrolyte resistance property are also weaker.In addition, make container.Characteristic is as shown in table 1.
[embodiment 9]
Among the embodiment 1, making plus-pressure is 1.4MPa, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.Characteristic is as shown in table 1.Likewise find the generation of bubble with embodiment 7, electrolyte resistance property is also weaker.In addition, make container.Characteristic is as shown in table 1.
[embodiment 10]
The only one side of the aluminium foil (living in the light ア Le ミ paper tinsel system BESPA8021 of Co., Ltd.) of thickness 40 μ m is contacted with the electrolyte that contains hydrochloric acid; Known engraving method through using AC power is handled, and only make a side surface turns to spongiform aluminium foil with the scope asperities of 4 μ m from the surface on thickness direction.Use this aluminium foil as aluminium foil (A) among the embodiment 1, the asperities treated side that makes A is the range upon range of A/B/C of B side, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 11]
The only one side of the aluminium foil (living in the light ア Le ミ paper tinsel system BESPA8021 of Co., Ltd.) of thickness 40 μ m is contacted with the electrolyte that contains hydrochloric acid; Known engraving method through using AC power is handled, and only make a side surface turns to spongiform aluminium foil with the scope asperities of 7 μ m from the surface on thickness direction.Use this aluminium foil as aluminium foil (A) among the embodiment 1, the asperities treated side that makes A is the range upon range of A/B/C of B side, in addition likewise makes aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[embodiment 12]
Aluminium foil (living in the light ア Le ミ paper tinsel system BESPA8021 of Co., Ltd.) for thickness 40 μ m; In containing the electrolyte of hydrochloric acid; Known engraving method through using AC power is handled, and makes both side surface and on thickness direction, turns to spongiform aluminium foil with the scope asperities of 4 μ m from the surface.Use this aluminium foil as aluminium foil (A) among the embodiment 1, in addition likewise make aluminium foil laminated of the present invention with embodiment 1.In addition, make container.Characteristic is as shown in table 1.
[comparative example 1]
Among the embodiment 1, making the pressurization pressing-in temp is 135 ℃, in addition likewise makes the aluminium foil laminated with embodiment 1.Immersion depth is 0.5 μ m, and adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 2]
Among the embodiment 2, making plus-pressure is 0.05MPa, in addition likewise makes the aluminium foil laminated with embodiment 2.Immersion depth is 0.8 μ m, and adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 3]
Among the embodiment 1, making the pressurization pressing-in temp is 175 ℃, in addition likewise makes the aluminium foil laminated with embodiment 1.Immersion depth is 7.5 μ m, though adaptation is good, produces a lot of bubbles, and electrolyte resistance property is also insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 4]
Among the embodiment 1, making plus-pressure is 2MPa, in addition likewise makes the aluminium foil laminated with embodiment 1.Immersion depth is 8.1 μ m, though adaptation is good, produces a lot of bubbles, and electrolyte resistance property is also insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 5]
Among the embodiment 1,, use the processing aluminium foil (ア of Mitsubishi Le ミ ニ ウ system Co., Ltd.'s system " Super-Ecoat ") that is formed with epithelium through electrolytic treatments, in addition likewise make the aluminium foil laminated with embodiment 1 as aluminium foil (A).Characteristic is as shown in table 1.The immersion of no B layer resin, adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 6]
As aluminium foil (A), the aluminium foil of used thickness 40 μ m (living in the light ア Le ミ paper tinsel system BESPA8021 of Co., Ltd.) is in addition likewise made the aluminium foil laminated with embodiment 1.The immersion of no B layer resin, adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 7]
Among the embodiment 1; Do not use improved polyalkene; Extrude and Ube Industries, Ltd is made high-pressure process low density polyethylene (LDPE) " UBE Port リ エ チ レ Application " L719 (fusing point is 108 ℃), making the pressurization pressing-in temp is 120 ℃, in addition likewise makes the aluminium foil laminated with embodiment 1.Though immersion depth is 1.6 μ m, adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[comparative example 8]
Among the embodiment 1, do not extrude B layer resin, and un-stretched polypropylene film (C) is directly overlapped on the aluminium foil pressing of under 165 ℃, pressurizeing.Adaptation, electrolyte resistance property are all insufficient.In addition, make container.Characteristic is as shown in table 1.
[table 1]
Industrial applicability
The processability of laminated material of the present invention is good; The exterior body of being made by aluminium foil laminated of the present invention is used laminated as the secondary cell that carries on electric automobile, PHEV, electric motor car with two wheels with exterior body suitably because adaptation, electrolyte resistance property, vibration resistance property, resistance to impact are excellent.
Claims (4)
1. the secondary cell exterior material is used the aluminium foil laminated; It is characterized in that; Stack gradually aluminium foil (A), improved polyalkene layer (B), un-stretched polypropylene film (C), the side surface of B at least of A is carried out the asperities processing, forms from surface that this quilt carries out the asperities processing spongy space continuous on thickness direction; B layer resin invades in this space, and maximum depth of invasion is 1～7 μ m.
2. the secondary cell exterior material is used the aluminium foil laminated; It is characterized in that; Stack gradually aluminium foil (A), improved polyalkene layer (B), un-stretched polypropylene film (C), only the B side surface of A is carried out the asperities processing, forms from this by continuous spongiform space of the degree of depth of 1/10 to the thickness of 1 μ m～A on thickness direction, the surface of asperitiesization; B layer resin invades in this space, and maximum depth of invasion is more than the 1 μ m.
3. according to claim 1 or claim 2 secondary cell exterior material is used the aluminium foil laminated, it is characterized in that improved polyalkene layer (B) is that fusing point is 140～170 ℃ a graft modification polypropylene.
4. secondary cell exterior material has formed at claim 1 or 2 described secondary cell exterior materials with the one side laminated nylon membrane of the not range upon range of B layer of the aluminium foil (A) of aluminium foil laminated and/or the laminated that polyester film forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011071816 | 2011-03-29 | ||
| JP2011-071816 | 2011-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102729541A true CN102729541A (en) | 2012-10-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100874622A Pending CN102729541A (en) | 2011-03-29 | 2012-03-29 | Aluminum foil laminated sheet for secondary battery packing material and secondary battery packaging material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2012216509A (en) |
| KR (1) | KR20120112136A (en) |
| CN (1) | CN102729541A (en) |
Cited By (4)
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| CN107207789A (en) * | 2015-03-06 | 2017-09-26 | 横滨橡胶株式会社 | Rubber composition for side wall and the pneumatic tire using the rubber composition for side wall |
| TWI603520B (en) * | 2015-12-04 | 2017-10-21 | 台虹科技股份有限公司 | Laminated film and fabrication method thereof |
| CN108140749A (en) * | 2015-10-15 | 2018-06-08 | 凸版印刷株式会社 | Electrical storage device encapsulating material and use its electrical storage device |
| TWI759309B (en) * | 2016-06-24 | 2022-04-01 | 日商昭和電工包裝股份有限公司 | Exterior material for power storage device, method for producing the same, and power storage device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6389096B2 (en) * | 2014-10-22 | 2018-09-12 | 昭和電工パッケージング株式会社 | Power storage device exterior material and power storage device |
| CN107431235B (en) * | 2015-03-23 | 2019-12-13 | 远景Aesc能源元器件有限公司 | Lithium ion secondary battery |
| JP2016222759A (en) * | 2015-05-27 | 2016-12-28 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
| JP6482399B2 (en) * | 2015-06-17 | 2019-03-13 | ニチコン株式会社 | Metallized film capacitors |
| JP6812633B2 (en) * | 2015-10-15 | 2021-01-13 | 凸版印刷株式会社 | Exterior material for power storage device and power storage device using it |
| JP6930065B2 (en) * | 2016-01-14 | 2021-09-01 | 凸版印刷株式会社 | Exterior materials for lithium-ion batteries and lithium-ion batteries using them |
| KR102322222B1 (en) | 2017-09-28 | 2021-11-05 | 주식회사 엘지에너지솔루션 | Pouch-Type Battery Case Comprising Metal Layer Having Concavo-convex Structure Surface |
| DE112019000429T5 (en) * | 2018-01-16 | 2021-05-12 | Toagosei Co., Ltd. | Battery adhesive composition and battery adhesive member using the same |
-
2012
- 2012-03-14 JP JP2012056790A patent/JP2012216509A/en active Pending
- 2012-03-28 KR KR1020120031693A patent/KR20120112136A/en not_active Application Discontinuation
- 2012-03-29 CN CN2012100874622A patent/CN102729541A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207789A (en) * | 2015-03-06 | 2017-09-26 | 横滨橡胶株式会社 | Rubber composition for side wall and the pneumatic tire using the rubber composition for side wall |
| CN108140749A (en) * | 2015-10-15 | 2018-06-08 | 凸版印刷株式会社 | Electrical storage device encapsulating material and use its electrical storage device |
| CN108140749B (en) * | 2015-10-15 | 2022-01-04 | 凸版印刷株式会社 | Packaging material for power storage device, and power storage device using same |
| TWI603520B (en) * | 2015-12-04 | 2017-10-21 | 台虹科技股份有限公司 | Laminated film and fabrication method thereof |
| TWI759309B (en) * | 2016-06-24 | 2022-04-01 | 日商昭和電工包裝股份有限公司 | Exterior material for power storage device, method for producing the same, and power storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012216509A (en) | 2012-11-08 |
| KR20120112136A (en) | 2012-10-11 |
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Application publication date: 20121017 |