CN115447248B - Composite polymer film, method for producing same, metallized composite polymer film and use - Google Patents
Composite polymer film, method for producing same, metallized composite polymer film and use Download PDFInfo
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- CN115447248B CN115447248B CN202211084788.XA CN202211084788A CN115447248B CN 115447248 B CN115447248 B CN 115447248B CN 202211084788 A CN202211084788 A CN 202211084788A CN 115447248 B CN115447248 B CN 115447248B
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- polymer film
- composite polymer
- surface layer
- oxide
- heat treatment
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- 239000002131 composite material Substances 0.000 title claims abstract description 185
- 229920006254 polymer film Polymers 0.000 title claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 229920000728 polyester Polymers 0.000 claims abstract description 118
- 239000002344 surface layer Substances 0.000 claims abstract description 91
- 239000010410 layer Substances 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000012792 core layer Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000002086 nanomaterial Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 70
- -1 polyethylene terephthalate Polymers 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 22
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- 239000011241 protective layer Substances 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000012748 slip agent Substances 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 235000012222 talc Nutrition 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical group CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010408 film Substances 0.000 description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 description 13
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 12
- 238000005266 casting Methods 0.000 description 10
- 229920006267 polyester film Polymers 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000007769 metal material Substances 0.000 description 8
- 229920001230 polyarylate Polymers 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 7
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 229920001748 polybutylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NXDJCCBHUGWQPG-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;terephthalic acid Chemical compound OCC1CCC(CO)CC1.OC(=O)C1=CC=C(C(O)=O)C=C1 NXDJCCBHUGWQPG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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Abstract
The application relates to a composite polymer film, a manufacturing method thereof, a metallized composite polymer film and application thereof, and belongs to the technical field of batteries. The application discloses a composite polymer film, which comprises a core layer, a first surface layer and a second surface layer, wherein the core layer is positioned between the first surface layer and the second surface layer; the core layer is manufactured from the following raw materials in percentage by mass: 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant, and the manufacturing raw materials of the first surface layer and the second surface layer respectively and independently comprise: 88 to 98.8 percent of polyester material, 1 to 10 percent of nano oxide and 0.2 to 2 percent of additive. Wherein the inorganic nanomaterial comprises one or more of nano oxide, graphene oxide, carbon nanotube and carbon nanofiber. The composite polymer film provided by the application can improve the surface adhesion performance, mechanical strength, heat resistance and firm strength with a surface metal conductive layer.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite polymer film, a manufacturing method thereof, a metallized composite polymer film and application.
Background
Metallized polymer films are widely used in electronics, packaging, and printing due to their excellent properties of electrical conductivity, barrier, flexibility, and light weight. Metallized polymer film products include composite current collectors, thin film electrodes, packaging aluminizes, printed films, and the like. The manufacturing process of the composite current collector is generally: and depositing a layer of metal material on the high polymer film by adopting a physical vapor deposition method to prepare a surface metallized film with certain conductivity, namely the composite current collector. Compared with the traditional current collector, the composite current collector based on the high-molecular polymer has lower cost, lighter weight and better internal insulation, so that the cost of the battery can be reduced and the energy density and the safety of the battery can be improved when the composite current collector is applied to the battery. However, the polyester film of the conventional technology has the problems of weak surface adhesion performance, low mechanical strength and poor heat resistance, and when the polyester film is compounded with a metal material, the adhesive strength between the polyester film and the metal material is low due to poor affinity.
Disclosure of Invention
Based on this, it is necessary to provide a composite polymer film, a method for producing the same, a metallized composite polymer film and applications thereof, so as to improve the surface adhesion property, mechanical strength, heat resistance and strength with the surface metal conductive layer of the composite polymer film.
The technical scheme adopted by the application is as follows:
the application provides a composite polymer film, which comprises a core layer, a first surface layer and a second surface layer, wherein the core layer is positioned between the first surface layer and the second surface layer;
the manufacturing raw materials of the core layer comprise the following components in percentage by mass: 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant, wherein the manufacturing raw materials of the first surface layer and the second surface layer respectively and independently comprise: 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive.
In some embodiments, the nano-oxide comprises one or more of alumina, silica, titania, zinc oxide, copper oxide, magnesium oxide, ferric oxide, zirconium dioxide, and tin dioxide.
In some embodiments, the inorganic nanomaterial comprises one or more of a nano-oxide, graphene oxide, carbon nanotubes, and carbon nanofibers.
In some embodiments, the polyester material comprises one or more of polyethylene terephthalate (PET), polyethylene 2, 6-naphthalate (PEN), polybutylene terephthalate (PBT), poly 1, 4-cyclohexanedimethanol terephthalate (PCT), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester (PETG), poly propylene 2, 6-naphthalate (PTN), poly propylene terephthalate (PTT), poly butylene 2, 6-naphthalate (PBN), poly butylene 2, 5-furandicarboxylate, poly Butylene Adipate Terephthalate (PBAT), polyarylate (PAR), and derivatives thereof.
In some embodiments, the additives include antioxidants and slip agents;
optionally, the antioxidant comprises one or more of phosphonate and bisphenol a phosphite;
optionally, the slipping agent comprises one or more of calcium carbonate, talcum powder, kaolin, diatomite, siloxane, clay, mica, aluminum silicate, potassium phosphate, barium sulfate and acrylic ester.
In some embodiments, the composite polymer film has a thickness of 1 to 50 μm, preferably 2 to 20 μm;
optionally, the thicknesses of the core layer, the first surface layer and the second surface layer are 70% -90%, 5% -15% and 5% -15% of the thickness of the composite polymer film in sequence, and the thicknesses of the first surface layer and the second surface layer are equal.
The application also provides a manufacturing method of the composite polymer film, which comprises the following steps:
s1, respectively manufacturing a polyester slice A, a polyester slice B and a polyester slice C, wherein the polyester slice A and the polyester slice C are respectively and independently prepared from 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive in percentage by mass, and the polyester slice B is prepared from 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant;
S2, carrying out melt extrusion treatment on the polyester chip A, the polyester chip B and the polyester chip C to obtain a molten polyester material with a core layer, a first surface layer and a second surface layer, wherein the core layer is positioned between the first surface layer and the second surface layer;
and S3, sequentially carrying out molding treatment and heat treatment on the molten polyester material.
In some embodiments, the heat treatment process of step S3 includes the steps of:
the first stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min;
and a second stage: the heat treatment temperature is 160-220 ℃, and the heat treatment time is 0.5-5 min;
and a third stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min.
The application also provides a metallized composite polymer film, which comprises a composite polymer film and a metal conductive layer, wherein the composite polymer film is prepared by the composite polymer film or the preparation method, and the metal conductive layer is arranged on at least one surface of the composite polymer film;
optionally, the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium, and silver.
In some embodiments, the thickness of the metal conductive layer is 20-2000 nm; preferably, the thickness of the metal conductive layer is 30-1000 nm.
The application also provides a composite current collector comprising the metallized composite polymer film.
In some embodiments, the composite current collector further comprises a protective layer on the metallic conductive layer of the metallized composite polymer film;
optionally, the protective layer comprises one or more of nickel, chromium, nickel-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers, and graphene;
optionally, the thickness of the protective layer is 100-150 nm, preferably 20-100 nm.
Further, the application also provides an electrode plate, which comprises the composite current collector.
Further, the application also provides a battery, which comprises the electrode plate.
Still further, the application also provides an electronic device comprising the battery.
Compared with the prior art, the composite polymer film and the manufacturing method thereof have the following advantages:
the nano oxide added in the first surface layer and the second surface layer can improve the surface adhesiveness, the mechanical strength and the heat resistance of the first surface layer and the second surface layer, and the inorganic nano material added in the core layer can improve the mechanical property and the heat resistance of the core layer, so that the surface adhesiveness, the mechanical strength and the heat resistance of the composite polymer film are effectively improved.
In the manufacturing process of the composite polymer film, the nano oxide segregates to the surface of the composite polymer film to form an organic-inorganic hybrid layer with the nano oxide content being dominant, and the good cohesiveness of the nano oxide and the metal material is utilized, so that the cohesive force of the composite polymer film and the metal conductive layer is improved.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Furthermore, the term "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
An embodiment of the present application provides a composite polymer film comprising a core layer, a first skin layer, and a second skin layer, the core layer being located between the first skin layer and the second skin layer;
the core layer is manufactured from the following raw materials in percentage by mass: 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant, wherein the manufacturing raw materials of the first surface layer and the second surface layer respectively and independently comprise: 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive.
The surface polarity of the polyester film is weaker (35 mN/m), so that the adhesion force of the polyester film and a metal material is poorer; the tensile strength of the polyester film is generally less than 250MPa, and the polyester film is easy to break under the environment of a PVD (physical vapor deposition) system due to the pressure of a winding system, the bombardment of metal atoms and the surface temperature rise of the polyester film; in addition, the polyester film has poor heat resistance and is easy to shrink when in heat, and the shrinkage is easy to occur under the bombardment and deposition actions of high-temperature metal atoms, so that the defects of products and the poor heat resistance of the composite current collector are caused; in addition, the application of the composite current collector to the battery involves coating, composite molding and other processes that also place relatively high demands on the tensile strength of the polyester film.
In view of this, the present application provides a composite polymer film, which improves the mechanical properties and heat resistance of the core layer by using intermolecular forces between inorganic nanomaterial and polyester material, and the nano-oxides in the first and second surface layers segregate to the surfaces of the first and second surface layers during film formation and cooling, so that the surface polarity and heat resistance of the first and second surface layers can be improved. Therefore, the composite polymer film has the advantages of good surface adhesion, high mechanical strength, good processability and good heat resistance. The metallized composite polymer film is manufactured by taking the composite polymer film as a base film, and the bonding strength of the composite polymer film and the surface metal conducting layer is also greatly improved. The content of the inorganic nano material in the core layer of the composite polymer film and the content of the nano oxide in the first surface layer and the second surface layer cannot be too low or too high, if the content of the inorganic nano material and the nano oxide is too low, the performance of the composite polymer film is not obviously improved, and if the content of the inorganic nano material and the nano oxide is too high, the film defect is easily caused.
In some embodiments, the nano-oxide comprises one or more of aluminum oxide, silicon dioxide, titanium dioxide, zinc oxide, copper oxide, magnesium oxide, ferric oxide, zirconium dioxide, and tin dioxide.
In some embodiments, the shape of the nano-oxide includes one or more of spherical, linear, and tubular.
In some embodiments, the spherical nano-oxide has a diameter of 5-80 nm, the linear nano-oxide has a diameter of 3-30 nm and a length of 0.1-1 μm, and the tubular nano-oxide has a diameter of 5-50 nm and a length of 0.1-1 μm.
In some embodiments, the graphene has a sheet diameter of 0.2-2 μm, a thickness of 0.8-0.9 nm, and a monolayer ratio of 60-80%; the sheet diameter of the graphene oxide is 0.2-2 mu m, and the thickness of the graphene oxide is 0.8-1.2 nm; the carbon nanotubes are single-walled carbon nanotubes with the diameter of 4-5 nm and the length of 0.2 nm-2 mu m; the carbon nanofibers have a diameter of 20-80 nm and a length of 0.2-2 μm.
It should be explained that, the size of the nano-oxide in the first surface layer and the second surface layer needs to be controlled, if the size of the nano-oxide in the first surface layer and the second surface layer is too small, the performance of the composite polymer film is not easy to be improved, and if the size of the nano-oxide is too large, the nano-oxide is difficult to segregate to the surfaces of the first surface layer and the second surface layer, so that the adhesion between the composite polymer film and the metal conductive layer is improved to a limited extent, and on the other hand, film defects are easy to be caused.
It is understood that the nano-oxide includes any one of alumina, silica, titania, zinc oxide, copper oxide, magnesium oxide, ferric oxide, zirconium dioxide, and tin dioxide, or includes a mixture of a plurality of alumina, silica, titania, zinc oxide, copper oxide, magnesium oxide, ferric oxide, zirconium dioxide, and tin dioxide formed in any ratio.
In some embodiments, the inorganic nanomaterial comprises one or more of a nano-oxide, graphene oxide, carbon nanotubes, and carbon nanofibers.
It is understood that the inorganic nanomaterial includes any one of nano oxide, graphene oxide, carbon nanotube, and carbon nanofiber, or includes a mixture of a plurality of nano oxide, graphene oxide, carbon nanotube, and carbon nanofiber formed in any ratio.
In some embodiments, the polyester material comprises one or more of polyethylene terephthalate (PET), polyethylene 2, 6-naphthalate (PEN), polybutylene terephthalate (PBT), poly 1, 4-cyclohexanedimethanol terephthalate (PCT), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester (PETG), poly propylene 2, 6-naphthalate (PTN), poly propylene terephthalate (PTT), poly butylene 2, 6-naphthalate (PBN), poly butylene 2, 5-furandicarboxylate, poly Butylene Adipate Terephthalate (PBAT), polyarylate (PAR), and derivatives thereof.
It is understood that the polyester material includes any one of polyethylene terephthalate (PET), polyethylene 2, 6-naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene 1, 4-cyclohexanedimethanol terephthalate (PCT), polyethylene terephthalate-1, 4-cyclohexanedimethanol terephthalate (PETG), polypropylene 2, 6-naphthalate (PTN), polypropylene terephthalate (PTT), polybutylene 2, 6-naphthalate (PBN), polybutylene 2, 5-furandicarboxylate, polybutylene adipate terephthalate (PBAT), polyarylate (PAR), and derivatives thereof, or the polyester material includes polyethylene terephthalate (PET), polyethylene 2, 6-naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene 1, 4-cyclohexanedimethanol terephthalate (PCT), polyethylene terephthalate-1, 4-cyclohexanedimethanol terephthalate (PETG), polypropylene 2, 6-naphthalate (PTN), polybutylene 2, 5-furandicarboxylate, polybutylene adipate (PBAT), polybutylene terephthalate (PBT), polybutylene 2, 6-naphthalate (PBT), polybutylene terephthalate (5, polybutylene terephthalate (PET) Polyarylates (PAR) and their derivatives in any ratio.
In some embodiments, the additives include antioxidants and slip agents;
optionally, the antioxidant comprises one or more of phosphonate and bisphenol a phosphite;
optionally, the slip agent comprises one or more of calcium carbonate, talc, kaolin, diatomaceous earth, silicone, clay, mica, aluminum silicate, potassium phosphate, barium sulfate, acrylate.
It is understood that the antioxidant comprises phosphonate or bisphenol a phosphite or a mixture of phosphonate and bisphenol a phosphite in any ratio.
It will be appreciated that the slip agent comprises any of calcium carbonate, talc, kaolin, diatomaceous earth, silicone, clay, mica, aluminum silicate, potassium phosphate, barium sulfate, acrylate, or a mixture of a plurality of calcium carbonate, talc, kaolin, diatomaceous earth, silicone, clay, mica, aluminum silicate, potassium phosphate, barium sulfate, and acrylate in any ratio.
In some embodiments, the thickness of the composite polymer film is 1 to 50 μm, preferably 2 to 20 μm;
optionally, the thicknesses of the core layer, the first surface layer and the second surface layer are 70% -90%, 5% -15% and 5% -15% of the thickness of the composite polymer film in sequence, and the thicknesses of the first surface layer and the second surface layer are equal.
It will be appreciated that the thickness of the composite polymer film may be any value between 1 and 50 μm, for example: 1 μm, 2 μm, 4 μm, 8 μm, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 55 μm, etc.; the thicknesses of the core layer, the first surface layer and the second surface layer can be any value between 70% -90%, 5% -15% and 5% -15% in sequence, and the ratio of the thicknesses of the core layer, the first surface layer and the second surface layer in the composite polymer film thickness can be 90%, 5% and 5% for example; or 84%, 8%; or 80%, 10%; or 76%, 12%; or 70%, 15%.
The application also provides a manufacturing method of the composite polymer film, which comprises the following steps:
s1, respectively manufacturing a polyester slice A, a polyester slice B and a polyester slice C, wherein the polyester slice A and the polyester slice C are respectively and independently prepared from 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive, and the polyester slice B is prepared from 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant according to mass percentage;
s2, carrying out melt extrusion treatment on the polyester chip A, the polyester chip B and the polyester chip C to obtain a molten polyester material with a core layer, a first surface layer and a second surface layer, wherein the core layer is positioned between the first surface layer and the second surface layer;
And S3, sequentially carrying out molding treatment and heat treatment on the molten polyester material.
It should be noted that polyester chip a forms the first skin layer, polyester chip B forms the core layer, and polyester chip C forms the second skin layer.
In the manufacturing process of the composite polymer film, the nano oxide segregates to the surface of the composite polymer film to form an organic-inorganic hybrid layer with the nano oxide content being dominant, and the good cohesiveness of the nano oxide and the metal material is utilized, so that the cohesive force of the composite polymer film and the metal conductive layer is improved.
In some embodiments, the molding process of step S3 includes the steps of:
(1) Casting sheet: casting the molten polyester material in the step S2 onto a casting roll, and obtaining a casting through casting roll and water cooling treatment;
(2) Stretching in the longitudinal direction: preheating the cast sheet at 70-100 ℃ and then carrying out longitudinal stretching treatment to obtain a membrane, then carrying out heat setting treatment at 165-180 ℃ and cooling treatment at 30-50 ℃, wherein the longitudinal stretching ratio is (3-5): 1, the longitudinal stretching temperature is 80-120 ℃;
(3) And (3) transversely stretching: preheating the membrane at 80-120 ℃, then carrying out transverse stretching treatment, then carrying out heat setting treatment at 150-250 ℃, and carrying out cooling treatment at 80-150 ℃, wherein the transverse stretching multiplying power is (3-5): 1, and the transverse stretching temperature is 90-140 ℃.
In some embodiments, the heat treatment process of step S3 includes the steps of:
the first stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min;
and a second stage: the heat treatment temperature is 160-220 ℃, and the heat treatment time is 0.5-5 min;
and a third stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min.
The application also provides a metallized composite polymer film, which comprises a composite polymer film and a metal conductive layer, wherein the composite polymer film is prepared by the composite polymer film or the preparation method, and the metal conductive layer is arranged on at least one surface of the composite polymer film;
optionally, the material of the metallic conductive layer includes one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium, and silver.
It will be appreciated that the metallic conductive layer may be made of one of copper, copper alloy, aluminum alloy, nickel alloy, titanium, and silver, or may be made of a plurality of copper, copper alloy, aluminum alloy, nickel alloy, titanium, and silver.
In some embodiments, the thickness of the metal conductive layer is 20-2000 nm; preferably, the thickness of the metal conductive layer is 30-1000 nm.
It is understood that the thickness of the metal conductive layer may be any value between 20 and 2000nm, for example, the thickness of the metal conductive layer may be 20nm, 25nm, 30nm, 50nm, 150nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm, 850nm, 950nm, 1000nm, 1050nm, 1150nm, 1250nm, 1350nm, 1450nm, 1550nm, 1650nm, 1750nm, 1850nm, 1950nm, 2000nm.
In some embodiments, the method of fabricating the metal conductive layer includes one or more of physical vapor deposition, electroplating, and electroless plating;
optionally, the physical vapor deposition method includes one or more of a resistance heating vacuum evaporation method, an electron beam heating vacuum evaporation method, a laser heating vacuum evaporation method, and a magnetron sputtering method.
In some embodiments, the thickness of the composite polymer film in the metallized composite polymer film is 1-20 μm.
It is understood that the thickness of the composite polymer film in the metallized composite polymer film may be any value between 1 and 20 μm, for example, the thickness of the composite polymer film in the metallized composite polymer film may be 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, 17 μm, 19 μm, 20 μm.
The application also provides a composite current collector comprising the metallized composite polymer film.
In some embodiments, the composite current collector further comprises a protective layer on the metallic conductive layer of the metallized composite polymer film;
optionally, the protective layer comprises one or more of nickel, chromium, nickel-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers, and graphene;
optionally, the thickness of the protective layer is 10-150 nm, preferably 20-100 nm.
It is understood that the thickness of the protective layer may be any value between 10 and 150nm, for example, the thickness of the protective layer may be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 45nm, 55nm, 65nm, 75nm, 85nm, 95nm, 100nm, 105nm, 115nm, 125nm, 135nm, 145nm, 150nm.
In some embodiments, the method of manufacturing the protective layer includes one or more of physical vapor deposition, in situ forming, and coating;
preferably, the physical vapor deposition method includes one or more of a vacuum evaporation method and a magnetron sputtering method;
preferably, the in-situ forming method includes a method of forming a metal oxide passivation layer in-situ on a surface of a metal conductive layer;
Preferably, the above coating method includes one or more of a die coating method, a blade coating method, and an extrusion coating method.
In some embodiments, the protective layer is two layers, and the materials of the two protective layers may be the same or different, and the thicknesses of the two protective layers may be equal or unequal.
Further, the application also provides an electrode plate, which comprises the composite current collector.
It can be understood that the electrode sheet of the present application may be formed of a slurry by mixing a positive electrode active material/negative electrode active material, a conductive agent, a binder and a solvent, and the slurry is coated on the composite current collector of the present application by a method for preparing an electrode sheet well known to those skilled in the art, and the electrode sheet may be divided into a positive electrode sheet and a negative electrode sheet according to the difference of the active materials. The preparation method of the electrode sheet is well known to those skilled in the art, and the present application is not particularly limited.
Further, the application also provides a battery, which comprises the electrode plate.
It is understood that the battery of the present application may be a lithium ion secondary battery, a lithium ion polymer secondary battery, a lithium metal secondary battery, a lithium polymer secondary battery, or the like, and the battery is not particularly limited in the present application.
Still further, the application also provides an electronic device comprising the battery.
It is understood that the electronic device in the present application is not particularly limited, and may be, for example, an electric vehicle, an intelligent home appliance, a digital camera, a mobile phone, a computer, etc., and the battery in the present application may be used as a power source or an energy storage unit in the electronic device.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
The polyester material of the core layer, the first surface layer and the second surface layer is selected from polyethylene terephthalate (PET) resin with the intrinsic viscosity of 0.731dL/g, and the molecular weight distribution of the polyester material is 2.2.
The inorganic nanometer material of the core layer is spherical nanometer alumina (average diameter is 40 nm), and the additive of the core layer is antioxidant 1222.
The nano-oxides of the first surface layer and the second surface layer are spherical nano-silica (average diameter is 30 nm), the antioxidant is antioxidant 1222, and the slipping agent is calcium carbonate.
A method of making a composite polymeric film comprising the steps of:
s1, manufacturing a polyester chip A, a polyester chip B and a polyester chip C
According to the mass percentage, the polyester slice A and the polyester slice C are respectively and independently prepared by heating, melting, mixing, extruding and shaping slice treatment of 98 percent of PET resin, 1 percent of nano silicon dioxide, 0.5 percent of antioxidant 1222 and 0.5 percent of calcium carbonate, the polyester slice B is prepared by heating, melting, mixing, extruding and shaping slice treatment of 99.4 percent of PET resin, 0.1 percent of nano aluminum oxide and 0.5 percent of antioxidant 1222 in sequence, the prepared polyester slice A, polyester slice B and polyester slice C are conveyed into a crystallizer, treated for 40min at 140 ℃, and then the polyester slice A, polyester slice B and polyester slice C after the crystallization treatment are conveyed into a drying tower and dried for 160min at 150 ℃;
S2, manufacturing molten polyester material
Adding the polyester chips A, B and C obtained in the step S1 into different double-screw extruders, carrying out melt processing at 280 ℃, extruding the melt through a die head by means of a metering pump to obtain a molten polyester material with a core layer, a first surface layer and a second surface layer, wherein the core layer is arranged between the first surface layer and the second surface layer, the extrusion quantity ratio of the core layer, the first surface layer and the second surface layer is 80%, 10% and 10% (mass ratio) in sequence, the polyester chips A form the first surface layer, the polyester chips B form the core layer, and the polyester chips C form the second surface layer;
s3, manufacturing composite polymer film
S3.1, shaping treatment
(1) Casting sheet: casting the molten polyester material in the step S2 onto a casting roll, and obtaining a casting through casting roll and water cooling treatment;
(2) Stretching in the longitudinal direction: preheating the cast sheet at 90 ℃, then carrying out longitudinal stretching treatment to obtain a membrane, carrying out heat setting treatment at 170 ℃, and then carrying out cooling treatment at 40 ℃, wherein the longitudinal stretching multiplying power is 4:1, the longitudinal stretching temperature is 110 ℃;
(3) And (3) transversely stretching: preheating the membrane at 90 ℃, then carrying out transverse stretching treatment, carrying out heat setting treatment at 170 ℃, and then carrying out cooling treatment at 110 ℃, wherein the transverse stretching multiplying power is 4:1, the transverse stretching temperature is 120 ℃;
S3.2 heat treatment
The film sheet obtained in S3.1 was subjected to a heat treatment to produce a composite polymer film having a thickness of 6 μm, the heat treatment process comprising the steps of:
the first stage: the heat treatment temperature is 140 ℃, and the heat treatment time is 0.5min;
and a second stage: the heat treatment temperature is 160 ℃, and the heat treatment time is 0.5min;
and a third stage: the heat treatment temperature is 140 ℃, and the heat treatment time is 0.5min.
The composite current collector was manufactured as follows:
(1) Manufacture of metal conductive layers
Placing the manufactured composite polymer film in a vacuum evaporation cabin, melting and evaporating high-purity aluminum wires (the purity is greater than 99.99%) in a metal evaporation chamber at 1300-2000 ℃, and depositing evaporated metal atoms on two surfaces of the composite polymer film through a cooling system in a vacuum coating chamber to form an aluminum metal conductive layer with the thickness of 1 mu m;
(2) Manufacturing a protective layer
1g of carbon nanotubes was uniformly dispersed into 999g of Nitrogen Methyl Pyrrolidone (NMP) by an ultrasonic dispersion method to prepare a coating liquid having a solid content of 0.1wt%, and then the coating liquid was uniformly coated on the surface of the metal conductive layer by a die coating process, wherein the coating amount was controlled to 90 μm, and finally dried at 100 ℃.
Example 2
Substantially the same as in example 1, except that: in step S1, the polyester chip a and polyester chip C layers were each independently prepared from 96% pet resin, 3% nano silica, 0.5% antioxidant 1222 and 0.5% calcium carbonate in mass percent.
Example 3
Substantially the same as in example 1, except that: in step S1, the polyester chip a and polyester chip C layers were each independently prepared from 94% pet resin, 5% nano silica, 0.5% antioxidant 1222 and 0.5% calcium carbonate in mass percent.
Example 4
Substantially the same as in example 1, except that: in step S1, the polyester chip a and polyester chip C layers were each independently prepared from 92% pet resin, 7% nano silica, 0.5% antioxidant 1222, and 0.5% calcium carbonate in mass percent.
Example 5
Substantially the same as in example 1, except that: in step S1, the polyester chip a and polyester chip C layers are each independently prepared from 90% pet resin, 9% nano silica, 0.5% antioxidant 1222 and 0.5% calcium carbonate in mass percent.
Example 6
Substantially the same as in example 1, except that: in step S1, the polyester chip a and polyester chip C layers were each independently prepared from 89% pet resin, 10% nano silica, 0.5% antioxidant 1222 and 0.5% calcium carbonate in mass percent.
Example 7
Substantially the same as in example 4, except that: the nano-oxides of the first surface layer and the second surface layer are tubular nano-silica (with the diameter of 25nm and the length of 0.4 μm).
Example 8
Substantially the same as in example 4, except that: the nano-oxides of the first surface layer and the second surface layer are linear nano-silica (with the diameter of 10nm and the length of 0.5 μm).
Example 9
Substantially the same as in example 8, except that: the nano-oxides of the first surface layer and the second surface layer are linear nano-alumina (with the diameter of 10nm and the length of 0.5 mu m).
Example 10
Substantially the same as in example 8, except that: the nano-oxide of the first surface layer and the second surface layer are linear nano-titanium dioxide (with the diameter of 10nm and the length of 0.5 mu m).
Example 11
Substantially the same as in example 8, except that: in the step S1, the polyester chip B layer is prepared from 99.2% of PET resin, 0.3% of nano alumina and 0.5% of antioxidant 1222 according to mass percentage.
Example 12
Substantially the same as in example 8, except that: in the step S1, the polyester chip B layer is prepared from 99.0% of PET resin, 0.5% of nano alumina and 0.5% of antioxidant 1222 according to mass percentage.
Example 13
Substantially the same as in example 8, except that: in the step S1, the polyester chip B layer is prepared from 98.8% of PET resin, 0.7% of nano alumina and 0.5% of antioxidant 1222 according to mass percentage.
Example 14
Substantially the same as in example 8, except that: in the step S1, the polyester chip B layer is prepared from 98.6% of PET resin, 0.9% of nano alumina and 0.5% of antioxidant 1222 according to mass percentage.
Example 15
Substantially the same as in example 8, except that: in the step S1, the polyester chip B layer is prepared from 98.5% of PET resin, 1.0% of nano alumina and 0.5% of antioxidant 1222 according to mass percentage.
Example 16
Substantially the same as in example 12, except that: the inorganic nanomaterial of the core layer is tubular nano alumina (25 nm in diameter and 0.4 μm in length).
Example 17
Substantially the same as in example 12, except that: the inorganic nanomaterial of the core layer is linear nano alumina (diameter 10nm, length 0.5 μm).
Example 18
Substantially the same as in example 17, except that: the inorganic nano material of the core layer is single-wall carbon nano tube (diameter is 5nm and length is 0.2 μm).
Example 19
Substantially the same as in example 17, except that: the inorganic nano material of the core layer is graphene (the sheet diameter is 0.2 μm, the thickness is 0.8nm, and the single layer rate is 80%).
Example 20
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment time is 1min.
Example 21
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment time is 2min.
Example 22
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment time is 3min.
Example 23
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment time is 5min.
Example 24
Substantially the same as in example 21, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment temperature is 180 ℃.
Example 25
Substantially the same as in example 21, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment temperature is 200 ℃.
Example 26
Substantially the same as in example 21, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment temperature is 220 ℃.
Example 27
Substantially the same as in example 1, except that: in step S1, polyester chips a and C were each independently prepared from 98.8% pet resin, 1% nano silica, 0.1% antioxidant 1222 and 0.1% calcium carbonate in mass percent.
Example 28
Substantially the same as in example 1, except that: in step S1, polyester chips a and C were each independently prepared from 88% pet resin, 10% nano silica, 1% antioxidant 1222 and 1% calcium carbonate in mass percent.
Example 29
Substantially the same as in example 8, except that: in step S1, polyester chip B is prepared from 99.8% pet resin, 0.1% nano alumina, and 0.1% antioxidant 1222 in mass percent.
Example 30
Substantially the same as in example 8, except that: in step S1, polyester chip B is prepared from 98% pet resin, 1% nano alumina and 1% antioxidant 1222 in mass percent.
Comparative example 1
Substantially the same as in example 1, except that: in step S1, the polyester chip a and the polyester chip C layers are each independently made of 99% pet resin, 0.5% antioxidant 1222 and 0.5% calcium carbonate, and the polyester chip B is made of 99.5% pet resin and 0.5% antioxidant 1222, in mass percent.
Comparative example 2
Substantially the same as in example 1, except that: in step S1, polyester chip a and polyester chip C layers were each independently prepared from 98.5% pet resin, 0.5% nano silica, 0.5% antioxidant 1222, and 0.5% calcium carbonate in mass percent.
Comparative example 3
Substantially the same as in example 1, except that: in step S1, polyester chip a and polyester chip C layers were each independently prepared from 87% pet resin, 12% nano silica, 0.5% antioxidant 1222, and 0.5% calcium carbonate in mass percent.
Comparative example 4
Substantially the same as in example 8, except that: in step S1, polyester chip B is prepared from 99.45% pet resin, 0.05% nano alumina, and 0.5% antioxidant 1222 in mass percent.
Comparative example 5
Substantially the same as in example 8, except that: in step S1, polyester chip B is prepared from 98% pet resin, 1.5% nano alumina and 0.5% antioxidant 1222 in mass percent.
Comparative example 6
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in the step S3.2, the heat treatment time is 0.1min.
Comparative example 7
Substantially the same as in example 19, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment time is 6min.
Comparative example 8
Substantially the same as in example 21, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment temperature is 155 ℃.
Comparative example 9
Substantially the same as in example 21, except that: in the second stage of the heat treatment process in step S3.2, the heat treatment temperature is 225 ℃.
Test example 1 Performance test of composite Polymer film and composite Current collector
The tensile strength, the elongation at break and the thermal shrinkage of the manufactured composite polymer film and the composite current collector are tested by referring to national standards GB/T1040.3-2006 and GB/T10003-2008;
the adhesion of the composite polymer film to the metallic conductive layer was tested: bonding a layer of Permacel P-94 double faced adhesive tape on a 1mm thick aluminum foil, bonding a composite current collector above the double faced adhesive tape, covering an ethylene acrylic acid copolymer film (DuPont Nurcel0903, thickness of 50 μm) above the composite current collector, and then coating a layer of polyethylene acrylic acid copolymer film on the aluminum foil with a thickness of 1.3X10 5 N/m 2 Hot-pressing at 120deg.C for 10s, cooling to room temperature, and cutting into strips of 150mm×15 mm; finally, fixing the ethylene acrylic acid copolymer film of the sample strip on an upper clamp of a tensile machine, fixing the rest part of the ethylene acrylic acid copolymer film on a lower clamp, peeling the ethylene acrylic acid copolymer film and the lower clamp at an angle of 180 DEG and a speed of 100mm/min after the ethylene acrylic acid copolymer film and the lower clamp are fixed, and testing the peeling force, namely the bonding force between the composite polymer film and the metal conductive layer, wherein the test result is as followsTables 1 to 2 show the results.
TABLE 1 results of Performance test of composite Polymer films
Note that: MD represents the longitudinal direction of the composite polymer film, TD represents the transverse direction of the composite polymer film, the longer side length direction of the composite polymer film is taken as the longitudinal direction, the shorter side length direction of the composite polymer film is taken as the transverse direction, and the two directions are mutually perpendicular; the heat shrinkage is data tested after heating the composite polymer film at 150℃for 30 minutes.
Table 2 results of performance test of composite current collector
Note that: MD represents the longitudinal direction of the composite current collector, TD represents the transverse direction of the composite current collector, the longer side length direction of the composite current collector is taken as the longitudinal direction, the shorter side length direction of the composite current collector is taken as the transverse direction, and the two directions are mutually perpendicular; heat shrinkage data from a test of the current collector after heating at 150 ℃ for 30 min.
From the analysis of tables 1-2, examples 1-6 examined the influence of the change of the nano silica content in the first and second surface layers on the performance of the composite polymer film, and as the nano silica content in the first and second surface layers increases, the tensile strength of the corresponding composite polymer film decreases after increasing, the elongation at break and the heat shrinkage gradually decrease, the adhesion between the composite polymer film and the metal conductive layer increases first and then decreases and the change is more obvious, and the optimal amount of silica is 7%, because: a. the content of silicon dioxide is increased, the rigidity of the composite polymer film is enhanced, and the elongation at break and the thermal shrinkage rate are reduced; b. due to the size effect of the nano silicon dioxide material, the nano silicon dioxide material can play a role of bridging when being dispersed in the polyester material, so that the tensile strength of the composite polymer film is improved, but the composite polymer film is easy to generate defects due to the fact that the content of silicon dioxide is too high and the dispersion is uneven, and when the silicon dioxide exceeds a certain amount, the tensile strength tends to be reduced; c. because silicon dioxide can segregate to the surface of the composite polymer film in the film preparation process, an organic-inorganic hybridization layer with the silicon dioxide content being dominant is formed on the surface (near surface layer) of the composite polymer film, and the good cohesiveness of the silicon dioxide and a metal material is utilized to improve the cohesiveness of the composite polymer film and the metal conductive layer, but the silicon dioxide content is too high, defects are easily formed on the surface, and the cohesiveness is reduced.
Examples 4, 7 and 8 examined the effect of the shape of the silica in the first and second layers on the properties of the composite polymer film, and compared to the overall properties, linear silica was superior to tubular nanosilica, which was superior to spherical nanosilica, due to: the linear nano-oxides can be better contacted with the polyester material and play a bridging role, so that the mechanical property and heat resistance of the composite polymer film are improved, porous structures can be formed by overlapping the linear nano-oxides segregated on the surface of the composite polymer film and the linear nano-oxides and the polyester material, and a bonding site is formed, so that the bonding force between the composite polymer film and the metal conductive layer is improved.
Examples 8-10 examined the effect of the type of nano-oxide in the first and second layers on the performance of the composite polymer film, and compared with the overall performance, silica was superior to alumina, which was superior to titania due to: the affinity of the nano silicon dioxide and polyester material and metal material is better.
Examples 8 and 11-15 examined the influence of the content of nano alumina in the core layer on the performance of the composite polymer film, and as the content of nano alumina increases, the tensile strength of the corresponding composite polymer film increases and decreases, the elongation at break and the thermal shrinkage gradually decrease, the adhesion between the composite polymer film and the metal conductive layer does not change, and the optimal amount of nano alumina is 0.5%. The reason is that: a. the content of nano alumina is increased, the rigidity of the composite polymer film is enhanced, and the elongation at break and the thermal shrinkage rate are reduced; b. due to the size effect of the nano aluminum oxide material, the nano aluminum oxide material can play a role of bridging when being dispersed in the polyester material, so that the tensile strength of the composite polymer film is improved, but the nano aluminum oxide is excessively high in content and can be agglomerated, so that uneven dispersion is caused, the composite polymer film is easy to generate defects, and the tensile strength of the composite polymer film tends to be reduced after the optimal dosage is exceeded; c. the adhesive property of the composite polymer film depends on the characteristics and types of the nano oxides in the first surface layer and the second surface layer, so that changing the content of the nano oxides in the core layer has no influence on the adhesive property of the composite polymer film.
Examples 12 and 16-17 examined the influence of the shape of the nano-alumina in the core layer on the performance of the composite polymer film, and the comprehensive performance was linear nano-alumina, tubular nano-alumina, spherical nano-alumina in order from good to bad, because: the linear nano oxide can be better contacted with the polyester material and plays a role of bridging, so that the performance of the composite polymer film is improved.
Examples 17-19 examined the influence of the types of inorganic nanomaterials in the core layer on the performance of the composite polymer film, and in terms of overall performance, graphene was superior to carbon nanotubes, which were superior to alumina mainly due to the excellent specific surface area of graphene and its good affinity with polyester materials.
Examples 19 to 23 examined the effect of the heat treatment time of the second stage of the heat treatment process on the properties of the composite polymer film, and by increasing the heat treatment time, the crystallinity of the composite polymer film could be increased, so that the tensile strength of the composite polymer film could be increased, and the heat shrinkage and elongation at break could be reduced. Among them, the composite polymer film manufactured in example 21 was optimal in combination properties. This is because: the heat treatment time is too short, and the performance of the composite polymer film is not obviously improved; the heat treatment time is too long, the crystallinity is too high, and the elongation at break of the composite polymer film is too low.
Examples 21 and 24-25 examined the effect of the heat treatment temperature at the second stage of the heat treatment process on the properties of the composite polymer film, and by increasing the heat treatment temperature, the crystallinity of the composite polymer film could be increased, so that the tensile strength of the composite polymer film could be increased, and the heat shrinkage and elongation at break could be reduced. Among them, the composite polymer film manufactured in example 24 was optimal in combination with properties. This is because: the heat treatment temperature in the second stage of the heat treatment process is not too high, and the temperature is too high, so that the polyester material is subjected to de-orientation, and the performance of the composite polymer film is deteriorated; the performance of the composite polymer film is not obviously improved when the temperature is too low. The composite polymer films produced in example 24 were most excellent in performance from the viewpoint of the combination of examples 1 to 30.
Compared with examples 1-6 and examples 27-28, the composite polymer films manufactured in comparative examples 1-2 have smaller tensile strength in both MD and TD, larger elongation at break and larger heat shrinkage in both MD and TD, and smaller adhesion between the composite polymer films manufactured in comparative examples 1-2 and the metal conductive layer, which means that too low or too high addition amount of PET resin in the first and second surface layers of comparative examples 1-2 is unfavorable for improving the surface adhesiveness, mechanical strength and heat resistance of the composite polymer films.
Compared with examples 1-6 and examples 27-28, the composite polymer film and the composite current collector manufactured in comparative example 3 have smaller heat shrinkage in both MD and TD, which means that the heat resistance is better, but the tensile strength in both MD and TD is obviously lower, which means that the mechanical strength is poorer.
Although the adhesion of the composite polymer films and the metal conductive layers manufactured in comparative examples 4 to 5 and examples 11 to 15 and 30 was 4.5N/cm, the tensile strength of the composite polymer films and the composite current collectors manufactured in comparative examples 4 to 5 was significantly lower in both MD and TD, compared with examples 11 to 15 and 30, indicating that the mechanical strength of the composite polymer films and the composite current collectors manufactured in comparative examples 4 to 5 was poor.
Although the adhesive force of the composite polymer film and the metal conductive layer manufactured in comparative example 6 and examples 19 to 23 was 4.5N/cm, the tensile strength of the composite polymer film and the composite current collector manufactured in comparative example 6 in both MD and TD was relatively small, the elongation at break and the heat shrinkage were relatively high, compared with examples 19 to 23, indicating that the mechanical strength and the heat resistance of the composite polymer film and the composite current collector manufactured in comparative example 6 were poor.
Although the adhesion of the composite polymer films and the metal conductive layers manufactured in comparative examples 8 to 9 was equal to that of examples 21 and 24 to 26, the tensile strength of the composite polymer films and the composite current collectors manufactured in comparative examples 8 to 9 in both MD and TD was relatively small, and the elongation at break and the heat shrinkage were relatively high, indicating that the mechanical strength of the composite polymer films and the composite current collectors manufactured in comparative examples 8 to 9 was poor.
From this, the surface adhesiveness, mechanical strength and heat resistance of the composite polymer film of the present application are remarkably improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (19)
1. A composite polymer film, wherein the composite polymer film comprises a core layer, a first surface layer and a second surface layer, and the core layer is positioned between the first surface layer and the second surface layer;
the manufacturing raw materials of the core layer comprise the following components in percentage by mass: 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant, wherein the manufacturing raw materials of the first surface layer and the second surface layer respectively and independently comprise: 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive; the nano oxide comprises one or more of aluminum oxide, silicon dioxide, titanium dioxide, zinc oxide, copper oxide, magnesium oxide, ferric oxide, zirconium dioxide and tin dioxide; the polyester material comprises polyethylene terephthalate;
The method for manufacturing the composite polymer film comprises the following steps:
respectively preparing a manufacturing raw material of the core layer, a manufacturing raw material of the first surface layer and a manufacturing raw material of the second surface layer into polyester chips;
carrying out melt extrusion treatment on the polyester chips to obtain a molten polyester material;
sequentially performing molding treatment and heat treatment on the molten polyester material;
the heat treatment process comprises the following steps:
the first stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min;
and a second stage: the heat treatment temperature is 160-220 ℃, and the heat treatment time is 0.5-5 min;
and a third stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min.
2. The composite polymer film of claim 1, wherein the inorganic nanomaterial comprises one or more of a nano-oxide, graphene oxide, carbon nanotubes, and carbon nanofibers.
3. The composite polymer film of claim 1, wherein the shape of the nano-oxide comprises one or more of spherical, linear, and tubular.
4. The composite polymer film of claim 1, wherein the additives include antioxidants and slip agents.
5. The composite polymer film of claim 4, wherein the antioxidant comprises one or more of phosphonate and bisphenol a phosphite.
6. The composite polymer film of claim 4, wherein the slip agent comprises one or more of calcium carbonate, talc, kaolin, diatomaceous earth, silicone, clay, mica, aluminum silicate, potassium phosphate, barium sulfate, and acrylate.
7. The composite polymer film according to any one of claims 1 to 6, wherein the thickness of the composite polymer film is 1 to 50 μm.
8. A method of producing the composite polymer film according to any one of claims 1 to 7, comprising the steps of:
s1, respectively manufacturing a polyester slice A, a polyester slice B and a polyester slice C, wherein the polyester slice A and the polyester slice C are respectively and independently prepared from 88% -98.8% of polyester material, 1% -10% of nano oxide and 0.2% -2% of additive in percentage by mass, and the polyester slice B is prepared from 98% -99.8% of polyester material, 0.1% -1% of inorganic nano material and 0.1% -1% of antioxidant;
s2, carrying out melt extrusion treatment on the polyester chip A, the polyester chip B and the polyester chip C to obtain a molten polyester material with a first surface layer, a core layer and a second surface layer, wherein the core layer is positioned between the first surface layer and the second surface layer;
S3, sequentially performing molding treatment and heat treatment on the molten polyester material;
the heat treatment process comprises the following steps:
the first stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min;
and a second stage: the heat treatment temperature is 160-220 ℃, and the heat treatment time is 0.5-5 min;
and a third stage: the heat treatment temperature is 130-160 ℃, and the heat treatment time is 0.5-2 min.
9. The method according to claim 8, wherein the thicknesses of the core layer, the first surface layer and the second surface layer are 70% -90%, 5% -15% of the thickness of the composite polymer film in order, and the thicknesses of the first surface layer and the second surface layer are equal.
10. A metallized composite polymer film comprising a composite polymer film according to any one of claims 1 to 7 or a composite polymer film produced by the production method according to any one of claims 8 to 9, and a metal conductive layer provided on at least one surface of the composite polymer film.
11. The metallized composite polymer film of claim 10, wherein the material of said metallic conductive layer comprises one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium and silver.
12. The metallized composite polymer film according to any one of claims 10 to 11, wherein the thickness of the metallic conductive layer is 20 to 2000nm.
13. A composite current collector comprising the metallized composite polymer film of any one of claims 10 to 12.
14. The composite current collector of claim 13 further comprising a protective layer on the metallic conductive layer of the metallized composite polymer film.
15. The composite current collector of claim 14 wherein said protective layer comprises one or more of nickel, chromium, nickel-based alloys, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers, and graphene.
16. The composite current collector of claim 14, wherein the protective layer has a thickness of 10 to 150nm.
17. An electrode sheet characterized by comprising the composite current collector of any one of claims 13-16.
18. A battery comprising the electrode sheet of claim 17.
19. An electronic device comprising the battery of claim 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| WO2024050688A1 (en) * | 2022-09-06 | 2024-03-14 | 扬州纳力新材料科技有限公司 | Composite polymer film, manufacturing method therefor, metallized composite polymer film, and use |
| CN115579479B (en) * | 2022-12-12 | 2023-07-04 | 安徽元琛环保科技股份有限公司 | Composite conductive film used as current collector, and preparation method and application thereof |
| WO2024145815A1 (en) * | 2023-01-04 | 2024-07-11 | 扬州纳力新材料科技有限公司 | Composite current collector, manufacturing method therefor, lithium battery, and electrical apparatus |
| CN116598044B (en) * | 2023-05-23 | 2024-05-24 | 扬州纳力新材料科技有限公司 | Conductive material, conductive substrate, composite current collector and application thereof |
| CN117691121A (en) * | 2023-12-13 | 2024-03-12 | 广东盈华电子科技有限公司 | Composite copper foil for enhancing adhesion force between copper foil and base material |
| CN117887224B (en) * | 2024-03-15 | 2024-05-28 | 江阴纳力新材料科技有限公司 | Polymer composite membrane, preparation method thereof, composite current collector and application |
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