CN117059817A - Composite current collector and preparation method thereof - Google Patents
Composite current collector and preparation method thereof Download PDFInfo
- Publication number
- CN117059817A CN117059817A CN202310937919.2A CN202310937919A CN117059817A CN 117059817 A CN117059817 A CN 117059817A CN 202310937919 A CN202310937919 A CN 202310937919A CN 117059817 A CN117059817 A CN 117059817A
- Authority
- CN
- China
- Prior art keywords
- base film
- current collector
- treating agent
- composite current
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 86
- 239000010410 layer Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000011241 protective layer Substances 0.000 claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims description 176
- -1 polypropylene Polymers 0.000 claims description 74
- 229920001155 polypropylene Polymers 0.000 claims description 62
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 34
- 238000002791 soaking Methods 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims description 11
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 10
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019864 coconut oil Nutrition 0.000 claims description 3
- 239000003240 coconut oil Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Natural products CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 150000001565 benzotriazoles Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 140
- 230000000052 comparative effect Effects 0.000 description 14
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a composite current collector and a preparation method thereof, wherein the composite current collector comprises the following components: a PP base film; the bonding layers are arranged on the upper side and the lower side of the PP base film and are obtained by treatment of a surfactant, an organic treating agent, a first treating agent and a second treating agent; the metal layers are arranged on the upper side and the lower side of the bonding layer; and the protective layers are arranged on the upper side and the lower side of the metal layer. The scheme of the invention can enhance the bonding performance of the PP base film and the metal layer.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite current collector and a preparation method thereof.
Background
At present, composite current collectors based on high molecular polymer films are widely focused and applied in new energy industries. The preparation process of the composite current collector is generally as follows: a layer of metal (aluminum, copper, etc.) material is deposited on a polymer film (such as polypropylene, polyethylene, polyesters, etc.) by Physical Vapor Deposition (PVD). The prepared surface metallized film with certain conductivity is the composite current collector. Compared with the traditional current collector, the composite current collector based on the high-molecular polymer film has the characteristics of low cost, light weight, good internal insulativity and the like. These features enable the composite current collector to reduce the cost of the battery and to improve the energy density and safety of the battery when applied in the battery.
In the existing current collector process, a layer of metal copper material with a certain conductivity is formed on a polymer film by magnetron sputtering, and then the metal copper material is thickened by 1 mu m on two sides of a PP base film (polypropylene film) by water electroplating to form a composite current collector. However, because PP (polypropylene) is a nonpolar material, the surface bond energy is higher, the chemical bond is not easy to open, the bonding force with metal is poor, the bonding force of the prepared composite copper current collector is poor, the metal layer is easy to fall off from the PP base film (polypropylene base film), and the condition of application in a battery is not provided.
Disclosure of Invention
The invention aims to solve the technical problem that the PP composite current collector has poor bonding performance by providing the composite current collector and the preparation method.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a composite current collector comprising:
a PP base film;
the bonding layers are arranged on the upper side and the lower side of the PP base film and are obtained by treatment of a surfactant, an organic treating agent, a first treating agent and a second treating agent;
the metal layers are arranged on the upper side and the lower side of the bonding layer;
and the protective layers are arranged on the upper side and the lower side of the metal layer.
Optionally, the PP base film includes polypropylene and an antioxidant, wherein the mass percentage of the polypropylene to the antioxidant is (99% -99.5%): (0.5% -1%).
Optionally, the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, alpha-alkenyl sodium sulfonate, sodium dodecyl sulfate, sodium fatty acid methyl sulfonate, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan fatty acid ester, coconut oil fatty acid diethanolamine, polyether series and the like;
the organic treating agent is one or more of toluene, xylene, cyclohexane, carbon tetrachloride, ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, ethyl acetate, acetone, butanone, cyclohexanone and the like;
the first treating agent is one or more of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, glycerol, ethyl acetate, acetone, butanone, ethyl acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether and the like;
the second treating agent is one or more of chlorinated polypropylene, itaconic acid, dipentene copolymer, methyl methacrylate, butyl acrylate, glycidyl acrylate and other grafted PP, polyethylene/polypropylene blend or copolymer, segmented copolymer formed by copolymerization of isobornyl acrylate and acrylic acid, and ethylene-octene segmented copolymer.
Optionally, the material of the protective layer is one or more of benzotriazole and derivatives thereof or a silane coupling agent.
Optionally, the thickness of the PP base film is between 2um and 20um, and the thickness of each side of the metal layer is between 400 nm and 1500 nm.
The invention also provides a preparation method of the composite current collector, which comprises the following steps:
preparing a PP base film, wherein the PP base film is obtained by mixing polypropylene with an antioxidant and then adopting a melt-biaxially stretching method;
soaking the PP base film in a surfactant, cleaning and drying, soaking in an organic treating agent, cleaning and drying, soaking in a first treating agent, drying, soaking in a second treating agent by ultrasonic, and drying in an oven to obtain a bonded PP base film;
placing the bonding PP base film in a magnetron sputtering cabin, taking metal as a target material, forming a metal thin layer on the bonding PP base film by a magnetron sputtering method, and respectively depositing two metal layers on two surfaces of the base film by an aqueous medium electroplating method to obtain metal layers;
and forming a stable oxide film on the metal layer through a benzotriazole antioxidant, and drying to obtain the composite current collector.
Optionally, the surfactant is a mixed solution of sodium dodecyl sulfate, sodium fatty acid methyl sulfonate and fatty alcohol polyoxyethylene ether; the organic treating agent is a mixed solution of acetone and tetrachloroethylene; the first treating agent is isopropanol, and the second treating agent is chlorinated polypropylene.
Optionally, the mass ratio of the sodium dodecyl sulfate, the sodium fatty acid methyl ester sulfonate and the fatty alcohol-polyoxyethylene ether in the mixed solution of the surfactant is 3:1:2.
Optionally, the mass ratio of the acetone to the tetrachloroethylene in the organic treating agent is 6:4.
Optionally, the concentration of the chlorinated polypropylene is 5-10 per mill, the soaking time is 30-300 s, and the drying temperature in an oven is 80-120 ℃.
The scheme of the invention at least comprises the following beneficial effects: the solvent in the bonding layer can expand and diffuse to the surface of the PP base film, so that the mechanical interlocking force with the surface of the PP base film is enhanced, the bonding performance of the PP base film and the metal layer is enhanced, the bonding force of the prepared composite current collector is enhanced, the mechanical performance of the composite current collector is obviously improved, and the PP base film and the metal layer are not easy to fall off.
Drawings
Fig. 1 is a schematic view of a composite current collector of the present invention.
Reference numerals illustrate:
1. a PP base film; 2. a bonding layer; 3. a metal layer; 4. and (3) a protective layer.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
As shown in fig. 1, an embodiment of the present invention proposes a composite current collector including: a PP base film 1; the bonding layers 2 are arranged on the upper side and the lower side of the PP base film 1, and the bonding layers 2 are obtained by treatment of a surfactant, an organic treating agent, a first treating agent and a second treating agent; metal layers 3 arranged on the upper side and the lower side of the bonding layer 2; and protective layers 4 arranged on the upper side and the lower side of the metal layer 3.
In this embodiment, the substance in the adhesive layer 2 diffuses to the surface of the PP base film 1, and mechanically interlocks with the area below the surface of the PP base film to provide adhesion, thereby improving the bonding capability of the PP base film 1 and the metal layer 3.
In this embodiment, the adhesive layer 2 is obtained by treating with a surfactant, an organic treating agent, a first treating agent, and a second treating agent; the surfactant treatment is a pretreatment mode, and mainly comprises the steps of removing oxide skin, rust products, dust, various salts and water, and powdering and decomposing products after surface oxidative decomposition and ultraviolet aging. After the surface of the PP base film 1 is treated by the solvent, the amorphous surface of the solvent corrosion part has the effect of increasing the roughness, so that the microcosmic surface area can be increased, the anchoring point of the metal layer 3 on the PP base material is increased, and the adhesion of the metal layer 3 is facilitated.
In this embodiment, the material of the metal layer 3 is one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium, silver, etc., and the metal layer 3 is prepared by one or more of physical vapor deposition (including but not limited to electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.), electroplating, electroless plating, etc. The thickness of the metal layer 3 is between 400 and 1500 nanometers.
In an alternative embodiment, the PP base film 1 includes polypropylene and an antioxidant, wherein the mass percentage of the polypropylene to the antioxidant is (99% -99.5%): (0.5% -1%).
In this embodiment, the mass percentages of polypropylene and antioxidant are preferably: 99.5%:0.5%.
In this example, the polypropylene has a melt index of 3.0-3.9g/10min (230 ℃ C./2.16 kg). The melt index is too low, the molecular weight is too large, and the film forming property in the film drawing process is poor; the melt index is too high, the molecular weight is too low, and the mechanical properties of the prepared PP film are poor. The thickness of the preferable composite polypropylene film is between 2 microns and 20 microns, which gives consideration to the process difficulty and the production cost.
In this embodiment, the antioxidant is one or more of triphenyl phosphite, butyl hydroxy anisole, 2, 6-di-tert-butyl-4-methylphenol, p-tert-butyl catechol, and the like.
In an alternative embodiment, the surfactant is one or more of sodium dodecyl benzene sulfonate (LAS), sodium fatty alcohol polyoxyethylene ether sulfate (AES), sodium alpha-alkenyl sulfonate (AOS), sodium Dodecyl Sulfate (SDS), sodium fatty acid methyl sulfonate (MES), fatty alcohol polyoxyethylene ether (AEO), nonylphenol polyoxyethylene ether (OP series), sorbitan fatty acid esters (Span series), coconut oil fatty acid diethanolamine, polyether series, and the like; the organic treating agent is one or more of toluene, xylene, cyclohexane, carbon tetrachloride, ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, ethyl acetate, acetone, butanone, cyclohexanone and the like; the first treating agent is one or more of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, glycerol, ethyl acetate, acetone, butanone, ethyl acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether and the like; the second treating agent is one or more of chlorinated polypropylene, itaconic acid, dipentene copolymer, methyl methacrylate, butyl acrylate, glycidyl acrylate and other grafted PP, polyethylene/polypropylene blend or copolymer, segmented copolymer formed by copolymerization of isobornyl acrylate and acrylic acid, and ethylene-octene segmented copolymer.
In this embodiment, the purpose of the first treating agent for treating the PP base film 1 is to change the surface structure of the base material, introduce polar groups such as c=o, -OH, and-COOH, and form a layer of film on the surface of the base material, so as to improve the surface wettability of the PP base material by the metal layer 3, enhance the polarity of the surface of the plastic base material, and increase the surface tension of the PP film.
In this embodiment, the second treating agent is used for treating the PP base film 1: (1) During the synthesis of the second treating agent, organic solvents such as toluene, xylene and the like are introduced, and are diffused into the PP base film 1 to swell molecules therein and mutually diffuse and intertwine to generate good adhesive force; (2) The adhesive force caused by the dispersive force between the non-polar backbone of the second treating agent and the non-polar polyolefin substrate; (3) When the second treating agent is equal to the crystal structure and size of the PP base film 1, one polymer crystal can be epitaxially grown on the other polymer crystal to form good adhesion.
In a preferred embodiment of the invention, the second treatment agent used is chlorinated polypropylene, the concentration of which in this example is 10% and the soaking time is 60s and the drying temperature is 90min.
In an alternative embodiment, the material of the protective layer 4 is one or more of benzotriazole and its derivatives or silane coupling agents.
In this embodiment, the agent of the protective layer 4 includes one or more of benzotriazole and its derivatives (such as BTA, TTA, irgamet 39) or silane coupling agent, the protective layer 4 is used to prevent the metal guiding layer from being chemically corroded or physically damaged, the protective layer 4 is used in principle that the passivating agent in the protective layer 4 reacts with copper first, and the generated compound adheres to the surface of copper, so as to prevent further reaction of copper and sulfur; or the silane coupling agent is hydrolyzed to generate silanol (X-Si (OH) n), and the silanol is combined with the metal surface and crosslinked on the metal surface to form a layer of compact protective film, so that the metal layer 3 and the air are prevented from further reacting.
In an alternative embodiment, the PP base film 1 has a thickness between 2um and 20um and the metal layer 3 on each side has a thickness between 400 and 1500 nm.
The invention also provides a preparation method of the composite current collector, which comprises the following steps: preparing a PP base film 1, wherein the PP base film 1 is obtained by mixing polypropylene with an antioxidant and then adopting a melt-biaxially stretching method;
soaking the PP base film 1 in a surfactant, cleaning and drying, soaking in an organic treating agent, cleaning and drying, soaking in a first treating agent, drying, soaking in a second treating agent by ultrasonic, and drying in an oven to obtain a bonded PP base film 1;
placing the bonding PP base film 1 in a magnetron sputtering cabin, taking metal as a target material, forming a metal thin layer on the bonding PP base film 1 by a magnetron sputtering method, and respectively depositing two metal layers 3 on two surfaces of the PP base film 1 by an aqueous medium electroplating method to obtain metal layers 3;
and forming a stable oxide film on the metal layer 3 through a benzotriazole antioxidant, and drying to obtain the composite current collector.
In a preferred embodiment of the present invention, the thickness of the PP base film 1 is 4.5um, the thickness of each side of the metal layer 3 is 1000nm, and in this embodiment, the metal layer 3 is formed by magnetron sputtering, that is, by using interaction of a magnetic field and an electric field, electrons are made to spiral near the target surface, so that the probability that the electrons strike the argon gas to generate ions is increased, and the generated ions strike the target surface under the action of the electric field to sputter the target.
In an alternative embodiment, the surfactant is a mixture of Sodium Dodecyl Sulfate (SDS), sodium fatty acid methyl sulfonate (MES), and fatty alcohol polyoxyethylene ether (AEO); the organic treating agent is a mixed solution of acetone and tetrachloroethylene; the first treating agent is isopropanol, and the second treating agent is chlorinated polypropylene.
In an alternative embodiment, the mass ratio of Sodium Dodecyl Sulfate (SDS), fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol polyoxyethylene ether (AEO) in the mixed solution of the surfactants is 3:1:2.
In an alternative embodiment, the mass ratio of acetone to tetrachloroethylene in the organic treatment agent is 6:4.
In an alternative embodiment, the chlorinated polypropylene has a concentration of 5 to 10 per mill and a soaking time of 30 to 300s and a drying temperature in an oven of 80 to 120 ℃.
The following are specific examples of the above method:
example 1:
preparation of PP base film
After 99.5% of polypropylene and 0.5% of triphenyl phosphite are mixed, a melt-biaxially oriented method is adopted to prepare the film, and the method comprises the following steps: mixing materials, melt extruding, casting, longitudinal stretching, transverse stretching and heat setting. The resulting film was prepared to have a thickness of 4.5 microns.
2. Preparation of the adhesive layer
Pretreatment: the PP base film is put into a mixed solution of Sodium Dodecyl Sulfate (SDS), fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol polyoxyethylene ether (AEO) with the mass ratio of 3:1:2, and is washed clean by pure water and dried.
Treatment with an organic treating agent: and (3) placing the pretreated PP base film into a mixed solution with the mass ratio of acetone to tetrachloroethylene of 6:4, soaking for 3min, washing with pure water, and drying.
Treating with a first treating agent: and soaking the PP base film treated and dried by the organic treating agent in isopropanol for 3min, taking out, and naturally airing.
And (3) treating with a second treating agent: and (3) placing the PP base film in chlorinated polypropylene with the content of 5 per mill, taking out the chlorinated polypropylene after ultrasonic soaking for 30s, wiping the residual liquid on the surface of the PP base film, and drying the PP base film in an oven at 80 ℃ for 10min.
3. Preparation of composite current collector
The prepared PP base film with enhanced performance is placed in a magnetron sputtering cabin body, a metal layer with the thickness is formed by sputtering, after the metal layer is formed by the magnetron sputtering, the metal layers on two sides are respectively deposited on two surfaces of the PP base film by an aqueous medium electroplating method, and a composite current collector with the thickness of about 1 mu m is formed. Secondly, preparing a protective layer: the prepared composite current collector forms a stable oxide film through a benzotriazole antioxidant, and finally is dried at 100 ℃.
Example 2:
substantially the same as in example 1, except that: the chlorinated polypropylene is used in an amount of 10% by weight.
Example 3:
substantially the same as in example 1, except that: the chlorinated polypropylene used is 15% in content.
Example 4:
substantially the same as in example 1, except that: the chlorinated polypropylene used was 20% in content.
Example 5:
example 2 is essentially the same, except that: the soaking time in chlorinated polypropylene was 60s.
Example 6:
substantially the same as in example 2, except that: the soaking time in chlorinated polypropylene was 120s.
Example 7:
substantially the same as in example 2, except that: the soaking time in chlorinated polypropylene was 300s.
Example 8:
substantially the same as in example 5, except that: the baking temperature was 90 ℃.
Example 9:
substantially the same as in example 5, except that: the baking temperature was 100 ℃.
Comparative example 1:
substantially the same as in example 1, except that: the prepared PP base film is not provided with a bonding layer, namely, the PP base film is not treated by a surfactant, an organic treating agent, a first treating agent and a second treating agent.
Preparation of PP base film
After 99.5% of polypropylene and 0.5% of triphenyl phosphite are mixed, a melt-biaxially oriented method is adopted to prepare the film, and the method comprises the following steps: mixing materials, melt extruding, casting, longitudinal stretching, transverse stretching and heat setting. The resulting film was prepared to have a thickness of 4.5 microns.
2. Preparation of composite current collector
And (3) placing the prepared PP base film in a cabin body of a magnetron sputtering machine, sputtering to form a metal layer with a thickness, and respectively depositing the metal layers on two sides on two surfaces of the PP base film by an aqueous medium electroplating method after the metal layer is formed by the magnetron sputtering machine to form the composite current collector with the thickness of about 1 mu m. Secondly, preparing a protective layer: the prepared composite current collector forms a stable oxide film through a benzotriazole antioxidant, and finally is dried at 100 ℃.
Comparative example 2
Substantially the same as in example 4, except that: the soaking time in chlorinated polypropylene was 300s and the baking temperature was 100 ℃.
Preparation of PP base film
After 99.5% of polypropylene and 0.5% of triphenyl phosphite are mixed, a melt-biaxially oriented method is adopted to prepare the film, and the method comprises the following steps: mixing materials, melt extruding, casting, longitudinal stretching, transverse stretching and heat setting. The resulting film was prepared to have a thickness of 4.5 microns.
2. Preparation of the adhesive layer
Pretreatment: the PP base film is put into a mixed solution of Sodium Dodecyl Sulfate (SDS), fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol polyoxyethylene ether (AEO) with the mass ratio of 3:1:2, and is washed clean by pure water and dried.
Treatment with an organic treating agent: and (3) placing the pretreated PP base film into a mixed solution with the mass ratio of acetone to tetrachloroethylene of 6:4, soaking for 3min, washing with pure water, and drying.
Treating with a first treating agent: and soaking the PP base film treated and dried by the organic treating agent in isopropanol for 3min, taking out, and naturally airing.
And (3) treating with a second treating agent: and (3) placing the PP base film in chlorinated polypropylene with 20 per mill content, taking out the chlorinated polypropylene after ultrasonic soaking for 300s, wiping off residual liquid on the surface of the PP base film, and drying the PP base film in a drying oven at 100 ℃ for 10min.
3. Preparation of composite current collector
The prepared PP base film with enhanced performance is placed in a magnetron sputtering cabin body, a metal layer with the thickness is formed by sputtering, after the metal layer is formed by the magnetron sputtering, the metal layers on two sides are respectively deposited on two surfaces of the PP base film by an aqueous medium electroplating method, and a composite current collector with the thickness of about 1 mu m is formed. Secondly, preparing a protective layer: the prepared composite current collector forms a stable oxide film through a benzotriazole antioxidant, and finally is dried at 100 ℃.
Comparative example 3
Preparation of PP base film
After 99.5% of polypropylene and 0.5% of triphenyl phosphite are mixed, a melt-biaxially oriented method is adopted to prepare the film, and the method comprises the following steps: mixing materials, melt extruding, casting, longitudinal stretching, transverse stretching and heat setting. The resulting film was prepared to have a thickness of 4.5 microns.
2. Preparation of the adhesive layer
Pretreatment: the PP base film is put into a mixed solution of Sodium Dodecyl Sulfate (SDS), fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol polyoxyethylene ether (AEO) with the mass ratio of 3:1:2, and is washed clean by pure water and dried.
Treatment with an organic treating agent: and (3) placing the pretreated PP base film into a mixed solution with the mass ratio of acetone to tetrachloroethylene of 6:4, soaking for 3min, washing with pure water, and drying.
Treating with a first treating agent: and soaking the PP base film treated and dried by the organic treating agent in isopropanol for 3min, taking out, and naturally airing.
And (3) treating with a second treating agent: and (3) placing the PP base film in chlorinated polypropylene with the content of 22 per mill, taking out the PP base film after ultrasonic soaking for 350s, wiping the residual liquid on the surface of the PP base film, and drying the PP base film in an oven at 110 ℃ for 10min.
3. Preparation of composite current collector
The prepared PP base film with enhanced performance is placed in a magnetron sputtering cabin body, a metal layer with the thickness is formed by sputtering, after the metal layer is formed by the magnetron sputtering, the metal layers on two sides are respectively deposited on two surfaces of the PP base film by an aqueous medium electroplating method, and a composite current collector with the thickness of about 1 mu m is formed. Secondly, preparing a protective layer: the prepared composite current collector forms a stable oxide film through a benzotriazole antioxidant, and finally is dried at 100 ℃.
Comparative example 4:
substantially the same as in example 1, the difference is that: without treatment with the second treatment agent.
Preparation of PP base film
After 99.5% of polypropylene and 0.5% of triphenyl phosphite are mixed, a melt-biaxially oriented method is adopted to prepare the film, and the method comprises the following steps: mixing materials, melt extruding, casting, longitudinal stretching, transverse stretching and heat setting. The resulting film was prepared to have a thickness of 4.5 microns.
2. Preparation of the adhesive layer
Pretreatment: the PP base film is put into a mixed solution of Sodium Dodecyl Sulfate (SDS), fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol polyoxyethylene ether (AEO) with the mass ratio of 3:1:2, and is washed clean by pure water and dried.
Treatment with an organic treating agent: and (3) placing the pretreated PP base film into a mixed solution with the mass ratio of acetone to tetrachloroethylene of 6:4, soaking for 3min, washing with pure water, and drying.
Treating with a first treating agent: and soaking the PP base film treated and dried by the organic treating agent in isopropanol for 3min, taking out, and naturally airing.
3. Preparation of composite current collector
The prepared PP base film with enhanced performance is placed in a magnetron sputtering cabin body, a metal layer with the thickness is formed by sputtering, after the metal layer is formed by the magnetron sputtering, the metal layers on two sides are respectively deposited on two surfaces of the PP base film by an aqueous medium electroplating method, and a composite current collector with the thickness of about 1 mu m is formed. Secondly, preparing a protective layer: the prepared composite current collector forms a stable oxide film through a benzotriazole antioxidant, and finally is dried at 100 ℃.
Testing and evaluation:
the purpose of the treatment of the PP base film is to improve the surface adhesion performance and mechanical performance of the film, and further improve the performance of the composite current collector prepared by taking the PP base film as a base material, wherein the factors influencing the surface adhesion performance of the PP base film, namely, the surface tension and the indexes such as the adhesion force between the PP base film and a surface metal layer in the composite current collector are tested and characterized, and in addition, the tensile strength of the prepared PP base film is tested, and the specific test method is as follows:
(1) surface tension: the surface tension of the PP base film prepared as described above was tested according to GB/T14216-2008.
(2) Binding force of PP base film and metal layer in composite current collector: a layer of Permacel P-94 double faced adhesive tape is adhered to an aluminum foil with the thickness of 1mm, a composite current collector is adhered to the upper side of the double faced adhesive tape, an ethylene acrylic acid copolymer film (DuPont Nurcel0903, the thickness is 50 μm) is covered on the composite current collector, and then the aluminum foil is hot-pressed for 10s at the temperature of 1.3X105N/m < 2 >, the aluminum foil is cooled to room temperature, and small strips with the thickness of 150mm multiplied by 15mm are cut. And 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 degrees 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 of the PP base film and the metal layer.
Table: the examples and comparative examples are surface tension of polypropylene film and adhesion of composite current collector
Note that: the elastic modulus, tensile strength and elongation at break of the polypropylene film and the composite current collector are all indexes in the MD direction (i.e. machine direction, direction of the film roll after being unwound).
In the above table, from examples 1-4, it can be seen that: in the concentration of the chlorinated polypropylene (namely 5-10 per mill), the concentration of the chlorinated polypropylene is improved, and the adhesive property of the polypropylene film and the composite current collector is improved; when the concentration of the chlorinated polypropylene is beyond 10 per mill, the adhesive property of the polypropylene film and the composite current collector is obviously reduced.
From examples 2 and 5-7, it can be seen that: the adhesion performance of the polypropylene film and the composite current collector is better within the treatment time of 60-300 s.
From examples 5 and 8-9, it can be seen that: in the baking temperature of 80-120 ℃, the baking temperature is increased, and the adhesive property of the polypropylene film and the composite current collector is slightly reduced after the improvement.
As can be seen from comparative examples 2 and 3, when the content of the chlorinated polypropylene exceeds 5-10 per mill, and the soaking time exceeds 60-300 s, the surface tension of the polypropylene film and the binding power of the composite current collector are reduced instead, which is unfavorable for improving the mechanical properties of the composite current collector, namely, the binding power of the composite current collector is enhanced when the content of the chlorinated polypropylene is 5-10 per mill and the soaking time is 60-300 s, the mechanical properties of the composite current collector are obviously improved, and the PP base film and the metal layer are not easy to fall off.
Comparative example 1 was obtained without providing a tie layer, i.e., without treatment with a surfactant, an organic treatment agent, a first treatment agent and a second treatment agent, and comparative example 4 was obtained with treatment with a surfactant, an organic treatment agent and a first treatment agent, but without treatment with a second treatment agent, and comparative example 4 was compared with comparative example 1 in terms of the effect of surface elevation of the polypropylene film in comparative example 4. The tension and the adhesion force of the composite current collector are both larger than those of comparative example 1, but the improvement effect of the surfactant, the organic treating agent and the first treating agent is smaller, the surface tension of the polypropylene film is only increased from 22mN/m to 23mN/m, the adhesion force of the composite current collector is only increased from 1.3N/cm to 1.5N/cm, and the adhesion force of the composite current collector is only slightly improved. Comparative example 4 in comparison with example 1, the surface tension of the polypropylene film treated by the second treating agent in example 1 is increased from 23mN/m of comparative example to 26mN/m in example 1, and the adhesion of the composite current collector is increased from 1.5N/cm to 1.8N/cm, i.e. the surface tension of the polypropylene film is obviously improved by the second treating agent, the adhesion of the composite current collector is obviously enhanced, and the mechanical property of the composite current collector is obviously improved.
In a word, the tie coat that the upper and lower both sides of PP basic film set up can be very big improvement polypropylene film surface tension and compound electric current collector adhesion, and solvent in the tie coat can expand and diffuse to the PP basic film surface, strengthen the mechanical linkage power with the PP basic film surface to strengthen the bonding performance of PP basic film and metal level, the compound electric current collector adhesion of this preparation strengthens, and the mechanical properties of compound electric current collector obviously promotes, and PP basic film and metal level are difficult for droing. The second treating agent has a decisive effect on improving the binding capacity of the PP base film and the metal layer, and organic solvents such as toluene, xylene and the like are introduced in the process of synthesizing the second treating agent, and are diffused into the PP base film to swell molecules in the PP base film and mutually diffuse and wind to generate good adhesive force; the adhesive force caused by the dispersive force between the non-polar backbone of the second treating agent and the non-polar polyolefin substrate; when the second treating agent is equal to the crystal structure and size of the PP base film 1, one polymer crystal can be epitaxially grown on the other polymer crystal to form good adhesion.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A composite current collector, comprising:
a PP base film;
the bonding layers are arranged on the upper side and the lower side of the PP base film and are obtained by treatment of a surfactant, an organic treating agent, a first treating agent and a second treating agent;
the metal layers are arranged on the upper side and the lower side of the bonding layer;
and the protective layers are arranged on the upper side and the lower side of the metal layer.
2. The composite current collector of claim 1, wherein the PP base film comprises polypropylene and an antioxidant in a mass ratio of (99% -99.5%) to (0.5% -1%).
3. The composite current collector according to claim 1, wherein the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium alpha-alkenyl sulfonate, sodium dodecyl sulfate, sodium fatty acid methyl ester sulfonate, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan fatty acid ester, coconut oil fatty acid diethanolamine, polyether series, and the like;
the organic treating agent is one or more of toluene, xylene, cyclohexane, carbon tetrachloride, ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, ethyl acetate, acetone, butanone, cyclohexanone and the like;
the first treating agent is one or more of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, glycerol, ethyl acetate, acetone, butanone, ethyl acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether and the like;
the second treating agent is one or more of chlorinated polypropylene, itaconic acid, dipentene copolymer, methyl methacrylate, butyl acrylate, glycidyl acrylate and other grafted PP, polyethylene/polypropylene blend or copolymer, segmented copolymer formed by copolymerization of isobornyl acrylate and acrylic acid, and ethylene-octene segmented copolymer.
4. The composite current collector according to claim 1, wherein the material of the protective layer is one or more of benzotriazoles and derivatives thereof or silane coupling agents.
5. The composite current collector of claim 1 wherein the PP base film has a thickness between 2um and 20um and the metal layer on each side has a thickness between 400 and 1500 nm.
6. A method of preparing a composite current collector, comprising:
preparing a PP base film, wherein the PP base film is obtained by mixing polypropylene with an antioxidant and then adopting a melt-biaxially stretching method;
soaking the PP base film in a surfactant, cleaning and drying, soaking in an organic treating agent, cleaning and drying, soaking in a first treating agent, drying, soaking in a second treating agent by ultrasonic, and drying in an oven to obtain a bonded PP base film;
placing the bonding PP base film in a magnetron sputtering cabin, taking metal as a target material, forming a metal thin layer on the bonding PP base film by a magnetron sputtering method, and respectively depositing two metal layers on two surfaces of the PP base film by an aqueous medium electroplating method to obtain metal layers;
and forming a stable oxide film on the metal layer through a benzotriazole antioxidant, and drying to obtain the composite current collector.
7. The method for preparing a composite current collector according to claim 6, wherein the surfactant is a mixed solution of sodium dodecyl sulfate, sodium fatty acid methyl sulfonate and fatty alcohol polyoxyethylene ether; the organic treating agent is a mixed solution of acetone and tetrachloroethylene; the first treating agent is isopropanol, and the second treating agent is chlorinated polypropylene.
8. The method for preparing a composite current collector according to claim 7, wherein the mass ratio of sodium dodecyl sulfate, sodium fatty acid methyl sulfonate and fatty alcohol-polyoxyethylene ether in the mixed solution of the surfactants is 3:1:2.
9. The method for preparing a composite current collector according to claim 8, wherein the mass ratio of acetone to tetrachloroethylene in the organic treating agent is 6:4.
10. The method for preparing a composite current collector according to claim 9, wherein the concentration of the chlorinated polypropylene is 5-10%o, the soaking time is 30-300 s, and the drying temperature in an oven is 80-120 ℃.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310937919.2A CN117059817A (en) | 2023-07-27 | 2023-07-27 | Composite current collector and preparation method thereof |
| PCT/CN2023/141152 WO2025020446A1 (en) | 2023-07-27 | 2023-12-22 | Composite current collector and preparation method therefor |
| PCT/CN2024/104948 WO2025020940A1 (en) | 2023-07-27 | 2024-07-11 | Composite current collector and preparation method |
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| CN202310937919.2A CN117059817A (en) | 2023-07-27 | 2023-07-27 | Composite current collector and preparation method thereof |
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| CN202310937919.2A Pending CN117059817A (en) | 2023-07-27 | 2023-07-27 | Composite current collector and preparation method thereof |
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| CN (1) | CN117059817A (en) |
| WO (2) | WO2025020446A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025020446A1 (en) * | 2023-07-27 | 2025-01-30 | 扬州纳力新材料科技有限公司 | Composite current collector and preparation method therefor |
| WO2025175633A1 (en) * | 2024-02-20 | 2025-08-28 | 江阴纳力新材料科技有限公司 | Composite current collector, manufacturing method therefor and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120902387A (en) * | 2025-10-09 | 2025-11-07 | 湖北龙辰科技股份有限公司 | Composite film and preparation method and application thereof |
| CN121123160A (en) * | 2025-11-12 | 2025-12-12 | 安徽浩天新能源科技有限公司 | Composite current collector based on PP (Polypropylene) base film/PET (polyethylene terephthalate) base film and production process |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1482528A (en) * | 1973-06-15 | 1977-08-10 | Sumitomo Metal Ind | Process for forming coatings on metal surfaces |
| IT1245251B (en) * | 1991-03-27 | 1994-09-13 | Himont Inc | ADHESIVE COMPOSITIONS AND WATER-BASED ADHESION PROMOTERS FOR POLYOLEFINS |
| CN102020903B (en) * | 2010-10-28 | 2013-02-13 | 苏州秩茂高分子材料有限公司 | Flame-free polypropylene finishing agent |
| CN110943227B (en) * | 2019-05-31 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Composite current collector, electrode plate and electrochemical device |
| CN113150723A (en) * | 2020-12-29 | 2021-07-23 | 江苏卓高新材料科技有限公司 | Conductive adhesive, and composite current collector, battery and object with conductive adhesive |
| CN113728475B (en) * | 2020-12-29 | 2024-04-26 | 宁德新能源科技有限公司 | Composite current collector and preparation method thereof and electrochemical device |
| CN113795954B (en) * | 2021-01-23 | 2022-08-26 | 宁德新能源科技有限公司 | Composite current collector, battery using same and electronic device |
| EP4228038A4 (en) * | 2021-12-10 | 2024-04-10 | Contemporary Amperex Technology Co., Limited | COMPOSITE CURRENT COLLECTOR, FOIL, SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK AND ELECTRICAL DEVICE |
| CN114773940B (en) * | 2022-05-10 | 2023-07-14 | 珠海格力电器股份有限公司 | Nonpolar polymer material surface treating agent and application thereof |
| CN115663200A (en) * | 2022-11-14 | 2023-01-31 | 楚能新能源股份有限公司 | Composite current collector, preparation method thereof, and lithium-ion battery |
| CN115911404A (en) * | 2023-02-02 | 2023-04-04 | 扬州纳力新材料科技有限公司 | Modified composite current collector and preparation method and application thereof |
| CN116314841A (en) * | 2023-03-28 | 2023-06-23 | 南通迈威电子材料有限公司 | A multilayer composite current collector |
| CN116072885A (en) * | 2023-04-03 | 2023-05-05 | 成都科成精化高分子材料有限公司 | Composite current collector and preparation method thereof |
| CN117059817A (en) * | 2023-07-27 | 2023-11-14 | 扬州纳力新材料科技有限公司 | Composite current collector and preparation method thereof |
-
2023
- 2023-07-27 CN CN202310937919.2A patent/CN117059817A/en active Pending
- 2023-12-22 WO PCT/CN2023/141152 patent/WO2025020446A1/en active Pending
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2024
- 2024-07-11 WO PCT/CN2024/104948 patent/WO2025020940A1/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025020446A1 (en) * | 2023-07-27 | 2025-01-30 | 扬州纳力新材料科技有限公司 | Composite current collector and preparation method therefor |
| WO2025020940A1 (en) * | 2023-07-27 | 2025-01-30 | 扬州纳力新材料科技有限公司 | Composite current collector and preparation method |
| WO2025175633A1 (en) * | 2024-02-20 | 2025-08-28 | 江阴纳力新材料科技有限公司 | Composite current collector, manufacturing method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2025020446A1 (en) | 2025-01-30 |
| WO2025020940A1 (en) | 2025-01-30 |
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