CN118039919A - Composite copper current collector with high mechanical property and preparation method and application thereof - Google Patents
Composite copper current collector with high mechanical property and preparation method and application thereof Download PDFInfo
- Publication number
- CN118039919A CN118039919A CN202410175504.0A CN202410175504A CN118039919A CN 118039919 A CN118039919 A CN 118039919A CN 202410175504 A CN202410175504 A CN 202410175504A CN 118039919 A CN118039919 A CN 118039919A
- Authority
- CN
- China
- Prior art keywords
- layer
- copper
- grain
- current collector
- composite
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 284
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 284
- 239000010949 copper Substances 0.000 title claims abstract description 284
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 39
- 229920006254 polymer film Polymers 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 379
- 239000003795 chemical substances by application Substances 0.000 claims description 61
- 238000009713 electroplating Methods 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- -1 polydithio-dipropyl Polymers 0.000 claims description 45
- 238000007747 plating Methods 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 30
- 239000011241 protective layer Substances 0.000 claims description 30
- 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 claims description 29
- 230000037452 priming Effects 0.000 claims description 29
- 229910052708 sodium Inorganic materials 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 29
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 28
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 28
- CNLHIRFQKMVKPX-UHFFFAOYSA-N 1,1-diethylthiourea Chemical compound CCN(CC)C(N)=S CNLHIRFQKMVKPX-UHFFFAOYSA-N 0.000 claims description 27
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 27
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 27
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 26
- 238000005282 brightening Methods 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000004513 sizing Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 11
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 11
- SPEYAJKGDLUARB-UHFFFAOYSA-M C(CC)S(=O)(=O)[O-].C(=S)NC.C(=S)NC.[Na+] Chemical compound C(CC)S(=O)(=O)[O-].C(=S)NC.C(=S)NC.[Na+] SPEYAJKGDLUARB-UHFFFAOYSA-M 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 241000486634 Bena Species 0.000 claims description 8
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001120 nichrome Inorganic materials 0.000 claims description 7
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- VKGYKXFNSKEHED-UHFFFAOYSA-M sodium;3-phenothiazin-10-ylpropane-1-sulfonate Chemical compound [Na+].C1=CC=C2N(CCCS(=O)(=O)[O-])C3=CC=CC=C3SC2=C1 VKGYKXFNSKEHED-UHFFFAOYSA-M 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube 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
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- ONVGBCNKVCPJCI-UHFFFAOYSA-N 3-(10h-phenothiazin-10-ium-10-yl)propane-1-sulfonate Chemical compound C1=CC=C2N(CCCS(=O)(=O)O)C3=CC=CC=C3SC2=C1 ONVGBCNKVCPJCI-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- HVNRJCGKBCZHJI-UHFFFAOYSA-N sodium;1,3-thiazolidine-2-thione Chemical compound [Na].S=C1NCCS1 HVNRJCGKBCZHJI-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a composite copper current collector with high mechanical property, and a preparation method and application thereof. The composite copper current collector comprises a polymer film layer; conductive layers positioned on the two side surfaces of the polymer film layer; wherein the conductive layer comprises a seed copper layer and a thickened copper layer, the thickened copper layer comprises a coarse-grain copper layer and a fine-grain copper layer, the coarse-grain copper layer and the fine-grain copper layer are alternately laminated, and the coarse-grain copper layer is positioned on at least part of the surface of the seed copper layer. The fine-grain copper layer in the composite copper current collector provided provides good tensile strength and yield strength, and the coarse-grain copper layer provides good elongation, so that the mechanical properties of the composite copper current collector are improved, and the stability of the composite copper current collector in the battery processing and circulating processes is promoted.
Description
Technical Field
The invention relates to the field of batteries, in particular to a composite copper current collector with high mechanical property, and a preparation method and application thereof.
Background
At present, a composite copper current collector based on a high-molecular polymer film is widely focused and applied in the new energy industry. The preparation of the composite copper current collector generally adopts a Physical Vapor Deposition (PVD) method to deposit a layer of copper metal on a high polymer film (such as polyesters, polyolefins and the like), so as to prepare the composite copper current collector with good electric conduction. Compared with the traditional copper current collector, the composite copper current collector based on the high-molecular polymer film has the characteristics of low cost, light weight, good internal insulation 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.
However, the traditional composite copper current collector has the problem of poor mechanical properties, namely lower tensile strength and yield strength, so that the traditional composite copper current collector is easy to deform in the preparation process of the pole piece to generate defects, the conductive property of the traditional composite copper current collector is caused to be poor, and finally the charge-discharge cycle performance of the battery is caused to be attenuated. Therefore, in order to further improve the mechanical properties of the composite copper current collector, it is necessary to develop a new composite copper current collector, thereby promoting the application and popularization of the composite copper current collector in batteries.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Aiming at the problem that the mechanical property of the composite copper current collector is to be improved, the invention provides the composite copper current collector and the preparation method thereof, and the provided composite copper current collector is provided with the coarse-grain copper layer and the fine-grain copper layer, so that the mechanical property of the composite copper current collector is improved through the correlation between the coarse-grain copper layer and the fine-grain copper layer, the processability of the composite copper current collector in the preparation process of a battery is promoted, and the charge-discharge cycle performance of the battery is further improved.
Specifically, the invention provides the following technical scheme:
the first aspect of the present invention provides a high mechanical property composite copper current collector, comprising:
a layer of the polymeric film is formed from a polymeric film,
And conductive layers positioned on the two side surfaces of the polymer film layer;
Wherein the conductive layer comprises a seed copper layer and a thickened copper layer,
The thickened copper layer comprises a coarse grain copper layer and a fine grain copper layer, the coarse grain copper layer and the fine grain copper layer are alternately laminated, and the coarse grain copper layer is positioned on at least part of the surface of the seed copper layer.
The invention starts from the construction of the conductive layer structure, and builds a multilayer structure with coarse-grain copper layers and fine-grain copper layers alternately arranged in the conductive layer of the composite copper current collector, wherein the fine-grain copper layers in the multilayer structure provide good tensile strength and yield strength for the composite copper current collector, and the coarse-grain copper layers provide good elongation for the composite copper current collector, so that the mechanical property of the composite copper current collector is improved under the combined action of the coarse-grain copper layers and the fine-grain copper layers, and the stability of the composite copper current collector in the battery processing and circulating process is promoted.
According to an embodiment of the present invention, the composite copper current collector described above may further include the following technical features:
In some embodiments of the invention, the coarse-grained copper layer and the fine-grained copper layer satisfy any one of the following conditions;
(a) The grain size d 1 of the coarse-grain copper layer satisfies the requirement that d 1 is less than or equal to 100 and less than or equal to 500nm, preferably 150-400 nm, and the grain size d 2 of the fine-grain copper layer satisfies the requirement that 0<d 2 <100nm, preferably 20-70 nm;
(b) The number of the coarse grain copper layers and the number of the fine grain copper layers are the same, and are recorded as n which is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 10;
(c) The thickness of the thickened copper layer is 500-2000 nm, preferably 800-1200 nm, and the thickness of the seed copper layer is 40-100 nm;
(d) The relation between the thickness t 1 of the thick copper layer of the adjacent coarse grains and the thickness t 2 of the copper layer of the fine grains is as follows: t 1/t2 is equal to or less than 0.5 is equal to or less than 2, preferably, t 1/t2 is equal to or less than 0.8 is equal to or less than 1.3.
In some embodiments of the invention, the coarse grain copper layer is prepared by:
Electroplating is carried out by using a first electroplating solution, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound.
In some embodiments of the invention, the first brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyldithio-carboxamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate, sodium 2-mercapto-thiazoline;
In some embodiments of the present invention, the first leveler is selected from at least one of N, N-diethylthiourea, 2-mercaptopyridine, bena green;
In some embodiments of the present invention, the first sizing agent is selected from at least one of polyethylene glycol, polypropylene glycol, polyoxyethylene ether.
In some embodiments of the invention, the fine-grained copper layer is prepared by:
Electroplating is carried out by using a second electroplating solution, wherein the second electroplating solution comprises 00-150g/L of copper sulfate, 80-160g/L of sulfuric acid, 20-80mg/L of chloride ions, 5-20ppm of a second brightening agent, 1-5ppm of a second leveling agent and 100-500ppm of a second impregnating compound.
In some embodiments of the invention, the second brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithio-carboxamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate, sodium 2-mercapto-thiazoline.
In some embodiments of the invention, the second leveler is selected from at least one of N, N-diethylthiourea, 2-mercaptopyridine, benalar green.
In some embodiments of the present invention, the second sizing agent is selected from at least one of polyethylene glycol, polypropylene glycol, polyoxyethylene ether.
In some embodiments of the present invention, the polymer film layer is obtained by melt extrusion of a polymer material selected from at least one of polyethylene terephthalate (PET), polypropylene (PP), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene Sulfide (PPs), polyphenylene oxide (PPO), polystyrene (PS), polyimide (PI).
In some embodiments of the invention, the thickness of the polymer film layer is 1.0-10 μm.
In some embodiments of the invention, the composite current collector further comprises a primer layer located on at least a portion of the surface of the polymer film layer, between the conductive layer and the polymer film layer; the material of the priming layer is at least one selected from aluminum oxide, silicon oxide, titanium oxide, nickel, chromium, titanium, nichrome copper alloy, silicon aluminum alloy, polyacrylic acid, polyacrylate, polyacrylamide and polyurethane.
In some embodiments of the invention, the primer layer has a thickness of 1 to 10nm, preferably 3 to 10nm.
In some embodiments of the invention, the composite current collector further comprises a protective layer located on at least a portion of a surface of the conductive layer; the material of the protective layer is at least one selected from nickel, chromium, nichrome, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper chromium oxide, graphite, carbon black, carbon nano quantum dots, carbon nano tubes, carbon nano fibers, graphene and graphene oxide.
In some embodiments of the invention, the protective layer has a thickness of 10 to 100nm, for example 20 to 80nm.
In some embodiments, the first protective layer, the first conductive layer, the first primer layer, the polymer film layer, the second primer layer, the second conductive layer, and the second protective layer are sequentially included from top to bottom;
The first priming layer is positioned on the upper surface of the polymer film layer, and the second priming layer is positioned on the lower surface of the polymer film layer;
the first conductive layer is positioned on the upper surface of the first priming layer, and the second conductive layer is positioned on the lower surface of the second priming layer;
the first protective layer is positioned on the upper surface of the first conductive layer, and the second protective layer is positioned on the lower surface of the second conductive layer;
wherein the first conductive layer comprises a first seed copper layer and a first thickened copper layer, and the second conductive layer comprises a second seed copper layer and a second thickened copper layer;
The first seed copper layer is positioned on the upper surface of the first priming layer, and the second seed copper layer is positioned on the upper surface of the second priming layer.
The second aspect of the invention provides a preparation method of the composite copper current collector, comprising the following steps:
Obtaining a polymer film layer by a melt extrusion and biaxial stretching method;
And depositing seed copper layers on the surfaces of two sides of the polymer film layer, sequentially electroplating at least part of the surfaces of the seed copper layers, respectively depositing coarse-grain copper layers and fine-grain copper layers, sequentially and alternately stacking the coarse-grain copper layers and the fine-grain copper layers to form thickened copper layers, and forming conductive layers by the seed copper layers and the thickened copper layers.
According to an embodiment of the invention, further comprising depositing a primer layer on at least part of the surface of the polymer film layer, the primer layer being located between the conductive layer and the polymer film layer.
According to an embodiment of the invention, further comprising depositing a protective layer on at least part of the surface of the conductive layer.
According to an embodiment of the present invention, the step of depositing a coarse grain copper layer includes:
Electroplating is carried out by using a first electroplating solution under the conditions that the average cathode current density is 0.5-2A/dm 2 and the plating solution temperature is 10-20 ℃, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound.
According to an embodiment of the present invention, the first brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate, sodium 2-mercapto thiazoline.
According to an embodiment of the present invention, the first leveling agent is at least one selected from the group consisting of N, N-diethylthiourea, 2-mercaptopyridine, and bena green.
According to an embodiment of the present invention, the first sizing agent is at least one selected from polyethylene glycol, polypropylene glycol, and polyoxyethylene ether.
According to an embodiment of the present invention, the step of depositing a fine-grained copper layer comprises:
Electroplating is carried out in a second electroplating solution under the conditions that the average cathode current density is 2.5-8A/dm 2 and the plating solution temperature is 25-40 ℃, wherein the second electroplating solution comprises 100-150g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 5-20ppm of a second brightening agent, 1-5ppm of a second leveling agent and 100-500ppm of a second sizing agent;
According to an embodiment of the present invention, the second brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate, sodium 2-mercapto thiazoline.
According to an embodiment of the present invention, the second leveling agent is at least one selected from the group consisting of N, N-diethylthiourea, 2-mercaptopyridine, and bena green;
According to an embodiment of the present invention, the second sizing agent is at least one selected from polyethylene glycol, polypropylene glycol, and polyoxyethylene ether.
A third aspect of the present invention provides a battery comprising the composite copper current collector described in the first aspect or the composite copper current collector obtained by the production method described in the second aspect.
The beneficial effects obtained by the invention are as follows:
the invention provides a novel composite copper current collector, which can realize the improvement of the mechanical property of the composite copper current collector due to the unique conductive layer structure, promote the stability of the composite copper current collector in battery processing and circulation, and has the advantages of simple and easy preparation method and easy amplified production.
Drawings
Fig. 1 is a schematic structural diagram of a composite copper current collector according to an embodiment of the present invention, wherein reference numeral 1 is a polymer film layer, 3 is a conductive layer, 30 is a thickened copper layer, 31 is a seed copper layer, 301 is a coarse-grain copper layer, and 302 is a fine-grain copper layer.
Fig. 2 is a schematic structural diagram of a composite copper current collector according to an embodiment of the present invention, wherein reference numeral 1 is a polymer film layer, 2 is a primer layer, 3 is a conductive layer, and 4 is a protective layer.
Detailed Description
The following detailed description of embodiments of the invention, examples of which are illustrated in the accompanying drawings and, by way of example, are intended to be illustrative, and not to be construed as limiting, of the invention.
The invention provides a composite copper current collector with high mechanical property, which comprises the following components:
a polymer film layer;
And conductive layers positioned on the two side surfaces of the polymer film layer;
the conductive layer comprises a seed copper layer and a thickened copper layer,
The thickened copper layer comprises a coarse grain copper layer and a fine grain copper layer, the coarse grain copper layer and the fine grain copper layer are alternately laminated, and the coarse grain copper layer is positioned on at least part of the surface of the seed copper layer.
The schematic structural diagram of the composite copper current collector may be shown in fig. 1 (it should be noted that the thicknesses of the layers in fig. 1 are not completely to scale, and are merely used as structural examples for reference, and are convenient for those skilled in the art to understand).
The invention starts from the construction of the conductive layer structure, and builds a multilayer structure with coarse-grain copper layers and fine-grain copper layers alternately arranged in the conductive layer of the composite copper current collector, wherein the fine-grain copper layers in the multilayer structure provide good tensile strength and yield strength for the composite copper current collector, and the coarse-grain copper layers provide good elongation for the composite copper current collector, so that the mechanical property of the composite copper current collector is improved under the combined action of the coarse-grain copper layers and the fine-grain copper layers, and the stability of the composite copper current collector in the battery processing and circulating process is promoted.
The provided composite copper current collector may further include a primer layer located on at least a portion of the surface of the polymer film layer and between the conductive layer and the polymer film layer. The provided composite copper current collector may further include a protective layer located on at least a portion of a surface of the conductive layer. According to the embodiment, as shown in fig. 2 (it should be noted that the thicknesses of the structures of the layers in fig. 1 are not completely to scale, and are only used as structural examples for reference, so that those skilled in the art will understand the structure, the composite copper current collector includes, sequentially from top to bottom, a first protective layer, a first conductive layer, a first primer layer, a polymer film layer, a second primer layer, a second conductive layer, and a second protective layer;
The first priming layer is positioned on the upper surface of the polymer film layer, and the second priming layer is positioned on the lower surface of the polymer film layer;
the first conductive layer is positioned on the upper surface of the first priming layer, and the second conductive layer is positioned on the lower surface of the second priming layer;
the first protective layer is positioned on the upper surface of the first conductive layer, and the second protective layer is positioned on the lower surface of the second conductive layer;
wherein the first conductive layer comprises a first seed copper layer and a first thickened copper layer, and the second conductive layer comprises a second seed copper layer and a second thickened copper layer;
The first seed copper layer is positioned on the upper surface of the first priming layer, and the second seed copper layer is positioned on the upper surface of the second priming layer.
The terms "first," "second," and the like herein do not denote any order or importance, but rather are used to distinguish one element from another.
The conductive layer is positioned on at least part of the surface of the priming layer and plays a main role in conduction. The conductive layer comprises a seed copper layer and a thickened copper layer, the thickness is between 500 and 2000nm, the composite conductive layer is too thin, and the conductivity is poor; too thick, the composite current collector prepared is too thick and heavy, which is unfavorable for improving the energy density of the battery. In view of conductivity and improvement of energy density, a thickness of 800 to 1200nm is more preferable. The material of the conductive layer is copper or an alloy thereof, preferably copper. The conductive layer consists of a seed copper layer and a thickening copper layer, wherein the seed copper layer is positioned on the surface of the priming layer and has the function of providing certain conductivity and providing a foundation for preparing the thickening layer. The thickness of the seed copper layer is 40-100 nm. Too low thickness and poor conductivity, and cannot ensure stable preparation of the thickened copper layer; the thickness is too thick, the stable preparation of the thickened copper layer cannot be further promoted, the energy consumption is high in the preparation process, and the mechanical property of the composite current collector can be influenced. In connection with the embodiments, the seed copper layer is prepared by physical vapor deposition (e.g., magnetron sputtering, evaporation, etc.).
The thickened copper layer is of a multi-layer structure and is formed by alternately laminating coarse-grain copper layers and fine-grain copper layers, wherein the coarse-grain copper layers are close to the seed copper layer, and the fine-grain copper layers are arranged on the outermost layer. The fine-grain copper layers in the multilayer structure with the coarse-grain copper layers and the fine-grain copper layers alternately arranged, which are built in the conductive layers, provide good tensile strength and yield strength for the composite copper current collector, and the coarse-grain copper layers provide good extensibility for the composite copper current collector, so that the mechanical properties of the composite copper current collector are improved under the combined action of the coarse-grain copper layers and the fine-grain copper layers, and the stability of the composite copper current collector in the battery processing and circulating processes is promoted.
According to a specific embodiment, the number of the coarse-grain copper layers and the number of the fine-grain copper layers are equal, and are all denoted by n, n is not less than 1, preferably not less than 1 and not more than 10 (for example, n is 1,2,3,4,5,6,7,8,9 and 10), and in this range, the preparation efficiency and the obtained effect are better. For example, n is too large, so that the preparation efficiency of the composite current collector is too low and the preparation difficulty is improved.
The size of grains in the coarse-grain copper layer in the multilayer structure needs to be within a proper range, and the grains are not excessively large, so that the tensile strength and the yield strength of the composite copper current collector are reduced excessively; the grains are too small, so that the preparation is difficult, and the related performance is also affected. The average grain size d 1 in the coarse grain copper layer satisfies the following: 100.ltoreq.d 1.ltoreq.500 nm, for example about 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm and 500nm. Preferred ranges are 150nm to 400nm, for example about 150nm, 200nm, 250nm, 300nm, 350nm, 400nm.
The size of the grains of the fine-grain copper layer in the multilayer structure is also required to be within a proper range, and the excessive grains can reduce the tensile strength and the yield strength of the composite copper current collector; too small a grain can reduce the elongation of the composite copper current collector. The average grain size d 2 of the fine-grain copper layer satisfies: 0<d 2 <100nm, for example about 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm. The preferred range is 20nm to 70nm, for example about 20nm, 30nm, 40nm, 50nm, 60nm, 70nm.
In some embodiments of the invention, the adjacent coarse grain copper layer thickness t 1 is related to the fine grain copper layer thickness t 2 by: 0.5.ltoreq.t 1/t2.ltoreq.2, preferably 0.8.ltoreq.t 1/t2.ltoreq.1.3 (for example, 0.9 to 1.1, may be 0.8,0.9,1.0,1.1,1.2,1.3 in particular).
In some embodiments of the invention, the coarse-grained copper layer is prepared by:
Electroplating is carried out by using a first electroplating solution, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound. According to a specific embodiment, the coarse-grained copper layer can be produced by means of electroplating, the production process being such that the average cathode current density is 0.5-2A/dm 2 and the bath temperature is 10-20 ℃. According to a specific embodiment, the chloride ion mentioned may be hydrochloric acid.
In some embodiments of the invention, the fine-grained copper layer is prepared by:
Electroplating is carried out by using a second electroplating solution, wherein the second electroplating solution comprises 00-150g/L of copper sulfate, 80-160g/L of sulfuric acid, 20-80mg/L of chloride ions, 5-20ppm of brightening agent, 1-5ppm of leveling agent and 100-500ppm of impregnating compound. According to an embodiment, the fine-grained copper layer may be prepared by electroplating, which may have an average cathode current density of 2.5-8A/dm 2 and a bath temperature of 25-40 ℃. According to a specific embodiment, the chloride ion mentioned may be hydrochloric acid.
In some embodiments of the invention, the first and second brighteners are each independently selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyldithioformamid propane sulfonate, phenothiazin-10-yl-propyl sulfonate, sodium 2-mercaptothiazoline.
In some embodiments of the invention, the first leveling agent and the second leveling agent are each independently selected from at least one of N, N-diethylthiourea, 2-mercaptopyridine, bena green.
In some embodiments of the present invention, the first sizing agent and the second sizing agent are each independently selected from at least one of polyethylene glycol, polypropylene glycol, polyoxyethylene ether.
According to a specific embodiment, the first impregnating compound and the second impregnating compound are the same and only have different concentrations; the first leveling agent and the second leveling agent are the same and only have different concentrations; the first and second brighteners mentioned are identical and differ only in concentration.
In some embodiments of the invention, the polymeric film layer is obtained by melt extrusion (e.g., obtained by melt-extrusion-biaxially stretching preparation) of a polymeric material selected from at least one of polyethylene terephthalate (PET), polypropylene (PP), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene Sulfide (PPs), polyphenylene oxide (PPO), polystyrene (PS), polyimide (PI).
In some embodiments of the present invention, the thickness of the polymer film layer is 1.0-10 μm, for example, about 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, considering the application requirements of the composite copper current collector, while taking into consideration the difficulty and cost of the manufacturing process.
The priming layer is positioned on the surface of the polymer film layer and plays a role in improving the cohesive force between the polymer film layer and the metal layer. In some embodiments of the invention, the material of the primer layer is selected from at least one of alumina, silica, titania, nickel, chromium, titanium, nichrome, aluminosilicate, polyacrylic acid, polyacrylate, polyacrylamide, polyurethane.
The thickness of the bottom layer is within a certain range, the improvement of the bonding force of the composite copper current collector is not obvious enough due to the fact that the thickness of the bottom layer is too thin, the bonding force cannot be further improved, and production efficiency is affected. In some embodiments of the invention, the primer layer has a thickness of 1 to 10nm, for example, about 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm. According to a preferred embodiment, the thickness of the primer layer is 3 to 10nm. In connection with the specific embodiment, the primer layer may be prepared by various methods such as physical vapor deposition or coating methods.
The protective layer is positioned on the surface of the conductive layer, so that the metal conductive layer can be prevented from being chemically corroded or physically damaged. In some embodiments of the present invention, the material of the protective layer is at least one selected from nickel, chromium, nichrome, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper chromium oxide, graphite, carbon black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers, graphene, and graphene oxide;
According to a specific embodiment, the thickness of the protective layer is between 10 and 100nm, preferably between 20 and 80nm, for example about 20nm, 30nm, 40nm, 50nm, 60nm, 70nm or 80nm. The thickness of the protective layer should not exceed one tenth of the thickness of the conductive layer. In connection with the specific embodiment, the protective layer may be prepared by various methods such as physical vapor deposition, chemical vapor deposition, in-situ forming, coating, etc.
The invention also provides a preparation method of the composite copper current collector, which comprises the following steps:
Obtaining a polymer film layer by a melt extrusion and biaxial stretching method;
And depositing seed copper layers on the surfaces of two sides of the polymer film layer, sequentially electroplating at least part of the surfaces of the seed copper layers, respectively depositing coarse-grain copper layers and fine-grain copper layers, sequentially and alternately stacking the coarse-grain copper layers and the fine-grain copper layers to form thickened copper layers, and forming conductive layers by the seed copper layers and the thickened copper layers.
According to a specific embodiment, the provided preparation method further comprises: and depositing a priming layer on at least part of the surface of the polymer film layer, wherein the priming layer is positioned between the conductive layer and the polymer film layer.
According to a specific embodiment, the provided preparation method further comprises: and depositing a protective layer on at least part of the surface of the conductive layer.
According to a specific embodiment, the step of depositing a coarse-grained copper layer comprises:
Electroplating is carried out by using a first electroplating solution under the conditions that the average cathode current density is 0.5-2A/dm 2 and the plating solution temperature is 10-20 ℃, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound.
According to a specific embodiment, the first brightening agent is selected from at least one of sodium polydithio-propane sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, sodium phenothiazin-10-yl-propyl sulfonate, 2-mercapto thiazoline.
According to a specific embodiment, the first levelling agent is selected from at least one of N, N-diethylthiourea, 2-mercaptopyridine, bena green.
According to a specific embodiment, the first sizing agent is selected from at least one of polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
According to an embodiment, the step of depositing a fine-grained copper layer comprises:
electroplating is carried out by using a second electroplating solution under the conditions that the average cathode current density is 2.5-8A/dm 2 and the plating solution temperature is 25-40 ℃, wherein the second electroplating solution comprises 100-150g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 5-20ppm of a second brightening agent, 1-5ppm of a second leveling agent and 100-500ppm of a second sizing agent.
According to a specific embodiment, the second brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, sodium phenothiazin-10-yl-propyl sulfonate, 2-mercapto thiazoline.
According to a specific embodiment, the second levelling agent is selected from at least one of N, N-diethylthiourea, 2-mercaptopyridine, and bena green.
According to a specific embodiment, the second sizing agent is at least one selected from polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
The invention also provides a battery, which comprises the composite copper current collector or the composite copper current collector prepared by the preparation method.
The following description of the embodiments of the present invention is provided by way of example only and should not be construed as limiting the scope of the invention, as it is intended that these embodiments be construed as being limited to those skilled in the art. The reagents used, not specifically described, are available either commercially or in self-made form.
Example 1
Example 1a composite copper current collector was prepared by the following method, comprising:
First, a primer layer is prepared on the surface of a polymer film. A biaxially oriented PET film (polyethylene terephthalate) with the thickness of 4.5 micrometers is placed in a magnetron sputtering machine, a nichrome target is used as a target, and a layer of 5nm priming layer is respectively deposited on two sides of the PET film, and the specific process conditions are as follows: the PET composite film with the surface containing the priming layer is prepared by taking a nickel-chromium target (purity: 99.99%) as a target material, wherein the target power is 5.0kW, the argon flow is 50mL/min, the vacuum degree of the film coating is 0.08Pa, the film coating time is 1s, and the temperature of a main roller in the film coating process is 0 ℃.
Secondly, preparing a conductive layer on the surface of the priming layer:
(1) Preparing a seed copper layer: the PET composite film with the surface containing the priming layer is placed in a magnetron sputtering machine, a copper target (purity: 99.99%) is used as a target material, and seed copper layers with the thickness of 50nm are respectively prepared on two sides of the composite film, and the preparation process comprises the following steps: the target power is 12kW, the argon flow is 50mL/min, the vacuum degree of the coating is 0.08Pa, the coating time is 5s, and the temperature of the main roller in the coating process is 2 ℃.
(2) Preparing a thickened copper layer: and sequentially depositing a coarse-grain copper layer and a fine-grain copper layer on the surface of the prepared composite film, wherein:
1) Coarse grain copper layer: the thickness of each layer is 100nm, the number of layers is 5, the average grain size is 100nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion (hydrochloric acid), 4ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density is 2.0A/dm 2, the plating solution temperature is 20 ℃, and the electroplating time is 24s;
2) Fine-grain copper layer: the thickness of each layer is 100nm, the number of layers is 5, the average grain size is 20nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions (hydrochloric acid), 16ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 7.6A/dm 2, the plating bath temperature was 38deg.C, and the plating time was 6.5s.
Finally, continuously preparing a protective layer on the surface of the prepared conductive layer: the prepared composite membrane is placed in a dipping liquid, the solute component of the dipping liquid is 0.5g/L chromic anhydride and 5g/L sodium gluconate, the solvent is water, and the dip-coating time is 30s. And after dip-coating, extruding to remove liquid, and then placing in a 60 ℃ oven for drying to obtain the composite copper current collector.
Example 2
Substantially identical to example 1, except that:
The average grain size of the coarse grain copper layer is 150nm, and the preparation conditions are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion, 3.5ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density was 1.8A/dm 2, the plating bath temperature was 17℃and the plating time was 27s.
Example 3
Substantially identical to example 1, except that:
The average grain size of the coarse grain copper layer is 300nm, and the preparation conditions are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ions, 2.2ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density was 1.2A/dm 2, the plating bath temperature was 15℃and the plating time was 45s.
Example 4
Substantially identical to example 1, except that:
The average grain size of the coarse grain copper layer is 400nm, and the preparation conditions are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ions, 1.4ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density was 0.9A/dm 2, the plating bath temperature was 13℃and the plating time was 60s.
Example 5
Substantially identical to example 1, except that:
The average grain size of the coarse grain copper layer is 500nm, and the preparation conditions are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion, 0.5ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density was 0.5A/dm 2, the plating bath temperature was 10℃and the plating time was 105s.
Example 6
Substantially identical to example 1, except that:
The average grain size of the fine-grain copper layer was 50nm, and the conditions for the preparation of each layer were: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 12ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 5.0A/dm 2, the plating bath temperature was 32℃and the plating time was 10s.
Example 7
Substantially identical to example 1, except that:
The average grain size of the fine-grain copper layer was 70nm, and the conditions for the preparation of each layer were: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 9ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 4.0A/dm 2, the plating bath temperature was 28℃and the plating time was 12.5s.
Example 8
Substantially identical to example 1, except that:
The average grain size of the fine-grain copper layer was 90nm, and the conditions for the preparation of each layer were: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 7ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 3.0A/dm 2, the plating bath temperature was 25℃and the plating time was 16s.
Example 9
Substantially identical to example 1, except that:
In the thickened copper layer:
1) Coarse grain copper layer: the thickness of each layer is 500nm, the number of layers is 1, the average grain size is 100nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion, 4ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density is 2.0A/dm 2, the plating solution temperature is 20 ℃, and the electroplating time is 120s;
2) Fine-grain copper layer: the thickness of each layer is 500nm, the number of layers is 1, the average grain size is 20nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 16ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 7.6A/dm 2, the plating bath temperature was 38deg.C, and the plating time was 32.5s.
Example 10
Substantially identical to example 1, except that: in the thickened copper layer:
1) Coarse grain copper layer: the thickness of each layer is 50nm, the number of layers is 10, the average grain size is 100nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion, 4ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density is 2.0A/dm 2, the plating solution temperature is 20 ℃, and the electroplating time is 12s;
2) Fine-grain copper layer: the thickness of each layer is 50nm, the number of layers is 10, the average grain size is 20nm, and the preparation conditions of each layer are as follows: the electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 16ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 7.6A/dm 2, the plating bath temperature was 38deg.C, and the plating time was 3.25s.
Comparative example 1
Substantially identical to example 1, except that: the thickened copper layer is a layer with the thickness of 1000nm, and the preparation process comprises the following steps:
The electroplating solution comprises the following components: 100g/L copper sulfate, 100g/L sulfuric acid, 60mg/L chloride ions, 2ppm sodium polydithio-dipropyl sulfonate, 1ppm N, N-diethyl thiourea and 100ppm polyoxyethylene ether; the average cathode current density was 2A/dm 2, the plating bath temperature was 25℃and the plating time was 260s.
Comparative example 2
Substantially identical to example 1, except that: the average grain size of the coarse grain copper layer is 550nm, and the preparation conditions are as follows:
The electroplating solution comprises the following components: 90g/L copper sulfate, 100g/L sulfuric acid, 40mg/L chloride ion, 0.3ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 80ppm polyoxyethylene ether; the average cathode current density was 0.2A/dm 2, the plating bath temperature was 10℃and the plating time was 270s.
Comparative example 3
Substantially identical to example 1, except that: the average grain size of the fine-grain copper layer was 120nm, and the conditions for the preparation of each layer were:
The electroplating solution comprises the following components: 120g/L copper sulfate, 130g/L sulfuric acid, 50mg/L chloride ions, 3ppm sodium polydithio-dipropyl sulfonate, 2ppm N, N-diethyl thiourea and 200ppm polyoxyethylene ether; the average cathode current density was 2.0A/dm 2, the plating bath temperature was 25℃and the plating time was 25s.
Testing and evaluation:
the tensile strength, yield strength and elongation at break of the composite copper current collector prepared in each of the above examples and comparative examples were tested here, and the specific test methods are as follows: samples were taken longitudinally along the prepared composite current collector and then tested for tensile strength, yield strength and elongation at break with reference to national standard GB/T1040.3-2006.
Table 1 test results for different examples and comparative examples
| Tensile Strength (MPa) | Yield strength (MPa) | Elongation at break (%) | |
| Example 1 | 319 | 255 | 22 |
| Example 2 | 298 | 239 | 26 |
| Example 3 | 279 | 222 | 32 |
| Example 4 | 261 | 207 | 37 |
| Example 5 | 245 | 195 | 41 |
| Example 6 | 292 | 236 | 28 |
| Example 7 | 272 | 218 | 34 |
| Example 8 | 250 | 198 | 39 |
| Example 9 | 248 | 196 | 40 |
| Example 10 | 265 | 210 | 36 |
| Comparative example 1 | 220 | 180 | 20 |
| Comparative example 2 | 228 | 185 | 45 |
| Comparative example 3 | 235 | 189 | 43 |
From the table above, it can be seen that:
(1) It can be seen in connection with the data given in examples 1-10 and comparative example 1: compared with the traditional composite copper current collector, the composite copper current collector provided by the invention is provided with the coarse-grain copper layers and the fine-grain copper layers which are alternately arranged, and the tensile strength, the yield strength and the elongation at break all show the tendency of improvement, namely the mechanical property is improved.
(2) It can be seen from the data given in connection with examples 1-5 and comparative example 2: as the average grain of the coarse grain copper layer in the thickened copper layer increases, the tensile strength and yield strength of the composite current collector show a tendency to decrease, while the elongation at break shows a tendency to increase, due to the grain becoming larger. The average grain size of the coarse grain copper layer should not be too large in order to ensure sufficient tensile strength and yield strength.
(3) It can be seen in connection with the data given in examples 1, 6, 7, 8 and comparative example 3 that: as the average grain of the fine-grain copper layer in the thickened copper layer increases, the tensile strength and yield strength of the composite current collector show a tendency to decrease, while the elongation at break shows a tendency to increase, due to the grain becoming larger. In order to ensure sufficient tensile strength and yield strength, the average grain size of the fine-grained copper layer is not easily excessively large.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "implementation," "particular implementations," and the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (12)
1. A high mechanical property composite copper current collector, comprising:
a polymer film layer;
And conductive layers positioned on the two side surfaces of the polymer film layer;
Wherein the conductive layer comprises a seed copper layer and a thickened copper layer,
The thickened copper layer comprises a coarse grain copper layer and a fine grain copper layer, the coarse grain copper layer and the fine grain copper layer are alternately laminated, and the coarse grain copper layer is positioned on at least part of the surface of the seed copper layer.
2. The composite copper current collector of claim 1 wherein the coarse-grained copper layer and the fine-grained copper layer satisfy any one of the following conditions:
(a) The grain size d 1 of the coarse-grain copper layer satisfies that d 1 is less than or equal to 100 and less than or equal to 500nm, the grain size d 1 of the preferable coarse-grain copper layer is 150-400 nm, the grain size d 2 of the fine-grain copper layer satisfies that 0<d 2 <100nm, and the grain size d 2 of the preferable fine-grain copper layer is 20-70 nm;
(b) The number of the coarse grain copper layers and the number of the fine grain copper layers are the same, and are recorded as n which is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 10;
(c) The thickness of the thickened copper layer is 500-2000 nm, the thickness of the thickened copper layer is preferably 800-1200nm, and the thickness of the seed copper layer is 40-100 nm;
(d) The relation between the thickness t 1 of the thick copper layer of the adjacent coarse grains and the thickness t 2 of the copper layer of the fine grains is as follows: t 1/t2 is equal to or less than 0.5 is equal to or less than 2, preferably, t 1/t2 is equal to or less than 0.8 is equal to or less than 1.3.
3. The composite copper current collector according to claim 1 or 2, wherein the coarse-grained copper layer is prepared by:
Electroplating by using a first electroplating solution, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound;
Optionally, the first brightening agent is at least one selected from sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate sodium salt and 2-mercapto thiazoline;
optionally, the first leveling agent is at least one selected from N, N-diethyl thiourea, 2-mercaptopyridine and Jianna green;
optionally, the first sizing agent is at least one selected from polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
4. The composite copper current collector according to claim 1 or 2, wherein the fine-grained copper layer is prepared by:
Electroplating by using a second electroplating solution, wherein the second electroplating solution comprises 100-150g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 5-20ppm of a second brightening agent, 1-5ppm of a second leveling agent and 100-500ppm of a second impregnating compound;
Optionally, the second brightening agent is at least one selected from sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate sodium salt and 2-mercapto thiazoline;
optionally, the second leveling agent is at least one selected from N, N-diethyl thiourea, 2-mercaptopyridine and bena green;
Optionally, the second sizing agent is at least one selected from polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
5. The composite copper current collector according to claim 1 or 2, wherein the polymer film layer is melt extruded from a polymer material selected from at least one of polyethylene terephthalate (PET), polypropylene (PP), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene Sulfide (PPs), polyphenylene oxide (PPO), polystyrene (PS), polyimide (PI);
Optionally, the thickness of the polymer film layer is 1.0-10 μm.
6. The composite copper current collector of claim 5, further comprising a primer layer located on at least a portion of a surface of said polymer film layer between said conductive layer and said polymer film layer;
the material of the priming layer is at least one selected from aluminum oxide, silicon oxide, titanium oxide, nickel, chromium, titanium, nichrome copper alloy, silicon aluminum alloy, polyacrylic acid, polyacrylate, polyacrylamide and polyurethane;
Optionally, the thickness of the primer layer is 1-10 nm, preferably the thickness of the primer layer is 3-10nm.
7. The composite copper current collector of claim 6, further comprising a protective layer on at least a portion of a surface of said conductive layer;
The material of the protective layer is at least one selected from nickel, chromium, nichrome, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper chromium oxide, graphite, carbon black, carbon nano quantum dots, carbon nano tubes, carbon nano fibers, graphene and graphene oxide;
Optionally, the thickness of the protective layer is 10-100nm, preferably, the thickness of the protective layer is 20-80nm.
8. The composite copper current collector according to claim 7, wherein the composite copper current collector comprises a first protective layer, a first conductive layer, a first primer layer, a polymer film layer, a second primer layer, a second conductive layer, and a second protective layer in this order from top to bottom;
The first priming layer is positioned on the upper surface of the polymer film layer, and the second priming layer is positioned on the lower surface of the polymer film layer;
the first conductive layer is positioned on the upper surface of the first priming layer, and the second conductive layer is positioned on the lower surface of the second priming layer;
the first protective layer is positioned on the upper surface of the first conductive layer, and the second protective layer is positioned on the lower surface of the second conductive layer;
wherein the first conductive layer comprises a first seed copper layer and a first thickened copper layer, and the second conductive layer comprises a second seed copper layer and a second thickened copper layer;
The first seed copper layer is positioned on the upper surface of the first priming layer, and the second seed copper layer is positioned on the upper surface of the second priming layer.
9. A method for preparing the composite copper current collector according to any one of claims 1 to 8, comprising the steps of:
Obtaining a polymer film layer by a melt extrusion and biaxial stretching method;
Depositing seed copper layers on the surfaces of two sides of the polymer film layer, sequentially electroplating at least part of the surfaces of the seed copper layers, respectively depositing coarse-grain copper layers and fine-grain copper layers, sequentially and alternately stacking the coarse-grain copper layers and the fine-grain copper layers to form thickened copper layers, and forming conductive layers by the seed copper layers and the thickened copper layers;
Optionally, further comprising depositing a primer layer on at least a portion of a surface of the polymer film layer, the primer layer being located between the conductive layer and the polymer film layer;
optionally, further comprising depositing a protective layer on at least a portion of a surface of the conductive layer.
10. The method of preparing a composite copper current collector according to claim 9, wherein the step of depositing a coarse-grained copper layer comprises:
Electroplating under the conditions that the average cathode current density is 0.5-2A/dm 2 and the plating solution temperature is 10-20 ℃ by using a first electroplating solution, wherein the first electroplating solution comprises 80-130g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 0.5-4ppm of a first brightening agent, 1-5ppm of a first leveling agent and 20-100ppm of a first impregnating compound;
Optionally, the first brightening agent is at least one selected from sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate sodium salt and 2-mercapto thiazoline;
optionally, the first leveling agent is at least one selected from N, N-diethyl thiourea, 2-mercaptopyridine and Jianna green;
optionally, the first sizing agent is at least one selected from polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
11. The method of preparing a composite copper current collector according to claim 9, wherein the step of depositing a fine-grained copper layer comprises:
Electroplating under the conditions that the average cathode current density is 2.5-8A/dm 2 and the plating solution temperature is 25-40 ℃ by using a second electroplating solution, wherein the second electroplating solution comprises 100-150g/L copper sulfate, 80-160g/L sulfuric acid, 20-80mg/L chloride ions, 5-20ppm of a second brightening agent, 1-5ppm of a second leveling agent and 100-500ppm of a second sizing agent;
Optionally, the second brightening agent is at least one selected from sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl dithioformamide propane sulfonate, phenothiazin-10-yl-propyl sulfonate sodium salt and 2-mercapto thiazoline;
optionally, the second leveling agent is at least one selected from N, N-diethyl thiourea, 2-mercaptopyridine and bena green;
Optionally, the second sizing agent is at least one selected from polyethylene glycol, polypropylene glycol and polyoxyethylene ether.
12. A battery comprising the composite copper current collector according to any one of claims 1 to 8 or the composite copper current collector obtained by the production method according to any one of claims 9 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410175504.0A CN118039919A (en) | 2024-02-07 | 2024-02-07 | Composite copper current collector with high mechanical property and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410175504.0A CN118039919A (en) | 2024-02-07 | 2024-02-07 | Composite copper current collector with high mechanical property and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118039919A true CN118039919A (en) | 2024-05-14 |
Family
ID=90985339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410175504.0A Pending CN118039919A (en) | 2024-02-07 | 2024-02-07 | Composite copper current collector with high mechanical property and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118039919A (en) |
-
2024
- 2024-02-07 CN CN202410175504.0A patent/CN118039919A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11355757B2 (en) | Electrolytic copper foil, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same | |
| TWI566459B (en) | Porous metal foil and its manufacturing method | |
| US9595719B2 (en) | Composite metal foil and production method therefor | |
| JP5730742B2 (en) | Electrolytic copper foil for lithium ion secondary battery and method for producing the same | |
| CN110235285B (en) | Method for manufacturing lithium electrode | |
| US10418635B2 (en) | Electrolytic copper foil for lithium secondary battery and lithium secondary battery comprising the same | |
| CN110249461B (en) | Method for manufacturing lithium electrode | |
| JP2012038700A (en) | Copper foil for current collector of lithium secondary battery | |
| CN112510210A (en) | Composite current collector, preparation method thereof and secondary battery | |
| CN214280014U (en) | Composite current collector and secondary battery | |
| KR20130077240A (en) | Additive for electroylite solution of electroplating process for copper coating with high elongation and electroylite solution of electroplating process for copper coating with high elongation comprising the same | |
| JP2005350761A (en) | Composite foil for negative electrode current collector of nonaqueous electrolyte secondary battery, and method for producing the same, negative electrode current collector using the composite foil, electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| CN118039919A (en) | Composite copper current collector with high mechanical property and preparation method and application thereof | |
| CN101997107B (en) | Magnesium electrode for magnesium battery and preparation method thereof | |
| KR102405236B1 (en) | Method for manufacturing electrolytic copper foil | |
| CN218896658U (en) | Composite copper foil and battery | |
| CN117913286B (en) | Composite copper-based current collector, preparation method thereof and lithium ion battery | |
| CN220856616U (en) | Composite copper foil with spherical structure on surface | |
| CN219997877U (en) | Conductive film | |
| KR102642389B1 (en) | Electrolytic copper foil and secondary battery comprising the same | |
| CN114075655B (en) | Conductive film, method for producing conductive film, current collecting and transmitting material, and energy storage device | |
| KR102535462B1 (en) | Electrolytic copper foil having high tensile strenth and secondary battery comprising the same | |
| CN117936795A (en) | High-strength low-resistance positive electrode composite current collector, preparation method thereof, positive electrode plate and electrochemical device | |
| CN118039920A (en) | Composite current collector and preparation method and application thereof | |
| CN117638087A (en) | Current collector, preparation method of current collector and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |