CN118039920A - Composite current collector and preparation method and application thereof - Google Patents
Composite current collector and preparation method and application thereof Download PDFInfo
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- CN118039920A CN118039920A CN202410190972.5A CN202410190972A CN118039920A CN 118039920 A CN118039920 A CN 118039920A CN 202410190972 A CN202410190972 A CN 202410190972A CN 118039920 A CN118039920 A CN 118039920A
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- 239000002131 composite material Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 76
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 225
- 238000000576 coating method Methods 0.000 claims description 40
- 230000008719 thickening Effects 0.000 claims description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 238000009713 electroplating Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 239000011241 protective layer Substances 0.000 claims description 16
- 238000005240 physical vapour deposition Methods 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910001120 nichrome Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 238000005282 brightening Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
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- 229920002125 Sokalan® Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
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- 229920001721 polyimide Polymers 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CNLHIRFQKMVKPX-UHFFFAOYSA-N 1,1-diethylthiourea Chemical compound CCN(CC)C(N)=S CNLHIRFQKMVKPX-UHFFFAOYSA-N 0.000 description 1
- 239000005734 Benalaxyl Substances 0.000 description 1
- 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 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- CJPQIRJHIZUAQP-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-(phenylacetyl)alaninate Chemical compound CC=1C=CC=C(C)C=1N(C(C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-UHFFFAOYSA-N 0.000 description 1
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- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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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 current collector, a preparation method and application thereof, wherein the composite current collector comprises a polymer base film, and a bonding layer and a composite conductive layer which are sequentially laminated on at least one side surface of the polymer base film; the composite conductive layer comprises a carbon layer. The invention develops a novel composite current collector, namely, a carbon layer is introduced into a composite conductive layer, and the defect rate of the composite current collector can be reduced due to the unique conductive layer structure, so that the stability of the structure and the performance of the composite current collector is improved, the stability of the composite current collector in the battery processing and circulating process is promoted, and the preparation method is simple and feasible and is easy to amplify production.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a composite current collector, 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 process of the composite copper current collector is generally divided into two steps: firstly, depositing a layer of copper on a polymer film (such as polypropylene, polyethylene or polyester) by adopting a magnetron sputtering method to prepare a semi-finished product of the composite copper current collector with certain electric conductivity; and then, further processing the semi-finished product of the composite copper current collector by electroplating to thicken the conductive copper layer, thereby preparing the composite copper current collector with good conductivity. Compared with the traditional current collector (copper foil), 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, so that the cost of the battery can be reduced and the energy density and the safety of the battery can be improved when the composite current collector is applied to the battery.
However, there are the following problems with the current preparation of composite copper current collectors: the method is characterized in that a winding magnetron sputtering device is adopted to deposit a copper layer on a polymer film to prepare a film surface contacted with each other in the winding process of a semi-finished product of the composite copper current collector, adhesion can occur, the film surface adhered in the unwinding process of a subsequent process (electroplating) can be torn, a microscopic copper layer on the film surface can fall off to generate microscopic defects, copper cannot be deposited due to non-conduction near a defect point in the electroplating process, and finally the prepared composite copper current collector has microscopic defects, so that the performance and the application of the composite current collector are affected.
Therefore, in order to solve the above-mentioned problems, it is necessary to develop a composite current collector with low defects, so that the stability of the structure and performance of the composite current collector is improved, and the popularization and application of the composite current collector are promoted.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite current collector, and a preparation method and application thereof. The invention develops a novel composite current collector, namely, a carbon layer is introduced into a composite conductive layer, and the defect rate of the composite current collector can be reduced due to the unique conductive layer structure, so that the stability of the structure and the performance of the composite current collector is improved, the stability of the composite current collector in the battery processing and circulating process is promoted, and the preparation method is simple and feasible and is easy to amplify production.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite current collector including a polymer base film, and a bonding layer and a composite conductive layer sequentially laminated on at least one side surface of the polymer base film;
the composite conductive layer comprises a carbon layer.
The invention develops a novel composite current collector, namely, a carbon layer is introduced into a composite conductive layer, and the defect rate of the composite current collector can be reduced due to the unique conductive layer structure, so that the stability of the structure and the performance of the composite current collector is improved, the stability of the composite current collector in the battery processing and circulating process is promoted, and the preparation method is simple and feasible and is easy to amplify production.
In the present invention, the presence of the carbon layer has the following advantages: ① The bonding between layers can be restrained, and defects caused by bonding of film surfaces in the electroplating unreeling process are prevented; ② The carbon layer has conductivity and does not influence the conductivity of the semi-finished product of the composite current collector; ③ Has stronger stability, can not introduce new impurities into the electroplating solution, and can not influence the protection effect.
In the present invention, the purpose of the adhesive layer is to promote adhesion between the polymer base film and the composite conductive layer.
As a preferable technical scheme of the invention, the composite conductive layer further comprises a seed layer and a thickening layer.
In the invention, the seed layer has the function of providing certain conductivity and providing a foundation for preparing the thickening layer.
In the present invention, the thickening layer functions to provide conductivity to the composite current collector.
Preferably, the composite conductive layer includes a seed layer, a carbon layer, and a thickening layer in this order in a direction away from the polymer base film.
According to the invention, the carbon layer is arranged between the seed layer and the thickening layer, so that the adhesion between copper layers of the semi-finished product of the composite current collector can be inhibited, defects caused by film surface adhesion in the unreeling process of preparing the thickening layer are prevented, and the conductive layer is arranged, so that the conductive performance of the semi-finished product of the composite current collector prepared by magnetron sputtering is not influenced, and the electroplating effect is further influenced; in addition, the carbon layer has strong stability, and can not react with the electroplating liquid after entering the electroplating process, so that new impurities can be prevented from being introduced into the electroplating liquid to influence the electroplating effect; finally, the carbon layer is in an amorphous state, so that the adhesion force between the carbon layer and the seed layer and between the carbon layer and the thickening layer can be improved, and the stability of the composite current collector structure is promoted.
It should be noted that adhesion occurs between film surfaces in contact with each other in the process of winding a semi-finished product of the composite copper current collector, so that the adhered film surfaces can be torn in the process of unreeling in the subsequent process (electroplating), a microscopic copper layer on the film surfaces falls off to generate microscopic defects, copper cannot be deposited due to non-conduction near defect points in the electroplating process, and finally the prepared composite copper current collector has microscopic defects, so that the performance and application of the composite current collector are affected. Therefore, the carbon layer is arranged on the surface of the seed layer, so that defects caused by adhesion of the seed layers on the surface of the semi-finished product of the composite current collector can be prevented, and further a thickening layer with lower defect rate is ensured to be generated.
Preferably, the carbon layer is an amorphous carbon layer.
In the invention, the carbon layer is in an amorphous state, so that the stability of the composite current collector structure can be promoted.
Preferably, the material of the seed layer comprises metallic copper and/or copper alloy, preferably metallic copper.
Preferably, the seed layer is further doped with a carbon element, and the content of the carbon element accounts for 0.1-5% of the total mass of the seed layer, for example, may be 0.1%, 0.5%, 1%, 2%, 3%, 4% or 5%.
According to the invention, the seed layer is doped with a certain content of carbon element, so that the adhesion between the seed layer and the carbon layer is improved, and the structural stability of the prepared composite current collector is improved.
Preferably, the material of the thickening layer comprises metallic copper and/or copper alloy, preferably metallic copper.
Preferably, the thickening layer is further doped with carbon element, and the content of the carbon element accounts for 0.1-5% of the total mass of the thickening layer, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4% or 5% and the like.
According to the invention, the thickening layer is doped with a certain content of carbon element, so that the adhesion between the thickening layer and the carbon layer is improved, and the structural stability of the prepared composite current collector is improved.
As a preferable embodiment of the present invention, the thickness of the seed layer is 40-100nm, for example, 40nm, 60nm, 80nm, 100nm, or the like.
In the invention, if the thickness of the seed layer is too low, stable preparation of the thickening layer cannot be ensured; if the thickness of the seed layer is too high, stable preparation of the thickening layer cannot be further promoted, and the energy consumption in the preparation process is high, so that the mechanical property of the composite current collector is affected.
Preferably, the thickness of the carbon layer is 1nm or more, for example, 1nm, 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc., preferably 5 to 20nm.
In the present invention, if the thickness of the carbon layer is too low, the conductivity is too poor; if the thickness of the carbon layer is too high, stable preparation of the thickening layer cannot be ensured, and after the thickness reaches a certain value, the defect rate of a finished product generated by bonding between the seed layer and the thickening layer in the semi-finished product of the composite current collector is reduced to 0, so that the effect of the invention cannot be improved by further improving the thickness, and the cost is wasted.
Preferably, the thickness of the thickening layer is 500-2000nm, for example 500nm, 1000nm, 1500nm or 2000nm, etc., preferably 800-1200nm.
In the invention, if the thickness of the thickening layer is too low, the conductivity is poor; if the thickness of the thickening layer is too high, the prepared composite current collector is too thick and heavy, which is not beneficial to improving the energy density of the battery. In view of conductivity and improvement of energy density, the thickness is preferably 800 to 1200nm.
As a preferable technical scheme of the invention, the material of the polymer base film is any one or a combination of at least two 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 or Polyimide (PI).
As a preferable embodiment of the present invention, the thickness of the polymer base film is 1 to 10. Mu.m, for example, 1. Mu.m, 3. Mu.m, 5. Mu.m, 7. Mu.m, 9. Mu.m, or the like.
In the invention, considering the application requirement of the composite copper current collector and simultaneously considering the difficulty and cost of the preparation process, the thickness of the polymer base film is preferably 1-10 mu m.
Preferably, the material of the bonding layer comprises any one or a combination of at least two of aluminum oxide, silicon oxide, titanium oxide, nickel, chromium, titanium, nichrome, silicon aluminum alloy, polyacrylic acid, polyacrylate, polyacrylamide or polyurethane.
Preferably, the thickness of the adhesive layer is 1-10nm, for example, 1nm, 3nm, 5nm, 7nm, 9nm, or the like.
Preferably, a protective layer is provided on a surface of the composite conductive layer on a side remote from the polymer base film.
In the present invention, the purpose of the protective layer is to prevent the composite copper layer from being chemically corroded or physically damaged.
Preferably, the material of the protective layer includes any one or a combination of at least two of 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 or graphene oxide.
Preferably, the thickness of the protective layer is 5-100nm, for example, 5nm, 10nm, 30nm, 50nm, 70nm or 90nm, etc., preferably 10-80nm.
Preferably, the thickness of the protective layer is less than or equal to one tenth of the thickness of the composite copper layer.
In a second aspect, the present invention provides a method for preparing a composite current collector according to the first aspect, the method comprising the steps of:
sequentially preparing a bonding layer and a composite conductive layer on at least one surface of a polymer base film;
the composite conductive layer comprises a carbon layer.
The preparation method provided by the invention is simple and feasible, and is easy for large-scale production.
As a preferred technical scheme of the present invention, the composite conductive layer sequentially includes a seed layer, a carbon layer and a thickening layer along a direction away from the polymer base film.
Preferably, the preparation method of the carbon layer comprises a magnetron sputtering method and/or a chemical vapor deposition method, preferably a magnetron sputtering method.
Preferably, the specific process parameters of the magnetron sputtering method comprise:
The power of the target is 2-10kW, for example, 2kW, 4kW, 6kW, 8kW or 10kW, and the like, the air source flow is 30-200mL/min, for example, 30mL/min, 50mL/min, 100mL/min, 150mL/min or 200mL/min, and the like, and the vacuum degree is less than or equal to 1Pa, for example, 1Pa, 0.8Pa or 0.5Pa, and the like.
Preferably, the gas source comprises nitrogen.
As a preferable technical scheme of the invention, the preparation method of the seed layer is a physical vapor deposition method.
Preferably, the physical vapor deposition method comprises a magnetron sputtering method and/or an evaporation method.
Preferably, the preparation method of the thickening layer comprises an electroplating method.
Preferably, in the electroplating method, the components of the electroplating solution include copper sulfate, sulfuric acid, HCl, a brightening agent, a leveling agent and a sizing agent.
Preferably, the concentration of the copper sulfate is 80-130g/L, for example, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, or the like, the concentration of the sulfuric acid is 80-160g/L, for example, 80g/L, 100g/L, 120g/L, 140g/L, or 160g/L, or the like, the concentration of the HCl is 20-80mg/L, for example, 20mg/L, 40mg/L, 60mg/L, or 80mg/L, or the like, the concentration of the brightening agent is 0.5-20ppm, for example, 0.5ppm, 5ppm, 10ppm, 15ppm, or 20ppm, or the like, the concentration of the leveling agent is 0.5-5ppm, for example, 0.5ppm, 1ppm, 3ppm, or 5ppm, or the like, and the concentration of the wetting agent is 20-200ppm, for example, 20ppm, 50ppm, 100ppm, 150ppm, or 200ppm, or the like.
Preferably, the brightening agent comprises any one or a combination of at least two of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate or sodium N, N-dimethyl dithio formamide propane sulfonate.
Preferably, the leveler comprises any one or a combination of at least two of N, N-diethylthiourea, 2-mercaptopyridine, or benalaxyl.
Preferably, the impregnating agent comprises any one or a combination of at least two of polyethylene glycol, polypropylene glycol or polyoxyethylene ether.
Preferably, the specific process parameters of the electroplating method include:
The average cathode current density is 0.5-5A/dm 2, for example, 0.5A/dm 2、1A/dm2、2A/dm2、3A/dm2、4A/dm2 or 5A/dm 2, the plating solution temperature is 15-35 ℃, for example, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, and the plating time is 1-20min. For example, it may be 1min, 5min, 10min, 15min or 20min.
As a preferred embodiment of the present invention, the method for preparing the adhesive layer includes physical vapor deposition and/or coating.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Preparing a polymer base film with the thickness of 1-10 mu m by adopting a melting-extrusion-biaxial stretching method;
(2) Depositing a layer of adhesive layer with the thickness of 1-10nm on two sides of the polymer base film by adopting a magnetron sputtering method, a physical vapor deposition method or a coating method to obtain a composite film with the adhesive layer on the surface;
(3) Depositing a seed layer with the thickness of 40-100nm on two sides of the composite film with the bonding layer on the surface by adopting a physical vapor deposition method, then depositing a carbon layer with the thickness of more than or equal to 1nm on two sides of the composite film with the seed layer by adopting a magnetron sputtering method and/or a chemical vapor deposition method, and then depositing a thickening layer with the thickness of 500-2000nm on the surface of the carbon layer by adopting an electroplating method to obtain the composite film with the composite conductive layer on the surface;
(4) And (3) adopting physical vapor deposition, chemical vapor deposition, in-situ forming or coating methods to respectively deposit a protective layer with the thickness of 5-100nm on two sides of the composite film with the composite conductive layer on the surface.
In a second aspect, the present invention provides a lithium ion battery, the negative electrode of which comprises the composite current collector according to the first aspect.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention develops a novel composite current collector, namely, a carbon layer is introduced into a composite conductive layer, and the defect rate of the composite current collector can be reduced due to the unique conductive layer structure, so that the stability of the structure and the performance of the composite current collector is improved, and the stability of the composite current collector in the battery processing and circulating process is promoted.
(2) In the present invention, the presence of the carbon layer has the following advantages: ① The bonding between layers can be restrained, and defects caused by bonding of film surfaces in the electroplating unreeling process are prevented; ② The carbon layer has conductivity and does not influence the conductivity of the semi-finished product of the composite current collector; ③ The method has stronger stability, does not introduce new impurities and does not influence the protection effect; ④ The carbon layer is in an amorphous state, which can promote the stability of the composite current collector structure.
(3) The preparation method provided by the invention is simple and feasible, and is easy for large-scale production.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a composite current collector, which comprises a polymer base film, and a bonding layer, a composite conductive layer and a protective layer which are sequentially laminated on the two side surfaces of the polymer base film;
the composite conductive layer sequentially comprises a seed layer, a carbon layer and a thickening layer along the direction away from the polymer base film;
The seed layer is a copper layer with the thickness of 50nm, the thickening layer is a copper layer with the thickness of 1100nm, the thickness of the carbon layer is 1nm, the polymer base film is a PET film with the thickness of 4.5 mu m, the bonding layer is a nichrome layer with the thickness of 5nm, and the protective layer is graphene with the thickness of 10 nm.
The embodiment also provides a preparation method of the composite current collector, which comprises the following steps:
(1) Preparing a PET film by adopting a melting-extrusion-biaxial stretching method;
(2) Placing the PET film in a magnetron sputtering machine, and respectively depositing a layer of bonding layer on two sides of the PET film, wherein the specific process conditions are as follows: 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 coating is 0.08Pa, the coating time is 1s, and the temperature of a main roller in the coating process is 0 ℃ to obtain a PET composite film with a bonding layer on the surface;
(3) Preparing a composite conductive layer:
① Preparing a seed layer: the PET composite film with the bonding layer on the surface is placed in a magnetron sputtering machine, a copper target (purity: 99.99%) is used as a target material, and a copper layer with the thickness of 50nm is respectively deposited on two sides of the composite film, and the specific process conditions are as follows: the target power is 12kW, the argon flow is 50mL/min, the vacuum degree of 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 carbon layer: graphite targets (purity: 99.99%) are used as targets, and a carbon layer with thickness of 1nm is deposited on two sides of a composite film with a seed layer on the surface, wherein the specific process conditions are as follows: the target power is 3kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 0.5s, and the temperature of the main roller in the coating process is 0 ℃;
③ Preparing a thickening layer: placing the prepared composite film with the carbon layer on the surface in an electroplating device, and preparing a thickening layer with the thickness of 1100nm on each of the two surfaces of the composite film, wherein the specific process conditions are as follows: the electroplating solution comprises 120g/L copper sulfate, 110g/L sulfuric acid, 50mg/LHCl, 10ppm of N, N-dimethyl dithioformamide sodium propane sulfonate, 2ppm of 2-mercaptopyridine and 80ppm of polyoxyethylene ether, wherein the average cathode current density is 2A/dm 2, the temperature of the electroplating solution is 25 ℃, and the electroplating time is 6min;
(4) Preparing a protective layer: uniformly dispersing 1g of graphene into 999g of Nitrogen Methyl Pyrrolidone (NMP) solution by an ultrasonic dispersion method to prepare a coating liquid with the solid content of 0.1wt.%, uniformly coating the coating liquid on the surface of the prepared thickening layer by a die head coating mode, and finally drying at 70 ℃ to obtain a protective layer with the thickness of 10nm to obtain the composite current collector.
Example 2
The difference between this example and example 1 is that the thickness of the carbon layer is 5nm, and the specific process conditions are as follows: the target power is 6kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 1s, and the temperature of the main roller in the coating process is 0 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 3
The difference between this example and example 1 is that the thickness of the carbon layer is 10nm, and the specific process conditions are as follows: the target power is 6kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 2s, and the temperature of the main roller in the coating process is 0 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 4
The difference between this example and example 1 is that the thickness of the carbon layer is 20nm, and the specific process conditions are as follows: the target power is 6kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 4s, and the temperature of the main roller in the coating process is 0 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 5
This example differs from example 1 in that a composite conductive layer containing a carbon layer was deposited on one side of the PET film and a composite conductive layer without a carbon layer was deposited on the other side of the PET film. The remaining preparation methods and parameters remain the same as in example 1.
Example 6
The difference between this example and example 3 is that the seed layer thickness is 40nm, and the specific process conditions are: the target power is 12kW, the argon flow is 50mL/min, the vacuum degree of the coating is 0.08Pa, the coating time is 4s, and the temperature of the main roller in the coating process is 2 ℃.
The remaining preparation methods and parameters remain the same as in example 3.
Example 7
The difference between this example and example 3 is that the seed layer thickness is 80nm, and the specific process conditions are: the target power is 12kW, the argon flow is 50mL/min, the vacuum degree of the coating is 0.08Pa, the coating time is 8s, and the temperature of the main roller in the coating process is 2 ℃.
The remaining preparation methods and parameters remain the same as in example 3.
Example 8
This example differs from example 3 in that the polymer-based film is a PP film.
The remaining preparation methods and parameters remain the same as in example 3.
Example 9
The difference between this example and example 1 is that the thickness of the carbon layer is 0.5nm, and the specific process conditions are as follows: the target power is 3kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 0.25s, and the temperature of the main roller in the coating process is 0 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 10
The difference between this example and example 1 is that the thickness of the carbon layer is 25nm, and the specific process conditions are as follows: the target power is 6kW, the argon flow is 100mL/min, the vacuum degree of the coating is 0.5Pa, the coating time is 5s, and the temperature of the main roller in the coating process is 0 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that no carbon layer was prepared on either side of the polymer-based film.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that the carbon layer is not provided in the composite conductive layer, but is provided between the adhesive layer and the composite conductive layer, i.e., the carbon layer is prepared first, and then the seed layer and the thickening layer are prepared.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that the carbon layer is not provided in the composite conductive layer, but is provided between the composite conductive layer and the protective layer, i.e., the seed layer and the thickening layer are prepared first, and then the carbon layer is prepared.
The remaining preparation methods and parameters remain the same as in example 1.
Performance testing
The sheet resistance, defect rate and adhesion force between the polymer base film and the composite conductive layer of the composite current collector prepared by the above examples and comparative examples are tested, and the specific test method is as follows:
1) Sheet resistance: placing the flat composite current collector finished product on a sample table, and testing the sheet resistance of the sample by using four probes Fang Zuyi;
2) Defect rate: placing a composite copper current collector finished product with the area of A 0 into a surface quality detection system (a micro vision charge coupled device CCD), scanning the surface of the composite copper current collector finished product, converting an optical signal into an electric signal, transmitting the electric signal to a computer, counting the defect area of the finished product, and recording A 1, wherein the defect rate is (A 0/A1) multiplied by 100%;
3) Adhesion of polymer base film to composite conductive layer: bonding a layer PERMACEL P-94 double faced adhesive tape on an aluminum foil with the thickness of 1mm, bonding a composite current collector finished product above the double faced adhesive tape, and covering a layer of ethylene acrylic acid copolymer film (DuPont Nurcel0903, the thickness is 50 μm) above the finished product; then hot-pressing at 1.3X10 5N/m2 and 120 ℃ for 10s, cooling to room temperature, and then cutting into strips with the length of 150mm multiplied by 15 mm; and finally, fixing the ethylene acrylic acid copolymer film of the finished product small 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 to obtain the bonding force between the polymer base film and the composite conductive layer.
The above test results are shown in table 1.
TABLE 1
Analysis:
As shown in the table, the composite current collector developed by the invention can realize the improvement of the mechanical performance of the composite current collector due to the unique conductive layer structure, and effectively promotes the stability of the composite current collector in the battery processing and circulating process.
As is apparent from examples 1 to 8 and comparative examples 1 to 3, the defect rate of the prepared composite current collector is reduced by introducing the carbon layer between the seed layer and the thickening layer, thereby causing a reduction in sheet resistance, i.e., an improvement in conductivity, and an improvement in adhesion of the polymer base film and the composite conductive layer in the composite current collector.
As can be seen from examples 1 to 4 and examples 9 to 10, the thickness of the carbon layer is increased, and the defect rate of the prepared composite current collector is reduced to 0 and then kept unchanged, so that the sheet resistance is reduced and then kept unchanged, and the adhesion between the polymer base film and the composite conductive layer in the composite current collector is increased and then kept unchanged.
As is clear from examples 1, 5 and 1, the composite current collector can still achieve good effect by introducing the carbon layer on one side, but the performance of the composite current collector with the carbon layer introduced on both sides is superior to that of the composite current collector with the carbon layer introduced on one side.
As is clear from examples 3, 6, 7 and 8, when the thickness of the seed layer is changed or the polymer base film is changed, the composite current collector can still obtain good effects due to the presence of the carbon layer.
As is clear from examples 1 and comparative examples 2 to 3, if a carbon layer is provided between the adhesive layer and the composite conductive layer, or between the composite conductive layer and the protective layer, the effect of the invention is not achieved, that is, defects caused by adhesion of the seed layers on the surface of the semi-finished product of the composite current collector due to the lack of the carbon layer on the surface of the seed layer cannot be prevented, and further, a thickened copper layer with a high defect rate is generated by electroplating, which affects the conductivity and structural stability of the composite current collector.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The composite current collector is characterized by comprising a polymer base film, and a bonding layer and a composite conductive layer which are sequentially laminated on at least one side surface of the polymer base film;
the composite conductive layer comprises a carbon layer.
2. The composite current collector of claim 1 wherein said composite conductive layer further comprises a seed layer and a thickening layer therein;
Preferably, the composite conductive layer comprises a seed layer, a carbon layer and a thickening layer in this order along a direction away from the polymer base film;
Preferably, the carbon layer is an amorphous carbon layer;
preferably, the material of the seed layer comprises metallic copper and/or copper alloy, preferably metallic copper;
Preferably, the seed layer is further doped with carbon element, and the content of the carbon element accounts for 0.1-5% of the total mass of the seed layer;
preferably, the material of the thickening layer comprises metallic copper and/or copper alloy, preferably metallic copper;
preferably, the thickening layer is further doped with carbon element, and the content of the carbon element accounts for 0.1-5% of the total mass of the thickening layer.
3. The composite current collector of claim 2, wherein said seed layer has a thickness of 40-100nm;
preferably, the thickness of the carbon layer is more than or equal to 1nm, preferably 5-20nm;
Preferably, the thickness of the thickening layer is 500-2000nm, preferably 800-1200nm.
4. A composite current collector according to any one of claims 1-3, wherein the thickness of the polymer-based film is 1-10 μm;
Preferably, the material of the bonding layer comprises any one or a combination of at least two of aluminum oxide, silicon oxide, titanium oxide, nickel, chromium, titanium, nichrome, silicon aluminum alloy, polyacrylic acid, polyacrylate, polyacrylamide or polyurethane;
Preferably, the thickness of the adhesive layer is 1-10nm;
preferably, a protective layer is arranged on the surface of one side of the composite conductive layer away from the polymer base film;
Preferably, the material of the protective layer comprises any one or a combination of at least two of 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 or graphene oxide;
preferably, the thickness of the protective layer is 5-100nm, preferably 10-80nm.
5. A method of preparing a composite current collector according to any one of claims 1 to 4, comprising the steps of:
sequentially preparing a bonding layer and a composite conductive layer on at least one surface of a polymer base film;
the composite conductive layer comprises a carbon layer.
6. The method of claim 5, wherein the composite conductive layer comprises a seed layer, a carbon layer, and a thickening layer in that order in a direction away from the polymer base film;
preferably, the preparation method of the carbon layer comprises a magnetron sputtering method and/or a chemical vapor deposition method, preferably a magnetron sputtering method;
Preferably, the specific process parameters of the magnetron sputtering method comprise:
The power of the target material is 2-10kW, the air source flow is 30-200mL/min, and the vacuum degree is less than or equal to 1Pa.
7. The method of claim 6, wherein the seed layer is prepared by physical vapor deposition;
preferably, the preparation method of the thickening layer comprises an electroplating method;
Preferably, in the electroplating method, the components of the electroplating solution comprise copper sulfate, sulfuric acid, HCl, brightening agent, leveling agent and impregnating agent;
preferably, the specific process parameters of the electroplating method include:
The average cathode current density is 0.5-5A/dm 2, the plating solution temperature is 15-35 ℃, and the electroplating time is 1-20min.
8. The method of any one of claims 5-7, wherein the method of preparing the tie layer comprises physical vapor deposition and/or coating.
9. The preparation method according to any one of claims 5 to 8, characterized in that the preparation method comprises the steps of:
(1) Preparing a polymer base film with the thickness of 1-10 mu m by adopting a melting-extrusion-biaxial stretching method;
(2) Depositing a layer of adhesive layer with the thickness of 1-10nm on two sides of the polymer base film by adopting a magnetron sputtering method, a physical vapor deposition method or a coating method to obtain a composite film with the adhesive layer on the surface;
(3) Depositing a seed layer with the thickness of 40-100nm on two sides of the composite film with the bonding layer on the surface by adopting a physical vapor deposition method, then depositing a carbon layer with the thickness of more than or equal to 1nm on two sides of the composite film with the seed layer by adopting a magnetron sputtering method and/or a chemical vapor deposition method, and then depositing a thickening layer with the thickness of 500-2000nm on the surface of the carbon layer by adopting an electroplating method to obtain the composite film with the composite conductive layer on the surface;
(4) And (3) adopting physical vapor deposition, chemical vapor deposition, in-situ forming or coating methods to respectively deposit a protective layer with the thickness of 5-100nm on two sides of the composite film with the composite conductive layer on the surface.
10. A lithium ion battery, characterized in that the negative electrode of the lithium ion battery comprises the composite current collector according to any one of claims 1 to 4 or the composite current collector manufactured by the method for manufacturing the composite current collector according to any one of claims 5 to 9.
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