WO2023070319A1 - 一种镀铜镀液及由其制备的负极复合集流体 - Google Patents

一种镀铜镀液及由其制备的负极复合集流体 Download PDF

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WO2023070319A1
WO2023070319A1 PCT/CN2021/126433 CN2021126433W WO2023070319A1 WO 2023070319 A1 WO2023070319 A1 WO 2023070319A1 CN 2021126433 W CN2021126433 W CN 2021126433W WO 2023070319 A1 WO2023070319 A1 WO 2023070319A1
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copper plating
copper
plating bath
plating solution
current collector
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PCT/CN2021/126433
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English (en)
French (fr)
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彭佳
李铭领
刘欣
黄起森
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宁德时代新能源科技股份有限公司
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Priority to EP21928341.3A priority Critical patent/EP4194589A4/en
Priority to JP2023502963A priority patent/JP7477707B2/ja
Priority to CN202180007555.7A priority patent/CN116348636A/zh
Priority to KR1020237001516A priority patent/KR20230062536A/ko
Priority to PCT/CN2021/126433 priority patent/WO2023070319A1/zh
Priority to US17/901,101 priority patent/US11932959B2/en
Publication of WO2023070319A1 publication Critical patent/WO2023070319A1/zh
Priority to US18/540,081 priority patent/US20240141532A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of lithium batteries, in particular to a copper plating solution and a negative electrode composite current collector prepared therefrom, a secondary battery, a battery module, a battery pack and an electrical device.
  • lithium-ion batteries have been widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of lithium-ion batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance. Especially when composite current collectors are used, the safety performance and cycle performance of lithium-ion batteries need to be further improved.
  • the present application is made in view of the above problems, and its purpose is to provide a copper plating solution, so that the negative electrode composite current collector prepared therefrom has excellent coating adhesion, high tensile strength and elongation.
  • the present application provides a copper plating solution and a negative electrode composite current collector prepared therefrom, a secondary battery, a battery module, a battery pack and an electrical device.
  • the first aspect of the present application provides a copper plating solution for composite current collectors, which includes a leveling agent represented by general formula (1)
  • anion X is F - , Cl - or Br - ;
  • R 1 , R 2 and R 3 are each independently selected from O or S;
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
  • leveler of specific structure in the copper plating bath of the present application Contain the leveler of specific structure in the copper plating bath of the present application, described leveler has lower energy level difference and higher dipole moment, can be adsorbed on the surface of copper in electroplating process, causes cathodic potential and The charge transfer resistance increases, inhibits the surface deposition of copper, and makes the electroplated copper layer more uniform, so that the composite current collector prepared by it has excellent coating adhesion, high tensile strength and elongation, thereby improving lithium ion The cycle performance of the battery.
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted alkyl groups with 1-6 carbon atoms, substituted or unsubstituted alkyl groups with 2-6 carbon atoms Alkenyl and substituted or unsubstituted pyrimidinyl.
  • the leveling agent is
  • the copper plating solution further includes copper sulfate, sulfuric acid, hydrochloric acid, brightener, wetting agent and deionized water.
  • the brightener is a compound containing a disulfide bond, a sulfonic acid group or a mercapto group.
  • the brightener is one or both of sodium polydithiodipropanesulfonate and sodium 3-mercaptopropanesulfonate.
  • the wetting agent is at least one of polyethylene glycol and polypropylene glycol.
  • the polyethylene glycol has a number average molecular weight of 4000-15000, and the polypropylene glycol has a number average molecular weight of 5000-20000.
  • a dense barrier layer can be formed on the cathode surface, thereby inhibiting the rapid deposition of copper.
  • the copper plating solution further includes a grain refiner.
  • the copper grains can be further refined.
  • the grain refiner is at least one of acetaldehyde and ethylenediaminetetraacetic acid (EDTA).
  • EDTA ethylenediaminetetraacetic acid
  • every liter of copper plating bath comprises: copper sulfate 60-120g/L, 98% sulfuric acid 80-110mL/L, hydrochloric acid 40-90ppm in terms of chloride ion, brightener 2-12mL/L, the whole Leveling agent 1-4mL/L, wetting agent 0.5-2mL/L, grain refiner 0.01-0.2mL/L, and the rest is deionized water.
  • the specific content of each component is controlled within the given range, the uniformity of the coating can be further improved.
  • the applicable temperature range of the copper plating solution is 20-50°C, optionally 20-45°C, and further optionally 20-35°C.
  • the temperature is controlled within the given range, the activity of organic additives can be more effectively exerted.
  • the suitable cathode current density of the copper plating solution is 1-20A/dm 2 , optionally 1-15A/dm 2 , and further optionally 1-10A/dm 2 .
  • the cathode current density is controlled within the given range, the resulting coating can be dense.
  • the suitable anode current density of the copper plating solution is 0.5-3A/dm 2 .
  • the brightness and levelness of the resulting coating can be further improved.
  • the pH value of the copper plating bath is 0.5-4.
  • the pH is controlled within the given range, the throwing ability and anode dissolution performance of the plating solution can be improved.
  • the second aspect of the present application also provides a negative electrode composite current collector, which includes a polymer material substrate and copper layers formed on both surfaces of the polymer material substrate, and the copper layer is obtained from the first aspect of the present application.
  • the copper plating solution is obtained by electroplating.
  • the third aspect of the present application provides a secondary battery, including the negative electrode composite current collector of the second aspect of the present application.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • the sixth aspect of the present application provides an electric device, including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application. kind.
  • Figure 1 is a scanning electron microscope (SEM) image of a copper layer prepared by a conventional PCB plating solution.
  • FIG. 2 is an SEM image of the copper layer prepared in Example 1-1 of the present application.
  • FIG. 3 is an SEM image of the copper layer prepared in Example 3-1 of the present application.
  • FIG. 4 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 4 .
  • FIG. 6 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 8 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 7 .
  • FIG. 9 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (a) and (b) performed in sequence
  • steps (b) and (a) performed in sequence.
  • step (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), also Steps (a), (c) and (b) may be included, and steps (c), (a) and (b) may also be included.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • the formulation of the plating solution has always been applicable to the PCB industry, and the main problem it solves is hole filling, and the thickness of the plating layer obtained by it is generally tens of microns.
  • the production process of composite current collectors also requires electroplating, but unlike the traditional electroplating industry, the production of composite current collectors is not electroplated on the metal surface, but on a polymer layer with a metal backing, and is composed of The thickness of the resulting coating is about 1 micron.
  • the electroplating process of the composite current collector does not need to pursue a high aspect ratio, but to pursue excellent coating adhesion and tensile strength and elongation that meet the requirements. Therefore, the plating solution formula in the traditional industry is not suitable for the production process of the composite current collector.
  • the inventors of the present application found that when the copper plating solution contains a specific leveling agent, the uniformity of the coating surface of the negative electrode composite current collector can be improved, thereby improving the coating adhesion and tensile strength of the negative electrode composite current collector and elongation, thereby improving the cycle performance of lithium-ion batteries.
  • the application proposes a copper plating solution for composite current collectors, which includes a leveling agent represented by general formula (1)
  • anion X is F - , Cl - or Br - ;
  • R 1 , R 2 and R 3 are each independently selected from O or S;
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
  • This application adds a leveling agent with a specific structure in the copper plating bath.
  • the leveling agent has a lower energy level difference and a higher dipole moment, and can be adsorbed on the surface of copper during the electroplating process, resulting in a cathodic potential Both the charge transfer resistance and the charge transfer resistance are increased, the surface deposition of copper is inhibited, and the electroplated copper layer is more uniform, so that the composite current collector prepared from it has excellent coating adhesion, high tensile strength and elongation.
  • the molecular structure of the leveling agent is mainly composed of two parts, namely the pyrimidine ring structure on the left and the N + ion structure on the right.
  • the pyrimidine ring structure is adsorbed on the copper surface in parallel, the effective area for electrochemical reaction is reduced, and the deposition rate on the copper surface is slowed down, so that the deposition layer is uniform; Strong electropositivity, under the action of electric field, it is easy to be adsorbed in the area with high current density, thereby reducing the deposition rate of Cu 2+ in the area with high current density, and further making the deposited copper layer uniform.
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted alkyl groups with 1-6 carbon atoms, substituted or unsubstituted alkyl groups with 2-6 carbon atoms Alkenyl and substituted or unsubstituted pyrimidinyl.
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted alkyl groups with 1-4 carbon atoms, substituted or unsubstituted alkyl groups with 2-4 carbon atoms Alkenyl.
  • R 4 , R 5 and R 6 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, vinyl, propenyl , butenyl, phenyl and pyrimidinyl.
  • R4 , R5 , and R6 are each independently selected from hydrogen, methyl, ethyl, propyl, vinyl, phenyl, and pyrimidinyl.
  • the leveling agent is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-oxide-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the content of the leveler in the copper plating solution is 1-4mL/L.
  • the copper plating solution further includes copper sulfate, sulfuric acid, hydrochloric acid, brightener, wetting agent and deionized water.
  • the main function of sulfuric acid is to reduce the resistance of the plating solution, improve the conductivity, prevent the hydrolysis of copper salts, and improve the throwing ability of the plating solution and the performance of anode dissolution;
  • the main function of copper sulfate is to conduct electricity and provide copper ions;
  • the main function of chloride ions is It helps the anode to dissolve and assists the cathode to crystallize;
  • the brightener mainly acts on the depression to increase nucleation;
  • the wetting agent is adsorbed on the surface of the coating, increasing the surface impedance and inhibiting the rapid growth of copper.
  • the brightener is a compound containing a disulfide bond, a sulfonic acid group or a mercapto group.
  • the brightener is one or both of sodium polydithiodipropanesulfonate and sodium 3-mercaptopropanesulfonate.
  • the wetting agent is at least one of polyethylene glycol and polypropylene glycol.
  • the polyethylene glycol has a number average molecular weight of 4,000-15,000, and the polypropylene glycol has a number average molecular weight of 5,000-20,000.
  • a dense barrier layer can be formed on the surface of the cathode, thereby inhibiting the rapid deposition of copper. If the molecular weight of the wetting agent is too small, it cannot form a dense barrier layer on the surface of the cathode, and cannot inhibit the deposition of copper; if the molecular weight is too large, its solubility will decrease, and micelles will be formed in the plating solution, making its wettability reduce.
  • the copper plating bath further includes a grain refiner.
  • the main function of the grain refiner is to increase the deposition of copper ions under low current, prevent it from being etched by sulfuric acid, and at the same time make the deposited copper grains more refined.
  • the grain refiner is at least one of acetaldehyde and ethylenediaminetetraacetic acid (EDTA).
  • EDTA ethylenediaminetetraacetic acid
  • every liter of copper plating bath contains: copper sulfate 60-120g/L, 98% sulfuric acid 80-110mL/L, hydrochloric acid 40-90ppm in terms of chloride ion, brightener 2-12mL/L, the whole Leveling agent 1-4mL/L, wetting agent 0.5-2mL/L, grain refiner 0.01-0.2mL/L, and the rest is deionized water.
  • the uniformity of the coating can be further improved. If the concentration of sulfuric acid is too high, the migration rate of Cu 2+ will be reduced, and the elongation of the coating will be reduced; if the concentration is too low, the conductivity of the solution will be poor, and the dispersibility of the plating solution will be poor.
  • the concentration of copper sulfate is too high, the leveling ability of the plating solution will decrease, the deposition speed will be too fast, and the generated particles will be larger, which will affect the uniformity of the plating layer; if the concentration is too low, although the covering ability and dispersion ability of the plating solution will be weak However, the brightness and flatness of the copper coating decrease, the deposition speed is slower, and burning occurs during high current density electroplating.
  • concentration of chloride ions is too high, it will lead to passivation of the anode, which will cause a white film on the cathode and release a large number of bubbles, and the efficiency of the electrode will decrease; Holes and burnt.
  • the grain refiner is acetaldehyde.
  • every liter of copper plating bath contains: copper sulfate 60-120g/L, 98% sulfuric acid 80-110mL/L, hydrochloric acid 40-90ppm in terms of chloride ion, brightener 2-12mL/L, the whole Leveling agent 1-4mL/L, wetting agent 0.5-2mL/L, acetaldehyde 0.01-0.05mL/L, the rest is deionized water.
  • the grain refiner is ethylenediaminetetraacetic acid.
  • each liter of copper plating solution includes: copper sulfate 60-120g/L, 98% sulfuric acid 80-110mL/L, hydrochloric acid 40-90ppm in terms of chloride ion, brightener 2-10mL/L, the whole Leveling agent 1-4mL/L, wetting agent 0.5-2mL/L, ethylenediaminetetraacetic acid 0.05-0.2mL/L, and the rest is deionized water.
  • the grain refiner is acetaldehyde and ethylenediaminetetraacetic acid.
  • every liter of copper plating bath contains: copper sulfate 60-120g/L, 98% sulfuric acid 80-110mL/L, hydrochloric acid 40-90ppm in terms of chloride ion, brightener 2-12mL/L, the whole Leveling agent 1-4mL/L, wetting agent 0.5-2mL/L, acetaldehyde and ethylenediaminetetraacetic acid 0.01-0.1mL/L, and the rest is deionized water.
  • the volume ratio of acetaldehyde and EDTA is 2:1.
  • the applicable temperature range of the copper plating solution is 20-50°C, optionally 20-45°C, and further optionally 20-35°C.
  • the temperature of the copper plating solution is too low, the reactivity of the organic additives will be affected, resulting in a decrease in the migration and deposition rate of copper ions; if the temperature is too high, the organic matter will be more easily decomposed, leading to its failure or reduced effect.
  • the suitable cathode current density of the copper plating solution is 1-20A/dm 2 , optionally 1-15A/dm 2 , and further optionally 1-10A/dm 2 .
  • the resulting coating can be dense. If the cathodic current density is too high, the coating will be blackened or scorched; if the cathodic current density is too small, the grains of the coating will be coarsened, and even the coating cannot be deposited.
  • the suitable anode current density of the copper plating solution is 0.5-3 A/dm 2 .
  • the brightness and levelness of the resulting coating can be further improved. If the anode current density is too high, the copper ions generated by electrolysis are greater than the deposited copper ions, the copper content in the bath will continue to increase, the consumption of additives will be accelerated, the copper powder and anode slime in the bath will increase, the utilization efficiency of the anode will decrease, and the coating will be extremely damaged. It is easy to produce burrs and rough defects; if the current density is too low, the copper content will continue to decrease, which will affect the brightness and leveling of the coating.
  • the pH value of the copper plating solution is 0.5-4.
  • the preparation method of described copper plating bath comprises the following steps:
  • a negative electrode composite current collector which includes a polymer material substrate and copper layers formed on both surfaces of the polymer material substrate, and the copper layer is obtained from the first aspect of the present application.
  • the copper plating solution is obtained by electroplating.
  • the polymer material substrate is selected from polyamide, polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butanediene Polyethylene-styrene copolymer, polybutylene terephthalate, poly-p-phenylene terephthalamide, polypropylene, polyoxymethylene, epoxy resin, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride , silicone rubber, polycarbonate.
  • the thickness of the copper layer is 2-12 ⁇ m.
  • the preparation method of the coating includes: using the polymer material PVD primer substrate as the cathode, using phosphor copper as the anode, and placing it in an electroplating tank containing the copper plating solution of the first aspect of the present application. DC plating.
  • the method for preparing the PVD base substrate includes: using a physical vapor deposition (PVD) method to plate a layer of copper on the surface of the polymer material substrate.
  • PVD physical vapor deposition
  • the PVD method is preferably at least one of evaporation method and sputtering method.
  • the temperature is 20-50°C, optionally 20-45°C, and further optionally 20-35°C.
  • the cathode current density is 1-20A/dm 2 , optionally 1-15A/dm 2 , further optionally 1-10A/dm 2 .
  • the anode current density is 0.5-3 A/dm 2 .
  • the electroplating time is 1-5 minutes.
  • a secondary battery is provided.
  • a secondary battery typically includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • active ions are intercalated and extracted back and forth between the positive electrode and the negative electrode.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the separator is arranged between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through.
  • the positive electrode sheet includes a positive electrode collector and a positive electrode film layer arranged on at least one surface of the positive electrode collector, and the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material known in the art for batteries.
  • the positive active material may include at least one of the following materials: olivine-structured lithium-containing phosphate, lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials of batteries can also be used. These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also abbreviated as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also abbreviated as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also abbreviated as NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as LiNi
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also may be abbreviated as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon At least one of a composite material, lithium manganese iron phosphate, and a composite material of lithium manganese iron phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also may be abbreviated as LFP)
  • composite materials of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer may also optionally include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the positive electrode sheet, such as positive electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode current collector is the negative electrode composite current collector of the second aspect of the present application, and the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the negative electrode active material can be a negative electrode active material known in the art for batteries.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of simple tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further optionally include a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • CMC-Na sodium carboxymethylcellulose
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is an electrolytic solution.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • a separator is further included in the secondary battery.
  • the present application has no special limitation on the type of isolation membrane, and any known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, without any particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft case may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 4 shows a secondary battery 5 having a square structure as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the accommodating cavity. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 6 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may also include a case having a housing space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electric devices may include mobile devices (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, etc.) , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its use requirements.
  • FIG. 9 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • a device may be a cell phone, tablet, laptop, or the like.
  • the device is generally required to be light and thin, and a secondary battery can be used as a power source.
  • a copper plating bath which consists of copper sulfate 90g/L, 98% sulfuric acid 95mL/L, hydrochloric acid 65ppm in terms of chloride ions, brightener 7mL/L L, leveling agent 2.5mL/L, wetting agent 1.3mL/L, the rest is deionized water; pH is 1.
  • PVD physical vapor deposition
  • the plating parameters were set as follows:
  • Anode current density 0.5A/dm 2 ;
  • Example 1-1 The preparation of the copper plating solution and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula II.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula III.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula IV.
  • Example 1-1 The preparation of the copper plating solution and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula V.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula VI.
  • Example 1-1 The preparation of the copper plating solution and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the leveler is replaced by the compound shown in formula VII.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that no leveling agent is added.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the amount of the leveling agent in the copper plating bath is 1 mL/L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the amount of the leveling agent in the copper plating bath is 4mL/L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the amount of the leveling agent in the copper plating bath is 0.5mL/L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the amount of the leveling agent in the copper plating bath is 6mL/L.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, except that the brightener is replaced by sodium 3-mercaptopropanesulfonate.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that the wetting agent is replaced by polypropylene glycol, and its number average molecular weight is 10,000.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde and ethylenediaminetetraacetic acid with a volume ratio of 2:1 are also added as grain refiners, and the crystal The amount of grain refiner in copper plating bath is 0.08mL/L.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde and ethylenediaminetetraacetic acid with a volume ratio of 2:1 are also added as grain refiners, and the crystal The amount of grain refiner in copper plating bath is 0.01mL/L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde and ethylenediaminetetraacetic acid with a volume ratio of 2:1 are also added as grain refiners.
  • the amount of grain refiner in copper plating bath is 0.1mL/L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde is also added as a grain refiner, and the amount of acetaldehyde in the copper plating bath is 0.01mL/ L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde is also added as a grain refiner, and the amount of acetaldehyde in the copper plating bath is 0.03mL /L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that acetaldehyde is also added as a grain refiner, and the amount of acetaldehyde in the copper plating bath is 0.05mL /L.
  • the preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that ethylenediaminetetraacetic acid is also added as a grain refiner, and ethylenediaminetetraacetic acid is added to the copper plating bath The amount is 0.05mL/L.
  • Example 1-1 The preparation of the copper plating bath and the preparation of the negative electrode composite current collector refer to Example 1-1 as a whole, the difference is that ethylenediaminetetraacetic acid is also added as a grain refiner, and ethylenediaminetetraacetic acid is added to the copper plating bath The amount is 0.12mL/L.
  • Metal layer adhesion test method paste double-sided tape on a smooth steel plate, cut the composite current collector to the same width as the double-sided tape, then attach the composite current collector to the surface of the double-sided tape, and then cut the surface tape Make it into the same width as the composite current collector, attach it to the surface of the composite current collector, and connect an A4 paper strip larger than the length of the steel plate at the head, roll back and forth on the surface with a 2.5kg roller until the tape is flattened, and fix one end of the steel plate under tension On the machine, the A4 paper is fixed on the other end of the tensile machine with the surface tape, and the tape is peeled off at a speed of 500mm/min to obtain a peeling force curve and calculate the average value of the peeling force.
  • the current collector is punched into strips of 15mm ⁇ 150mm with a strip sampler, and the punched strip sample is tested with a tensile machine.
  • the initial distance of the tensile machine is 50mm, and it is stretched at a constant speed of 50mm/min. , until the sample is broken, the tensile strength is read directly from the tensile machine.
  • the current collector is punched into strips of 15mm ⁇ 150mm with a strip sampler, and the punched strip sample is tested with a tensile machine.
  • the negative electrode composite current collectors obtained in the above examples and comparative examples were respectively prepared into secondary batteries as shown below, and performance tests were performed.
  • the positive electrode sheet (compacted density: 3.4g/cm3), PP/PE/PP separator and negative electrode sheet (compacted density: 1.6g/cm3) are wound together into a bare cell. Then put it into the battery case, inject electrolyte (EC:EMC volume ratio is 3:7, LiPF 6 is 1mol/L), and then carry out sealing, chemical conversion and other processes, and finally obtain a lithium-ion battery.
  • electrolyte EMC volume ratio is 3:7, LiPF 6 is 1mol/L
  • Example 1-1 when the copper plating solution contains the leveling agent of the structure, the coating adhesion of the negative electrode composite current collector obtained therefrom is all higher than 2.3N, and the tensile The strength is higher than 186MPa, the elongation is higher than 4.4%, and the 80% capacity battery cycle number of the lithium-ion battery containing the negative electrode composite current collector is higher than 2221, and the capacity retention rate after 1000 cycles is higher than 90.3%.
  • Example 1-1 and Example 2-1 to Example 2-6 when the content of the leveling agent in the copper plating bath was 1-4mL/L, the coating viscosity of the negative electrode composite current collector prepared by it was Knot, tensile strength and elongation are further improved.
  • Example 1-1 and Example 3-1 to Example 3-8 when the copper plating bath further contains a grain refiner, the coating adhesion, tensile strength and tensile strength of the negative composite current collector prepared by it The tensile strength and elongation are further improved, thereby further improving the cycle performance of lithium-ion batteries.
  • the grain refiner can further improve the uniformity of the obtained copper layer.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请提供了一种用于复合集流体的镀铜镀液，其包含通式|（1）所示的整平剂其中阴离子X为F-、Cl-或Br-；R1、R2和R3各自独立地选自O或S；R4、R 5和R6各自独立地选自氢、取代或未取代的烷基、取代或未取代的烯基、取代或未取代的芳基和取代或未取代的杂芳基。

Description

一种镀铜镀液及由其制备的负极复合集流体 技术领域
本申请涉及锂电池技术领域，尤其涉及一种镀铜镀液及由其制备的负极复合集流体、二次电池、电池模块、电池包和用电装置。
背景技术
近年来，随着锂离子电池的应用范围越来越广泛，锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于锂离子电池取得了极大的发展，因此对其能量密度、循环性能和安全性能等也提出了更高的要求。尤其是当使用复合集流体时，锂离子电池的安全性能和循环性能亟待进一步改善。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种镀铜镀液，使得由其制备的负极复合集流体具有优异的镀层粘结力以及高的拉伸强度和延展率。
为了达到上述目的，本申请提供了一种镀铜镀液及由其制备的负极复合集流体、二次电池、电池模块、电池包和用电装置。
本申请的第一方面提供了一种用于复合集流体的镀铜镀液，其包含通式(1)所示的整平剂
Figure PCTCN2021126433-appb-000001
其中阴离子X为F -、Cl -或Br -；
R 1、R 2和R 3各自独立地选自O或S；
R 4、R 5和R 6各自独立地选自氢、取代或未取代的烷基、取代或未取代的烯基、取代或未取代的芳基和取代或未取代的杂芳基。
本申请的镀铜镀液中含有特定结构的整平剂，所述整平剂具有较低的能级差和较高的偶极矩，在电镀过程中可以吸附在铜的表面，导致阴极电势和电荷转移电阻都增加，抑制铜的表面沉积，使得电镀铜层更加均匀，从而使由其制备的复合集流体具有优异的镀层粘结力，以及高的拉伸强度和延展率，进而改善锂离子电池的循环性能。
在任意实施方式中，R 4、R 5和R 6各自独立地选自氢、取代或未取代的碳原子数为1-6的烷基、取代或未取代的碳原子数为2-6的烯基和取代或未取代的嘧啶基。
在任意实施方式中，所述整平剂为
Figure PCTCN2021126433-appb-000002
在任意实施方式中，所述镀铜镀液还包含硫酸铜、硫酸、盐酸、光亮剂、润湿剂以及去离子水。
在任意实施方式中，所述光亮剂为含有二硫键、磺酸基团或巯基的化合物。
在任意实施方式中，所述光亮剂为聚二硫二丙烷磺酸钠和3-巯基丙烷磺酸钠中的一种或两种。
在任意实施方式中，所述润湿剂为聚乙二醇和聚丙二醇中的至少一种。
在任意实施方式中，所述聚乙二醇的数均分子量为4000-15000，所述聚丙二醇的数均分子量为5000-20000。当润湿剂的分子量控制在所给范围内时，可在阴极表面形成致密的阻挡层，从而抑制铜的快速 沉积。
在任意实施方式中，所述镀铜镀液还包含晶粒细化剂。当所述镀铜镀液还包含晶粒细化剂时，可以使铜晶粒更加细化。
在任意实施方式中，所述晶粒细化剂为乙醛和乙二胺四乙酸(EDTA)中的至少一种。
在任意实施方式中，每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-12mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，晶粒细化剂0.01-0.2mL/L，其余为去离子水。当各组分的具体含量控制在所给范围内时，能够进一步改善镀层的均匀性。
在任意实施方式中，所述镀铜镀液适用的温度范围为20-50℃，可选为20-45℃，进一步可选为20-35℃。当温度控制在所给范围内时，可更有效地发挥有机添加剂的活性。
在任意实施方式中，所述镀铜镀液适用的阴极电流密度为1-20A/dm 2，可选为1-15A/dm 2，进一步可选为1-10A/dm 2。当阴极电流密度控制在所给范围内时，可使得到的镀层致密。
在任意实施方式中，所述镀铜镀液适用的阳极电流密度为0.5-3A/dm 2。当阳极电流密度控制在所给范围内时，能够进一步改善所得镀层的光亮度和整平度。
在任意实施方式中，所述镀铜镀液的pH值为0.5-4。当pH控制在所给范围内时，能改善镀液的均镀能力和阳极溶解性能。
本申请的第二方面还提供一种负极复合集流体，其包括高分子材料基材和形成于所述高分子材料基材两个表面上的铜层，所述铜层由本申请第一方面的镀铜镀液通过电镀得到。
本申请的第三方面提供一种二次电池，包括本申请第二方面的负极复合集流体。
本申请的第四方面提供一种电池模块，包括本申请的第三方面的二次电池。
本申请的第五方面提供一种电池包，包括本申请的第四方面的电 池模块。
本申请的第六方面提供一种用电装置，包括选自本申请的第三方面的二次电池、本申请的第四方面的电池模块或本申请的第五方面的电池包中的至少一种。
附图说明
图1是由传统PCB镀液制备得到的铜层的扫描电子显微镜(SEM)图。
图2是由本申请实施例1-1制备得到的铜层的SEM图。
图3是由本申请实施例3-1制备得到的铜层的SEM图。
图4是本申请一实施方式的二次电池的示意图。
图5是图4所示的本申请一实施方式的二次电池的分解图。
图6是本申请一实施方式的电池模块的示意图。
图7是本申请一实施方式的电池包的示意图。
图8是图7所示的本申请一实施方式的电池包的分解图。
图9是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的镀铜镀液及由其制备的负极复合集流体、二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围 是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假 (或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
镀液的配方一直适用的是PCB行业，其解决的主要问题是填孔问题，由其得到的镀层厚度一般为几十微米。复合集流体的生产过程也需要用到电镀，但是与传统的电镀行业不同的是，复合集流体生产不是在金属表面电镀，而是在有一层金属打底的高分子层上进行，并且由其得到的镀层厚度约为1微米。复合集流体的电镀过程不需要追求高的纵横比，而是追求优异的镀层粘结力以及满足需求的拉伸强度和延展率。故传统行业的镀液配方不适用复合集流体的生产过程。
经过大量实验，本申请发明人发现当镀铜镀液中含有特定的整平剂时，能够改善负极复合集流体镀层表面的均匀性，从而改善负极复合集流体的镀层粘结力以及拉伸强度和延展率，进而改善锂离子电池的循环性能。
镀铜镀液
本申请的一个实施方式中，本申请提出了一种用于复合集流体的镀铜镀液，其包含通式(1)所示的整平剂
Figure PCTCN2021126433-appb-000003
其中阴离子X为F -、Cl -或Br -；
R 1、R 2和R 3各自独立地选自O或S；
R 4、R 5和R 6各自独立地选自氢、取代或未取代的烷基、取代或未取代的烯基、取代或未取代的芳基和取代或未取代的杂芳基。
本申请在镀铜镀液中添加具有特定结构的整平剂，所述整平剂具有较低的能级差和较高的偶极矩，在电镀过程中可以吸附在铜的表面，导致阴极电势和电荷转移电阻都增加，抑制铜的表面沉积，使得电镀铜层更加均匀，从而使由其制备的复合集流体具有优异的镀层粘结力， 以及高的拉伸强度和延展率。
所述整平剂的分子结构主要由两部分组成，即左侧的嘧啶环结构，和右侧的N +离子结构。在电镀过程中，嘧啶环结构平行地吸附于铜表面，进行电化学反应的有效面积减小，铜的表面沉积速度变慢，从而使沉积层均匀；N +离子结构在强酸溶液中带有很强的正电性，在电场作用下容易吸附在电流密度较大的区域，从而降低电流密度较大区域Cu 2+的沉积速率，进一步使沉积铜层均匀。
在一些实施方式中，R 4、R 5和R 6各自独立地选自氢、取代或未取代的碳原子数为1-6的烷基、取代或未取代的碳原子数为2-6的烯基和取代或未取代的嘧啶基。
在一些实施方式中，R 4、R 5和R 6各自独立地选自氢、取代或未取代的碳原子数为1-4的烷基、取代或未取代的碳原子数为2-4的烯基。
在一些实施方式中，R 4、R 5和R 6各自独立地选自氢、甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、乙烯基、丙烯基、丁烯基、苯基和嘧啶基。
在一些实施方式中，R 4、R 5和R 6各自独立地选自氢、甲基、乙基、丙基、乙烯基、苯基和嘧啶基。
在一些实施方式中，所述整平剂为
Figure PCTCN2021126433-appb-000004
在一些实施方案中，所述整平剂在镀铜镀液中的含量为1-4mL/L。
在一些实施方式中，所述镀铜镀液还包含硫酸铜、硫酸、盐酸、光亮剂、润湿剂以及去离子水。
硫酸主要作用是降低镀液的电阻，提高导电性，防止铜盐的水解，同时改善镀液的均镀能力和阳极溶解的性能；硫酸铜主要作用是导电以及提供铜离子；氯离子主要作用是帮助阳极溶解，同时协助阴极结 晶；光亮剂主要作用于凹陷处增加成核；润湿剂则吸附在镀层表面，增加表面阻抗，抑制铜快速生长。
在一些实施方式中，所述光亮剂为含有二硫键、磺酸基团或巯基的化合物。
在一些实施方式中，所述光亮剂为聚二硫二丙烷磺酸钠和3-巯基丙烷磺酸钠中的一种或两种。
在一些实施方式中，所述润湿剂为聚乙二醇和聚丙二醇中的至少一种。
在一些实施方式中，所述聚乙二醇的数均分子量为4000-15000，所述聚丙二醇的数均分子量为5000-20000。
当润湿剂的分子量控制在所给范围内时，可在阴极表面形成致密的阻挡层，从而抑制铜的快速沉积。如果润湿剂分子量太小，则其在阴极表面不能形成致密的阻挡层，不能抑制铜的沉积；如果分子量太大，则其溶解度下降，在镀液中会形成胶束，使其润湿性降低。
在一些实施方式中，所述镀铜镀液还包含晶粒细化剂。
晶粒细化剂主要作用是增加铜离子在小电流下沉积，防止其被硫酸刻蚀，同时使得沉积的铜晶粒更加细化。
在一些实施方式中，所述晶粒细化剂为乙醛和乙二胺四乙酸(EDTA)中的至少一种。
在一些实施方式中，每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-12mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，晶粒细化剂0.01-0.2mL/L，其余为去离子水。
当各组分的具体含量控制在所给范围内时，能够进一步改善镀层的均匀性。如果硫酸的浓度过高，会降低Cu 2+的迁移速率，使镀层的延展率下降；如果浓度过低，则溶液导电性差，镀液分散能力差。如果硫酸铜的浓度过高，则镀液的整平能力下降，沉积速度过快，生成的颗粒较大，影响镀层的均匀性；如果浓度过低，虽然镀液的覆盖能力与分散能力均有所提高，但是铜镀层的光亮度和整平度下降，沉积 速度较慢，且高电流密度电镀时还会出现烧焦现象。当氯离子的浓度过高，会导致阳极钝化，使阴极上产生一层白色膜且放出大量气泡，电极效率降低；当浓度过低时，镀层无光泽并且呈台阶状粗糙镀层，易出现针孔和烧焦。
在一些实施方式中，所述晶粒细化剂为乙醛。
在一些实施方式中，每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-12mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，乙醛0.01-0.05mL/L，其余为去离子水。
在一些实施方式中，所述晶粒细化剂为乙二胺四乙酸。
在一些实施方式中，每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-10mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，乙二胺四乙酸0.05-0.2mL/L，其余为去离子水。
在一些实施方式中，所述晶粒细化剂为乙醛和乙二胺四乙酸。
在一些实施方式中，每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-12mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，乙醛和乙二胺四乙酸0.01-0.1mL/L，其余为去离子水。
在一些实施方式中，乙醛和乙二胺四乙酸的体积比为2∶1。
在一些实施方式中，所述镀铜镀液适用的温度范围为20-50℃，可选为20-45℃，进一步可选为20-35℃。
镀铜镀液的使用温度过低会影响有机添加剂的反应活性，导致铜离子的迁移及沉积速度降低；温度过高会导致有机物更容易分解，导致其失效或作用降低。
在一些实施方式中，所述镀铜镀液适用的阴极电流密度为1-20A/dm 2，可选为1-15A/dm 2，进一步可选为1-10A/dm 2。
当阴极电流密度控制在所给范围内时，可使得到的镀层致密。如果阴极电流密度过大，镀层会被烧黑或烧焦；如果阴极电流密度过小， 镀层的晶粒粗化，甚至不能沉积镀层。
在一些实施方式中，所述镀铜镀液适用的阳极电流密度为0.5-3A/dm 2。
当阳极电流密度控制在所给范围内时，能够进一步改善所得镀层的光亮度和整平度。如果阳极电流密度过高，电解生成的铜离子大于沉积的铜离子，槽液中的铜含量不断升高，添加剂消耗加快，槽液中的铜粉和阳极泥增多，阳极利用效率降低，镀层极易产生毛刺和粗糙缺陷；如果电流密度过低，则会导致铜含量不断降低，影响镀层光亮度和整平度。
在一些实施方式中，所述镀铜镀液的pH值为0.5-4。
当pH控制在所给范围内时，能改善镀液的均镀能力和阳极溶解性能。
在一些实施方式中，所述镀铜镀液的制备方法包括以下步骤：
1.向容器中加入去离子水，加入的量为所需去离子水体积的2/3；
2.在搅拌下，按配比加入浓硫酸，在搅拌过程中保持液体温度不超过50℃，静置1h，至液体温度冷却至30℃以下；
3.按配比加入硫酸铜，搅拌至其完全溶解；
4.在搅拌下，按配比加入盐酸、光亮剂、整平剂、润湿剂、晶粒细化剂；
5.加入剩余1/3体积的去离子水，搅拌均匀，得到所述镀铜镀液。
本申请的一个实施方式中，提供一种负极复合集流体，其包括高分子材料基材和形成于所述高分子材料基材两个表面上的铜层，所述铜层由本申请第一方面的镀铜镀液通过电镀得到。
在一些实施方式中，所述高分子材料基材选自聚酰胺、聚对苯二甲酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚对苯二甲酸丁二醇酯、聚对苯二甲酰对苯二胺、聚丙乙烯、聚甲醛、环氧树脂、酚醛树脂、聚四氟乙烯、聚偏氟乙烯、硅橡胶、聚碳酸酯。
在一些实施方式中，所述铜层的厚度为2-12μm。
在一些实施方式中，所述镀层的制备方法包括：以高分子材料PVD打底基材作为阴极，以磷铜作为阳极，置于含有本申请第一方面的镀铜镀液的电镀槽中进行直流电镀。
在一些实施方式中，所述PVD打底基材的制备方法包括：使用物理气相沉积(PVD)方法，在高分子材料基材的表面镀上一层铜层。
在一些实施方式中，所述PVD方法优选蒸发法、溅射法中的至少一种。
在一些实施方式中，在电镀过程中，温度为20-50℃，可选为20-45℃，进一步可选为20-35℃。
在一些实施方式中，在电镀过程中，阴极电流密度为1-20A/dm 2，可选为1-15A/dm 2，进一步可选为1-10A/dm 2。
在一些实施方式中，在电镀过程中，阳极电流密度为0.5-3A/dm 2。
在一些实施方式中，电镀的时间为1-5min。
另外，以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
本申请的一个实施方式中，提供一种二次电池。
通常情况下，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流 体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例， 所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极集流体为本申请第二方面的负极复合集流体，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1，4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性 和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图4是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图5，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图6是作为一个示例的电池模块4。参照图6，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多 个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图7和图8是作为一个示例的电池包1。参照图7和图8，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图9是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具 体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1-1
[镀铜镀液的制备]
1.向容器中加入去离子水，加入的量为所需去离子水体积的2/3；
2.在搅拌下，按配比加入98％的浓硫酸，在搅拌过程中保持液体温度不超过50℃，静置1h，至液体温度冷却至30℃以下；
3.按配比加入硫酸铜，搅拌至其完全溶解；
4.在搅拌下，按配比加入盐酸、聚二硫二丙烷磺酸钠作为光亮剂、式I所示的化合物作为整平剂、聚乙二醇(其数均分子量为10000)作为润湿剂；
Figure PCTCN2021126433-appb-000005
5.加入剩余1/3体积的去离子水，搅拌均匀，得到镀铜镀液，其组成为硫酸铜90g/L，98％的硫酸95mL/L，盐酸以氯离子计65ppm，光亮剂7mL/L，整平剂2.5mL/L，润湿剂1.3mL/L，其余为去离子水；pH为1。
[负极复合集流体的制备]
使用物理气相沉积(PVD)方法，在聚酰亚胺高分子材料基材的表面镀上一层铜层，得到聚酰亚胺PVD打底基材；以所述聚酰亚胺PVD打底基材作为阴极，以磷铜作为阳极，置于含有所述镀铜镀液的电镀槽中进行直流电镀。
电镀参数如下设置：
电镀温度：25℃；
阴极电流密度：2A/dm 2；
阳极电流密度：0.5A/dm 2；
电镀时间：2min。
实施例1-2
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式II所示的化合物。
Figure PCTCN2021126433-appb-000006
实施例1-3
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式III所示的化合物。
Figure PCTCN2021126433-appb-000007
实施例1-4
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式IV所示的化合物。
Figure PCTCN2021126433-appb-000008
实施例1-5
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式V所示的化合物。
Figure PCTCN2021126433-appb-000009
对比例1-1
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式VI所示的化合物。
Figure PCTCN2021126433-appb-000010
对比例1-2
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂替换为式VII所示的化合物。
Figure PCTCN2021126433-appb-000011
对比例1-3
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，不加入整平剂。
实施例2-1
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂在镀铜镀液中的量为1mL/L。
实施例2-2
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂在镀铜镀液中的量为4mL/L。
实施例2-3
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂在镀铜镀液中的量为0.5mL/L。
实施例2-4
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，整平剂在镀铜镀液中的量为6mL/L。
实施例2-5
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，光亮剂替换为3-巯基丙烷磺酸钠。
实施例2-6
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，润湿剂替换为聚丙二醇，其数均分子量为10000。
实施例3-1
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入体积比为2∶1的乙醛和乙二胺四乙酸作为晶粒细化剂，晶粒细化剂在镀铜镀液中的量为0.08mL/L。
实施例3-2
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入体积比为2∶1的乙醛和乙二胺四乙酸作为晶粒细化剂，晶粒细化剂在镀铜镀液中的量为0.01mL/L。
实施例3-3
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1， 区别在于，还加入体积比为2∶1的乙醛和乙二胺四乙酸作为晶粒细化剂，晶粒细化剂在镀铜镀液中的量为0.1mL/L。
实施例3-4
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入乙醛作为晶粒细化剂，乙醛在镀铜镀液中的量为0.01mL/L。
实施例3-5
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入了乙醛作为晶粒细化剂，乙醛在镀铜镀液中的量为0.03mL/L。
实施例3-6
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入了乙醛作为晶粒细化剂，乙醛在镀铜镀液中的量为0.05mL/L。
实施例3-7
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入乙二胺四乙酸作为晶粒细化剂，乙二胺四乙酸在镀铜镀液中的量为0.05mL/L。
实施例3-8
镀铜镀液的制备和负极复合集流体的制备整体上参照实施例1-1，区别在于，还加入乙二胺四乙酸作为晶粒细化剂，乙二胺四乙酸在镀铜镀液中的量为0.12mL/L。
负极复合集流体的性能测试：
1.镀层粘结力
金属层粘结力测试方法：在平滑的钢板上贴双面胶，将复合集流体裁成与双面胶相同宽度，而后将复合集流体平贴在双面胶表面，再将表面的胶带裁成与复合集流体相同宽度，贴附在复合集流体表面，并在头部连接大于钢板长度的A4纸条，用2.5kg滚轮在表面来回滚 动，直至把胶带贴平，将钢板一端固定在拉力机上，A4纸连着表面胶带固定在拉力机另一端，以500mm/min的速度，将胶带进行剥离，得到剥离力曲线，进行剥离力平均值计算。
2.拉伸强度
将集流体用条形取样器冲切成15mm×150mm的条状，将冲切好的条状样品用拉力机进行测试，拉力机的起始间距为50mm，以50mm/min的速度匀速拉伸，直到将试样拉断为止，拉伸强度直接从拉力机上读取。
3.延展率
将集流体用条形取样器冲切成15mm×150mm的条状，将冲切好的条状样品用拉力机进行测试，拉力机的起始间距为50mm，以50mm/min的速度匀速拉伸，直到将试样拉断为止，断裂延伸率＝拉伸距离/起始间距×100％即为延展率。
二次电池的性能测试
将上述实施例和对比例中得到负极复合集流体分别如下所示制备成二次电池，进行性能测试。
1.二次电池的制备
通过常规的电池制作工艺，将正极极片(压实密度：3.4g/cm3)、PP/PE/PP隔膜和负极极片(压实密度：1.6g/cm3)一起卷绕成裸电芯，然后置入电池壳体中，注入电解液(EC∶EMC体积比为3∶7，LiPF 6为1mol/L)，随之进行密封、化成等工序，最终得到锂离子电池。
2.二次电池的循环测试
对锂离子电池进行循环寿命测试，具体测试方法如下：
将锂离子电池于25℃下进行充放电，即先以1C的电流充电至4.2V，然后再以1C的电流放电至2.8V，记录下第一周的放电容量； 然后使电池进行1C/1C充放电循环1000周，记录第1000周的电池放电容量，将第1000周的放电容量除以第一周的放电容量，得到第1000周的容量保有率；并记录容量剩余80％时电池循环的周数。
Figure PCTCN2021126433-appb-000012
Figure PCTCN2021126433-appb-000013
Figure PCTCN2021126433-appb-000014
根据表1-表3可知，上述所有实施例的负极复合集流体的镀层粘结力、拉伸强度和延展率显著高于对比例，相应地，所有实施例对应的锂离子电池的循环性能也优于对比例。此外，对比图1和图2可知，由包含本申请所述结构整平剂的镀铜镀液得到的铜层的均匀性明显优于由传统PCB镀液制备得到的铜层。
综合比较实施例1-1至实施例1-5，当镀铜镀液含有所述结构的整平剂时，由其得到的负极复合集流体的镀层粘结力均高于2.3N，拉伸强度均高于186MPa，延展率均高于4.4％，并且包含负极复合集流体的锂离子电池的80％容量电池循环次数均高于2221，1000次循环后容量保持率均高于90.3％。
综合比较实施例1-1和实施例2-1至实施例2-6，当镀铜镀液中整平剂的含量为1-4mL/L时，由其制备的负极复合集流体的镀层粘结力、拉伸强度和延展率得到进一步改善。
综合比较实施例1-1和实施例3-1至实施例3-8，当镀铜镀液中进一步含有晶粒细化剂时，由其制备的负极复合集流体的镀层粘结力、拉伸强度和延展率得到进一步改善，从而进一步改善了锂离子电池的循环性能。此外，由图2和图3可以看出，晶粒细化剂能够进一步改善所得铜层的均匀性。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (20)

  1. 一种用于复合集流体的镀铜镀液，其特征在于，
    包含通式(1)所示的整平剂
    Figure PCTCN2021126433-appb-100001
    其中阴离子X为F -、Cl -或Br -；
    R 1、R 2和R 3各自独立地选自O或S；
    R 4、R 5和R 6各自独立地选自氢、取代或未取代的烷基、取代或未取代的烯基、取代或未取代的芳基和取代或未取代的杂芳基。
  2. 根据权利要求1所述的镀铜镀液，其特征在于，
    R 4、R 5和R 6各自独立地选自氢、取代或未取代的碳原子数为1-6的烷基、取代或未取代的碳原子数为2-6的烯基和取代或未取代的嘧啶基。
  3. 根据权利要求1或2所述的镀铜镀液，其特征在于，
    所述整平剂为
    Figure PCTCN2021126433-appb-100002
  4. 根据权利要求1-3中任一项所述的镀铜镀液，其特征在于，
    其还包含硫酸铜、硫酸、盐酸、光亮剂、润湿剂以及去离子水。
  5. 根据权利要求4所述的镀铜镀液，其特征在于，
    所述光亮剂为含有二硫键、磺酸基团或巯基的化合物。
  6. 根据权利要求5所述的镀铜镀液，其特征在于，
    所述光亮剂为聚二硫二丙烷磺酸钠和3-巯基丙烷磺酸钠中的一种或两种。
  7. 根据权利要求4-6中任一项所述的镀铜镀液，其特征在于，
    所述润湿剂为聚乙二醇和聚丙二醇中的至少一种。
  8. 根据权利要求7所述的镀铜镀液，其特征在于，
    所述聚乙二醇的数均分子量为4000-15000，所述聚丙二醇的数均分子量为5000-20000。
  9. 根据权利要求1-8中任一项所述的镀铜镀液，其特征在于，
    其还包含晶粒细化剂。
  10. 根据权利要求9所述的镀铜镀液，其特征在于，
    所述晶粒细化剂为乙醛和乙二胺四乙酸中的至少一种。
  11. 根据权利要求1-10中任一项所述的镀铜镀液，其特征在于，
    每升镀铜镀液包含：硫酸铜60-120g/L，98％的硫酸80-110mL/L，盐酸以氯离子计40-90ppm，光亮剂2-12mL/L，整平剂1-4mL/L，润湿剂0.5-2mL/L，晶粒细化剂0.01-0.2mL/L，其余为去离子水。
  12. 根据权利要求1-11中任一项所述的镀铜镀液，其特征在于，
    所述镀铜镀液适用的温度范围为20-50℃，可选为20-45℃，进一步可选为20-35℃。
  13. 根据权利要求1-12中任一项所述的镀铜镀液，其特征在于，
    所述镀铜镀液适用的阴极电流密度为1-20A/dm 2，可选为1-15A/dm 2，进一步可选为1-10A/dm 2。
  14. 根据权利要求1-13中任一项所述的镀铜镀液，其特征在于，
    所述镀铜镀液适用的阳极电流密度为0.5-3A/dm 2。
  15. 根据权利要求1-14中任一项所述的镀铜镀液，其特征在于，
    所述镀铜镀液的pH值为0.5-4。
  16. 一种负极复合集流体，其包括高分子材料基材和形成于所述高分子材料基材两个表面的铜层，其特征在于，所述铜层由权利要求1至15中任一项所述的镀铜镀液通过电镀得到。
  17. 一种二次电池，其特征在于，包括权利要求16所述的负极复合集流体。
  18. 一种电池模块，其特征在于，包括权利要求17所述的二次电池。
  19. 一种电池包，其特征在于，包括权利要求18所述的电池模块。
  20. 一种用电装置，其特征在于，包括选自权利要求17所述的二次电池、权利要求18所述的电池模块或权利要求19所述的电池包中的至少一种。
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