CN116180165A - High-performance ultrathin electronic copper foil and preparation method and application thereof - Google Patents

High-performance ultrathin electronic copper foil and preparation method and application thereof Download PDF

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Publication number
CN116180165A
CN116180165A CN202310141540.0A CN202310141540A CN116180165A CN 116180165 A CN116180165 A CN 116180165A CN 202310141540 A CN202310141540 A CN 202310141540A CN 116180165 A CN116180165 A CN 116180165A
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copper foil
foil
additive
electronic copper
ultrathin electronic
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Inventor
王俊义
韩永强
孙德旺
李大双
王同
吴斌
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Hefei Tongguan Electronic Copper Foil Co ltd
Tongling Tongguan Electronic Copper Foil Co ltd
Anhui Tongguan Copper Foil Group Co ltd
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Hefei Tongguan Electronic Copper Foil Co ltd
Tongling Tongguan Electronic Copper Foil Co ltd
Anhui Tongguan Copper Foil Group Co ltd
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Priority to CN202310141540.0A priority Critical patent/CN116180165A/en
Publication of CN116180165A publication Critical patent/CN116180165A/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
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The embodiment of the invention relates to the technical field of manufacturing of electronic copper foil for lithium batteries, and particularly discloses a high-performance ultrathin electronic copper foil, a preparation method and application thereof. Moreover, the preparation method provided by the embodiment of the invention is simple, can realize continuous and stable production, is easy to adjust the system, has high foil-making yield and has wide market prospect.

Description

High-performance ultrathin electronic copper foil and preparation method and application thereof
Technical Field
The embodiment of the invention belongs to the technical field of manufacturing of electronic copper foil for lithium batteries, and particularly relates to a high-performance ultrathin electronic copper foil, and a preparation method and application thereof.
Background
With the continuous development of the lithium ion battery manufacturing technology, the lithium ion battery in the market at present usually adopts an electronic copper foil as a negative current collector, so that the quality of the electronic copper foil directly influences the manufacturing process, performance and production cost of the lithium ion battery. The high-performance ultrathin electronic copper foil plays a role in collecting and transmitting electrons in the lithium ion battery, and is a key base material for manufacturing the lithium ion battery.
In recent years, with the rapid development of the domestic new energy industry, new research on new lithium ion batteries with high reliability, high energy density and high safety is continuously made, and market demands are also in a rapidly growing situation. At present, domestic electronic copper foil manufacturing enterprises mainly produce common performance products of 6-10 mu m and small batches of copper foil products of 4.5 mu m, and the tensile strength requirements cannot be met. However, the new generation lithium ion battery products have higher requirements on the tensile strength of copper foil, and the extremely thin (less than or equal to 6 μm) electronic copper foil technology which is required to have higher tensile strength performance has become a great subject of research in the copper foil industry at home and abroad.
Thus, the prior art solutions described above have the following drawbacks: in the prior art, most copper foil produced by copper foil production enterprises belongs to common performance products, and the tensile strength is low, and even if the technology is adopted to enable the tensile strength to meet the requirement, other performances such as overlarge roughness, small elongation percentage and the like are disqualified and do not meet the requirement of clients.
Disclosure of Invention
The embodiment of the invention aims to provide a high-performance ultrathin electronic copper foil, which solves the problem that the existing electronic copper foil provided in the background art cannot meet the requirements of roughness and elongation while meeting the tensile strength.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
a high-performance ultrathin electronic copper foil is prepared by placing a cathode roller in electrolyte to carry out electroplating to generate a green foil, and then carrying out surface treatment on the green foil in an anti-oxidation liquid; wherein the oxidation preventing liquid contains 0.5-1.0g/L hexavalent chromium, 1.0-2.0g/L sulfuric acid and a proper amount of alpha-D-glucose.
Preferably, the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additives; wherein, the raw materials of the raw foil additive comprise: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea.
Further preferably, the raw foil additive comprises: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, the additive amount of the raw foil additive is 500-800ml/min.
Another object of the embodiment of the present invention is to provide a method for preparing a high-performance ultrathin electronic copper foil, which includes the following steps:
electroplating the cathode roller in electrolyte to obtain green foil, and heating the green foil at 20-30deg.C with current density of 10-20A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-performance ultrathin electronic copper foil.
Another object of the embodiment of the present invention is to provide a high-performance ultrathin electronic copper foil prepared by the method for preparing a high-performance ultrathin electronic copper foil.
Another object of the embodiment of the present invention is to provide an application of the above-mentioned high-performance ultrathin electronic copper foil in preparing lithium ion batteries.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
compared with the prior art, the high-performance ultrathin electronic copper foil provided by the embodiment of the invention is prepared by a raw foil additive process and a copper foil surface oxidation prevention process, the prepared high-performance ultrathin electronic copper foil has high tensile strength, and the normal-temperature extensibility and roughness of the high-performance ultrathin electronic copper foil are kept at high levels, so that the new energy lithium battery industry can advance to high-end manufacturing, and the problem that the existing electronic copper foil cannot meet the requirements of the tensile strength and the roughness and the extensibility at the same time is solved. Moreover, the preparation method of the high-performance ultrathin electronic copper foil provided by the embodiment of the invention is simple, meanwhile, the method can continuously and stably produce, the system is easy to adjust, the foil manufacturing yield is high, and the market prospect is wide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention.
FIG. 1 is a 1000-fold SEM image of the smooth surface of an electronic copper foil according to one embodiment of the present invention.
Fig. 2 is a 1000-fold SEM image of the appearance of an electronic copper foil according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clearly apparent, the technical schemes in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. It will be apparent that the following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the embodiments of the invention. These are all within the scope of embodiments of the present invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Firstly, it should be noted that in the prior art, the high-performance ultrathin electronic copper foil serves as a negative current collector in the lithium ion battery, plays a role in collecting and transmitting electrons, is a key base material for manufacturing the lithium ion battery, and the quality of the high-performance ultrathin electronic copper foil directly affects the manufacturing process, performance and production cost of the lithium ion battery. In recent years, with the rapid development of the domestic new energy industry, new research on new lithium ion batteries with high reliability, high energy density and high safety is continuously made, and market demands are also in a rapidly growing situation. At present, domestic electronic copper foil manufacturing enterprises mainly produce common resistance products with the thickness of 6-10 mu m and small batches of copper foil products with the thickness of 4.5 mu m, but the requirements of new generation lithium ion battery products on the tensile strength of copper foil are higher and higher, the extremely thin (less than or equal to 6 mu m) electronic copper foil technology pursuing higher tensile strength performance becomes a major subject of research of domestic and foreign copper foil industry, the manufacturing technology is complex, the requirements on product quality, equipment and technology are extremely high, the research and development and production fields of the series of products are blank in the state at present, and the technology becomes an important difficult problem for preventing the domestic new energy lithium battery industry from advancing to high-end manufacturing.
Therefore, the electronic copper foil solves the problem that the existing electronic copper foil cannot meet the requirements of the tensile strength and the roughness and the elongation percentage. The embodiment of the invention provides a high-performance ultrathin electronic copper foil, and a preparation method and application thereof. The high-performance ultrathin electronic copper foil is particularly a high-tensile strength ultrathin electronic copper foil which is suitable for preparing lithium ion batteries, and is generally prepared by placing a cathode roller in electrolyte for electroplating to generate a green foil, and then carrying out surface treatment on the green foil in an anti-oxidation liquid; wherein the oxidation preventing liquid contains 0.5-1.0g/L hexavalent chromium, 1.0-2.0g/L sulfuric acid and a proper amount of alpha-D-glucose. The prepared high-performance ultrathin electronic copper foil has good tensile strength, wherein the tensile strength is more than 50kgf/cm 2 In additionThe method has the advantages of small roughness, large elongation, small fluctuation, high stability and consistency, and can meet the requirements of high-end clients.
Furthermore, the high-performance ultrathin electronic copper foil belongs to an ultrathin electronic copper foil with high tensile strength, has the characteristics of excellent high-temperature heat resistance, excellent surface appearance quality and the like, is mainly used for manufacturing a new generation of high-safety, high-energy-density and long-service-life lithium ion battery, and belongs to a novel high-end product in the electronic copper foil industry.
In addition, in the prior art, most copper foil produced by copper foil production enterprises belong to common performance products, or the tensile strength meets the requirement, and other performances such as super-large roughness, small elongation and the like are unqualified and do not meet the requirements of clients. And moreover, the phenomenon that the performance of the copper foil deviates from a control index occurs in continuous production, the electrolyte is difficult to adjust under abnormal conditions, the machine is restarted, the production stability is poor, and the efficiency is low. According to the embodiment of the invention, the tensile strength of the prepared high-performance ultrathin electronic copper foil is more than 50kgf/cm through a raw foil additive process and a copper foil surface oxidation prevention process 2 (equal to the object surface bearing a pressure of 1kgf per square centimeter), a roughness of less than 2.0 μm, and an elongation of more than 6.0%.
As another preferable mode of the embodiment of the invention, the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additive; wherein, the raw materials of the raw foil additive comprise: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea.
As another preferable example of the invention, the electrolyte contains 90-120g/L sulfuric acid, 80-100g/L cupric ion, 20-30ppm chloridion and proper amount of foil-forming additive.
As another preferable embodiment of the invention, the additive amount of the green foil additive in the electrolyte is 500-800ml/min.
As another preferable example of the invention, the electroplating-generated green foil is produced at a temperature of 55-60 ℃ and a current density of 60-80A/dm 2 Is carried out under the condition of (2).
As another preferable embodiment of the invention, the raw foil additive comprises the following raw materials in parts by weight: 4.0 to 6.0 parts of sodium polydithio-dipropyl sulfonate, 1.6 to 2.0 parts of hydrolyzed collagen, 2.0 to 4.0 parts of polyethylene glycol, 3.0 to 5.0 parts of cellulose ether and 5.0 to 7.0 parts of ethylene thiourea.
As another preferable embodiment of the invention, the raw foil additive comprises the following raw materials in parts by weight: 5.0 parts of sodium polydithio-dipropyl sulfonate, 1.8 parts of hydrolyzed collagen, 3.0 parts of polyethylene glycol, 4.0 parts of cellulose ether and 6.0 parts of ethylene thiourea. Namely, the raw foil additive comprises: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, and the additive amount is 500-800ml/min.
The embodiment of the invention also provides a preparation method of the high-performance ultrathin electronic copper foil, which comprises a raw foil additive process and a copper foil surface oxidation prevention process, and specifically comprises the following steps:
electroplating the cathode roller in electrolyte to obtain green foil, and heating the green foil at 20-30deg.C with current density of 10-20A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-performance ultrathin electronic copper foil.
As another preferable mode of the embodiment of the invention, the oxidation preventing liquid contains 0.5-1.0g/L hexavalent chromium, 1.0-2.0g/L sulfuric acid and a proper amount of alpha-D-glucose, wherein the adding flow rate of the alpha-D-glucose is 100-300ml/min.
As another preferable mode of the embodiment of the invention, in the preparation method of the high-performance ultrathin electronic copper foil, the preparation method further comprises a regulating step, in particular, regulating electrolyte and regulating oxidation preventing liquid. Specifically, for the electrolyte, the cupric ion, sulfuric acid concentration and chloride ion in the electrolyte are regulated to reach the expected indexes, the temperature of the electrolyte is regulated to a specified value, the raw foil additive is prepared and stirred uniformly according to a certain concentration, the raw foil additive is pre-added for 4-6 hours at a high-level tank according to a certain amount, so that the raw foil additive is fully dissolved and dispersed in the electrolyte, when the concentration of the raw foil additive in the electrolyte reaches the expected indexes, the electrolyte is electrified and started, and meanwhile, the adding amount of the raw foil additive is regulated to realize continuous guarantee of the using amount of the raw foil additive so as to maintain the consumption of the raw foil additive during electrolysis. For the anti-oxidation liquid, adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, taking alpha-D-glucose which is prepared and stirred uniformly according to a certain concentration as an anti-oxidation liquid additive, pre-adding the anti-oxidation liquid additive for 1-2 hours according to a certain amount, fully dissolving and dispersing the anti-oxidation liquid additive, and stopping adding the anti-oxidation liquid additive when the concentration of the anti-oxidation liquid additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the adding amount of the anti-oxidation liquid additive is adjusted, and the normal consumption of the anti-oxidation liquid additive is maintained continuously.
Preferably, the preparation method of the high-performance ultrathin electronic copper foil comprises the steps of a foil additive production process and a surface oxidation prevention process. Wherein, (1) a foil producing additive process: at 55-60deg.C, current density of 60-80A/dm 2 Under the condition, electroplating is carried out on the surface of the cathode roller by using electrolyte containing 90-120g/L sulfuric acid, 80-100g/L cupric ions and 20-30ppm chloride ions to generate the green foil. The electrolyte comprises a green foil additive comprising: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, and the additive amount is 500-800ml/min. (2) surface oxidation prevention process: at 20-30deg.C, current density of 10-20A/m 2 Under the condition, the surface of the green foil is electroplated by using an oxidation preventing liquid containing 0.5-1.0g/L hexavalent chromium and 1.0-2.0g/L sulfuric acid. The antioxidant fluid comprises an antioxidant fluid additive comprising: the flow rate of the reducing agent alpha-D glucose is 100-300ml/min.
The embodiment of the invention also provides the high-performance ultrathin electronic copper foil prepared by the preparation method of the high-performance ultrathin electronic copper foil.
The embodiment of the invention also provides application of the high-performance ultrathin electronic copper foil in preparation of lithium ion batteries.
The technical effects of the high-performance extra thin electronic copper foil according to the embodiment of the present invention will be further described below by referring to specific examples.
Example 1
The preparation method of the high-performance ultrathin electronic copper foil specifically comprises the steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-performance ultrathin electronic copper foil specifically comprises the following steps:
(1) Electrolytic foil production process: electroplating at 55 ℃ and a current density of 60A/dm2, using an electrolyte of 90g/L sulfuric acid, 80g/L cupric ions and 20ppm chloride ions to generate a green foil on the surface of a cathode roller, wherein the electrolyte comprises green foil additives, the green foil additives comprise sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, and the proportion of the additives is 5.0:1.8:3.0:4.0:6.0, additive flow rate 500ml/min.
(2) Surface oxidation prevention process: performing surface electroplating treatment in an anti-oxidation liquid with the temperature of 20 ℃ and the current density of 10A/dm < 2 >, the hexavalent chromium ion concentration of 0.5g/L and the sulfuric acid concentration of 1.0g/L to obtain the high-performance ultrathin electronic copper foil; the flow rate of the antioxidant liquid additive is 100ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, preparing an additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 2
The preparation method of the high-performance ultrathin electronic copper foil specifically comprises the steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-performance ultrathin electronic copper foil specifically comprises the following steps:
(1) Electrolytic foil production process: electroplating at 58 ℃ and a current density of 70A/dm2, using an electrolyte of 110g/L sulfuric acid, 90g/L cupric ions and 25ppm chloride ions to generate a green foil on the surface of a cathode roller, wherein the electrolyte comprises green foil additives, the green foil additives comprise sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, and the proportion of the additives is 5.0:1.8:3.0:4.0:6.0, additive flow rate 650ml/min.
(2) Surface oxidation prevention process: performing surface electroplating treatment in an anti-oxidation liquid with the temperature of 25 ℃ and the current density of 15A/dm2, the hexavalent chromium ion concentration of 0.8g/L and the sulfuric acid concentration of 1.5g/L to obtain the high-performance ultrathin electronic copper foil; the flow rate of the antioxidant liquid additive is 200ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, preparing an additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
In this example, a sample of the high performance ultrathin electronic copper foil produced was subjected to Scanning Electron Microscopy (SEM), wherein a 1000-fold SEM image of the smooth surface of the copper foil produced in example 2 is shown in fig. 1. An SEM image of the appearance surface 1000 times of the copper foil produced in example 2 is shown in fig. 2.
The high-performance ultrathin electronic copper foil prepared by the preparation method provided by the embodiment of the invention has good smooth surface roughness and overall flatness, high tensile strength (more than 50kgf/cm < 2 >), small fluctuation, high stability and high consistency, and can meet the requirements of high-end clients; the roughness Rz is small (< 2.0 μm) and the elongation is large (> 6.0%). Wherein, the additive system sodium polydithio-dipropyl sulfonate can improve the flatness and brightness of the copper foil; the low molecular hydrolyzed collagen can improve the normal temperature tensile strength and the elongation of the copper foil; polyethylene glycol (preferably polyethylene glycol 8000) can refine grains and maintain leveling effect under high current; the cellulose ether can enhance the elongation of the copper foil and improve the toughness of the copper foil; the ethylene thiourea can effectively improve the tensile strength and the elongation of the copper foil at high temperature.
Example 3
The preparation method of the high-performance ultrathin electronic copper foil specifically comprises the steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-performance ultrathin electronic copper foil specifically comprises the following steps:
(1) Electrolytic foil production process: electroplating at 60 ℃ and current density of 80A/dm2, using an electrolyte solution of 120g/L sulfuric acid, 100g/L cupric ions and 30ppm chloride ions to generate a green foil on the surface of a cathode roller, wherein the electrolyte solution comprises green foil additives, the green foil additives comprise sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, and the proportion of the additives is 5.0:1.8:3.0:4.0:6.0, additive flow rate 800ml/min.
(2) Surface oxidation prevention process: performing surface electroplating treatment in an anti-oxidation liquid with the temperature of 30 ℃ and the current density of 20A/dm2, the hexavalent chromium ion concentration of 1.0g/L and the sulfuric acid concentration of 2.0g/L to obtain the high-performance ultrathin electronic copper foil; the flow rate of the antioxidant liquid additive is 300ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, preparing an additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 4
The preparation method of the high-performance ultrathin electronic copper foil, in particular to a preparation method of the ultrathin electronic copper foil with high tensile strength, which comprises the following steps of an electrolytic foil production process and a surface oxidation prevention process:
(1) Electrolytic foil production process: the raw foil was produced by electroplating on the surface of a cathode roll at a temperature of 58℃and a current density of 65A/dm2 using an electrolyte containing 100g/L sulfuric acid, 80g/L cupric ion and 20ppm chloride ion. The electrolyte comprises a green foil additive comprising: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, additive amount 500ml/min.
(2) Surface oxidation prevention process: the surface of the green foil was subjected to surface plating treatment at a temperature of 20℃and a current density of 10A/m2 using an antioxidant liquid containing hexavalent chromium 0.5g/L and sulfuric acid 1.0 g/L. The antioxidant fluid comprises an antioxidant fluid additive comprising: the flow rate of the reducing agent alpha-D glucose is 100ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, preparing an additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 5
The preparation method of the high-performance ultrathin electronic copper foil, in particular to a preparation method of the ultrathin electronic copper foil with high tensile strength, which comprises the following steps of an electrolytic foil production process and a surface oxidation prevention process:
(1) Electrolytic foil production process: the green foil was produced by electroplating on the surface of a cathode roll at a temperature of 60℃and a current density of 70A/dm2 using an electrolyte containing 120g/L sulfuric acid, 100g/L cupric ion and 30ppm chloride ion. The electrolyte comprises a green foil additive comprising: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, additive amount 800ml/min.
(2) Surface oxidation prevention process: the surface of the green foil was subjected to surface plating treatment at a temperature of 30℃and a current density of 20A/m2 using an antioxidant liquid containing 1.0g/L hexavalent chromium and 2.0g/L sulfuric acid. The antioxidant fluid comprises an antioxidant fluid additive comprising: the flow rate of the reducing agent alpha-D glucose is 300ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 6 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting hexavalent chromium ions, sulfuric acid concentration and temperature in the anti-oxidation liquid to reach expected indexes, preparing an additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 2 hours according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 6
A high-performance ultrathin electronic copper foil is prepared through electroplating cathode roller in electrolyte to obtain raw foil, and electroplating at 25 deg.C with current density of 15A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-performance ultrathin electronic copper foil.
In this embodiment, the preparation methods of the high-performance ultrathin electronic copper foil refer to embodiment 1, and are not described herein.
Example 7
The procedure of example 1 was repeated except that the amount of the green foil additive in the electrolyte was 650ml/min as compared with example 1.
Example 8
The procedure of example 1 was repeated except that the amount of the green foil additive in the electrolyte was 700ml/min as compared with example 1.
Performance detection
The raw foils prepared by electroplating in examples 1 to 3 were subjected to performance test, specifically, tensile strength, elongation and surface roughness of the raw foils, and the data obtained are shown in table 1 below.
Table 1 table of test results
Figure BDA0004087654700000101
As can be seen from the data in Table 1, the green foil prepared by the preparation method of the high-performance ultrathin electronic copper foil provided by the embodiment of the invention has good tensile strength which can reach more than 50kgf/mm < 2 >.
Further, the high-performance ultrathin electronic copper foil finally prepared by the preparation method in examples 1 to 3 is subjected to oxidation resistance and dyne value detection, and specific performance detection results are shown in Table 2.
Table 2 table of performance test results
Figure BDA0004087654700000102
As can be seen from the data in table 2, the high-performance ultrathin electronic copper foil prepared by the preparation method of the high-performance ultrathin electronic copper foil provided by the embodiment of the invention has good oxidation resistance and good dyne value. The prepared ultrathin electronic copper foil has high tensile strength (more than 50kgf/cm < 2 >), small fluctuation, high stability and high consistency, and can meet the requirements of high-end clients; the roughness Rz is small (< 2.0 mu m), the extensibility is large (> 6.0%), and the copper foil has uniform and good appearance and no flaws. The preparation method of the invention has the advantages of easy adjustment of the additive system, strong continuous production stability and high product yield.
According to the results, the beneficial effects of the embodiment of the invention are as follows, the high-performance ultrathin electronic copper foil of the embodiment of the invention is an ultrathin electronic copper foil with high tensile strength, and the manufacturing method of the ultrathin electronic copper foil with high tensile strength comprises a raw foil additive process and a copper foil surface oxidation prevention process. The electronic copper foil with high tensile strength is prepared by changing the microstructure of the copper foil and the grain orientation of the copper foil through utilizing the additive with specific properties, and the normal temperature elongation and the roughness of the electronic copper foil are kept at higher levels. Moreover, the preparation method provided by the embodiment of the invention is simple and has wide market prospect. The sodium polydithio-dipropyl sulfonate, the hydrolyzed collagen, the polyethylene glycol, the cellulose ether, the ethylene thiourea and the like in the invention are all products of the existing manufacturer. And is specifically selected according to needs, and is not described herein in detail.
The foregoing has outlined the more detailed description of the preferred embodiment of the invention in order that the basic principles, features and advantages of the invention may be described. However, it should be understood by those skilled in the art that the embodiments of the present invention are not limited to the foregoing embodiments, but rather the foregoing examples and descriptions are merely preferred examples of the present invention, and that various changes, modifications and variations may be made by those skilled in the art without departing from the spirit and scope of the invention, and equivalent changes may be made using the technical matters disclosed above; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the embodiments of the present invention.

Claims (10)

1. The high-performance ultrathin electronic copper foil is characterized in that a cathode roller is placed in electrolyte to be electroplated to generate a green foil, and the green foil is subjected to surface treatment in an anti-oxidation liquid to obtain the high-performance ultrathin electronic copper foil; wherein the oxidation preventing liquid contains 0.5-1.0g/L hexavalent chromium, 1.0-2.0g/L sulfuric acid and a proper amount of alpha-D-glucose.
2. The high-performance ultrathin electronic copper foil according to claim 1, wherein the high-performance ultrathin electronic copper foil has a tensile strength of more than 50kgf/cm 2 The roughness is less than 2.0 mu m, and the extensibility is more than 6.0 percent.
3. The high-performance ultrathin electronic copper foil according to claim 2, wherein the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil producing additives; wherein, the raw materials of the raw foil additive comprise: sodium polydithio-dipropyl sulfonate, hydrolyzed collagen, polyethylene glycol, cellulose ether and ethylene thiourea.
4. The high-performance ultrathin electronic copper foil according to claim 3, wherein the electrolyte contains 90-120g/L sulfuric acid, 80-100g/L cupric ion, 20-30ppm chloride ion and an appropriate amount of raw foil additive.
5. The high performance ultrathin electronic copper foil according to claim 4, wherein the as-plated green foil is formed at a temperature of 55 to 60 ℃ and a current density of 60 to 80A/dm 2 Is carried out under the condition of (2).
6. The high performance ultrathin electronic copper foil according to claim 5, wherein the raw foil additive comprises the following raw materials in parts by weight: 4.0 to 6.0 parts of sodium polydithio-dipropyl sulfonate, 1.6 to 2.0 parts of hydrolyzed collagen, 2.0 to 4.0 parts of polyethylene glycol, 3.0 to 5.0 parts of cellulose ether and 5.0 to 7.0 parts of ethylene thiourea.
7. The high performance ultrathin electronic copper foil according to claim 6, wherein the raw foil additive comprises the following raw materials in parts by weight: 5.0 parts of sodium polydithio-dipropyl sulfonate, 1.8 parts of hydrolyzed collagen, 3.0 parts of polyethylene glycol, 4.0 parts of cellulose ether and 6.0 parts of ethylene thiourea.
8. A method for producing the high-performance extra thin electronic copper foil according to any one of claims 1 to 7, comprising the steps of:
electroplating the cathode roller in electrolyte to obtain green foil, and heating the green foil at 20-30deg.C with current density of 10-20A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-performance ultrathin electronic copper foil.
9. A high-performance ultrathin electronic copper foil produced by the production method of the high-performance ultrathin electronic copper foil according to claim 8.
10. Use of the high-performance ultrathin electronic copper foil according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 9 for preparing lithium ion batteries.
CN202310141540.0A 2023-02-13 2023-02-13 High-performance ultrathin electronic copper foil and preparation method and application thereof Pending CN116180165A (en)

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