CN115287726B

CN115287726B - Preparation device and method of titanium roller oxide film, copper foil and preparation method thereof

Info

Publication number: CN115287726B
Application number: CN202211025369.9A
Authority: CN
Inventors: 盛银莹; 单大勇
Original assignee: Institute of Corrosion Science and Technology
Current assignee: Institute of Corrosion Science and Technology
Priority date: 2022-08-25
Filing date: 2022-08-25
Publication date: 2023-06-23
Anticipated expiration: 2042-08-25
Also published as: CN115287726A

Abstract

The invention discloses a preparation device and method of a titanium roller oxide film, a copper foil and a preparation method thereof, and belongs to the technical field of copper foils. The device comprises a titanium plate, an oxidation tank and a titanium roller; the titanium roller and the titanium plate are arranged at intervals, and the titanium plate and at least part of the area of the circumferential direction of the titanium roller are positioned in the oxidation tank; the oxidizing liquid contained in the oxidizing tank submerges the gap between the titanium roller and the titanium plate in the preparation process, so that the oxidizing liquid forms an oxide film on the surface of the titanium roller under the condition of electrifying. The preparation device does not need to grind and polish the titanium roller in the production process, and the surface state is ensured to be stable by timely carrying out supplementary oxidation, so that the production and maintenance cost is greatly reduced, the damage of arc points and the like can be avoided, and the service life of the titanium roller is prolonged. The titanium roller with the oxide film is used for further preparing the copper foil, so that the speed of absorbing hydrogen by the titanium material can be reduced, the corrosion of the titanium roller is slowed down, the high-performance ultrathin and ultrathin copper foil can be effectively and stably prepared, and the qualification rate of the whole roll of copper foil is improved.

Description

Preparation device and method of titanium roller oxide film, copper foil and preparation method thereof

Technical Field

The invention relates to the technical field of copper foil, in particular to a preparation device and method of a titanium roller oxide film, a copper foil and a preparation method of the copper foil.

Background

The electrolytic copper foil has excellent signal and power transmission capability and plays a role in the new energy electric car industry and the 5G electronic information industry. To meet the ever-increasing demand of power cells for high specific energy density, it is imperative to develop thinner, stronger, and tougher copper foils. However, in the conventional copper foil production method, a roll continuous electrolytic method is adopted, and a cathode roll is a core device of an electrolytic copper foil, and the crystal grain size, crystal structure, surface state and the like of the cathode roll determine the initial crystal state of the electrolytic copper foil, so that the quality of the electrolytic copper foil is greatly affected. The finer the surface grains of the cathode roller, the finer the grains of the electrolytic copper foil, the more uniform the geometric arrangement, and the more easily the ultra-thin and tough copper foil is obtained. On the contrary, the copper foil is thick because of coarse crystals and thicker foil formation.

Particularly, the initial deposition of the copper foil is greatly influenced by the surface state, and the copper foil which is uncoiled on production is more in pinholes of about 100-200 m, has poor performance and needs to be discarded, so that waste and increase of production cost are caused. This is because the oxide layer on the surface of the fresh titanium roll is unstable, which is unfavorable for the adsorption of the additive, and thus affects the deposition of copper ions. After the copper foil is used for a period of time, the surface of the cathode roller is always in a change state due to electrochemical corrosion and mechanical corrosion, the titanium roller is easy to absorb hydrogen to form titanium hydride to accelerate corrosion, a corrosion layer is thicker and thicker, the surface of the cathode roller is blackened, the surface is not bright, the roughness is increased, the internal stress of the copper foil is possibly increased, the copper foil is rolled, the smooth surface of the copper foil is possibly provided with special brightness or stripes and the like, the qualification rate of the copper foil production is greatly reduced, and the problems are more serious for producing the ultrathin copper foil with the thickness of below 4.5 mu m.

In order to reduce the adverse effect caused by the change of the surface state of the cathode roller, when in actual production, the cathode roller needs to be subjected to surface grinding and polishing after being used for a period of time, so that a corrosion layer on the surface is removed, an extremely thin new oxide film is generated on the surface, the metal activity of the surface of the cathode roller is ensured, the surface potential is more negative and is not easy to corrode, and the current is ensured to be uniformly distributed on the surface of the titanium roller. However, the mechanical polishing steps of the cathode roll are difficult to be completely consistent, and greatly affect the stability of the formulation and process, and greatly increase the production and maintenance costs. The off-line polishing requires the foil producing machine to stop production, and the cathode roller with the weight of 10t is removed, so that the production is not safe and is also influenced; the online polishing is performed on a normal running foil producing machine, but damages such as arc points and the like generated on the surface of a cathode roller are difficult to repair, and when a newly polished titanium roller is used for deposition production, the copper foil is inevitably wasted during uncoiling.

In view of this, the present invention has been made.

Disclosure of Invention

An object of the present invention is to provide a device for preparing a titanium roller oxide film, which solves at least one of the above technical problems.

The second object of the invention is to provide a method for preparing the titanium roller oxide film by adopting the preparation device.

The invention further aims to provide a preparation method of the copper foil on the surface of the titanium roller.

The fourth object of the present invention is to provide a copper foil produced by the above production method.

The application can be realized as follows:

in a first aspect, the present application provides a device for preparing a titanium roller oxide film, which includes a titanium plate, an oxidation tank, and a titanium roller;

at least part of the area of the titanium plate is positioned in the oxidation tank, the titanium roller and the titanium plate are arranged at intervals, and at least part of the area of the titanium roller in the circumferential direction is positioned in the oxidation tank in the preparation process of the oxide film; the oxidizing liquid contained in the oxidizing tank submerges the gap between the titanium roller and the titanium plate in the preparation process, so that the oxidizing liquid forms an oxide film on the surface of the titanium roller under the condition of electrifying.

In an alternative embodiment, the oxidation tank is further provided with an oxidizing liquid inlet and outlet for connection with an external oxidizing liquid supply container.

In an alternative embodiment, the oxidizing liquid inlet and outlet are also provided with valves for controlling the inlet and outlet of the oxidizing liquid.

In an alternative embodiment, the preparation device further comprises a power supply, wherein the power supply is connected with the titanium plate and the titanium roller simultaneously.

In a second aspect, the present application provides a method for preparing a titanium roller oxide film, including the steps of: the production apparatus according to any one of the above embodiments is configured such that the titanium plate is used as a cathode, the titanium roller is used as an anode, and the titanium roller is rotated under an energization condition so that the oxidizing liquid in the oxidation tank forms a titanium oxide film on the surface of the titanium roller.

In an alternative embodiment, the rotation speed of the titanium roller is 2-6m/min.

In an alternative embodiment, the voltage is controlled to 20-50V during the oxide film preparation process.

In an alternative embodiment, the oxidizing liquid includes at least 2 of oxalic acid, sulfuric acid, nitrilotriacetic acid, citric acid, and fatty acid methyl ester polyoxyethylene ether.

In an alternative embodiment, the oxidizing solution comprises at least 10-20g/L oxalic acid and 100-200g/L sulfuric acid.

In an alternative embodiment, the method further comprises polishing the titanium roller prior to depositing the titanium oxide film.

In an alternative embodiment, the roughness Ra of the titanium roller after the polishing treatment is 0.2-0.4 μm.

In a third aspect, the present application provides a method for preparing a copper foil on a surface of a titanium roller, including the following steps: the titanium roller with the oxide film prepared by the embodiment is adopted as a cathode, a titanium plate in a preparation device used for preparing the oxide film of the titanium roller is replaced by a titanium iridium tantalum coating anode plate, electrolyte is introduced into an oxidation tank, and copper foil is deposited on the surface of the titanium roller with the oxide film under the electrolysis condition.

In an alternative embodiment, the method further comprises stripping and winding the titanium roller deposited with the copper foil.

In an alternative embodiment, the current is 25000-35000A, the temperature is 48-55deg.C, and the rotation speed of the titanium roller is 5-10m/min.

In an alternative embodiment, the electrolyte comprises a major component of 350-360g/L copper sulfate, 100-130g/L sulfuric acid, and 10-20mg/L chloride.

In an alternative embodiment, the chloride salt is copper chloride or sodium chloride.

In an alternative embodiment, additives are also included in the composition of the electrolyte.

In an alternative embodiment, the additive includes at least one of a wetting agent, a brightening agent, a leveling agent, a high resistance agent, and a toughening agent.

In an alternative embodiment, the wetting agent comprises a polyether compound; and/or the brightening agent comprises at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithiocarbonyl propane sulfonate and thiazolidinethione; and/or, the leveling agent comprises an amine compound; and/or, the high resistance agent comprises ethylene thiourea; and/or the toughening agent comprises at least one of organic sulfide with sulfonic acid groups, quaternary amine compounds and semicarbazide modified polymers.

In an alternative embodiment, the wetting agent comprises at least one of hydroxyethyl cellulose and polyethylene glycol; preferably, the polyethylene glycol has a molecular weight of 6000 to 8000.

In an alternative embodiment, the leveling agent comprises at least one of polypeptide protein, gelatin, bone cement, and alkylated polyethylenimine.

In an alternative embodiment, the toughening agent includes at least one of an L-aliphatic amine ethoxysulfonate, a quaternary amine compound, and an semicarbazide-type modified polymer.

In an alternative embodiment, the electrolyte contains at least one of 50-200mg/L hydroxyethyl cellulose and 10-100mg/L polyethylene glycol;

and/or the electrolyte contains at least one of 0-50mg/L of polydithio-dipropyl sodium sulfonate, 0-50mg/L of 3-mercapto-1-propane sodium sulfonate, 0-10mg/L of N, N-dimethyl-dithio carbonyl sodium propane sulfonate and 2-6mg/L of thiazolidinedione;

and/or the electrolyte contains 50-100mg/L of polypeptide protein and 20-60mg/L of at least one of alkylated polyethylenimine;

and/or the electrolyte contains 0.2-0.5mg/L ethylene thiourea;

and/or the electrolyte contains at least one of 1-5mL/L fatty amine ethoxy sulfonate, 2-10mL/L quaternary amine compound and 5-10mL/L amino urea modified polymer.

In an alternative embodiment, when the electrolyte contains at least one of sodium 3-mercapto-1-propane sulfonate and sodium polydithio-dipropyl sulfonate and polypeptide protein, the dosage ratio of the sodium 3-mercapto-1-propane sulfonate and the sodium polydithio-dipropyl sulfonate to the polypeptide protein is 0-1:1 respectively.

In an alternative embodiment, when the electrolyte contains both sodium polydithio-dipropyl sulfonate and sodium N, N-dimethyl-dithio carbonyl propane sulfonate, the dosage ratio of sodium polydithio-dipropyl sulfonate to sodium N, N-dimethyl-dithio carbonyl propane sulfonate is 5-8:1.

In a fourth aspect, the present application provides a copper foil prepared by the method of any one of the preceding embodiments.

In an alternative embodiment, the copper foil has a thickness of 4-6 μm.

The beneficial effects of this application include:

the preparation facilities that this application provided need not to grind the throwing to the titanium roller any more at production process, in good time carry out supplementary oxidation guarantee surface state stable can, not only greatly reduced production and maintenance cost, can avoid damage such as arc point moreover, prolonged the life of titanium roller. The titanium roller with the oxide film is used for further preparing the copper foil, so that the speed of absorbing hydrogen by the titanium material can be reduced, the corrosion of the titanium roller is slowed down, the high-performance ultrathin and ultrathin copper foil can be effectively and stably prepared, and the qualification rate of the whole roll of copper foil is improved. The prepared copper foil has no pinholes, no curling, excellent performance (such as normal temperature tensile strength and elongation), fine microstructure and good flexibility.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a schematic structural diagram of a preparation apparatus provided in the present application.

Icon: 1-titanium plate; a 2-oxidation tank; 3-titanium roller; 4-oxidizing liquid supply container; 5-a liquid inlet and outlet channel; 6-valve; 7-electrolyte inlet.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The apparatus and method for producing the titanium roll oxide film, the copper foil and the production method thereof are specifically described below.

The application provides a preparation device of a titanium roller oxide film, which is shown in fig. 1 and comprises a titanium plate 1, an oxidation tank 2 and a titanium roller 3.

At least part of the area of the titanium plate 1 is positioned in the oxidation tank 2, the titanium roller 3 and the titanium plate 1 are arranged at intervals, and in the preparation process of the oxide film, at least part of the area of the titanium roller 3 in the circumferential direction is positioned in the oxidation tank 2; the gap between the titanium roller 3 and the titanium plate 1 is immersed by the oxidizing liquid contained in the oxidizing tank 2 in the preparation process, so that an oxidizing film is formed on the surface of the titanium roller 3 by the oxidizing liquid under the condition of electrifying.

Preferably, during the preparation of the oxide film, a half area of the titanium roll 3 in the circumferential direction is located in the oxidation tank 2. The area of the titanium plate 1 located in the oxidation tank 2 can correspond to the surface of the titanium roll 3 located in the oxidation tank 2 so that the surface of the titanium roll located in the oxidation tank 2 can form an oxide film.

The oxidation tank 2 is also provided with an oxidation liquid inlet and outlet which is used for being connected with an external oxidation liquid supply container 4 through a liquid inlet and outlet channel 5.

Preferably, the oxidizing liquid inlet and outlet are also provided with a valve 6 for controlling the inlet and outlet of the oxidizing liquid, so that the oxidizing liquid in the oxidizing liquid supply container 4 is led into the oxidizing tank 2 when the liquid needs to be fed; when the preparation of the oxide film is completed, the oxidizing liquid can be returned to the oxidizing liquid supply container 4 through the valve 6; when the oxidation tank 2 needs to be reused, the valve 6 is opened, so that the oxidation tank 2 is filled with the oxidation tank again, and further the recycling is realized.

Further, the preparation device also comprises a power supply, and the power supply is connected with the titanium plate 1 and the titanium roller 3 at the same time.

Correspondingly, the application also provides a preparation method of the titanium roller oxide film, which comprises the following steps: by adopting the preparation device, the titanium plate 1 is used as a cathode, the titanium roller 3 is used as an anode, and the titanium roller 3 is rotated under the condition of electrifying, so that the oxidizing liquid in the oxidation tank 2 forms a titanium oxide film on the surface of the titanium roller 3.

Preferably, the titanium roller 3 may also be subjected to a polishing treatment prior to the deposition of the titanium oxide film. The roughness Ra of the titanium roll 3 after the polishing treatment is preferably controlled to be 0.2 to 0.4 μm.

As a reference, the grinding and polishing of the titanium roller 3 can adopt SiC abrasive belts and scouring cloths with different specifications, and the defects, oxide layers and abrasive belt marks remained in the processing of the titanium roller 3 are gradually removed. In addition, chemical polishing can be used instead of mechanical polishing to achieve the roughness values. The chemical polishing liquid used can be HF or HNO ₃ And lactic acid in a certain ratioThe example configuration is made.

In the above rotation process, the rotation speed of the titanium roller 3 may be 2-6m/min, such as 2m/min, 2.5m/min, 3m/min, 3.5m/min, 4m/min, 4.5m/min, 5m/min, 5.5m/min or 6m/min, etc., or any other value within the range of 2-6m/min. And uniformly rotating for 1-3 weeks according to the rotating speed to form a uniform titanium oxide film.

It should be noted that in the potentiostatic mode, the current is changed during the oxidation phase, the current is large during the oxidation start phase, then the current is rapidly reduced to a minimum value, and then the current density is slowly increased due to the oxygen evolution reaction. The proper rotating speed can ensure that the oxide film with proper thickness and uniform composition and morphology is finally generated. If the rotating speed is too high, the formed oxide film is rough and the crystallization is uneven; if the rotating speed is too slow, oxygen evolution reaction is triggered, and the aging stage is started.

In the preparation process of the oxide film, the voltage can be controlled to be 20-50V, such as 20V, 25V, 30V, 35V, 40V, 45V or 50V, and the like, and can be any other value within the range of 20-50V.

The titanium anodic oxide film growth and crystallization process are different under different applied potentials. If the voltage is less than 20V, the growth and crystallization of the oxide film are slow. If the voltage is too high, the current density during oxidation is high, and the oxide film grows and dissolves rapidly, resulting in high surface roughness of the oxide film.

For reference, the oxidizing liquid used in the preparation process includes at least 2 of oxalic acid, sulfuric acid, nitrilotriacetic acid, citric acid, and fatty acid methyl ester polyoxyethylene ether.

Preferably, the oxidizing solution comprises at least 10-20g/L (e.g., 10g/L, 12g/L, 15g/L, 18g/L, or 20g/L, etc.) oxalic acid and 100-200g/L (e.g., 100g/L, 120g/L, 150g/L, 180g/L, or 200g/L, etc.) sulfuric acid.

By the above method, an oxide film having a thickness of not more than 100 μm can be formed on the surface of the titanium roller, the oxide film mainly comprising titanium oxide. The oxide film formed was observed to be uniformly blue, dark cyan, and gold with naked eyes.

In addition, the application also provides a preparation method of the copper foil on the surface of the titanium roller, which comprises the following steps: the titanium roller with the oxide film is used as a cathode, a titanium plate 1 in a preparation device used for preparing the oxide film of the titanium roller is replaced by a titanium iridium tantalum coating anode plate, electrolyte is introduced into an oxidation tank 2, and copper foil is deposited on the surface of the titanium roller with the oxide film under the electrolysis condition.

Preferably, in the above-mentioned preparation apparatus for preparing the titanium roller oxide film, the bottom of the oxidation tank 2 may be further provided with an electrolyte inlet 7 for introducing an electrolyte as needed.

And after the electrolytic deposition is finished, stripping and rolling the titanium roller deposited with the copper foil.

As reference ground, in the above electrolytic process, the current may be 25000-35000A, the temperature is 48-55deg.C, and the rotation speed of the titanium roller is 5-10m/min.

The current may be 25000A, 26000A, 27000A, 28000A, 29000A, 30000A, 31000A, 32000A, 33000A, 34000A, 35000A, or the like, or may be any other value within a range of 25000 to 35000A.

It is emphasized that current density is a core parameter of the deposited copper foil, which, in addition to determining production efficiency, also affects mainly grain nucleation and growth. If the current is lower than 25000A, the production efficiency is low, and the grains are coarse; if the current is higher than 35000A, the edge of the copper foil is easy to burn, and more importantly, the oxide film is dissolved too quickly due to the excessive current density.

The temperature may be 48℃at 49℃at 50℃at 51℃at 52℃at 53℃at 54℃or 55℃at 55℃or any other value within the range of 48-55 ℃.

It should be noted that, if the temperature is too low, the current density will be low; if the temperature is too high, the additives (such as proteins) are liable to decompose and fail.

The rotation speed may be 5m/min, 5.5m/min, 6m/min, 6.5m/min, 7m/min, 7.5m/min, 8m/min, 8.5m/min, 9m/min, 9.5m/min, 10m/min, etc., or any other value within the range of 5-10m/min.

By controlling the rotation speed in the above range, the effect of controlling the deposition rate in a preferable range can be achieved by combining the above current conditions.

By way of reference, the main components of the above electrolyte include 350-360g/L (e.g., 350g/L, 352g/L, 355g/L, 358g/L, 360g/L, etc.), 100-130g/L (e.g., 100g/L, 105g/L, 110g/L, 115g/L, 120g/L, 125g/L, 130g/L, etc.), and 10-20mg/L (e.g., 10mg/L, 12mg/L, 15mg/L, 18mg/L, 20mg/L, etc.) of sulfuric acid and chloride salts.

Wherein the chloride salt can be sodium chloride after copper chloride.

Further, additives may be included in the components of the above-described electrolytic solution, and may include, for example, at least one of a wetting agent, a brightening agent, a leveling agent, a high resistance agent, and a toughening agent.

Wherein the wetting agent may include polyether compounds, such as at least one of Hydroxyethylcellulose (HEC) and polyethylene glycol (PEG, molecular weight 6000-8000).

The brightening agent may include at least one of sodium polydithio-propane sulfonate (SPS), sodium 3-mercapto-1-propane sulfonate (MPS), sodium N, N-dimethyl-Dithiocarbonyl Propane Sulfonate (DPS), and thiazolidinethione (H1). The brightening agent can play a role in increasing cathode polarization, refining grains and improving the brightness of the rough surface of the copper foil.

The leveler may include an amine compound, such as may include at least one of polypeptide protein (QS), gelatin, bone cement, and alkylated polyethylenimine.

The high resistance agent may include ethylene thiourea. By adding a high-resistance agent to the electrolytic solution, a copper foil with high tensile strength can be obtained.

The toughening agent may include at least one of an organic sulfide, a quaternary amine compound, and an amino urea-based modified polymer having a sulfonic acid group, and may include at least one of an L-aliphatic amine ethoxy sulfonate, a quaternary amine compound, and an amino urea-based modified polymer, for example. By adding a toughening agent to the electrolytic solution, a copper foil with high elongation can be obtained.

In some embodiments, the electrolyte may contain 50-200mg/L (e.g., 50mg/L, 80mg/L, 100mg/L, 120mg/L, 150mg/L, 180mg/L, or 200mg/L, etc.) of hydroxyethylcellulose and 10-100mg/L (e.g., 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L, or 100mg/L, etc.) of at least one of polyethylene glycol.

In some embodiments, the electrolyte may contain 0-50mg/L (e.g., 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, etc.) of sodium polydithio-dipropyl sulfonate, 0-50mg/L (e.g., 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, or 50mg/L, etc.) of sodium 3-mercapto-1-propane sulfonate, 0-10mg/L (e.g., 0mg/L, 2mg/L, 4mg/L, 6mg/L, 8mg/L, or 10mg/L, etc.) of sodium N, N-dimethyl-dithiocarbonyl propane sulfonate, and 2-6mg/L of thiazolidinethione.

In some embodiments, the electrolyte may contain 50-100mg/L (e.g., 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L, or 100mg/L, etc.) of the polypeptide protein and 20-60mg/L (e.g., 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, or 60mg/L, etc.) of the alkylated polyethyleneimine.

In some embodiments, the electrolyte may contain 0.2-0.5mg/L (e.g., 0.2mg/L, 0.25mg/L, 0.3mg/L, 0.35mg/L, 0.4mg/L, 0.45mg/L, 0.5mg/L, etc.) of ethylene thiourea.

In some embodiments, the electrolyte may contain at least one of 1-5mL/L (e.g., 1mL/L, 1.5mL/L, 2mL/L, 2.5mL/L, 3mL/L, 3.5mL/L, 4mL/L, 4.5mL/L, or 5mL/L, etc.) of an aliphatic amine ethoxysulfonate, 2-10mL/L (e.g., 2mL/L, 3mL/L, 4mL/L, 5mL/L, 6mL/L, 7mL/L, 8mL/L, 9mL/L, or 10mL/L, etc.), and 5-10mL/L (e.g., 5mL/L, 6mL/L, 7mL/L, 8mL/L, 9mL/L, or 10mL/L, etc.) of an aminourea-based modified polymer.

Preferably, when the electrolyte contains at least one of sodium 3-mercapto-1-propane sulfonate and sodium polydithio-dipropyl sulfonate and polypeptide protein, the dosage ratio of the sodium 3-mercapto-1-propane sulfonate to the polypeptide protein is 0-1:1, such as 0:1, 0.2:1, 0.5:1, 0.8:1 or 1:1, respectively, so as to obtain the optimal surface glossiness and roughness.

When the electrolyte contains both sodium polydithio-dipropyl sulfonate and sodium N, N-dimethyl-dithiocarbonyl propane sulfonate, the dosage ratio of sodium polydithio-dipropyl sulfonate to sodium N, N-dimethyl-dithiocarbonyl propane sulfonate may be 5-8:1, such as 5:1, 6:1, 7:1 or 8:1.

Accordingly, the present application provides a copper foil prepared by the above preparation method.

Preferably, the prepared copper foil has the thickness of 4-6 mu m, no pinholes or curling, excellent performance, fine microstructure and good flexibility. The tensile strength at normal temperature reaches 480-680MPa, and the elongation reaches 5-15%.

The features and capabilities of the present invention are described in further detail below in connection with the examples.

Example 1

The embodiment provides a titanium roller oxide film, which is prepared by adopting the following method and device:

the device comprises a titanium plate 1, an oxidation tank 2, a titanium roller 3 and a power supply.

Half of the area of the titanium roller 3 in the circumferential direction is positioned in the oxidation tank 2, the titanium plate 1 is positioned in the oxidation tank 2, the titanium roller 3 and the titanium plate 1 are arranged at intervals, and the area of the titanium plate 1 positioned in the oxidation tank 2 corresponds to the surface of the titanium roller 3 positioned in the oxidation tank 2. The bottom of the oxidation tank 2 is provided with an oxidation liquid inlet and an oxidation liquid outlet which are used for being connected with an external oxidation liquid supply container 4. The inlet and outlet of the oxidizing liquid are provided with a valve 6 for controlling the inlet and outlet of the oxidizing liquid. The power supply is connected with the titanium plate 1 and the titanium roller 3 at the same time.

The method comprises the following steps:

(1) Polishing and grinding treatment of a titanium cathode roller: the polishing of the titanium cathode roller adopts SiC abrasive belts and scouring cloths with different specifications, defects, oxide layers and abrasive belt marks remained in the processing of the titanium roller are gradually removed, and finally the roughness Ra value reaches 0.2 mu m;

(2) Anodic oxidation treatment of cathode titanium roller: the cathode titanium roller after polishing and grinding is used as an anode, a titanium metal plate is used as a cathode, and in the preparation process of an oxide film, an oxidizing liquid contained in an oxidation tank 2 submerges a gap between a titanium roller 3 and a titanium plate 1 in the preparation process.

The oxidation power supply is turned on, the voltage is set to be 35V, the rotating speed of the titanium roller is set to be 4m/min, the titanium roller rotates at a constant speed for 2 weeks, a layer of uniform titanium oxide film is formed, and the power supply is turned off.

The oxidation solution consists of 10g/L oxalic acid, 200g/L sulfuric acid (98 wt%) and 30g/L nitrilotriacetic acid.

(3) After oxidation, the oxidizing liquid in the oxidation tank 2 is discharged and stored in an oxidizing liquid supply container 4 for storing the oxidizing liquid, and when the oxidizing liquid is reused, the oxidizing liquid is introduced into the oxidation tank 2 through a liquid inlet pipe and a valve 6.

The thickness of the oxide film produced on the surface of the titanium roll 3 was 20. Mu.m.

Example 2

The embodiment provides a copper foil, which is prepared by the following steps:

(1) With the apparatus of example 1, the cathode titanium plate 1 for oxidation was replaced with a titanium iridium tantalum coated anode plate, and a titanium roll having an oxide film was used as the cathode roll, and an electrolyte was introduced from the bottom of the oxidation tank 2.

Wherein the electrolyte comprises main components and additives. The main components of the electrolyte comprise 355g/L of copper sulfate, 115g/L of sulfuric acid and 15mg/L of copper chloride per L of electrolyte. The additives include 100mg/L of hydroxyethyl cellulose, 50mg/L of sodium polydithio-dipropyl sulfonate, 10mg/L of sodium N, N-dimethyl-dithio carbonyl propane sulfonate, 50mg/L of polypeptide protein, 0.35mg/L of ethylene thiourea and 7.5mL/L of amino urea modified polymer.

That is, the ratio of the amount of sodium polydithio-dipropyl sulfonate to the amount of polypeptide protein was 1:1, and the ratio of the amount of sodium polydithio-dipropyl sulfonate to the amount of sodium N, N-dimethyl-dithiocarbonyl propane sulfonate was 5:1.

(2) And (3) turning on a power supply to electrodeposit copper foil, wherein the current is 30000A, the temperature of the electrolyte is controlled to be 50 ℃, and the rotating speed of a cathode roller is 7.5m/min.

(3) And stripping and rolling to obtain the copper foil with the thickness of 5 mu m.

Example 3

This embodiment provides an oxide film which differs from embodiment 2 only in that: in the preparation process of the oxide film, the rotation speed of the titanium roller is 2m/min.

Example 4

This embodiment provides an oxide film which differs from embodiment 2 only in that: in the preparation process of the oxide film, the rotation speed of the titanium roller is 6m/min.

Example 5

This embodiment provides an oxide film which differs from embodiment 2 only in that: in the preparation process of the oxide film, the voltage is 20V.

Example 6

This embodiment provides an oxide film which differs from embodiment 2 only in that: in the preparation process of the oxide film, the voltage is 50V.

Comparative example 1

The difference between this comparative example and example 2 is that: in the preparation process of the oxide film, the rotation speed of the titanium roller is 1m/min.

Comparative example 2

The difference between this comparative example and example 2 is that: in the preparation process of the oxide film, the rotation speed of the titanium roller is 8m/min.

Comparative example 3

The difference between this comparative example and example 2 is that: in the preparation process of the oxide film, the voltage is 10V.

Comparative example 4

The difference between this comparative example and example 2 is that: in the preparation process of the oxide film, the voltage is 60V.

Comparative example 5

The difference between this comparative example and example 2 is that: the main components of the electrolyte comprise 355g/L of copper sulfate, 115g/L of sulfuric acid and 15mg/L of copper chloride per L of electrolyte. The additive comprises 100mg/L of hydroxyethyl cellulose, 100mg/L of sodium polydithio-dipropyl sulfonate, 10mg/L of sodium N, N-dimethyl-dithio carbonyl propane sulfonate, 50mg/L of polypeptide protein, 0.35mg/L of ethylene thiourea and 7.5mL/L of amino urea modified polymer.

That is, the dosage ratio of sodium polydithio-dipropyl sulfonate to polypeptide protein is 2:1.

Comparative example 6

The difference between this comparative example and example 2 is that: the main components of the electrolyte comprise 355g/L of copper sulfate, 115g/L of sulfuric acid and 15mg/L of copper chloride per L of electrolyte. The additive comprises 100mg/L of hydroxyethyl cellulose, 50mg/L of sodium polydithio-dipropyl sulfonate, 5mg/L of sodium N, N-dimethyl-dithio carbonyl propane sulfonate, 50mg/L of polypeptide protein, 0.35mg/L of ethylene thiourea and 7.5mL/L of amino urea modified polymer.

That is, the dosage ratio of sodium polydithio-dipropyl sulfonate to sodium N, N-dimethyl-dithio carbonyl propane sulfonate was 10:1.

Comparative example 7

The difference between this comparative example and example 2 is that:

the main components of the electrolyte comprise 360g/L of copper sulfate, 130g/L of sulfuric acid and 20mg/L of copper chloride per L of electrolyte. The additives include 50mg/L polyethylene glycol (molecular weight 7000), 50mg/L sodium 3-mercapto-1-propane sulfonate, 50mg/L polypeptide protein, 40mg/L alkylated polyethylene imine, 0.5mg/L ethylene thiourea, 5mL/L fatty amine ethoxy sulfonate.

I.e. the additive contains only a part of the ingredients.

Test examples

(1) Observations made for examples 2-6, the results of which show: the copper foils prepared in examples 2-6 all had no pinholes, no curling and fine microstructure.

(2) According to GB/T228.1-201 section 1 of tensile test of metallic materials: room temperature test method and GB/T29847-2013 copper foil test method for printed boards the copper foils obtained in examples 2-6 and comparative examples 1-7 were subjected to performance tests, and the results are shown in Table 1.

Table 1 test results

As can be seen from table 1:

A. as can be seen from comparative example 2 and comparative examples 1 to 2, the rotation speed of the titanium roll is too low or too high during the preparation of the oxide film, which results in a decrease in mechanical properties of the copper foil.

B. As can be seen from comparative examples 2 and comparative examples 3 to 4, too low or too high voltage leads to deterioration of mechanical properties of the copper foil during the preparation of the oxide film.

C. As can be seen from comparative example 2 and comparative examples 5 and 6, when the ratio of MPS/SPS and QS is out of the range of 0 to 1:1 (comparative example 5), or when the ratio of SPS and DPS is out of the range of 5 to 8:1 (comparative example 6), the corresponding resulting copper foil is worse than example 2 in terms of tensile strength, yield strength or elongation, indicating that the difference in the ratio between the components has a significant effect on the tensile strength, yield strength or elongation of the copper foil even under the same electrolyte composition.

D. As can be seen from comparative examples 2 and 7, the tensile strength, yield strength, and elongation of the resulting copper foil are significantly reduced after the additive types are changed.

Therefore, in the preparation process of the oxide film, proper rotation speed, proper voltage and proper additive components and proper proportion can effectively improve the tensile strength and the yield strength elongation of the copper foil in the electrolysis process.

In summary, the electrolytic copper foil is prepared based on the titanium roller with oxidized surface, and the stable oxide film can reduce the adverse effect of the surface state of the titanium roller on the copper foil deposition, so that the initial deposition is uniform, and the qualification rate of the whole copper foil is improved. When the oxide film is arranged on the surface of the titanium roller, the flatness of the copper foil is greatly improved, and the method has absolute advantages for producing ultrathin even ultrathin copper foil. In addition, the oxide film can reduce the speed of absorbing hydrogen by the titanium material and slow down the corrosion of the titanium roller. Before the titanium roller is used, the titanium roller is polished to Ra0.4 in an offline manner, the titanium roller is not required to be polished in the production process, and the titanium roller is timely subjected to supplementary oxidation to ensure that the surface state is stable, so that the service life of the titanium roller is prolonged. The copper foil deposited on the oxide film has the advantages of no pinholes and low warpage, and can be prepared into the high-strength and high-toughness ultrathin copper foil by combining the additive process formula. By microstructure characterization, the copper foil has fine rough surface unit cells, uniform structure and no obvious polishing scratch on a smooth surface. The method solves the technical bottleneck problem that the quality of the copper foil is affected and the thickness of the copper foil is limited due to the difference of the surface states of the titanium rollers in the prior art.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the copper foil on the surface of the titanium roller is characterized by comprising the following steps of: a titanium roller with an oxide film is used as a cathode, a titanium plate in a preparation device used for preparing the oxide film of the titanium roller is replaced by a titanium iridium tantalum coating anode plate, electrolyte is introduced into an oxidation tank, and copper foil is deposited on the surface of the titanium roller with the oxide film under the electrolysis condition;

wherein, the preparation of the titanium roller oxide film comprises the following steps: adopting a preparation device of a titanium roller oxide film, taking a titanium plate as a cathode, taking a titanium roller as an anode, and rotating the titanium roller under the condition of electrifying so as to enable the oxidizing liquid in the oxidation tank to form a titanium oxide film on the surface of the titanium roller;

the preparation device of the titanium roller oxide film comprises a titanium plate, an oxidation tank and a titanium roller; at least part of the area of the titanium plate is positioned in the oxidation tank, the titanium roller and the titanium plate are arranged at intervals, and in the preparation process of the oxide film, at least part of the area of the titanium roller in the circumferential direction is positioned in the oxidation tank; the gap between the titanium roller and the titanium plate is immersed by the oxidizing liquid contained in the oxidizing tank in the preparation process, so that an oxidizing film is formed on the surface of the titanium roller by the oxidizing liquid under the electrifying condition;

the rotation speed of the titanium roller is 2-6m/min; in the preparation process of the oxide film, the voltage is controlled to be 20-50V;

the thickness of the copper foil is 4-6 mu m.

2. The method according to claim 1, wherein the oxidation tank is further provided with an oxidizing liquid inlet and outlet for connection with an external oxidizing liquid supply container.

3. The preparation method according to claim 2, wherein the oxidizing liquid inlet and outlet are further provided with a valve for controlling the inlet and outlet of the oxidizing liquid.

4. The method of claim 1, wherein the apparatus further comprises a power source connected to the titanium plate and the titanium roller simultaneously.

5. The method according to claim 1, wherein the oxidizing liquid comprises at least 2 of oxalic acid, sulfuric acid, nitrilotriacetic acid, citric acid, and fatty acid methyl ester polyoxyethylene ether.

6. The method according to claim 5, wherein the oxidizing liquid comprises at least 10-20g/L oxalic acid and 100-200g/L sulfuric acid.

7. The method according to claim 1, further comprising polishing the titanium roller before depositing the titanium oxide film;

the roughness Ra of the polished titanium roller is 0.2-0.4 mu m.

8. The method of manufacturing according to claim 1, further comprising peeling and winding the titanium roll deposited with the copper foil.

9. The method according to claim 1, wherein the current is 25000-35000A, the temperature is 48-55deg.C, and the rotation speed of the titanium roller is 5-10m/min.

10. The method according to claim 1, wherein the main components of the electrolyte include 350-360g/L copper sulfate, 100-130g/L sulfuric acid, and 10-20mg/L chloride salt.

11. The method of claim 10, wherein the chloride salt is copper chloride or sodium chloride.

12. The method of claim 10, wherein the electrolyte further comprises an additive;

the additives include at least one of a wetting agent, a brightening agent, a leveling agent, a high resistance agent, and a toughening agent.

13. The method of claim 12, wherein the wetting agent comprises a polyether compound; and/or the brightening agent comprises at least one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithiocarbonyl propane sulfonate and thiazolidinethione; and/or, the leveling agent comprises an amine compound; and/or, the high resistance agent comprises ethylene thiourea; and/or the toughening agent comprises at least one of organic sulfide with sulfonic acid groups, quaternary amine compounds and amino urea modified polymers.

14. The method of claim 12, wherein the wetting agent comprises at least one of hydroxyethylcellulose and polyethylene glycol.

15. The method of claim 14, wherein the polyethylene glycol has a molecular weight of 6000 to 8000.

16. The method of preparing according to claim 14, wherein the leveling agent comprises at least one of polypeptide protein, gelatin, bone glue, and alkylated polyethylenimine.

17. The method of preparing according to claim 16, wherein the toughening agent comprises at least one of L fatty amine ethoxysulfonate, quaternary amine compound, and semicarbazide-type modified polymer.

18. The method according to claim 17, wherein the electrolyte contains at least one of 50-200mg/L of hydroxyethyl cellulose and 10-100mg/L of polyethylene glycol;

and/or the electrolyte contains 0.2-0.5mg/L ethylene thiourea;

19. The method according to claim 18, wherein when the electrolyte contains at least one of sodium 3-mercapto-1-propane sulfonate and sodium polydithio-dipropane sulfonate and polypeptide protein, the ratio of the amount of each of sodium 3-mercapto-1-propane sulfonate and sodium polydithio-propane sulfonate to the amount of polypeptide protein is 0-1:1.

20. The production method according to claim 19, wherein when sodium polydithio-dipropyl sulfonate and sodium N, N-dimethyl-dithio carbonyl propane sulfonate are contained in the electrolyte at the same time, the use amount ratio of the sodium polydithio-dipropyl sulfonate to the sodium N, N-dimethyl-dithio carbonyl propane sulfonate is 5 to 8:1.

21. A copper foil prepared by the preparation method according to any one of claims 1 to 20.