CN113529140B

CN113529140B - Novel electrolytic copper foil production method

Info

Publication number: CN113529140B
Application number: CN202110875703.9A
Authority: CN
Inventors: 贾永良; 胡文义; 胡增开; 何雄英
Original assignee: Fujian Clear View Copper Foils Co ltd
Current assignee: Fujian Clear View Copper Foils Co ltd
Priority date: 2021-07-30
Filing date: 2021-07-30
Publication date: 2022-08-23
Anticipated expiration: 2041-07-30
Also published as: CN113529140A

Abstract

The invention discloses a novel electrolytic copper foil production method, wherein copper electrodeposition is carried out on the surface of a metal annular carrier belt or other suitable flexible material carrier belt, wherein the carrier belt is provided with a path passing through a device, the device comprises a plurality of electrolytic tanks arranged in series, and the path comprises that one side of the carrier belt continuously traverses the plurality of electrolytic tanks and is immersed in electrolyte; adjustable anode plates are correspondingly arranged in each electrolytic tank and filled with electrolytic solution; and continuously depositing copper ions in the plurality of electrolytic tanks along the advancing direction of one side of the carrier belt immersed in the electrolyte to generate copper foil with a denser surface. Compared with the prior art, the method adjusts the process parameters of the electrolytic solution such as concentration, temperature, flow, additives, polar distance and the like in stages according to the characteristics of crystal nucleus formation and growth in the electrolytic copper foil production process, and is beneficial to continuously producing copper foil products with more and more compact and smooth surfaces and physical and mechanical properties meeting application requirements.

Description

Novel electrolytic copper foil production method

Technical Field

The invention relates to the technical field of electrolytic copper foil production, in particular to a novel electrolytic copper foil production method.

Background

The existing electrolytic copper foil production mainly adopts a roll type continuous electrolytic method, and the principle of the method is that cathode copper or wire return material with the same purity as the cathode copper is taken as a raw material, the raw material is dissolved and ionized in acid copper sulfate solution containing sulfuric acid, electrolysis is carried out in an electrolytic tank which takes an insoluble material as an anode and a cathode roll with the bottom part immersed in copper sulfate electrolyte and rotating rapidly as a cathode, copper ions in the solution are deposited on the surface of a cathode roll to form the copper foil, and the thickness of the copper foil is controlled by the current density of the cathode roll and the rotating speed of the cathode roll. Although the method is generally adopted, the defects that the current density adjustment is not flexible, the post-treatment needs to be carried out on a separate device, and particularly thin metal foils cannot be produced exist. Although the current density adjustment at different stages is realized by independently arranging the conductive rollers in different electrolytic cells, at least 2-3 driving rollers and two conductive rollers are needed in each electrolytic cell with the structure, the structure is very complex, the installation and maintenance are inconvenient, and the cost control is not facilitated. Secondly, by adopting the method, the uninterrupted continuous electrodeposition of the carrier belt in the conveying process of different electrolytic tanks cannot be realized, the waste of electric power is caused, and the uncontrollable property of products is increased. Thirdly, the two sides of the carrying belt are plated with metal, and the integrity and all aspects of the performance of the metal coating on the side contacting with the driving roller are easily affected.

The process of electro-crystallization of copper is a rather complicated process, and in the process of forming a cathodically electrodeposited copper foil, there are two parallel processes: formation of crystal nuclei and growth of crystals. In fact, during the electrodeposition of copper foil, some atoms are undergoing nucleation and the other are undergoing crystal growth, and the nucleation rate and the growth rate determine the thickness of the resulting crystal. In the production of a raw foil of an electrolytic copper foil, it is desired that the formation rate of crystal nuclei be made fast and the growth rate of the crystal nuclei be made slow, so that the resulting copper foil has a fine structure and high copper foil performance. Therefore, how to influence the formation and growth speed and process of crystal nuclei, so as to produce copper foil products with fine structure, smooth surface and physical and mechanical properties meeting the application requirements becomes a research subject with great practical significance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a novel electrolytic copper foil production method.

In order to achieve the purpose, the invention provides the following technical scheme:

a novel electrolytic copper foil production process, electrodeposition of copper taking place on the surface of a metal endless carrier belt or other carrier belt of suitable flexible material, wherein said carrier belt has a path through an apparatus comprising a plurality of cells arranged in succession, said path comprising one side of said carrier belt traversing said plurality of cells in succession and being immersed in an electrolyte; adjustable anode plates are correspondingly arranged in each electrolytic tank and filled with electrolytic solution; and continuously depositing copper ions in the plurality of electrolytic tanks along the advancing direction of one side of the carrier belt immersed in the electrolyte to generate copper foil with a denser surface.

Further, the plurality of electrolysis cells comprise at least one or more of the following parameters: the polar distance between the anode plate and one side of the carrying belt immersed in the electrolyte, the acid concentration, the copper concentration, the electrolyte temperature, the electrolyte flow and the types of main additives.

Further, along the advancing direction of one side of the carrying belt immersed in the electrolyte, the polar distance between the anode plate in each electrolytic tank and one side of the carrying belt immersed in the electrolyte is reduced in sequence.

Further, along the advancing direction of the side of the carrying belt immersed in the electrolyte, the acid concentration and/or the copper concentration and/or the electrolyte temperature and/or the electrolyte flow rate in each electrolytic tank are sequentially increased, and/or the types of main additives are sequentially increased.

Further, the polar distance between the anode plate in each electrolytic tank and one side of the carrying belt immersed in the electrolyte is 6-55 mm.

Further, the acid concentration in each electrolytic cell is 90-110g/L, the copper concentration is 80-100g/L, the temperature of the electrolyte is 50-55 ℃, and the liquid inlet flow of the electrolyte is 30-50m ³ /h。

Further, the main additive at least comprises one or more of chloride ions, collagen and a brightening agent SPS.

Furthermore, the electrolytic tank and the anode plates are arranged in a one-to-one correspondence mode, and in the same electrolytic tank, the pole distance of one side, immersed in the electrolyte, of the carrying belt and the pole distance of the anode plates arranged correspondingly are set to be equal everywhere.

Further, one side of the carrying belt is immersed in the electrolyte and is arranged in parallel with the anode plate correspondingly arranged.

According to another aspect of the present invention, there is provided a copper foil product prepared by any one of the methods as described above.

The invention has the beneficial effects that:

the invention adjusts the process parameters of the concentration, the temperature, the flow, the additive, the polar distance and the like of the electrolytic solution in stages according to the characteristics of crystal nucleus formation and growth in the electrolytic copper foil production process, and is beneficial to continuously producing the copper foil product with more and more compact and smooth surface and physical and mechanical properties which can meet the application requirements.

Drawings

FIG. 1 is a schematic view of a novel electrolytic copper foil forming apparatus according to the present invention.

Fig. 2 is a schematic cross-sectional view a-a of a carrier tape according to an embodiment of the invention.

The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", "one side", "the other side", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be configured and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "disposed", "connected", and the like are to be construed broadly, such as "connected", may be fixedly connected, or detachably connected or integrally connected; can be mechanically or electrically connected; either directly or indirectly through intervening media, or may be interconnected between two elements. The specific meanings of the above terms in the present invention can be specifically understood in specific cases by those of ordinary skill in the art.

The present invention will be described in detail with reference to the following examples.

According to one embodiment of the invention, a novel electrolytic copper foil production method is provided, wherein copper electrodeposition is carried out on the surface of a metal annular carrier belt or other suitable flexible material carrier belt 1, wherein the carrier belt 1 is provided with a path passing through a device, the device comprises a plurality of electrolytic tanks 2 which are arranged in series, and the path comprises that one side of the carrier belt 1 continuously traverses the plurality of electrolytic tanks 2 and is immersed in electrolyte; adjustable anode plates 3 are correspondingly arranged in the electrolytic tanks 1 and filled with electrolytic solution; and along the advancing direction of the side of the carrier belt 1 immersed in the electrolyte, copper ions are continuously deposited in the plurality of electrolytic tanks 2 to generate copper foils with increasingly dense surfaces.

Further, controlling the density of the copper foil produced by the deposition of copper ions in the plurality of electrolytic cells 2 may be achieved by setting at least one or more of the following parameters: the polar distance between the anode plate 3 and one side of the carrying belt 1 immersed in the electrolyte, the acid concentration, the copper concentration, the electrolyte temperature, the electrolyte flow and the types of main additives. Specifically, along the advancing direction of the side of the carrying belt 1 immersed in the electrolyte, the polar distances between the anode plates 3 in the electrolytic cells 2 and the side of the carrying belt 1 immersed in the electrolyte are set to be sequentially reduced. The production of electrolytic copper foil is essentially the process of discharge reduction of copper ions on a cathode by the action of direct current. The distribution of the current on the cathode may affect the uniformity of copper ion deposition to some extent. Experiments show that under certain other conditions, the current can be more uniformly distributed on the surface of the cathode by increasing the polar distance. But the polar distance between the cathode and the anode is increased, the voltage of the cell required by electrolysis is also increased, and thus the electrolysis is realizedMore power is consumed. In the invention, the polar distance ranges from 6 mm to 55 mm. The range of the polar distance is 8-12mm, and the copper foil with more and more compact surface can be continuously produced under the premise of energy conservation and emission reduction by matching with the setting of other process parameters, so that the physical and mechanical properties of the copper foil are improved. Further, along the advancing direction of the side of the carrier tape 1 immersed in the electrolyte, the acid concentration and/or the copper concentration and/or the electrolyte temperature and/or the electrolyte flow rate in each electrolytic tank 2 are sequentially increased, and/or the types of main additives are sequentially increased. The acid concentration in each electrolytic tank 2 is 90-110g/L, the copper concentration is 80-100g/L, the electrolyte temperature is 50-55 ℃, and the electrolyte inlet flow is 30-50m ³ H is used as the reference value. The main additive at least comprises one or more of chloride ions, collagen and brightener SPS.

A novel electrolytic copper foil forming device comprises a metal titanium carrying belt 1, three vertical electrolytic tanks 2 which are arranged in parallel and adjacently, a passivation treatment device 6 and a winding device 7. The metal titanium carrying belt 1 is circularly driven by the transmission component group, and the lower side of the metal titanium carrying belt 1 passes through the gaps reserved on the side walls of the adjacent electrolytic tanks 2, traverses the plurality of electrolytic tanks 2 and is immersed in the electrolyte. The inner side surface and the front and rear end surfaces of the metal titanium carrier tape 1 are sealed by insulating layers 4. In each electrolytic tank 2, an anode plate 3 with adjustable height is respectively arranged below the lower side of the metal titanium carrying belt 1. In the same electrolytic tank 2, the distance between the lower side of the metal titanium carrying belt 1 and the anode plate 3 is equal everywhere. Specifically, the lower side of the metal titanium carrying belt 1 and the anode plate 3 are arranged in parallel in a flat plate type. The anode plate 3 is connected with the positive pole of direct current, and the carrying belt 1 is connected with the negative pole of direct current by respectively arranging

conductive rollers

501 and 502 on the first lower transmission piece 51 and the second lower transmission piece 52. An electrolyte inlet and an electrolyte outlet are arranged on the side walls of two opposite sides of the electrolytic tank 2 at the position 12-80mm below one side of the metal titanium carrying belt 1 immersed in the electrolyte. The distances between the anode plate 3 and the lower side of the metal titanium carrying belt 1 are 12mm,10mm and 8mm in sequence along the advancing direction of the metal titanium carrying belt 1 immersed in the electrolyte. Along the advancing direction of the side of the metal titanium carrying belt 1 immersed in the electrolyte, the concentration, the temperature, the flow rate and the additive type of the electrolyte solution filled in each electrolytic tank are sequentially increased. And the width of the electrolytic tank is reduced in sequence along the advancing direction of the metal titanium carrying belt 1 immersed in the electrolyte. That is, in each electrolytic cell, the length of the metallic titanium carrier tape 1 immersed in the electrolytic solution is successively reduced. The produced copper foil is peeled off from the peeling roller 503, fed into a potassium dichromate solution filled with an appropriate concentration to produce a chromium oxidation preventive layer, and then fed into the take-up unit 7 to be wound.

Examples

A novel electrolytic copper foil forming device comprises a metal titanium carrying belt 1, three vertical electrolytic tanks 2 arranged in parallel and adjacently, a passivation treatment device 6 and a winding device 7. The metal titanium carrying belt 1 is circularly driven by the driving group, and the lower side of the metal titanium carrying belt 1 passes through the gaps reserved on the side walls of the adjacent electrolytic tanks 2 to cross the plurality of electrolytic tanks 2 and is immersed in the electrolyte. In each electrolytic tank 2, an anode plate 3 with adjustable height is respectively arranged below the lower side of the metal titanium carrying belt 1, and the lower side of the metal titanium carrying belt 1 and the anode plate 3 are arranged in a flat plate type parallel manner. The anode plate 3 is connected with a direct current anode, and the carrying belt 1 is connected with a direct current cathode by arranging

conductive rollers

501 and 502 on the first lower transmission piece 51 and the second lower transmission piece 52 respectively. The distances between the anode plate 3 and the lower side of the metal titanium carrying belt 1 are 12mm,10mm and 8mm in sequence along the advancing direction of the side, immersed in the electrolyte, of the metal titanium carrying belt 1. Along the advancing direction of one side of the metal titanium carrying belt 1 immersed in the electrolyte, the concentration, the temperature, the flow and the additive type of the electrolyte solution filled in each electrolytic tank are sequentially increased. Specifically, along the advancing direction of one side of the metal titanium carrying belt 1 immersed in the electrolyte, the acid content in the three electrolytic tanks 2 is as follows in sequence: 90-100g/l,90-100g/l,100-110 g/l; the copper content is as follows in sequence: 80-90g/l, 90-95g/l, 95-100 g/l; the temperature of the electrolyte is 50 ℃, 53 ℃ and 55 ℃ in sequence; the inlet flow/flow velocity of the electrolyte is 30m in sequence ³ /h，40m ³ /h，50m ³ The additive comprises chloride ions, collagen, chloride ions, collagen and a brightening agent SPS in sequence. The resulting copper foil is peeled off from the peeling roller 542, and fed to the fillingA chromium oxidation-proof layer is generated in the potassium dichromate solution with proper concentration, and then the solution is sent into a rolling device 7 for rolling. Copper foils with thicknesses of 6, 8 and 9 μm were produced by the method, and physical and chemical property parameters thereof were measured as shown in table 1.

TABLE 1 examples physicochemical property parameters for copper foil production

Comparative example 1

A comparative test is carried out by a traditional cathode roller direct current electrolytic method, the acid content of the electrolyte is 90-100g/l, the copper content is 80-90g/l, the temperature of the electrolyte is 50 ℃, and the inlet flow/flow rate of the electrolyte is 30m ³ The additive is chloride ion, the polar distance is 12mm, copper foils with the thickness of 6 micrometers, copper foils with the thickness of 8 micrometers and copper foils with the thickness of 9 micrometers are produced respectively, and the physical and chemical performance parameters are shown in table 2 after testing.

TABLE 2 physicochemical properties of copper foil produced in comparative example 1

Comparative example 2

A comparative test is carried out by a traditional cathode roller direct current electrolytic method, the acid content of the electrolyte is 90-100g/l, the copper content is 90-95g/l, the temperature of the electrolyte is 53 ℃, and the inlet flow/flow speed of the electrolyte is 40m ³ The additives are chloride ions and collagen, the polar distance is 10mm, copper foils with the thicknesses of 6 micrometers, 8 micrometers and 9 micrometers are respectively produced, and the physical and chemical performance parameters are shown in table 3 after testing.

TABLE 3 physicochemical properties of copper foil produced in comparative example 2

Comparative example 3

A comparative test is carried out by a traditional cathode roller direct current electrolysis method, the acid content of the electrolyte is 100-110g/l, the copper content is 95-100g/l, the temperature of the electrolyte is 55 ℃, and the inlet flow/flow speed of the electrolyte is 50m ³ The additive is chloride ion, collagen and brightener SPS, the polar distance is 8mm, copper foils with the thickness of 6 micrometers, copper foils with the thickness of 8 micrometers and copper foils with the thickness of 9 micrometers are respectively produced, and the physical and chemical performance parameters are shown in table 4 after testing.

TABLE 4 physicochemical properties of copper foil produced in comparative example 3

Comparing the above tables, the invention adjusts the process parameters of concentration, temperature, flow, additive, polar distance and the like of the electrolytic solution by stages according to the characteristics of crystal nucleus formation and growth in the electrolytic copper foil production process, and is beneficial to continuously producing copper foil products with more and more compact and smooth surfaces and physical and mechanical properties meeting the application requirements.

The embodiments in the above embodiments can be further combined or replaced, and the embodiments are only used for describing the preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and various changes and modifications made to the technical solution of the present invention by those skilled in the art without departing from the design idea of the present invention belong to the protection scope of the present invention.

Claims

1. A method for producing an electrolytic copper foil is characterized in that,

electrodeposition of copper occurs on the surface of a metal endless carrier belt or other suitable flexible material carrier belt, wherein said carrier belt has a path through an apparatus comprising a plurality of cells arranged in succession, said path comprising one side of said carrier belt traversing said plurality of cells arranged in succession and being immersed in an electrolyte;

adjustable anode plates are correspondingly arranged in each electrolytic tank and filled with electrolytic solution;

the polar distances between the anode plates of the plurality of continuously arranged electrolytic tanks and the side of the carrier belt, which is immersed in the electrolyte, are sequentially reduced along the advancing direction of the side of the carrier belt, which is immersed in the electrolyte; the acid concentration, the copper concentration, the electrolyte temperature and the electrolyte flow are increased in sequence; the types of the main additives at least comprise one or more of chloride ions, collagen and brightener SPS, and the types of the main additives are increased in sequence;

and continuously depositing copper ions in the plurality of continuously arranged electrolytic tanks along the advancing direction of one side of the carrier belt immersed in the electrolyte to generate copper foil with increasingly dense surface.

2. The method for producing an electrolytic copper foil as claimed in claim 1, wherein a polar distance between the anode plate and a side of the carrier tape immersed in the electrolyte in each of the electrolytic cells is 6 to 55 mm.

3. The method for producing electrolytic copper foil according to claim 2, wherein the acid concentration in each of the electrolytic cells is 90 to 110g/L, the copper concentration is 80 to 100g/L, the temperature of the electrolyte is 50 to 55 ℃, and the feed rate of the electrolyte is 30 to 50m 3/h.

4. The method as claimed in claim 1, wherein the electrolytic bath is provided in one-to-one correspondence with the anode plates, and the pole pitch of the anode plates provided in correspondence with the side of the carrier tape immersed in the electrolyte is set to be equal everywhere in the same electrolytic bath.

5. The method for producing electrolytic copper foil according to claim 4, wherein the carrier tape is immersed in the electrolyte and is disposed in parallel with the anode plate disposed correspondingly.