CN114481233A - Foil generating device for preparing ultrathin electrolytic copper foil and application thereof - Google Patents
Foil generating device for preparing ultrathin electrolytic copper foil and application thereof Download PDFInfo
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Abstract
The invention discloses a raw foil device for preparing an ultrathin electrolytic copper foil and application thereof, belonging to the field of electronic material manufacturing, wherein the device comprises an electrolytic tank, a cathode plate, an anode plate, a flow guide inclined plate, a stirring tank, a flow dividing device, a heating device and a temperature control device; the cathode plate and the anode plate are arranged in the electrolytic cell, and are arranged in parallel, and the distance between the pole plates and the inclination angle of the pole plates are adjustable; the top of the electrolytic cell is connected with the stirring tank through the diversion inclined plate; the bottom of the electrolytic tank is connected with the stirring tank through the shunt device; and a stirring paddle is arranged in the stirring tank. The foil generating device for preparing the ultrathin electrolytic copper foil can be applied to copper salt electrolysis for preparing the ultrathin copper foil, and the obtained ultrathin copper foil is fine in crystal grain and smooth and bright. In addition, the method for preparing the ultrathin electrolytic copper foil has the advantages of simple process, mild condition, good repeatability, stable raw foil parameters, contribution to industrial popularization and the like.
Description
Technical Field
The invention belongs to the field of electronic material manufacturing, and particularly relates to a foil generating device for preparing an ultrathin electrolytic copper foil and application thereof.
Background
In the production process of the ultrathin electrolytic copper foil, a cathode usually adopts a pure titanium round roller, an electrolytic tank is semicircular, an anode plate is arranged on the lower surface of the electrolytic tank in a circular arc shape, electrolyte is injected into the electrolytic tank through a pipeline, the cathode continuously rolls to carry out chemical deposition, and the copper foil is obtained through stripping and post-treatment. Generally, in actual production, the diameter of a cathode roller is 1-2 m, the capacity of electrolyte in an electrolytic cell is hundreds of liters, and if parameter adjustment or trial production of new products is needed, a large amount of acid electrolyte and power resources are consumed, so that the method is not environment-friendly.
The existing laboratory device usually adopts a Hall cell to simulate an electrolysis process, metal polar plates are respectively arranged at two sides of the Hall cell, a copper sulfate and sulfuric acid mixed solution is used as an electrolyte to be injected into the Hall cell, two polar plates are electrified, and copper foil is obtained by deposition on a negative plate. If the device does not stir in the electrolytic process, the electrolyte can not flow, so that the concentration difference is large, and copper ions can not be tightly deposited to obtain the complete copper foil. The complete copper foil can be obtained through electrolysis by introducing the airflow stirring device, but the airflow stirring is usually implemented by opening a hole on a pipeline and injecting inert gas, the size and the direction of the airflow cannot be accurately controlled, so that the thickness of the ultra-thin copper foil below 6 mu m is not uniform during electrolytic deposition, the surface is not flat, the high-quality ultra-thin copper foil cannot be obtained, and further reference basis is difficult to provide for actual production.
Reference documents:
[1] suyao, Panming, Huang Hui, etc. the current state of research and the prospect of additive in the copper electrolytic deposition process [ J ] mining, 2021,30(05):61-69.
[2] The surface treatment technology and additive research progress of electrolytic copper foil [ J ] China non ferrous metal academic newspaper 2021,31(05): 1270-.
Disclosure of Invention
The invention aims to provide a foil generating device for preparing an ultrathin electrolytic copper foil and application thereof.
In order to achieve the above purpose, the solution of the invention is:
a foil generating device for preparing an extremely thin electrolytic copper foil is characterized by comprising an electrolytic bath, a cathode plate, an anode plate, a flow guide inclined plate, a stirring pool, a flow dividing device, a heating device and a temperature control device; the cathode plate and the anode plate are arranged in the electrolytic cell, and are arranged in parallel, and the distance between the pole plates and the inclination angle of the pole plates are adjustable; the top of the electrolytic cell is connected with the stirring tank through the diversion inclined plate; the bottom of the electrolytic tank is connected with the stirring tank through the shunt device; be provided with the stirring rake in the stirring pond, stirring bottom of the pool portion is provided with supersonic generator.
Preferably, the lower ends of the cathode plate and the anode plate are fixed on the rotating shaft, the other ends of the cathode plate and the anode plate can change the angle and the distance of the cathode plate and the anode plate around the rotating shaft, and the inclination angle of the cathode plate and the anode plate ranges from 45 degrees to 90 degrees.
Preferably, the material of the electrolytic cell is one of acrylic, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the height of the electrolytic cell is 100-220 mm, the width is 100-220 mm, and the thickness is 8-26 mm.
Preferably, one end of the diversion inclined plate is connected with the electrolytic cell, the other end of the diversion inclined plate is connected with the stirring tank, and the bottom of the diversion inclined plate and the flow dividing device form a closed hollow structure so as to reduce the usage amount of electrolyte; the heating device is positioned at the outlet of the stirring pool; a temperature control device is placed at each shunt outlet of the shunt device, and the temperature adjusting range is 40-70 ℃.
Preferably, the cathode plate is made of a pure titanium plate or a stainless steel plate, the length of the cathode plate is 80-200 mm, the width of the cathode plate is 80-200 mm, and the thickness of the cathode plate is 1-3 mm; the anode plate is made of one of a titanium iridium-plated plate, a lead plate or a copper plate, the length of the anode plate is 80-200 mm, the width of the anode plate is 80-200 mm, and the thickness of the anode plate is 1-3 mm; the distance between the cathode plate and the anode plate is 6-20 mm; external terminal columns are welded on the tops of the cathode plate and the anode plate and used for being connected with a power supply; the negative plate can be pasted with adhesive tape to change the area of the raw foil, and the area of the raw foil is (10-200) mm x (10-200) mm.
Preferably, the material of the shell of the stirring pool is one of acrylic, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the stirring pool is cylindrical, the diameter of the stirring pool is 40-100 mm, and the height of the stirring pool is 60-130 mm.
Preferably, the stirring paddle is a downward pushing type inclined blade stirring paddle; the stirring paddle is made of one of polytetrafluoroethylene, polypropylene, polyvinyl chloride, acrylic, resin, titanium alloy or stainless steel; the number of the blades of the stirring paddle is 3-6.
Preferably, the ultrasonic generator is positioned at the bottom of the stirring tank, the frequency is 20-40 kHz, and the dispersion degree of copper ions and additives in the stirring tank can be improved, so that the copper ions and the additives are distributed more uniformly.
The application of the green foil device for preparing the ultrathin electrolytic copper foil is characterized by comprising the following steps:
(1) preparing electrolyte: dissolving copper salt in ultrapure water, then adding sulfuric acid and an additive, heating and stirring, and uniformly oscillating by ultrasonic waves;
(2) and (3) treating the cathode plate and the anode plate: cleaning the anode plate by adopting ultrapure water, and drying for later use; polishing the cathode plate by using sand paper, then sequentially carrying out alkali washing, ultrapure water washing, acid washing and ultrapure water washing, and blow-drying for later use;
(3) assembling the cathode plate and the anode plate: attaching an adhesive tape to the cathode plate to form a square shape, wherein the exposed part of the cathode plate, to which the adhesive tape is not attached, is an effective cathode deposition area, then installing the bottoms of the cathode plate and the anode plate on an electrolytic bath and fixing, and adjusting the angles of the cathode plate and the anode plate;
(4) and (2) adding the electrolyte prepared in the step (1) into an electrolytic bath for electrolytic reaction to prepare the ultrathin copper foil.
Preferably, said in step (4)The temperature of the electrolytic reaction is 40-70 ℃, and the current density of the electrolytic reaction is 0.1-1.5A/cm2The time of the electrolytic reaction is 10 to 120 s.
Compared with the existing electrolytic copper foil raw foil device and the method for preparing the copper foil, the principle and the gain effect of the invention are as follows:
1. the foil generating device for the electrolytic copper foil provided by the invention can enable the electrolyte to be pushed by the stirring paddle, enter the electrolytic tank through the sub-runner below for electrolytic deposition, and then flow back to the stirring tank from the upper part of the electrolytic tank through the inclined plate. Therefore, the electrolyte can form a stirring-shunting-electrolysis-refluxing mode, can be recycled without discharge, and can furthest reduce the influence of the discharge of copper salt solution, sulfuric acid and various additives used in the electrolysis process on the environment.
2. The method for preparing the copper foil provided by the invention adopts a copper salt solution as an electrolyte, under the action of direct current, anions move to an anode, and cations move to a cathode, so that the copper ions obtain two electrons at the cathode, are reduced into copper, and are deposited on the cathode to generate the copper foil. In order to prepare the ultrathin copper foil with the thickness of less than 6 mu m, the current and the electrolysis time need to be controlled very accurately, and the electrolysis time of the method provided by the invention is 10-120 s, so that the high-quality ultrathin copper foil with uniform thickness and smooth surface can be prepared; the electrolytic copper foil generation device adopts a mechanical stirring and ultrasonic vibration mode, the structure, the stirring speed and the ultrasonic frequency of the stirring paddle can be adjusted, and the shunting device is added, so that copper ions near the cathode plate can be uniformly distributed to the maximum extent, and the copper foil with uniform thickness is obtained through electrolysis; in addition, the front end of the shunt device is provided with a heating rod for heating, and the tail end of the shunt device is provided with a thermocouple, so that the constant temperature during electrolysis can be ensured to the maximum extent.
3. The raw foil preparation method for the copper foil provided by the invention also has the advantages of simple process, mild condition, good repeatability, stable raw foil parameters, contribution to industrial popularization and the like, provides a new experimental device for preparing high-quality ultrathin copper foil, and develops a new idea.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for producing a green foil of an extra thin electrolytic copper foil according to the present invention;
in the drawings: 1. the device comprises an electrolytic bath, 2 parts of a cathode plate, 3 parts of an anode plate, 4 parts of a flow guide inclined plate, 5 parts of a stirring tank, 6 parts of a stirring paddle, 7 parts of a flow dividing device and 10 parts of an ultrasonic generator.
FIG. 2 is a top view showing the structure of a green sheet forming apparatus for producing an extra thin electrolytic copper foil according to the present invention;
in the drawings: 8. heating device and 9. temperature control device.
FIG. 3 is a microstructure (magnification ×. 5000) of the copper foil in example 2 prepared by the apparatus for producing an extremely thin green electrolytic copper foil of the present invention.
FIG. 4 shows the microstructure (magnification ×. 5000) of the copper foil in example 3 produced by the apparatus for producing an extremely thin raw electrolytic copper foil of the present invention.
FIG. 5 shows the microstructure (magnification ×. 5000) of the copper foil in example 4 prepared by the apparatus for producing an extremely thin raw electrolytic copper foil of the present invention.
FIG. 6 shows the microstructure (magnification ×. 5000) of the copper foil in example 5 prepared by the apparatus for producing an extremely thin raw electrolytic copper foil of the present invention.
FIG. 7 shows the microstructure (magnification ×. 5000) of the copper foil in example 6 produced by the apparatus for producing an extremely thin raw electrolytic copper foil of the present invention.
FIG. 8 shows the microstructure (magnification ×. 5000) of the copper foil of comparative example 1 electrolytically fabricated using a Hall cell.
Detailed Description
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention.
Example 1
FIG. 1 shows a schematic structural diagram of a green sheet apparatus for producing an extra thin electrolytic copper foil according to the present invention: in order to achieve the above purpose, the solution of the invention is:
a foil generating device for preparing an extremely-thin electrolytic copper foil comprises an electrolytic tank, a cathode plate, an anode plate, a flow guide inclined plate, a stirring tank, a flow dividing device, a heating device and a temperature control device; the cathode plate and the anode plate are arranged in the electrolytic cell, and are arranged in parallel, and the distance between the pole plates and the inclination angle of the pole plates are adjustable; the top of the electrolytic cell is connected with the stirring tank through the diversion inclined plate; the bottom of the electrolytic tank is connected with the stirring tank through the shunt device; be provided with the stirring rake in the stirring pond, stirring bottom of the pool portion is provided with supersonic generator.
The lower extreme of negative plate and anode plate is fixed on the rotation axis, and the other end can change the angle and the distance of negative and anode plate around the rotation axis, the inclination angle scope of negative and anode plate is 45 ~ 90.
The material of the electrolytic cell is one of acrylic, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the height of the electrolytic cell is 100-220 mm, the width is 100-220 mm, and the thickness is 8-26 mm.
One end of the flow guide sloping plate is connected with the electrolytic cell, the other end of the flow guide sloping plate is connected with the stirring tank, and the bottom of the flow guide sloping plate and the flow dividing device form a closed hollow structure so as to reduce the using amount of electrolyte; the heating device is positioned at the outlet of the stirring pool; a temperature control device is placed at each shunt outlet of the shunt device, and the temperature adjusting range is 40-70 ℃.
The cathode plate is made of a pure titanium plate or a stainless steel plate, the length of the cathode plate is 80-200 mm, the width of the cathode plate is 80-200 mm, and the thickness of the cathode plate is 1-3 mm; the anode plate is made of one of a titanium iridium-plated plate, a lead plate or a copper plate, the length of the anode plate is 80-200 mm, the width of the anode plate is 80-200 mm, and the thickness of the anode plate is 1-3 mm; the distance between the negative plate and the positive plate is 6-20 mm; external terminal columns are welded on the tops of the cathode plate and the anode plate and used for being connected with a power supply; the negative plate can be pasted with an adhesive tape to change the area of the raw foil, and the area of the raw foil is (10-200) mmX (10-200) mm.
The shell of the stirring pool is made of one of acrylic, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the stirring pool is cylindrical, the diameter of the stirring pool is 40-100 mm, and the height of the stirring pool is 60-130 mm.
The stirring paddle is a downward pushing type inclined blade stirring paddle; the stirring paddle is made of one of polytetrafluoroethylene, polypropylene, polyvinyl chloride, acrylic, resin, titanium alloy or stainless steel; the number of the blades of the stirring paddle is 3-6.
The ultrasonic generator is located at the bottom of the stirring tank, the frequency is 20-40 kHz, the dispersity of copper ions and additives in the stirring tank can be improved, and the copper ions and the additives are distributed more uniformly.
In order to more clearly understand the design of the invention, a structural top view of an extra thin electrolytic copper foil green foil experimental device is specially provided, as shown in FIG. 2; the heating device is positioned at the outlet of the stirring pool and is an electric heating rod; a temperature control device is placed at each shunt outlet of the shunt device and is a thermocouple, and the adjustable temperature range is 40-70 ℃.
Example 2
The specific preparation process of the copper foil green foil by adopting the device for preparing the ultrathin electrolytic copper foil green foil provided by the invention comprises the following steps:
(1) preparing electrolyte, wherein the content of copper ions (copper sulfate) is 80g/L, the content of sulfuric acid is 90g/L, the content of additives is 100mg/L of collagen, the content of chloride ions (dilute hydrochloric acid) is 40mg/L, and the content of sodium polydithio-dipropyl sulfonate is 12mg/L, and heating to 55 ℃ by using a heating rod;
(2) respectively taking a pure titanium plate with the thickness of 100mm multiplied by 100mm as a cathode plate and a titanium iridium-plated plate as an anode plate, polishing a copper ion deposition surface of the cathode plate by using No. 800, 1500 and 3000 abrasive paper, cleaning the copper ion deposition surface with ultrapure water, drying the copper ion deposition surface by blowing, then performing alkali cleaning, ultrapure water washing, acid cleaning and ultrapure water washing, drying the copper ion deposition surface for later use, cleaning the anode plate with the ultrapure water, and drying the anode plate for later use;
(3) sticking an adhesive tape on the central part of the copper ion deposition surface of the cathode plate to ensure that the exposed part, namely the effective deposition area is 30mm multiplied by 60mm, adjusting the inclination angle of the two polar plates to be vertical to the bottom edge of the electrolytic cell, and ensuring the electrode distance to be 10 mm;
(4) adding 150ml of prepared electrolyte into an electrolytic cell, starting a stirring paddle to rotate at 8000 r/min, starting an ultrasonic generator to reach the frequency of 25KHz, starting a heating rod, monitoring the real-time temperature through a thermocouple, stabilizing the electrolysis temperature at 55 ℃, and keeping the temperature for 120 s;
(5) setting the direct current power supply to be 20A, and electrolyzing for 25 s;
(6) after the electrolysis is finished, turning off a power supply and the stirring paddle;
(7) and taking out the negative plate, cleaning the electrolyte with ultrapure water, drying, slightly tearing off the copper foil with tweezers, putting into a sample bag, and vacuumizing for storage.
The obtained copper foil has a thickness of 3.8 μm, a surface roughness of 0.1588 μm, a microstructure shown in FIG. 3, a weight deviation rate of 4.3% after punching detection, uniform thickness distribution, and smoothness and brightness.
Example 3
Reference example 2 was a stepwise polymerization process for producing a green foil of an extra thin electrolytic copper foil, except that: changing the additive collagen in the step (1) into a cysteine solution, wherein the concentration of the cysteine solution is 50 mg/L; in the step (3), the electrode distance is 15 mm; in the step (5), the current is 12A, and the electrolysis time is 20 s; the rest steps are the same as example 2; the thickness of the obtained copper foil is 3.1 mu m, the surface roughness is 0.1237 mu m, the microstructure is shown in figure 4, the weight deviation rate after punching detection is 4.6%, the thickness distribution is uniform, and the copper foil is flat and bright.
Example 4
Step-polymerization reference example 2 for producing an extra thin electrolytic copper foil green foil, except that: changing the additive collagen in the step (1) into an N-acetylcysteine solution, wherein the concentration of the cysteine solution is 50 mg/L; in the step (3), the electrode distance is 12 mm; in the step (5), the current is 12A, and the electrolysis time is 20 s; the rest steps are the same as example 2; the obtained copper foil has a thickness of 3.3 μm, a surface roughness of 0.1468 μm, a microstructure shown in FIG. 5, a weight deviation rate of 3.9% after punching detection, uniform thickness distribution, and smoothness and brightness.
Example 5
Reference example 2 was a stepwise polymerization process for producing a green foil of an extra thin electrolytic copper foil, except that: changing the additive collagen in the step (1) into an N-acetylcysteine derivative solution, wherein the concentration of the cysteine solution is 50 mg/L; in the step (3), the electrode distance is 10 mm; in the step (5), the current is 10A, and the electrolysis time is 20 s; the rest steps are the same as example 2; the obtained copper foil has a thickness of 3.2 μm, a surface roughness of 0.1226 μm, a microstructure shown in FIG. 6, a weight deviation rate of 3.2% after punching detection, uniform thickness distribution, and smoothness and brightness. The acetylcysteine derivative used in this example is a non-commercial product, and can be synthesized by reference (julienfu, shijiajun, zhao yanmei, heyu, zhangjiakang, smitting, liu shou rong, zhuang wai smile. synthesis of novel acetylcysteine derivative containing disulfide bond and thioester bond and evaluation of anti-liver injury activity [ J ] modern applied medicine in china, 2018, 35 (03): 340-: adding acetylcysteine (5mmol, 816mg) into a 150mL round-bottom flask, adding 50mL dichloromethane, slowly adding a dichloromethane solution (12.5mL) of p-fluorobenzoyl chloride (5.5mmol, 0.65mL) dropwise under ice bath, reacting for 1.5h, and continuing to stir the obtained mixture at room temperature for 4 h; after the reaction was completed, the obtained product was washed with saturated sodium bicarbonate (75 mL. times.3) and saturated sodium chloride (75 mL. times.1), respectively, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and finally dried under vacuum at 50 ℃ for 24 hours to obtain 1.329g of a pure N-acetylcysteine derivative product as a white solid, with a yield of 93.2%. The chemical structure of the synthesized acetylcysteine derivative is shown as follows:
example 6
Reference example 2 was a stepwise polymerization process for producing a green foil of an extra thin electrolytic copper foil, except that: replacing the collagen serving as the additive in the step (1) with a dried orange peel extract solution, wherein the mass percentage concentration of the dried orange peel extract solution is 7%; in the step (3), the electrode distance is 10 mm; the current in the step (5) is 10A, the electrolysis time is 20s, and the rest steps are the same as the step 2; the thickness of the obtained copper foil is 3.0 μm, the surface roughness is 0.1588 μm, the microstructure is shown in figure 7, the weight deviation rate after punching detection is 4.2%, the thickness distribution is uniform, and the copper foil is flat and bright. The preparation steps of the dried orange peel extract solution used in this example are as follows: soaking 20g of pericarpium Citri Tangerinae powder in 200ml of ethanol for more than 48h, refluxing at 75 deg.C for more than 2h, cooling, vacuum filtering to remove insoluble substances, and evaporating excessive ethanol to obtain pericarpium Citri Tangerinae extract. Then putting the filtered solid insoluble substances into a drying oven for drying, and weighing to obtain the dried orange peel extract with the weight of 7 g; adding deionized water into 7g of the dried orange peel extract to fix the volume to 100mL to obtain the additive with the dried orange peel extract mass percentage concentration of 7%.
Comparative example 1
The method adopts a common Hall groove device, and the specific preparation process comprises the following steps:
(1) preparing electrolyte, wherein the content of copper ions is 80g/L, the content of sulfuric acid is 90g/L, the content of additives is 100mg/L of collagen, the content of chloride ions (dilute hydrochloric acid) is 40mg/L, and the content of sodium polydithio-dipropyl sulfonate is 12mg/L, and heating the electrolyte to 55 ℃ by using a heating rod;
(2) respectively taking a pure titanium plate with the thickness of 100mm multiplied by 100mm as a cathode plate and a titanium iridium-plated plate as an anode plate, polishing a copper ion deposition surface of the cathode plate by using No. 800, 1500 and 3000 abrasive paper, cleaning the copper ion deposition surface with ultrapure water, drying the copper ion deposition surface by blowing, then performing alkali cleaning, ultrapure water washing, acid cleaning and ultrapure water washing, drying the copper ion deposition surface for later use, cleaning the anode plate with the ultrapure water, and drying the anode plate for later use;
(3) sticking an adhesive tape on the central part of the copper ion deposition surface of the cathode plate to ensure that the exposed part, namely the effective deposition area is 30mm multiplied by 60mm, and the electrode spacing is 10 mm;
(4) adding the prepared electrolyte into an electrolytic cell;
(5) setting the direct current power supply to be current 14A, and electrolyzing for 25 s;
(6) after the electrolysis is finished, the power supply is turned off;
(7) and taking out the negative plate, cleaning the electrolyte with ultrapure water, drying, slightly tearing off the copper foil with tweezers, putting into a sample bag, and vacuumizing for storage.
The obtained copper foil had a thickness of 3.1 μm, a surface roughness of 0.4688 μm, a microstructure shown in FIG. 8, a weight deviation ratio of 11.7% after punching detection, non-uniform thickness distribution, and uneven surface.
From the above results, it can be seen that the high-quality ultra-thin copper foil with uniform thickness and smooth surface can be prepared by using the ultra-thin electrolytic copper foil green foil experimental device provided by the invention for only 20s, which fully proves that the ultra-thin electrolytic copper foil green foil experimental device and the preparation method provided by the invention can not only prepare the ultra-thin copper foil with excellent performance, but also reduce pollution and protect the environment, and can bring good economic benefits.
Claims (10)
1. A foil generating device for preparing an ultrathin electrolytic copper foil is characterized by comprising an electrolytic tank (1), a cathode plate (2), an anode plate (3), a flow guide inclined plate (4), a stirring tank (5), a flow dividing device (7), a heating device (8) and a temperature control device (9); the cathode plate and the anode plate are arranged in the electrolytic cell, and are arranged in parallel, and the distance between the pole plates and the inclination angle of the pole plates are adjustable; the top of the electrolytic cell is connected with the stirring tank through the diversion inclined plate; the bottom of the electrolytic tank is connected with the stirring tank through the flow dividing device; be provided with stirring rake (6) in the stirring pond, stirring pond bottom is provided with supersonic generator (10).
2. The foil-producing apparatus for producing an extra thin electrolytic copper foil as claimed in claim 1, wherein the lower ends of said cathode plate and said anode plate are fixed to a rotary shaft, and the other ends thereof are capable of changing the angle and distance of said cathode plate and said anode plate around said rotary shaft, and the inclination angle of said cathode plate and said anode plate is in the range of 45 to 90 °.
3. The green foil producing apparatus for producing an extra thin electrolytic copper foil according to claim 1, wherein the material of the electrolytic bath is one of acryl, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the height of the electrolytic cell is 100-220 mm, the width is 100-220 mm, and the thickness is 8-26 mm.
4. The green foil producing apparatus for producing an extra thin electrolytic copper foil according to claim 1, wherein one end of said sloping plate is connected to said electrolytic bath, and the other end is connected to said stirring tank, and the bottom of said sloping plate and said flow dividing means form a closed hollow structure; the heating device is positioned at the outlet of the stirring pool; and a temperature control device is arranged at the outlet of each branch channel of the flow dividing device.
5. The foil generation apparatus for producing an extra thin electrolytic copper foil according to claim 1, wherein the cathode plate is made of a pure titanium plate or a stainless steel plate, and has a length of 80 to 200mm, a width of 80 to 200mm, and a thickness of 1 to 3 mm; the anode plate is made of one of a titanium iridium-plated plate, a lead plate or a copper plate, the length of the anode plate is 80-200 mm, the width of the anode plate is 80-200 mm, and the thickness of the anode plate is 1-3 mm; the distance between the negative plate and the positive plate is 6-20 mm; and external terminal columns are welded on the tops of the cathode plate and the anode plate and are used for connecting a power supply.
6. The apparatus for producing an ultra-thin green electrolytic copper foil as claimed in claim 1, wherein the stirring tank casing is made of one of acryl, polypropylene, polyvinyl chloride or polytetrafluoroethylene; the stirring pool is cylindrical, the diameter of the stirring pool is 40-100 mm, and the height of the stirring pool is 60-130 mm.
7. The foil producing apparatus for producing an extra thin electrolytic copper foil according to claim 1, wherein the stirring paddle is a push-down type inclined blade stirring paddle; the stirring paddle is made of one of polytetrafluoroethylene, polypropylene, polyvinyl chloride, acrylic, resin, titanium alloy or stainless steel; the number of the blades of the stirring paddle is 3-6.
8. The foil forming apparatus for producing an extra thin electrolytic copper foil according to claim 1, wherein the ultrasonic generator is located at the bottom of the stirring tank at a frequency of 20 to 40 kHz.
9. The use of the green sheet apparatus for producing an extra thin electrolytic copper foil according to claim 1, comprising the steps of:
(1) preparing electrolyte: dissolving copper salt in ultrapure water, then adding sulfuric acid and an additive, heating and stirring, and uniformly oscillating by ultrasonic waves;
(2) and (3) treating the cathode plate and the anode plate: cleaning the anode plate by adopting ultrapure water, and drying for later use; polishing the cathode plate by using sand paper, then sequentially carrying out alkali washing, ultrapure water washing, acid washing and ultrapure water washing, and blow-drying for later use;
(3) assembling the cathode plate and the anode plate: attaching an adhesive tape to the cathode plate to form a square shape, wherein the exposed part of the cathode plate, to which the adhesive tape is not attached, is an effective cathode deposition area, then installing the bottoms of the cathode plate and the anode plate on an electrolytic bath and fixing, and adjusting the angles of the cathode plate and the anode plate;
(4) and (2) adding the electrolyte prepared in the step (1) into an electrolytic bath for electrolytic reaction to prepare the ultrathin copper foil.
10. The use of the green sheet producing apparatus for producing an extra thin electrolytic copper foil as set forth in claim 9, wherein the temperature of the electrolytic reaction in the step (4) is 40 to 70 ℃ and the current density of the electrolytic reaction is 0.1 to 1.5A/cm2The time of the electrolytic reaction is 10 to 120 s.
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