A preparation device and preparation method of electrolytic metal foil

Abstract

The present invention relates to a preparation device and preparation method of an electrolytic metal foil, wherein the preparation device of the electrolytic metal foil comprises: an electrolytic cell, a cathode system, an anode system and an insulating partition; wherein the cathode system comprises a rotating device and a cathode; the cathode is located in the electrolytic cell; the rotating device is connected to the cathode to drive the cathode to rotate during the electrolytic deposition process; the anode system comprises an anode; wherein the anode is placed in the electrolytic cell and arranged around the cathode; the insulating partition is placed in the electrolytic cell and is located between the cathode and the anode; the insulating partition is arranged around the cathode, and the anode is arranged around the insulating partition; a plurality of meshes are provided on the insulating partition to adjust the uniformity of the electrolytic metal foil in the width direction by adjusting the aperture and distribution of the meshes. The electrolytic metal foil preparation device of the present invention can ensure the uniformity of the metal foil, and it is small in size, flexible in operation, and can meet industrial production conditions, providing an experimental device for the development of high-performance electrolytic metal foil preparation technology.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic metal foil production, and in particular to a preparation device and method of electrolytic metal foil. Background Art

[0002] Copper foil refers to an extremely thin material of copper. Copper and copper alloy sheets with a thickness of less than 200μm are called copper foil. According to different production processes, industrial copper foil can be divided into rolled copper foil and electrolytic copper foil. Compared with the complex technology and small application scale of rolled copper foil, electrolytic copper foil has a lower production cost and a large application scale, and is the main type of copper foil. Electrolytic copper foil can be divided into lithium battery copper foil and electronic circuit copper foil according to different application fields.

[0003] Lithium battery copper foil is commonly used in power batteries, 3C digital, energy storage systems and other fields. It is the key basic material for the negative electrode of lithium batteries. In lithium-ion batteries, it is not only a carrier of negative electrode active materials, but also a collector and conductor of negative electrode electrons. Against the background of increasing demand for the mileage of new energy vehicles, the thinning of lithium battery copper foil helps to improve the energy density of batteries. The thinning of thickness is one of the most important development trends in the lithium battery copper foil industry and has become the main focus of related manufacturers.

[0004] Electronic circuit copper foil is mainly used in the electronic information industry, such as lower-power printed circuit boards (PCBs), copper clad laminates (CCLs), etc. Downstream applications include consumer electronics, automotive electronics, communications equipment, computers, aerospace, etc. Electronic circuit copper foil can be divided into two categories: conventional copper foil and high-performance copper foil. High-performance electronic circuit copper foil has specific requirements on many performance indicators such as profile, thickness, tensile strength, and elongation, and has high technical barriers. The proportion of high-end electronic circuit copper foil products of Chinese domestic enterprises is relatively low, and a large amount of imports are required. The price of China's imported copper foil products has long been higher than that of exported products, indicating that domestic companies still have a gap with leading overseas companies in high-end, high-value-added copper foil products.

[0005] There are two main barriers to the development of high-quality copper foil: one is the cathode roller construction equipment barrier. The core equipment for producing copper foil is the foil machine, and the cathode roller is the technical key to the foil machine. my country's high-performance cathode rollers are mainly imported, and the price is very expensive. At the same time, the equipment customization and debugging time is long. The other is the additive and process control technology barrier. Additives are one of the core technologies of electrolytic copper foil and also the way for my country to achieve overtaking. Additives determine the product performance and use of copper foil. Copper foils for different purposes require different additives; there are many types of them, and they play different roles in the electrodeposition process. Mastering and developing mixed additives is a high-input, long-cycle, and low-output scientific research work. In addition, other formulation conditions include current density, electrolyte temperature, electrolyte pH value, electrolyte cleanliness, etc. For the above research, a large number of experiments are often required. If the experiment is conducted directly on the production line or pilot line, the cost is huge. Therefore, it is particularly important to develop an experimental device close to actual production.

[0006] At present, the common method for conducting electrolytic copper foil production experiments in the laboratory is flat-plate electrolytic deposition. The cathode and anode are uniformly flat and placed in parallel, and the solution is circulated by stirring or water pumping. Although this method can produce copper foil materials, due to the uneven distribution of the electric field of the flat-plate electrode and the difficulty in making the solution flow rate on the cathode surface uniform due to the circulation of the solution, the copper foil thickness, strength, elongation and other properties are often uneven.

[0007] In addition, the electrolytic copper foil system used in industry can solve the problem of inhomogeneity encountered in the laboratory. The electrolytic copper foil system mainly includes multiple stages such as copper dissolution, filtration, additive addition and foil production. Its operation process is to generate copper sulfate solution through chemical reaction of sulfuric acid and copper material under heating conditions in the copper dissolution tank and multiple filtration, and then enter the electroplating tank of the foil production machine through the pipeline; the additive is connected to the liquid inlet pipe of the foil production machine through the liquid inlet pipe, and enters the electroplating tank after being fully mixed with copper sulfate; through direct current, the Cu in the electrolyte between the cathode and the anode in the electroplating tank 2+Reduced to Cu to obtain copper foil. Among them, during the copper electrodeposition process, the current between the cathode and anode is not evenly distributed, especially the edge power lines of the cathode roller and the anode roller are densely distributed, which will produce an "edge effect". Therefore, auxiliary cathodes are added to both sides of the electrolytic cell, and cooperate with the sealing rubber O-rings on the edge of the titanium roller to reduce this "edge effect". The electrolytic copper foil system can greatly improve the problem of copper foil non-uniformity through precise equipment configuration, and can be produced continuously in large quantities. However, the cost of the electrolytic copper foil system is relatively high (several million yuan / unit), and the consumables such as copper, water, and acid used are extremely large and extremely consumable, making it difficult to use for experimental exploration of electrolytic copper foil. In addition, the electrolytic copper foil system in the industry has complex equipment and a stable layout, making it difficult to effectively adjust the equipment parameters; since the electrolytic copper foil system is a non-interrupted continuous production, when the electrolytic deposition parameters change, it is also difficult to judge the changes in the properties of the copper foil caused; more importantly, the additives are separated from the foil machine by a distance, and it is difficult to quickly and accurately feedback the properties of the copper foil when the additives change. Summary of the invention

[0008] In view of this, the present invention provides a device and method for preparing an electrolytic metal foil, the main purpose of which is to ensure the uniformity of the prepared electrolytic metal foil.

[0009] In order to achieve the above object, the present invention mainly provides the following technical solutions:

[0010] In one aspect, an embodiment of the present invention provides a device for preparing an electrolytic metal foil, wherein the device for preparing an electrolytic metal foil comprises:

[0011] Electrolyzer;

[0012] A cathode system, the cathode system comprising a rotating device and a cathode; wherein the cathode is located in the electrolytic cell; the rotating device is connected to the cathode to drive the cathode to rotate during the electrolytic deposition process;

[0013] An anode system, the anode system comprising an anode; wherein the anode is placed in the electrolytic cell and arranged around the cathode;

[0014] An insulating partition is placed in the electrolytic cell and located between the cathode and the anode; wherein the insulating partition is arranged around the cathode, and the anode surrounds the insulating partition; a plurality of mesh holes are provided on the insulating partition to adjust the uniformity of the electrolytic metal foil in the width direction by adjusting the aperture and distribution of the mesh holes.

[0015] Preferably, the cathode is made of any one of titanium, titanium alloy and stainless steel.

[0016] Preferably, the cathode is a roller cathode; preferably, the roller cathode includes a top surface, a bottom surface and a roller surface; wherein the top surface and the bottom surface are arranged opposite to each other, and the bottom surface is close to the inner bottom of the electrolytic cell, and the top surface is far away from the inner bottom of the electrolytic cell; wherein one end of the roller surface is connected to the top surface, and the other end is connected to the bottom surface; preferably, the bottom surface and the top surface are arranged as insulating surfaces; preferably, the roller surface is a polished surface; further preferably, the roughness Ra of the roller surface is not higher than 0.3μm.

[0017] Preferably, the rotating device comprises:

[0018] Motor;

[0019] A driving shaft, wherein the motor is drivingly connected to one end of the driving shaft, and the other end of the driving shaft is drivingly connected to the cathode;

[0020] Preferably, the rotating device further comprises a support frame; wherein the motor is mounted on the support frame.

[0021] Preferably, a conductive device is connected to the driving shaft, the driving shaft is a conductor, and the driving shaft is connected to the conductive device; preferably, the conductive device is sleeved on the driving shaft.

[0022] Preferably, the anode is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the anode is placed on the inner bottom of the electrolytic cell; preferably, a conductive strip is provided at the upper end of the anode.

[0023] Preferably, the material of the anode is selected from any one of copper, lead-antimony alloy, lead-silver alloy, and coated titanium plate; preferably, the coating in the coated titanium plate is selected from any one of iridium tantalum, lead dioxide, ruthenium dioxide, and iridium dioxide.

[0024] Preferably, the effective area ratio of the anode and cathode is (1:1)-(1.5:1), and the spacing distance is 1-5 cm.

[0025] Preferably, the cathode is completely located in the electrolytic cell, the cathode is completely located in the space surrounded by the insulating partition, and the cathode is completely located in the space surrounded by the anode.

[0026] Preferably, the central axes of the cathode and the anode are located on the same straight line.

[0027] Preferably, the insulating partition is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the insulating partition is placed on the inner bottom of the electrolytic cell.

[0028] Preferably, the mesh on the insulating partition meets the following requirements: the opening rate of the upper end part of the insulating partition is 10-44%, the opening rate of the lower end part is 10-44%, and the opening rate of the middle part is 16-70%, so as to regulate the uniformity of the electrolytic metal foil in the width direction.

[0029] Preferably, the device for preparing the electrolytic metal foil further comprises:

[0030] A heat exchange tank, wherein the electrolytic cell is placed in the heat exchange tank;

[0031] A liquid feeding pipe, the bottom of the electrolytic cell is connected to the liquid feeding pipe;

[0032] A circulation pump, which is placed in the heat exchange tank and connected to the liquid delivery pipe, and is used to continuously deliver the solution in the heat exchange tank from the bottom of the electrolytic tank into the electrolytic tank; after the electrolytic tank is filled with the solution, the solution will overflow from the upper open end of the electrolytic tank back into the heat exchange tank, thereby realizing the circulation of the solution;

[0033] Preferably, a heat exchange device is provided in the heat exchange tank to exchange heat with the solution in the heat exchange tank;

[0034] Preferably, the volume of solution required by the electrolytic cell metal foil preparation device during the electrolytic deposition process is 0.5-20L.

[0035] Preferably, the device for preparing the electrolytic metal foil is used for electrolytically depositing metal foil; wherein, the metal foil includes pure copper foil, alloy copper foil, graphene composite copper foil, and nickel foil; preferably, the device for preparing the electrolytic metal foil is used for surface treatment of metal foil; preferably, it is used for plating treatment on the surface of the metal foil; preferably, the device for preparing the electrolytic copper foil is used for electroplating decorative treatment, preferably, the part is used as the cathode to electrolytically deposit a decorative coating; preferably, the decorative coating includes a copper coating, a silver coating, a nickel coating, a chromium coating, and a nickel-chromium coating.

[0036] On the other hand, an embodiment of the present invention provides a method for preparing an electrolytic metal foil, wherein the electrolytic metal foil is electrolytically deposited using any of the above-mentioned apparatuses for preparing an electrolytic metal foil.

[0037] Preferably, in the method for preparing the electrolytic metal foil, when electrolytically depositing the metal foil, the current mode includes a direct current mode and a pulse mode; preferably, the current density of the direct current mode is 0.1-120A / dm 2 ; The peak current range of pulse mode is 10-5000A / dm 2 The current on and off times of a pulse cycle are 0.1-1000ms and 100-5000ms respectively.

[0038] Preferably, in the method for preparing the electrolytic metal foil, the temperature is 0-90° C. during the electrolytic deposition of the metal foil; preferably, the temperature control mode includes one or a combination of a constant mode, an increasing mode, and a decreasing mode;

[0039] Preferably, in the method for preparing the electrolytic metal foil, during the electrolytic deposition of the metal foil, the solution flow rate is 0.01-10 m / s. 3 / h, the cathode speed range is 0-1500rpm / min; further preferably, the mechanical properties and surface quality of the electrolytic copper foil can be adjusted by adjusting the cathode speed;

[0040] Preferably, after the electrolytic metal foil is electrolytically deposited using the preparation method of the electrolytic metal foil, the thickness of the electrolytic metal foil obtained is in the range of 4-200 μm, the thickness error is within 5%, and the area range is 8-500 cm 2 .

[0041] Compared with the prior art, the device and method for preparing the electrolytic metal foil of the present invention have at least the following beneficial effects:

[0042] On the one hand, an embodiment of the present invention provides a device for preparing an electrolytic metal foil, which includes an electrolytic cell, a cathode system, an anode system and an insulating partition. The cathode system includes a rotating device and a cathode; the cathode is located in the electrolytic cell; the rotating device is connected to the cathode to drive the cathode to rotate during the electrolytic deposition process. The anode system includes an anode; the anode is placed in the electrolytic cell and arranged around the cathode. The insulating partition is placed in the electrolytic cell and is located between the cathode and the anode; the insulating partition is arranged around the cathode and the anode is arranged around the insulating partition; a plurality of mesh holes are provided on the insulating partition to adjust the uniformity of the electrolytic metal foil in the width direction by adjusting the aperture and distribution of the mesh holes. Here, taking electrolytic copper foil as an example, the electrolytic metal foil provided in this embodiment drives the cathode to rotate through a rotating device when electrolytically depositing copper foil, so that the flow rate of the solution in contact with each part of the cathode can be the same, and then the concentration of copper ions and additives on the cathode surface can be kept uniform, thereby ensuring the thickness and performance uniformity of the copper foil along the length direction of the copper foil (along the circumference direction of the cathode), while it is difficult to ensure the uniformity of the solution on the flat cathode surface in the existing flat electrolytic cell deposition device. In addition, the embodiment of the present invention adopts the anode shielding method, that is, an insulating partition is placed between the cathode and the anode, and the uniformity of the thickness and performance of the copper foil along the width direction of the copper foil (along the cathode height direction) can be achieved by adjusting the mesh size and distribution along the cathode height direction, while the anode shielding of the flat electrolytic cell is relatively complicated and the effect is poor, because it is necessary to take care of the electric field shielding of the anode plate up and down, left and right, and at right angles. Therefore, the metal foil preparation device provided in this embodiment can prepare a uniform copper foil sample (excellent uniformity of thickness and performance), and has a simple and ingenious structure and low cost. Similarly, when the preparation setting of the electrolytic metal foil provided in this embodiment is used to electrolytically deposit other metals, the same technical effect is also achieved.

[0043] Furthermore, the preparation device of the electrolytic metal foil provided by the embodiment of the present invention uses a small volume of solution (0.5-20L) in the process of preparing the metal foil, which is far lower than the solution volume requirement of tens of cubic meters of the industrial device; accordingly, the electrolytic metal foil prepared by the present invention has a small area, consumes less metal (copper) and power, and thus the test cost is significantly reduced. At the same time, the operation of the electrolytic metal foil device provided by the present invention is more flexible, and can timely reflect the changes in additive parameters such as type or concentration, while the industrial system electrolytic copper foil device system is longer (occupying hundreds of square meters) and more complex. When the additive parameters change, the change can be seen on the copper foil after a delay of a period of time, and the delay time is difficult to accurately determine. The flexibility of the electrolytic metal foil device provided by the embodiment of the present invention is also reflected in the ability to effectively adjust the additive parameters by replacing the solution. In the industrial electrolytic copper foil device, additives can only be added continuously. Although the filter can filter out some polymer additives, it cannot eliminate small molecule additives or other inorganic additives, so it is difficult to effectively adjust the additives.

[0044] Furthermore, the thickness and performance of the metal foil (copper foil) prepared by the electrolytic metal foil preparation device provided in the embodiment of the present invention are uniform, which is significantly better than the flat electrolytic cell deposition device commonly used in the current laboratory. The electrolytic metal foil device of the present invention uses a circulation pump to circulate the solution from bottom to top, which can replenish metal ions and additives in time, and can also discharge oxygen and hydrogen generated in the process of electrolytic deposition of metal foil in time, which helps to reduce the pinholes of the metal foil (copper foil) and further improve its surface quality.

[0045] On the other hand, an embodiment of the present invention further provides a method for preparing an electrolytic metal foil, which uses the above-mentioned device for preparing an electrolytic metal foil to electrolytically deposit the metal foil, so it has the above-mentioned beneficial effects, which will not be repeated here.

[0046] In summary, the electrolytic metal foil device and preparation method of the embodiment of the present invention can produce metal foil with excellent thickness and performance uniformity, and also has the characteristics of low cost and flexible operation, which greatly meets the needs of developing experimental devices and preparation methods for high-performance electrolytic metal foil, and therefore has huge application prospects.

[0047] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 It is a structural schematic diagram of a device for preparing an electrolytic metal foil provided by an embodiment of the present invention;

[0049] Figure 2 is a top view of a device for preparing an electrolytic metal foil provided by an embodiment of the present invention;

[0050] Figure 3 is a cross-sectional view of a central plane of a device for preparing an electrolytic metal foil provided by an embodiment of the present invention;

[0051] Figure 4 This is a physical picture of a copper foil prepared in a comparative example.

[0052] Figure 5 This is a physical picture of a copper foil prepared according to an experimental example of the present invention. DETAILED DESCRIPTION

[0053] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention application are described in detail below in conjunction with the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "embodiment" does not necessarily refer to the same embodiment. In addition, specific features, structures, or characteristics in one or more embodiments may be combined in any suitable form.

[0054] In view of the equipment problems encountered in the exploration of electrolytic copper foil mentioned in the background technology, the embodiment of the present invention provides an electrolytic metal foil preparation device and preparation method that can prepare metal foil samples with high thickness and performance uniformity, small size, low cost, and flexible operation, and provides an equipment foundation for the innovation and development of electrolytic metal foil technology. The electrolytic metal foil preparation device provided by the embodiment of the present invention is particularly suitable for laboratory research use.

[0055] The present invention is described below by specific embodiments:

[0056] Example 1

[0057] On the one hand, if Figures 1 to 3 As shown, this embodiment provides a device for preparing an electrolytic metal foil, which includes an electrolytic cell 5, a cathode system, an anode system and an insulating partition 7. The cathode system includes a rotating device and a cathode 8; wherein the cathode 8 is located in the electrolytic cell 5; the rotating device is connected to the cathode 8 to drive the cathode 8 to rotate during the electrolytic deposition process. The anode system includes an anode 6; wherein the anode 6 is placed in the electrolytic cell 5 and is arranged around the cathode 8. The insulating partition 7 is placed in the electrolytic cell 5 and is located between the cathode 8 and the anode 6; wherein the insulating partition 7 is arranged around the cathode 8, and the anode 6 surrounds the insulating partition 7; a plurality of meshes are provided on the insulating partition 7 to adjust the uniformity of the electrolytic metal foil in the width direction by adjusting the aperture and distribution of the meshes.

[0058] Here, taking electrolytic copper foil as an example, the electrolytic metal foil provided in this embodiment drives the cathode 8 to rotate through a rotating device when electrolytically depositing copper foil, so that the flow rate of the solution in contact with each part of the cathode 8 can be the same (making the solution circulation in the electrolytic cell more uniform), thereby keeping the concentration of copper ions and additives on the cathode surface uniform, thereby ensuring the thickness and performance uniformity of the copper foil along the length direction of the copper foil (along the circumference direction of the cathode), while it is difficult to ensure the uniformity of the solution on the flat cathode surface in the existing flat electrolytic cell deposition device. In addition, the embodiment of the present invention adopts the method of anode shielding, that is, an insulating partition is placed between the cathode and the anode, and by adjusting the mesh size and distribution along the cathode height direction, the uniformity of the copper foil thickness and performance along the copper foil width direction (along the cathode height direction) can be achieved (specifically, due to the concentrated electric field distribution at the edge, that is, the edge effect; here, this embodiment adds an insulating partition to perform electric field shielding, and by adjusting the size and distribution of the mesh holes on it, the electric field shielding degree at the edge is large and the electric field shielding degree in the middle is small, and finally the electric field distribution at the edge is the same as the electric field distribution in the middle), while the anode shielding of the flat electrolytic cell is more complicated and less effective, because it is necessary to take care of the electric field shielding of the upper, lower, left, right and right angles of the anode plate. Therefore, the metal foil preparation device provided in this embodiment can prepare uniform copper foil samples, and has a simple and ingenious structure and low cost. Similarly, when the preparation setting of the electrolytic metal foil provided in this embodiment is used for electrolytic deposition of other metals, the same technical effect is also achieved.

[0059] In summary, the thickness and performance of the metal foil prepared by the electrolytic metal foil device provided by the present invention are uniform, and are significantly better than the flat-plate electrolytic cell deposition device commonly used in laboratories.

[0060] Example 2

[0061] Preferably, this embodiment provides a device for preparing an electrolytic metal foil. Compared with Embodiment 1, Figures 1 to 3 As shown, this embodiment further designs the cathode system as follows:

[0062] The material of cathode 8 can be any one of titanium, titanium alloy and stainless steel.

[0063] The cathode 8 is a roller cathode (roller-shaped structure); wherein the roller cathode includes a top surface, a bottom surface and a roller surface; wherein the top surface and the bottom surface are arranged opposite to each other, and the bottom surface is close to the inner bottom of the electrolytic cell 5, and the top surface is far from the inner bottom of the electrolytic cell 5; wherein one end of the roller surface is connected to the top surface, and the other end is connected to the bottom surface. wherein the bottom surface and the top surface are arranged as insulating surfaces. The roller surface is a polished surface; further preferably, the roughness Ra of the roller surface is not higher than 0.3 μm.

[0064] In addition, the rotating device includes a motor 1 and a drive shaft; wherein the motor 1 is drivingly connected to one end of the drive shaft (the motor 1 is connected to the drive shaft through a connecting device 10), and the other end of the drive shaft is drivingly connected to the cathode 8 for driving the cathode to rotate. The rotating device also includes a support frame 3; wherein the motor 1 is mounted on the support frame 3.

[0065] Here, in order to connect the cathode 8 to the power supply, a conductive device 9 is connected to the drive shaft; wherein the drive shaft is a conductor connected to the inside of the cathode 8; and the conductive device 9 is sleeved on the drive shaft.

[0066] Example 3

[0067] Preferably, this embodiment provides a device for preparing an electrolytic metal foil. Compared with the above embodiment, Figures 1 to 3 As shown, this embodiment further designs the anode system as follows:

[0068] The anode 6 is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the anode 6 is placed on the inner bottom of the electrolytic cell 5 .

[0069] The material of the anode 6 is selected from any one of copper, lead-antimony alloy, lead-silver alloy, and coated titanium plate. Preferably, the coating in the coated titanium plate is selected from any one of iridium-tantalum, lead dioxide, ruthenium dioxide, and iridium dioxide.

[0070] Here, in order to connect the anode 6 to a power source, a conductive strip 11 is provided at the upper end of the anode 6 .

[0071] Example 4

[0072] Preferably, this embodiment provides a device for preparing an electrolytic metal foil. Compared with the above embodiment, Figures 1 to 3 As shown, in this embodiment, the cathode, anode and insulating separator are further designed as follows:

[0073] The effective area ratio of the anode 6 and the cathode 8 is (1:1)-(1.5:1) to ensure the distribution of the electric lines of the anode so that the cathode can obtain a complete and uniform coating. The spacing distance is 1-5cm, which can reduce the cell pressure and discharge the generated oxygen and hydrogen in time to reduce pinholes. The "effective area" here refers to the conductive area.

[0074] Preferably, cathode 8 is completely located in electrolytic cell 5, cathode 8 is completely located in the space surrounded by insulating partition 7, and cathode 8 is completely located in the space surrounded by anode 6. The central axes of cathode 8 and anode 6 are located on the same straight line (ie, anode and cathode are coaxial).

[0075] Preferably, the insulating partition 7 is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the insulating partition 7 is placed on the inner bottom of the electrolytic cell 5 .

[0076] Regarding the mesh requirements on the insulating partition, the opening rate of the upper end part of the insulating partition is 10-44%, the opening rate of the lower end part is 10-44%, and the opening rate of the middle part is 16-70%, so as to regulate the uniformity of the electrolytic metal foil in the width direction.

[0077] Example 5

[0078] Preferably, this embodiment provides a device for preparing an electrolytic metal foil. Compared with the above embodiment, Figures 1 to 3 As shown, this embodiment is further designed as follows:

[0079] The preparation device of the electrolytic metal foil of this embodiment also includes a heat exchange tank 2, a liquid feeding pipe 12, and a circulation pump 13; wherein the electrolytic tank 5 is placed in the heat exchange tank 2; the bottom of the electrolytic tank 5 is connected to the liquid feeding pipe 12; the circulation pump 13 (or a submersible pump) is placed in the heat exchange tank 2 and connected to the liquid feeding pipe 12, and is used to continuously transport the solution in the heat exchange tank 2 from the bottom of the electrolytic tank 5 into the electrolytic tank 5; after the electrolytic tank 5 is filled with the solution, the solution will overflow from the upper end of the electrolytic tank 5 back to the heat exchange tank 2, thereby realizing the circulation of the solution.

[0080] Preferably, the solution temperature is increased, decreased or kept constant by the heat exchange tank 2, in which a heat exchange device 4 (heating and / or cooling device) may be placed, and the heat exchange medium may include water or copper sulfate solution.

[0081] Preferably, the volume of solution required by the electrolytic metal foil preparation device during the electrolytic deposition process is 0.5-20L.

[0082] Here, regarding the preparation device of the electrolytic metal foil provided in the above embodiment, the volume of solution used in the preparation process of the metal foil is relatively small (0.5-20L), which is far lower than the solution volume requirement of several tens of cubic meters of the industrial device; accordingly, the electrolytic metal foil prepared by the present invention has a smaller area, consumes less copper and power, and thus the test cost is significantly reduced (it should be noted that the smaller the area of ​​the metal foil, the more difficult it is to achieve uniformity, and the present invention is mainly aimed at small areas (8-500cm 2) metal foil to improve its uniformity; while industrial devices generally prepare large-area copper foil (width of 1380mm and length of nearly 10,000 meters). At the same time, the operation of the electrolytic metal foil device provided by the present invention is more flexible, and can promptly reflect changes in additive parameters such as type or concentration, while the industrial system electrolytic copper foil device system is longer (occupying several hundred square meters) and more complex. When the additive parameters change, it takes a period of time before the change can be seen on the copper foil, and the delay time is difficult to accurately determine. The flexibility of the electrolytic metal foil device provided by the present invention is also reflected in the ability to effectively adjust the additive parameters by replacing the solution. In the industrial electrolytic copper foil device, additives can only be added continuously. Although the filter can filter out some polymer additives, it cannot eliminate small molecule additives or other inorganic additives. Therefore, it is difficult to effectively adjust the additives.

[0083] The thickness and performance of the metal foil (copper foil) prepared by the electrolytic metal foil preparation device provided by the above embodiment of the present invention are uniform, which is significantly better than the flat electrolytic cell deposition device commonly used in laboratories. The electrolytic metal foil device of the present invention uses a circulation pump to circulate the solution from bottom to top, which can replenish metal ions and additives in time, and can also discharge oxygen and hydrogen generated during the electrolytic deposition of metal foil in time, which helps to reduce the pinholes of the metal foil (copper foil) and further improve its surface quality.

[0084] In summary, the device for preparing electrolytic metal foil provided in the embodiment of the present invention is more suitable as an experimental research and development device.

[0085] Example 6

[0086] On the other hand, this embodiment provides a method for preparing an electrolytic metal foil, wherein a cathode and an anode are immersed in an electrolytic cell, and the anode is arranged around the cathode; wherein during the electrolytic deposition process, the cathode rotates and the anode is fixed.

[0087] Preferably, the electrolytic metal foil preparation device described in any one of embodiments 1 to 5 is used to electrolytically deposit the metal foil. In the electrolytic metal foil preparation method, when electrolytically depositing the metal foil:

[0088] The current mode includes DC mode and pulse mode. The current density of DC mode is 0.1-120A / dm 2 ; The peak current range of pulse mode is 10-5000A / dm 2 The current on and off times of a pulse cycle are 0.1-1000ms and 100-5000ms respectively.

[0089] The temperature is 0-90°C; preferably, the temperature control mode includes one or a combination of constant mode, increasing mode and decreasing mode.

[0090] Solution flow rate is 0.01-10m 3 / h, cathode speed range is 0-1500rpm / min.

[0091] After the electrolytic metal foil is electrolytically deposited by the preparation method of the electrolytic metal foil, the thickness of the obtained electrolytic metal foil is in the range of 4-200 μm, the thickness error is within 5%, and the area range is 8-500 cm 2 .

[0092] Here, the preparation method of the electrolytic metal foil provided in this embodiment adopts a coaxially placed rotating cathode and annular anode, which are immersed in an electrolyte. By adjusting the cathode rotation speed, the mechanical properties, surface quality and other properties of the electrolytic copper foil can be controlled. The thickness of the obtained electrolytic copper foil can be extremely thin (4μm), and the thickness is uniform, and the thickness error can be within 5%.

[0093] In addition, the preparation device and preparation method of the electrolytic metal foil provided by the embodiment of the present invention are mainly used for electrolytic deposition of metal foil. Among them, the metal foil includes pure copper foil (that is, non-alloy, non-composite copper foil, copper foil composed only of copper elements), alloy copper foil, graphene composite copper foil, and nickel foil. Preferably, the preparation device of the electrolytic metal foil can also be used for surface treatment of metal foil; preferably, it is used for plating treatment on the surface of the metal foil. Preferably, the preparation device of the electrolytic copper foil can also be used for electroplating decoration treatment, preferably, the part is used as the cathode to electrolytically deposit a decorative coating; preferably, the decorative coating includes a copper coating, a silver coating, a nickel coating, a chromium coating, and a nickel-chromium coating.

[0094] The following is further described by comparative examples and experimental examples.

[0095] Comparative Example

[0096] The comparative example mainly adopts a flat plate electrolytic cell deposition device to carry out direct current electrolytic deposition of copper foil, as follows:

[0097] Electrolyte composition: The base solution is mainly composed of 300g / L CuSO4·5H2O, 100g / L H2SO4 and deionized water. The electrolyte also contains electroplated copper foil additives.

[0098] The flat cathode is made of titanium alloy, and the roughness Ra is not higher than 0.3μm after surface treatment. The flat anode is made of coated titanium; the cathode and anode are placed parallel to each other with a distance of 45mm, and the effective area ratio is 1:1;

[0099] The electrolysis time is controlled by the power supply; the electrolysis temperature is controlled by the heat exchanger. A circulation pump is used to directly blow the flat cathode to realize the circulation of the electrolyte. The pump power is 35W. The electrolyte volume of the whole device is 13L.

[0100] The area of ​​the copper foil prepared in this comparative example is 100×100 mm 2 The strength and elongation were measured by electronic universal testing machine, the roughness was measured by MarSurf M300 roughness tester, and the thickness was measured by weighing method.

[0101] Here, taking the constant current method as an example, the current density is selected as 60A / dm 2 , temperature 50℃, flow rate 1m 3 / h, time 70s, electrolytic reaction, to obtain a certain thickness of copper foil, different positions (see Figure 4 ) was weighed and tested (see Table 1) to obtain a thickness of 8.0±1.5μm, with a thickness deviation of 19%. The overall appearance was thick at the edges and thin in the middle.

[0102] The properties of the electrolytic copper foil prepared in this comparative example are as follows: strength of 310±18 MPa, elongation of 2.5±0.8%, and Rz of 2.08 μm.

[0103] Table 1

[0104] Serial number Area / cm Mass / g Thickness / μm 1 1.27×2.5 0.0243 8.6 2 1.27×2.5 0.0185 6.5 3 1.27×2.5 0.0238 8.4 4 1.27×2.5 0.0233 8.2 5 1.27×2.5 0.0235 8.3

[0105] Experimental Examples

[0106] This experimental embodiment mainly adopts the electrolytic metal foil device described in the above embodiment of the present invention (i.e., Figure 1-Figure 3 The electrolytic metal foil device) performs direct current electrolytic deposition of copper foil as follows:

[0107] Electrolyte composition: The base solution is mainly composed of 300g / L CuSO4·5H2O, 100g / L H2SO4 and deionized water. The electrolyte also contains electroplated copper foil additives.

[0108] The roller cathode is made of titanium alloy, and the roughness Ra is not higher than 0.3μm after surface treatment. The cylindrical structure (ring) anode is made of coated titanium; the cathode and anode are coaxially placed with a spacing of 25mm, and the effective area ratio is 1:1; an insulating partition with mesh is placed between the cathode and the anode (the porosity of the upper end part and the porosity of the lower end part of the insulating partition are both smaller than the porosity of the middle part, so as to adjust the uniformity of the electrolytic copper foil in the width direction).

[0109] Current density is 60A / dm 2 ; The electrolysis time is controlled by the power supply; the electrolysis temperature is controlled by the heat exchange tank; the cathode rotation is achieved by the rotation of the external motor. The circulation pump is used to circulate the electrolyte, and the pump power is 5W. The electrolyte volume of the entire device is 3L.

[0110] The area of ​​the copper foil prepared in this experimental example is 190×70 mm2 The strength and elongation were measured by electronic universal testing machine, the roughness was measured by MarSurf M300 roughness tester, and the thickness was measured by weighing method.

[0111] Here, taking the constant current method as an example, the current density is selected as 60A / dm 2 , temperature 50℃, flow rate 1m 3 / h, speed 500rpm / min, time 50s, electrolysis reaction, to obtain a copper foil with uniform thickness, at different positions (see Figure 5 ) was weighed and tested (see Table 2) to obtain a thickness of 8.0±0.4μm, and the overall thickness deviation of the copper foil was only 5%.

[0112] The properties of the prepared electrolytic copper foil are strength of 378±2MPa, elongation of 11.1±0.2%, and Rz of 1.63μm.

[0113] Table 2

[0114] Serial number Area / cm Mass / g Thickness / μm 1 1.27×2.5 0.0230 8.1 2 1.27×2.5 0.0224 7.9 3 1.27×2.5 0.0233 8.2 4 1.27×2.5 0.0215 7.6 5 1.27×2.5 0.0232 8.2

[0115] Here, the thickness deviation at different positions on the copper foil prepared in this experimental embodiment is only 5%, reflecting that the thickness of the copper foil is uniform. From the performance of the test, the error is very small, indicating that the copper foil has high uniformity, which is beneficial to the improvement of the strength and elongation of the electrolytic copper foil, especially the elongation is improved by nearly 5 times. At the same time, it has a lower surface roughness, which can meet the preparation of high-performance copper foil. The research on the types of additives can be done by replacing the solution, and the whole process only takes a few minutes; in addition, the effect feedback time of the content of the additive is very short, only a few minutes. The preparation operation of the entire process is simple and the efficiency is very high. The solution consumption is only 3L each time, and the consumption of copper, acid, additives, water and electricity is less, which can significantly reduce costs.

[0116] Here, the area of ​​the copper foil can be changed by replacing the cathode, etc., and the preparation of alloy copper foil, graphene composite copper foil, nickel foil and surface treatment of copper foil can be achieved by replacing the solution. In addition, the thickness of the copper foil can be controlled by changing the time and current density, etc., and the temperature, flow rate, rotation speed, etc. can be adjusted as needed. The preparation conditions of the copper foil can be fully controlled from chemical parameters and physical parameters. In addition, the cathode can be replaced with the parts to be plated and applied to the electrolytic deposition decorative coating.

[0117] In summary, the electrolytic metal foil device and preparation method of the embodiment of the present invention can produce metal foil with excellent thickness and uniformity, and also has the characteristics of low cost and flexible operation, which greatly meets the needs of developing experimental devices and preparation methods for high-performance electrolytic metal foil, and therefore has huge application prospects.

[0118] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A device for preparing electrolytic metal foil, characterized in that: The preparation device of the electrolytic metal foil comprises: Electrolyzer; A cathode system, the cathode system comprising a rotating device and a cathode; wherein the cathode is located in the electrolytic cell; the rotating device is connected to the cathode to drive the cathode to rotate during the electrolytic deposition process; An anode system, the anode system comprising an anode; wherein the anode is placed in the electrolytic cell and arranged around the cathode; An insulating partition is placed in the electrolytic cell and located between the cathode and the anode; wherein the insulating partition is arranged around the cathode, and the anode surrounds the insulating partition; a plurality of mesh holes are provided on the insulating partition to adjust the uniformity of the electrolytic metal foil in the width direction by adjusting the aperture and distribution of the mesh holes.

2. The device for preparing electrolytic metal foil according to claim 1, characterized in that: The cathode is made of any one of titanium, titanium alloy and stainless steel.

3. The device for preparing electrolytic metal foil according to claim 1, characterized in that: The cathode is a roller cathode.

4. The device for preparing electrolytic metal foil according to claim 3, characterized in that: The roller cathode includes a top surface, a bottom surface and a roller surface; wherein the top surface and the bottom surface are arranged opposite to each other, and the bottom surface is close to the inner bottom of the electrolytic cell, and the top surface is far away from the inner bottom of the electrolytic cell; wherein one end of the roller surface is connected to the top surface, and the other end is connected to the bottom surface.

5. The device for preparing electrolytic metal foil according to claim 4, characterized in that: The bottom surface and the top surface are configured as insulating surfaces.

6. The device for preparing electrolytic metal foil according to claim 4, characterized in that: The roller surface is a ground and polished surface.

7. The device for preparing electrolytic metal foil according to claim 6, characterized in that: The roughness Ra of the roller surface is not higher than 0.3 μm.

8. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The rotating device comprises: Motor; The motor is connected to one end of the drive shaft and the other end of the drive shaft is connected to the cathode.

9. The device for preparing electrolytic metal foil according to claim 8, characterized in that: The rotating device also includes a supporting frame; wherein the motor is mounted on the supporting frame.

10. The device for preparing electrolytic metal foil according to claim 8, characterized in that: The driving shaft is a conductor, and a conducting device is connected to the driving shaft.

11. The device for preparing electrolytic metal foil according to claim 10, characterized in that: The conductive device is sleeved on the driving shaft.

12. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The anode is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the anode is placed on the inner bottom of the electrolytic cell.

13. The device for preparing electrolytic metal foil according to claim 12, characterized in that: A conductive strip is disposed at the upper end of the anode.

14. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The material of the anode is selected from any one of copper, lead-antimony alloy, lead-silver alloy, and coated titanium plate.

15. The device for preparing electrolytic metal foil according to claim 14, characterized in that: The coating in the coated titanium plate is selected from any one of iridium tantalum, lead dioxide, ruthenium dioxide and iridium dioxide.

16. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The effective area ratio of the anode and cathode is (1:1)-(1.5:1), and the spacing distance is 1-5 cm; and / or The cathode is completely located in the electrolytic cell, completely located in the space surrounded by the insulating partition, and completely located in the space surrounded by the anode; and / or The central axes of the cathode and the anode are located on the same straight line.

17. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The insulating partition is a cylindrical structure with both the upper and lower ends open; wherein the lower end of the insulating partition is placed on the inner bottom of the electrolytic cell; and / or The mesh on the insulating partition meets the following requirements: the opening rate of the upper end part of the insulating partition is 10-44%, the opening rate of the lower end part is 10-44%, and the opening rate of the middle part is 16-70%, so as to adjust the uniformity of the electrolytic metal foil in the width direction.

18. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The device for preparing the electrolytic metal foil also includes: A heat exchange tank, wherein the electrolytic cell is placed in the heat exchange tank; A liquid feeding pipe, the bottom of the electrolytic cell is connected to the liquid feeding pipe; A circulation pump is placed in the heat exchange tank and connected to the liquid delivery pipe, and is used to continuously transport the solution in the heat exchange tank from the bottom of the electrolytic tank into the electrolytic tank; after the electrolytic tank is filled with the solution, the solution will overflow from the upper open end of the electrolytic tank back into the heat exchange tank, thereby realizing the circulation of the solution.

19. The device for preparing electrolytic metal foil according to claim 18, characterized in that: A heat exchange device is provided in the heat exchange tank to exchange heat with the solution in the heat exchange tank; and / or The volume of solution required by the electrolytic cell metal foil preparation device during the electrolytic deposition process is 0.5-20L.

20. The device for preparing electrolytic metal foil according to any one of claims 1 to 7, characterized in that: The device for preparing the electrolytic metal foil is used for electrolytically depositing a metal foil; wherein the metal foil comprises any one of pure copper foil, alloy copper foil, graphene composite copper foil and nickel foil.

21. The device for preparing electrolytic metal foil according to claim 20, characterized in that: The device for preparing electrolytic metal foil is used for surface treatment of metal foil.

22. The device for preparing electrolytic metal foil according to claim 21, characterized in that: The device for preparing the electrolytic metal foil is used for performing a coating treatment on the surface of the metal foil.

23. The device for preparing electrolytic metal foil according to claim 20, characterized in that: The device for preparing the electrolytic metal foil is used for electroplating decoration treatment.

24. The device for preparing electrolytic metal foil according to claim 23, characterized in that: The part is used as a cathode to electrolytically deposit a decorative coating; and / or The decorative coating includes any one of a copper coating, a silver coating, a nickel coating, a chromium coating, and a nickel-chromium coating.

25. A method for preparing an electrolytic metal foil, characterized in that: The electrolytic metal foil is electrolytically deposited using the device for preparing the electrolytic metal foil as described in any one of claims 1 to 24.

26. The method for preparing an electrolytic metal foil according to claim 25, characterized in that: In the method for preparing the electrolytic metal foil, when the metal foil is electrolytically deposited, the current mode includes a direct current mode and a pulse mode.

27. The method for preparing an electrolytic metal foil according to claim 26, characterized in that: The current density in DC mode is 0.1-120A / dm 2 ; The peak current range of pulse mode is 10-5000A / dm 2 The current on and off times of a pulse cycle are 0.1-1000ms and 100-5000ms respectively.

28. The method for preparing an electrolytic metal foil according to claim 25, characterized in that: In the preparation method of the electrolytic metal foil, the temperature is 0-90° C. during the electrolytic deposition of the metal foil.

29. The method for preparing an electrolytic metal foil according to claim 25, characterized in that: The preparation method of the electrolytic metal foil is that during the electrolytic deposition of the metal foil, the solution flow rate is 0.01-10m 3 / h, cathode speed range is 0-1500rpm / min.

30. The method for preparing an electrolytic metal foil according to claim 29, characterized in that: The mechanical properties and surface quality of electrolytic copper foil can be controlled by adjusting the cathode rotation speed.

31. The method for preparing an electrolytic metal foil according to claim 25, characterized in that: After the electrolytic metal foil is electrolytically deposited by the preparation method of the electrolytic metal foil, the thickness of the obtained electrolytic metal foil is in the range of 4-200 μm, the thickness error is within 5%, and the area range is 8-500 cm 2 .

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