CN115717255A - Zero-stress electrolytic metal foil preparation method, system used thereby and application of method - Google Patents
Zero-stress electrolytic metal foil preparation method, system used thereby and application of method Download PDFInfo
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Abstract
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method of a zero-stress electrolytic metal foil, and a system and an application of the method. The method comprises the following steps: 1) Arranging a movable conductive medium, wherein the conductive medium can dynamically pass through electrolyte, is electrically connected with an anode arranged in the electrolyte when in the electrolyte, and is used as a cathode to carry out electrodeposition preparation of metal foil on the conductive medium to obtain a conductive medium-metal foil; 2) And separating and removing the conductive medium component in the conductive medium-metal foil by a phase state change and/or chemical method and/or a dissolution and/or expansion and contraction method, namely completing the zero-stress preparation of the electrolytic metal foil. Through the improvement of the process, the preparation thickness, the size and the specification of the electrolytic metal foil can be effectively controlled, continuous production is realized, the applicability is strong, the yield of products is high, and the economic benefit is high.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method of a zero-stress electrolytic metal foil, and a system and an application of the method.
Background
Metal foil is a thin sheet-like metal product such as copper foil which is usually made of copper plus a certain proportion of other metals. Typical commercially available copper foils have a copper content of 80wt% or 90wt%, respectively, corresponding to 80 foil and 90 foil, respectively. In the market environment, the most widely used decorative material is used because the decorative material has low surface oxygen, can be adhered to various substrates such as metal, insulating materials and the like, and has a wide temperature use range.
However, with the development of metal foils, the market has generated a wide variety of demands. As in the field of copper foil, high-purity electronic grade copper foil having a copper content of 99.7wt% or more has been developed and is also commonly used for electronic equipment because of its excellent conductivity and the effect of providing electromagnetic shielding. The electronic grade copper foil is one of basic materials in the electronic industry, the electronic information industry is rapidly developed, the usage amount of the electronic grade copper foil is increased, and the product is widely applied to industrial calculators, communication equipment, QA equipment, lithium ion copper foil, copper foil storage batteries, civil televisions, video recorders, CD players, copiers, telephones, cooling and heating air conditioners, electronic parts for automobiles, game machines and the like. The demands of domestic and foreign markets for electronic grade copper foils, especially high-performance electronic grade copper foils, are increasing.
The present inventors have made corresponding research and development in the process of manufacturing metal foils and have filed three patent applications, namely, cn202111335008.X, CN202111335007.5 and CN202111335012.6, in association with the corresponding cooperative units earlier, and in the three patent applications, effective and nondestructive manufacturing of ultra-thin and ultra-high purity metal foils has been achieved, and the present inventors can be used for manufacturing high-standard ultra-thin special metal foils. However, in the actual industrialization process, it is found that when the three invented technologies are used for producing and preparing large-thickness and large-size metal foils, the problems of wrinkles, cracks and the like are very easy to occur, the production adaptability of the metal foils such as small-size ultrathin special copper foils with the thickness of 1-3 μm or even less than 1 μm is good, good quantitative production can be realized, and huge economic benefits are generated, but the production adaptability of the metal foils with the thickness of 3-8 μm, which are required conventionally, especially large-size metal foil rolls is poor, the production cannot be realized effectively, and the cost is relatively high.
In the prior art, the production of electrolytic metal foil with the thickness of 4-6 microns has a more obvious defect, namely, the existing electrolytic method directly deposits the metal foil on a cathode roller or an intermediate material on the surface of the cathode roller, but only peels off the metal foil when the metal foil is peeled off, so that the metal foil is very easy to tear, and the quantitative production effect is poor, the existing electrolytic process can only be basically applicable and suitable for continuous production of metal foil rolls with the thickness of more than 6 microns even in high-standard fine production, and even most of devices which cannot realize high-precision fine production can only prepare the thick copper foil with the thickness of more than 18 microns.
Disclosure of Invention
The invention provides a zero-stress electrolytic metal foil preparation method, application thereof and an obtained metal foil, and aims to solve the problems that the metal foil is easy to break and damage due to large stress borne by the metal foil when the metal foil is stripped in the existing electrolytic metal foil preparation process, and the existing other processes cannot be effectively adapted to efficient and lossless continuous production of 3-6 mu m metal foil.
The primary objects of the present invention are:
1. can be effectively adapted to the electrolytic preparation of any kind of metal foils;
2. the metal foil can be peeled off under zero stress, and the yield of the metal foil is improved;
3. the continuous production of the metal foil with the thickness of 2-8 mu m can be realized;
4. the production cost of the high-quality metal foil is reduced;
5. the control and adjustment of the metal foil surface micro-morphology and the texture coefficient can be automatically realized.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing a zero-stress electrolytic metal foil,
the method comprises the following steps:
1) Arranging a movable conductive medium, wherein the conductive medium can dynamically pass through electrolyte, is electrically connected with an anode arranged in the electrolyte when in the electrolyte, and is used as a cathode to carry out electrodeposition preparation of metal foil on the conductive medium to obtain a conductive medium-metal foil;
2) And separating and removing the conductive medium component in the conductive medium-metal foil in a phase state changing and/or chemical method and/or a dissolving and/or swelling and shrinking method mode, namely completing the zero-stress preparation of the electrolytic metal foil.
Preferably, the movable conductive medium in step 1) is in the form of a strip and/or a sheet of a target shape and/or a setting solidified slurry enters into the electrolyte.
Preferably, the sizing and curing slurry is filled into a specific carrier to be subjected to gravity leveling and/or shape pressing, and the sizing and curing slurry is used as a conductive medium after curing.
As a matter of preference,
step 1) the electrolyte contains soluble metal salt of a target metal foil component;
the anode in the step 1) is an insoluble anode.
The core of the process of the invention is to avoid the stripping process in conventional preparation methods completely and to ensure a high flexibility in the implementation and use of the protocol. The core of the technical concept of the invention is obviously different from the prior basic scheme, and in the three atomic method (or gas phase method) schemes of CN202111335008.X, CN202111335007.5 and CN202111335012.6 developed by the inventor of the application, the core lies in gravity stripping, and the separation and the acquisition of the metal foil are realized through the gravity action, so that the method is more practically suitable for the sheet preparation within certain specifications, and because the atomic deposition preparation method of evaporation is adopted, the ultrahigh precision preparation is realized, the specification size and the thickness of the production are also limited, the process difficulty and the cost are improved, and the core lies in the preparation, the elimination and the gravity stripping of the middle layer, and the spontaneous falling of the metal foil is realized. The core of the method is that a proper conductive medium is selected, the conductive medium is used as a template to be electrolyzed firstly, and then the conductive medium is removed by a lost foam method, so that the process of 'peeling' is avoided completely, the 'peeling' process is not separated by an atomic method, a novel peeling form is provided, the effective nondestructive preparation of the ultrathin metal foil is realized by combining a vapor deposition method, but the metal foil is still subjected to a larger peeling stress effect, so that the peeling stress can be completely avoided, and the medium-metal foil separation which is completely nondestructive is realized.
The stress effect is very obvious whether the ultrathin metal foil or the large-size metal foil is prepared. The original gas phase method scheme reduces the stress action of the metal foil and realizes the preparation of the ultrathin special metal foil by matching with a specific deposition form, but cannot overcome the influence on the large-size metal foil under the action of gravity stress and the limitation of the deposition mode used by the large-size metal foil on the thickness, and the invention realizes the continuous production of completely zero stress and realizes the continuous and thickness-controllable production by combining with a mature electrolysis process.
In addition, the method also integrates various technical advantages, such as the advantages of low cost, high efficiency and simplicity of an electrolytic method and the advantage of controllable microscopic appearance brought by a conductive medium, and can realize 2-6 mu m ultrathin metal foil with super-hydrophobic performance by adopting the galvanized aluminum foil with the nano bowl structure on the surface as the conductive intermediate layer.
In addition, under the condition that all technologies are effectively combined, the selection range of the conductive medium is greatly expanded, and because the thickness of the conductive medium is selected to be thinner, even part of organic film materials can be selected as the conductive medium, so that the low conductivity can not be regarded as the technical obstacle of the electrolytic deposition of the metal foil any more.
A zero-stress electrolytic metal foil system is provided,
the system is used for carrying out electrodeposition on a conductive medium and comprises a deposition device and a post-treatment device;
the deposition device comprises an electrolytic cell, a cathode, an anode and a power supply;
the cathode, the anode and the power supply are electrically connected;
the electrolytic cell is used for containing electrolyte, the anode is arranged in the electrolytic cell, the cathode is electrically connected with the conductive medium, and the conductive medium is used as an extension part of the cathode, so that the conductive medium exists as the cathode in the electrolytic cell for electrodeposition;
the post-treatment device is used for removing the conductive medium and comprises a solvent pool and/or a heating device and/or a refrigerating device and/or a combustion device and/or an atmosphere treatment device.
As a preference, the first and second liquid crystal compositions are,
the system further comprises a conveying device for enabling transport of the conductive medium.
As a matter of preference,
the system also comprises a pretreatment device;
the pretreatment device loads a conductive medium on a carrier and/or performs surface treatment on the conductive medium;
the carrier is driven by the conveying device to move, and the carrying conductive medium sequentially passes through the deposition device and the post-processing device.
Preferably, the pretreatment device comprises a spraying device and/or a brushing device and/or a solvent pool and/or a heating device and/or a refrigerating device and/or a UV curing device and/or a spraying device.
The most central part of the system used in the present invention is the deposition apparatus and the post-treatment apparatus, and the present invention will be described in detail only for the core and the irreplaceable parts because of the high flexibility of the solution of the method of the present invention and the freedom of adjustment and selection in actual use according to the requirements.
As for the deposition apparatus, the practical approach is closer to the conventional electrodeposition apparatus, but the most different is that the conventional electrodeposition apparatus needs to ensure that at least half of the cathode is immersed in the electrolyte, and the formed electrolytic metal foil is stripped directly on the cathode, while the present invention uses the conductive medium as an extension of the cathode, actually as a "second cathode" which is "constantly moving and can be consumed", so that the cathode can be completely separated from the electrolyte and preferably also completely separated from the electrolyte, or even can be regarded as a conductive joint, which can only function as a conductor and distinguish the anode, which also avoids the deposition of the consumed metal ions on the surface of the cathode when the cathode is placed in the electrolyte, and causes the accumulation of the deposits on the surface of the cathode to change the travel process of the conductive medium, etc.
In addition, the post-processing device can be more flexibly selected and used according to the material of the conductive medium. If the conductive carbon cloth is used as a conductive medium, the atmosphere treatment device can be used for controlling low oxygen partial pressure and matching with the combustion device for incomplete combustion, so that the components of the carbon cloth are thoroughly removed, the oxidation of the metal foil can be avoided by CO gas formed by incomplete combustion, and the internal stress of the metal foil can be eliminated to a certain extent. And for another example, the PAN/PMMA conductive film can be quickly dissolved and removed by a solvent, so that the metal foil can be effectively protected and cleaned. If an alloy strip such as copper alloy is used as a conductive medium to prepare the metal foil, the reasonable arrangement can enable the linear thermal expansion coefficient difference between the alloy strip and the metal foil to be large, even realize separation through proper cold and hot alternate treatment, and simultaneously can effectively improve the internal stress of the metal foil. It can be seen that for the technical solution of the present invention, through reasonable application of known material properties, on the basis of the core of the technical idea of the present invention, the nondestructive separation of the metal foil can be realized by any combination of various ways.
The transport device is also freely selectable depending on the conductive medium and the carrier. The conductive medium in a belt shape can be conveyed simply by using a roller.
The pre-treatment device is another characteristic of the system of the invention, and because part of the conductive medium is not easy to prepare and use in large area or has insufficient strength, or has special requirements on the shape of the metal foil, and the like, the conductive medium is required to be matched with the carrier for use, the conductive medium is firstly prepared on the carrier through the pre-treatment device, and then the conductive medium on the carrier is removed through the post-treatment device to be separated to obtain the metal foil. The preparation process matched with the carrier is the closest to that of the previously developed scheme, but the scheme is only adopted aiming at the preparation of the metal foil with the specific shape or the specific appearance, namely, the microstructure of the surface of the conductive medium with insufficient strength is symmetrically engraved on the surface of the metal foil by a complex forming method to realize the regulation and control of the microstructure of the metal foil, or the preparation of the regular hexagonal metal foil is required to be realized in a targeted way, and the like, and the scheme is still an improved scheme which is integrally optimized in multiple aspects by combining the technical scheme of the invention. The above effects cannot be achieved by the atomic deposition method.
The pretreatment device is used for treating the surface of the conductive medium, such as controlling the texture of the metal foil through additive treatment, and the preparation effect of the metal foil is further enhanced through the additive.
An application of a zero-stress electrolytic metal foil preparation method,
the method is used for producing metal foils with the thickness dimension being more than or equal to 2 mu m, and/or is used for producing large-size metal foils with the length dimension being more than or equal to 3m and the width dimension being more than or equal to 1.2m, and/or is used for continuously producing metal foil rolls.
In a specific production test, the technical scheme of the invention can realize continuous production and preparation of the metal foil roll with super-long and super-large specification, the thickness of the metal foil contained in the metal foil roll is 4.2 mu m, the width reaches 1.35m, and the total length reaches 220m. It can be seen that it can be practically used for the quantitative production of ultra-large gauge metal foils. Reaches the industrial mature standard.
The invention has the beneficial effects that:
according to the invention, through the improvement of the process, the preparation thickness, the size and the like of the electrolytic metal foil can be effectively controlled, the continuous production is realized, the applicability is strong, the yield of the product is high, the economic benefit is high, and meanwhile, the technical scheme of the invention can also effectively control the surface appearance of the metal foil, and has the advantages of wide application range, strong process flexibility, high industrial maturity and the like.
Drawings
FIG. 1 is a schematic view of a system according to embodiment 1 of the present invention;
FIG. 2 is a schematic view of a deposition apparatus according to embodiment 1 of the present invention;
FIG. 3 is a schematic view of a deposition apparatus according to example 1;
FIG. 4 is a schematic view of a deposition apparatus according to example 1;
fig. 5 is a schematic view of a conductive carrier according to embodiment 3 of the present invention;
FIG. 6 is a schematic view of a system according to embodiment 3 of the present invention;
FIG. 7 is a schematic view of a system according to embodiment 4 of the present invention;
FIG. 8 is a schematic view of a partial structure of a deposition apparatus according to example 4 of the present invention;
FIG. 9 is a schematic view of a system according to embodiment 5 of the present invention;
FIG. 10 is a schematic view of a partial structure of a deposition apparatus according to embodiment 5 of the present invention.
In the figure: 100 conveying devices, 200 pretreatment devices, 201 treatment liquid spray heads, 202 ink drippers, 203UV lamps, 204 medium material spray heads, 205 cold air cylinders, 300 deposition devices, 301 cathodes, 302 anodes, first anodes 302a, second anodes 302b,303 power supplies, 304 electrolytic baths, 3041 main tanks, 3042 auxiliary tanks, 3043 through tanks, 305 deposition rollers, 306 scrapers, 400 aftertreatment devices, 401 flame spray heads, 402 box type atmosphere furnaces, 4021 air inlet pipes, 4022 air outlet pipes, 403 spray devices, 500 winding drums, A conductive media, A01 conductive copper alloy strips, A011 die tanks, A012 insulating layers, B medium-foils, B01 conductive media layers, B02 foil layers, C product foils, C01 first electrolytic copper foils and C02 second electrolytic copper foils.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Furthermore, the embodiments of the present invention described in the following description are generally only a part of the embodiments of the present invention, and not all of the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "thickness", "upper", "lower", "horizontal", "top", "bottom", "inner", "outer", "circumferential", and the like, are used in the orientations and positional relationships indicated in the drawings, which are based on the orientation or positional relationship shown in the drawings, and are used for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., and "a plurality" means one or more unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Unless otherwise specified, all the raw materials used in the examples of the present invention are commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
The technical solution of the present invention is illustrated by a system with strong universality and high industrial maturity, as shown in the schematic diagram of fig. 1, the system of the present invention includes a conveying device 100, a pre-treatment device 200, a deposition device 300 and a post-treatment device 400;
the system has good running condition between 1 month and 5 months in 2022 and is particularly used for preparing oxygen-free electrolytic copper foil; in the system, the conveyer 100 adopts a roller conveyer 100 sold in the market, an electric roller is used as the conveyer 100 for conveying and conveying, the conductive medium A used by the invention is a PU conductive film roll sold in the market, and the size specification is 1.2m multiplied by 60m; under the action of the conveying device 100, the conductive medium A (PU conductive film) of the present embodiment is first sent to the pretreatmentThe apparatus 200, in the pre-treatment apparatus 200, the present embodiment is provided with an atomizing nozzle as a treatment liquid nozzle 201, the treatment liquid nozzle 201 uniformly sprays 50wt% of an aqueous solution of polyethyleneimine onto the deposition surface of the conductive medium A film, and the spraying amount of the surface of the deposition surface of the conductive medium A film is about 12 to 15g/m by controlling the feeding rate of the conveyer 100 and the flow rate of the treatment liquid nozzle 201 2 Then, under the driving of the conveying device 100, the conductive medium a film enters the deposition device 300, as can be seen from fig. 1, the cathode 301 of the deposition device 300 of the system of the present embodiment is disposed outside the electrolytic cell 304, the conductive medium a film first passes through the cathode 301 and is attached to the cathode 301, and after entering the electrolyte of the electrolytic cell 304, the conductive medium a film can be used as an extension of the cathode 301 to form electrodeposition;
the anode 302 is a commercially available graphite anode 302 and is arranged at the bottom of an electrolytic cell 304, the power supply 303 is a silicon controlled rectifier power supply 303 purchased from SanRex, an electrolyte is injected into the electrolytic cell 304, the electrolyte is 280-320 g/L of blue vitriol solution, the blue vitriol solution also contains 120g/L of sulfuric acid and 10mg/L of gelatin, and the copper ion concentration of the electrolyte is dynamically controlled by adding blue vitriol through feeding;
when the conductive medium A film enters the electrolytic cell 304, the deposition surface faces downwards and faces the anode 302, after the power supply 303 is turned on, the electrolytic cell 304 works to realize the electrodeposition on the deposition surface of the conductive medium A film, the preparation of electrolytic copper foil is carried out, and then after the preparation of the electrolytic copper foil on the deposition surface of the conductive medium A film is finished, the medium-foil B (namely, a PU conductive film medium-electrolytic copper foil composite) is sent out of the deposition device 300 through the conveying device 100 and sent into the post-processing device 400;
specifically, the partial structure of the deposition apparatus 300 is shown in fig. 2, 3 and 4 except for the power supply 303, and it can be clearly seen that the deposition apparatus 300 and the specially arranged anode 302 can realize effective deposition on the thin film deposition surface of the conductive medium a, and after deposition, a dielectric foil B composed of the conductive medium a and a product foil C (copper foil) is formed; in this embodiment, the post-treatment apparatus 400 is composed of an atmosphere treatment apparatus which is a box-type atmosphere furnace 402, and a combustion apparatus which is a flame shower 401 and in which the flame shower 401 extends into the box-type atmosphere furnace 402, the box-type atmosphere furnace 402 is provided with an intake pipe 4021 and an outlet pipe 4022, the intake pipe 4021 feeds low oxygen partial pressure gas having an oxygen concentration of not more than 14 vol%, the present embodiment controls the oxygen concentration of the fed gas to be 12 to 14 vol%, the outlet pipe 4022 is for exhausting combustion gas, the intake pipe 4021 is provided at the top end of the box-type atmosphere furnace 402, the outlet pipe 4022 is provided at the bottom end of the box-type atmosphere furnace 402, an environment more favorable for deoxidizing the electrolytic copper foil and avoiding oxidation is formed, the flame nozzle 401 is aligned to the conductive medium A film layer of the medium-foil B to perform continuous flame spraying, the PU film is burnt and removed, the gas flow rate of the gas inlet pipe 4021 and the gas flow rate of the gas outlet pipe 4022 are controlled, the gas exhausted by the gas outlet pipe 4022 is detected, the CO in at least 2% VOL is ensured to be contained in the discharged gas, incomplete combustion is ensured in the box-type atmosphere furnace 402, complete combustion removal of the PU film is required to be ensured, the product foil C (namely, metal foil and oxygen-free copper foil) is obtained after the process, the obtained product foil C is driven by the transmission device 100 to be drawn outside the post-processing device 400 and is coiled and stored by the winding drum 500, and the oxygen-free copper foil product is obtained.
The oxygen content of the oxygen-free copper foil product is characterized, and the characterization result shows that the oxygen content of the prepared product foil C is 3.1-3.5 ppm, the oxygen content accords with the oxygen-free copper foil standard, and the oxygen content is extremely low;
in addition, the oxygen content of the intermediate product, namely the medium-foil B is characterized by sampling and peeling the copper foil, and the characterization result shows that the oxygen content is 2.8-3.2, so that the oxygen content is not obviously increased in the subsequent post-treatment process.
In addition, the current density of the present example was controlled to be 3A/dm 2 The temperature of the electrolyte is 50 ℃, the loading time is calculated by controlling the conductive medium A through the conveying device 100 from the time when the conductive medium A enters the electrolyte to the time when the conductive medium A exits the electrolyte, the loading time is 4min in the embodiment, the thickness of the obtained product foil C is 3.3 mu m, the tensile strength of the product foil C is represented, and the representation result shows that the tensile strength can reach 462MPa and the product foil C has excellent tensile property.
Example 2
On the basis of example 1, the electrodeposition parameters and some of the variable parameters of the product were subjected to an adjustment test, and the product foil C was characterized, with the results shown in the following table. Wherein the product thickness is characterized as the maximum thickness (delta) max ) And a minimum thickness (delta) min ) Satisfies delta max -δ min When the thickness is less than or equal to 0.03 mu m, the average thickness is recorded by ten times of measurement, and if the thickness is not less than the average thickness, the interval between the maximum value and the minimum value is recorded. The product characterization precision is 0.05 μm.
| Current density | Time of loading | Other variables | Thickness of the product | Tensile strength |
| 2A/dm 2 | 3min | Is free of | 1.55μm | 371MPa |
| 2A/dm 2 | 4min | Is free of | 2.1μm | 400MPa |
| 2A/dm 2 | 5min | Is composed of | 2.65μm | 429MPa |
| 2A/dm 2 | 6min | Is free of | 3.2μm | 460MPa |
| 3A/dm 2 | 3min | Is free of | 2.4μm | 413MPa |
| 3A/dm 2 | 4min | Is free of | 3.3μm | 462MPa |
| 3A/dm 2 | 5min | Without pretreatment | 4.0μm | 407MPa |
| 3A/dm 2 | 6min | Is free of | 4.8μm | 539MPa |
| 4A/dm 2 | 3min | Is free of | 3.2μm | 455MPa |
| 4A/dm 2 | 4min | Is free of | 4.3μm | 516MPa |
| 4A/dm 2 | 5min | Is free of | 5.35μm | 561MPa |
| 4A/dm 2 | 6min | Is composed of | 6.4μm | 620MPa |
| 5A/dm 2 | 3min | Is free of | 4.0μm | 492MPa |
| 5A/dm 2 | 4min | Is free of | 5.3μm | 566MPa |
| 5A/dm 2 | 5min | Is composed of | 6.8μm | 639MPa |
| 5A/dm 2 | 6min | Is composed of | 7.9μm | 663MPa |
| 3A/dm 2 | 4min | Without pretreatment | 3.3μm | 372MPa |
Each of the above test groups was tested to produce 2 rolls of copper foil having a width of 0.8m and a length of 62m, except 2A/dm 2 Except certain wrinkles of the copper foil obtained in the test group of/3 min, the copper foils produced in the other test groups have no damage or wrinkles.
As can be seen from the above table, for the solution of the invention, the thickness of the product foil C can be controlled by adjusting the current density and the load time, and is related by a certain factor. By combining the previous experiments, the thickness of the prepared product foil C can be controlled by an empirical formula in actual production. The specific empirical formula is as follows:
d＝A+B×J+C×T
in the formula: d is the thickness of the product foil C in mum, A, B and C are empirical coefficients, A is influenced by the composition of the metal foil in mum, B and C are influenced by the spacing between the anode 302 and the deposition surface, the arrangement position of the anode 302, the advancing path of the deposition surface of the conductive medium A and the like, and B is in mum-dm 2 A, C in μm/min and J in current density in A/dm 2 And T is load time in min.
The formula can calculate the empirical coefficients A, B and c after three times of trial production, and simply fit the empirical coefficients to obtain a reference formula for actual production for guiding the actual production, wherein the reference formula has higher precision when the trial production times are more.
In addition, it can be seen from other variable tests that, for the technical solution of the present invention, the pretreatment device 200 does not affect the thickness of the product foil C, that is, the treatment agent of this embodiment has no significant effect on the thickness of the copper foil, but has a significant effect on the mechanical properties of the copper foil. As the tensile strength of the copper foil can be effectively improved by spraying and using the polyethyleneimine in the embodiment, the pretreatment apparatus 200 in the embodiment has a good performance in improving the performance of the copper foil, and the pretreatment scheme in the embodiment is adjusted based on the technologies of 202110636882.0, 202110638177.4 and the like disclosed by the achievements of the research and development cooperation project.
Comparative example 1
Based on the technical scheme of the embodiment 1, the following differences are only provided:
the medium foil B produced by the deposition apparatus 300 is transferred to a full-automatic foil tearing machine (commercially available: madake full-automatic copper foil tearing machine) by a transfer apparatus 100, and a peeling and separating process of the conductive medium a and the product foil C (copper foil) is performed.
Compared with the technical scheme of the embodiment 1, the time length required for preparing the copper foil with the thickness of 1.2m multiplied by 60m in the embodiment 1 through the separation by the post-treatment device 400 is 26min, the time length for the peeling separation treatment of the full-automatic peeling machine in the comparative example 1 is 2h 11min, and great difference exists in efficiency. In addition, the copper foil is not damaged and wrinkled in the whole process of the post-processing device 400 in the embodiment 1, the yield of products reaches 100%, and the copper foil 6 in the comparative example 1 is slightly damaged and has wrinkles in a plurality of positions by adopting a full-automatic tearing machine. The tensile strength of the copper foil prepared by the two is represented, the representation result of the embodiment 1 is 462MPa, while the representation result of the comparative example 1 is only about 417MPa, so that the tearing treatment can generate certain adverse effect on the mechanical property of the copper foil, the copper foil is easy to damage, the treatment efficiency is low, and the technical scheme of the invention has obvious superiority compared with the conventional electrolytic metal foil preparation scheme.
Comparative example 2
Based on the atomic method scheme developed in advance, the method and the technical scheme are used for carrying out transverse comparative preparation tests.
Based on the embodiment of example 3 in the 202111335007.5 technical solution, copper foils with thicknesses of 1.2 μm, 3.2 μm and 6.8 μm and dimensions of 0.8m × 1.0m were prepared by controlling the thickness of an atomic layer (copper foil) by adjusting the vapor deposition time, respectively, and rolls with a thickness of 3.2 μm and dimensions of 0.6m × 22m were continuously produced.
A foil roll having the same thickness of 3.2 μm and a dimensional specification of 0.6 m.times.22 m was produced without pretreatment based on the embodiment of example 1.
Example 3
Building a production system of metal foil:
the conductive copper alloy belt A01 is used as a conductive carrier, and the thickness of the conductive copper alloy belt A01 is 2.2cm, so that the conductive copper alloy belt has good flexibility and conductivity;
specifically, as shown in fig. 5, a 0.8m × 1.0 m-sized cavity a011 is opened on one side of a conductive copper alloy strip a01 (a beryllium bronze alloy strip of C17000), an insulating layer a012 is formed by insulating the side of the conductive copper alloy strip a01 opened with the cavity a011, and an insulating layer a012 is formed by insulating the side wall of the cavity a 011;
the die cavity A011 is filled with UV curing conductive ink to be paved at the bottom of the die cavity A011 through gravity leveling, and the UV curing conductive ink is commercially available and purchased from Yuxi new materials;
the whole system is shown in fig. 6, and comprises the same electric roller as the conveying device 100 of the embodiment 1, and is used for conveying the conductive copper alloy belt A01 as a conductive carrier;
the conductive copper alloy strip a01 firstly enters a pretreatment device 200, for the embodiment, the pretreatment device 200 is provided with an ink dripper 202 and a UV lamp 203, the ink dripper 202 drips UV curable conductive ink into a die cavity a011 of the conductive copper alloy strip a01, gravity leveling is realized before reaching an irradiation range of the UV lamp 203 along with a conveying process of the conductive copper alloy strip a01, and then UV curing is performed, as shown in a partially enlarged view in fig. 6, a conductive medium a thin film (UV curable conductive ink thin film) is formed in the die cavity a011, and then the conductive copper alloy strip enters a deposition device 300 under the driving of a conveying device 100, the deposition device 300 in the embodiment is similar to that in embodiment 1 and comprises a cathode 301, an anode 302, an electrolytic cell 304 and a power supply 303;
the cathode 301 is arranged outside the electrolytic cell 304, the back surface (the surface provided with the die cavity A011 is the front surface, and the opposite surface is the back surface) of the conductive copper alloy strip A01 firstly passes through the cathode 301 and is attached to the cathode 301, and after the conductive copper alloy strip A01 enters the electrolyte of the electrolytic cell 304, the conductive copper alloy strip A01 and the UV curing conductive ink film (conductive medium A film) can be used as the extension part of the cathode 301 to form electrodeposition;
the anode 302 is a commercially available graphite anode 302 and is arranged at the bottom of an electrolytic cell 304, the power supply 303 is a silicon controlled rectifier power supply 303 purchased from SanRex, an electrolyte is injected into the electrolytic cell 304, the electrolyte is 280-320 g/L of blue vitriol solution, the blue vitriol solution also contains 120g/L of sulfuric acid and 10mg/L of gelatin, and the copper ion concentration of the electrolyte is dynamically controlled by adding blue vitriol through feeding;
when the conductive medium A film enters the electrolytic cell 304, the deposition surface faces downwards and faces the anode 302, after the power supply 303 is turned on, the electrolytic cell 304 works to realize electrodeposition on the deposition surface of the conductive medium A film, the electrolytic copper foil is prepared, and then after the preparation of the electrolytic copper foil on the deposition surface of the conductive medium A film is completed, the conductive copper alloy strip A01 loaded with a medium-foil B (namely, a UV curing conductive ink film-electrolytic copper foil composite) is sent out of the deposition device 300 through the conveying device 100 and sent into the post-processing device 400;
the post-treatment device 400 comprises a solvent tank, the solvent tank is matched with a heating device to heat a solvent in the solvent tank, an acetone-cyclohexanone solution is filled in the solvent tank, wherein the volume ratio of acetone to cyclohexanone is 1:3, heating the acetone-cyclohexanone solution in the solvent pool to 85 ℃ by a heating device, and putting the conductive copper alloy strip A01 loaded with the medium-foil B into the solvent pool for hot dipping treatment, wherein the film of the conductive medium A is partially softened and dissolved, the viscosity is obviously weakened, and the product foil C on the surface of the film of the conductive medium A falls off into the solvent pool;
the bottom of the solvent pool is a slope, a flow guide opening is formed in the low slope end of the solvent pool, an acetone-cyclohexanone solution flows out of the flow guide opening and drives the falling electrolytic copper foil to leave the solvent pool so as to recover a product foil C, the recovery can be realized by pre-storing the solvent and the electrolytic copper foil into a recovery barrel and cooling to normal temperature and then fishing out the electrolytic copper foil, or a better scheme can be adopted like the embodiment, the embodiment adopts a slope separator, so that the electrolytic copper foil can be retained on a slope plate of the slope separator by surface tension and friction force, and the solvent part flows to the slope bottom for separation; as can be seen from fig. 6, a large amount of the conductive medium a is also removed from the solvent bath, and the conductive copper alloy strip a01 can enter the pretreatment device 200 again under the driving of the conveying device 100, so that the single-strip recycling of the conductive copper alloy strip a01 is realized; although the components of the conductive medium A film (UV curing conductive ink film) cannot be thoroughly and effectively removed and cleaned by the treatment device 400, due to the characteristics of the pretreatment device 200 matched with the treatment device, the UV curing conductive ink can undergo a gravity leveling process after being dropped into the die groove A011, the flatness of the formed conductive medium A film can be ensured within a certain period, only the die groove A011 needs to be cleaned regularly, the process cost is low, and a system can be quickly built to realize the production and preparation of medium and small-batch electrolytic metal foils.
In addition, the pre-processing apparatus 200 can also realize loading of the conductive medium a on the conductive copper alloy strip a01 in a form of a film, such as the PU conductive film described in the attachment example 1, at this time, the front surface of the conductive copper alloy strip a01 is completely subjected to oxidation insulation treatment, and in combination with the thermal expansion characteristic of the conductive copper alloy strip a01, the post-processing apparatus 400 is first provided with a heating device, a refrigerating device, an atmosphere processing device and a combustion device correspondingly, separation of the conductive medium a film from the conductive carrier is first realized by the expansion and contraction method through the heating device and the refrigerating device, and then the medium-foil B is recovered and is treated by the atmosphere processing device and the combustion device to remove the conductive medium a, so as to realize effective preparation of the metal foil.
The metal foils (copper foils) produced in example 3 and comparative example 2 were characterized and analyzed as shown in the following table.
In addition, ten single foils (0.8 m × 1.0m single foil) are divided into judgment areas of 5 × 5cm, and if a dead pixel (including deformation, obvious folding, scratching, hole breaking, obvious corrosion trace, or obvious dirt difficult to remove) exists in each judgment area, the area is judged to be damaged, and at the boundaries of a plurality of judgment areas, only one judgment area is damaged.
Thereby calculating the bad pixel rate. The results are shown in the following table.
In the table: the gas phase method (202111335007.5) is the method described in example 3 (iodine intermediate layer), and the zero stress method is the method of the present invention.
From the above table, it can be seen that the zero stress method has the advantage of preparing the copper foil by electrolysis compared with the vapor phase method, the texture characteristics of the electrolytic copper foil are more excellent than those of the vapor deposition copper foil, and have a larger (220) crystal face texture coefficient, so that the tensile strength is higher than that of the vapor phase method, that is, the mechanical properties are more excellent, but in the case of actually performing oxygen content characterization, the vapor phase method has more strict control on the atmosphere, and the oxygen content is lower. On the other hand, as can be seen from the data of the defective pixel rate, the defective pixel rate is lower for preparing a single metal foil within a certain specification by the gas phase method, but once the long foil coil is prepared, the defective pixel rate is sharply increased, and the method does not have good applicability for preparing the long foil coil, but when the special ultra-thin (1.2 μm thickness) metal foil is prepared by the method, the defective pixel rate is increased to a certain extent, but the technical scheme of the invention has good preparation effect for the electrolytic metal foil with the thickness of more than 2 μm basically by combining with the comparative test of the embodiment 2.
Example 4
The method and the system in the technical scheme of the invention can also realize the synchronous preparation of single-system double-foil materials, and construct a double-foil system as shown in figure 7;
the dual foil system comprises a transport device 100, a deposition device 300 and a post-treatment device 400;
as shown in fig. 7, under the action of the conveying device 100, the conductive medium a of this embodiment is a PU conductive film with a low melting point, the melting point of the PU conductive film is less than or equal to 136 ℃, the conductive medium a enters the deposition device 300, as can be seen from fig. 7 and 8, the cathode 301 of the deposition device 300 of this embodiment is disposed outside the electrolytic cell 304, the film of the conductive medium a first passes through the cathode 301 and is attached to the cathode 301, and the film of the conductive medium a can be used as an extension of the cathode 301 to form electrodeposition after entering the electrolyte of the electrolytic cell 304;
the anode 302 is a commercially available graphite anode 302, the system is a double-anode 302 system, a first anode 302a is arranged at the bottom of an electrolytic cell 304, a second anode 302b is arranged at the top of the electrolytic cell 304, the first anode 302a and the second anode 302b respectively face to two opposite sides of a conductive medium A, a power supply 303 is a silicon controlled power supply 303 purchased from SanRex, an electrolyte is injected into the electrolytic cell 304, the electrolyte in the electrolyte is 280-320 g/L of a blue vitriol solution, the blue vitriol solution also contains 120g/L of sulfuric acid and 10mg/L of gelatin, and the concentration of copper ions in the electrolyte is dynamically controlled by adding blue vitriol through feeding;
when the conductive medium A film enters the electrolytic cell 304, the first deposition surface faces downwards and faces towards the first anode 302a, the second deposition surface faces upwards and slantways towards the second anode 302B, after the power supply 303 is turned on, the electrolytic cell 304 works to realize electrodeposition on the two deposition surfaces of the conductive medium A film and prepare electrolytic copper foil, and then after the preparation of the electrolytic copper foil is finished on the deposition surface of the conductive medium A film, the medium-foil B (namely, a first electrolytic copper foil C01-PU conductive film medium-second electrolytic copper foil C02 composite) is sent out of the deposition device 300 through the conveying device 100 and sent into the post-treatment device 400;
the post-treatment device 400 of this embodiment is composed of an atmosphere treatment device and a spraying device 403, the atmosphere treatment device is a box-type atmosphere furnace 402, the spraying device 403 is arranged in the box-type atmosphere furnace 402 and at an outlet side of a material belt of the box-type atmosphere furnace 402, it is ensured that a medium-foil B enters the box-type atmosphere furnace 402, is subjected to atmosphere treatment first and then passes through the spraying device 403, the box-type atmosphere furnace 402 is provided with an air inlet pipe 4021 and an air outlet pipe 4022, the air inlet pipe 4021 sends a thermal protection gas, the thermal protection gas fed in this embodiment is controlled to be nitrogen gas at 150 ℃, the air outlet pipe 4022 is used for discharging the gas and the melted PU or PU particles, the gas inlet pipe 4021 is arranged at the top end of the box-type atmosphere furnace 402, the gas outlet pipe 4022 is arranged at the bottom end of the box-type atmosphere furnace 402, so that molten PU or PU particles can be discharged from the electrolytic copper foil better, the molten PU conductive film conductive medium A is thermally blown and cleaned, zero stress separation of the first electrolytic copper foil C01 and the second electrolytic copper foil C02 is realized, the spraying device 403 is favorable for thoroughly removing residual molten polyurethane, the liquid sprayed by the spraying device 403 is cyclohexanol heated to 135 ℃, and the cyclohexanol has the characteristics of difficult volatilization and high boiling point, so that the technical scheme of the invention has good adaptability, but due to slight toxicity and slight irritation, recovery and worker protection need to be paid attention during use;
the obtained product foil C (the first electrolytic copper foil C01 and the second electrolytic copper foil C02) is then driven by the conveying device 100 together to be drawn out of the post-processing device 400 and is respectively received by the two reels 500.
In addition, the current density of the present example was controlled to be 2.5A/dm 2 The temperature of the electrolyte is 50 ℃, the load time is calculated by controlling the conductive medium A through the conveying device 100 from the time when the conductive medium A enters the electrolyte to the time when the conductive medium A exits the electrolyte, the load time is 5min in the embodiment, the thickness of the obtained first electrolytic copper foil C01 is 3.8 micrometers, the tensile strength of the first electrolytic copper foil C01 is represented, the representation result shows that the tensile strength of the first electrolytic copper foil C01 can reach 386MPa, the thickness of the obtained second electrolytic copper foil C02 is 3.2 micrometers, the tensile strength of the second electrolytic copper foil C02 is represented, and the representation result shows that the tensile strength of the second electrolytic copper foil C02 reaches 369MPa.
In addition, the positions of the first anode 302a and the second anode 302b relative to the conductive medium A, the traveling path of the conductive medium A in the electrolytic cell 304 and the like are controlled in various aspects, the thickness of the first electrolytic copper foil C01 and the thickness of the second electrolytic copper foil C02 can be simultaneously regulated, the actual production preparation efficiency is greatly improved, the synchronous preparation of single-system double-foil materials can be simply and efficiently realized, and the method can not be realized by the conventional electrolytic metal foil technology and the gas-phase method metal foil preparation technology.
Example 5
The method of the technical scheme of the invention can be combined with a conventional metal foil electrolytic system to form a continuous stripping type zero-stress electrolytic metal foil system shown in figures 9 and 10;
the continuous peel-off type zero-stress electrolytic metal foil system comprises a conveying device 100, a deposition device 300 and a post-treatment device 400; as shown in fig. 9, firstly, the deposition device 300 of the system of the embodiment includes an electrolytic cell 304, a cathode 301, an anode 302 and a power source 303, and a deposition roller 305 and a scraper 306 which are specially arranged;
specifically, the deposition roller 305 is braked by a motor to rotate at a controlled speed, and is preferably made of an insulating material and a scratch-resistant material, for example, in this embodiment, the deposition roller 305 is made of wear-resistant corundum ceramics, has extremely high surface flatness, high strength, high hardness, acid and alkali corrosion resistance, and is not easy to deposit dirt on the surface, so that the deposition roller can be used as a good carrier for loading the conductive medium a;
the anode 302 is a commercially available graphite anode 302 and is arranged at the bottom of an electrolytic cell 304, a power supply 303 is a silicon controlled power supply 303 purchased from SanRex, an electrolyte is injected into the electrolytic cell 304, the electrolyte in the electrolyte is 280-320 g/L of a blue vitriol solution, the blue vitriol solution also contains 120g/L of sulfuric acid and 10mg/L of gelatin, and the electrolyte is fed with blue vitriol to dynamically control the concentration of copper ions in the electrolyte;
the electrolytic cell 304 described in this embodiment is a double-tank electrolytic cell 304, which has a main tank 3041 and an auxiliary tank 3042, respectively, where the main tank 3041 is used for realizing electrodeposition, the auxiliary tank 3042 is used for controlling the liquid level of an electrolyte and the concentration of the electrolyte in a matching manner, and a through groove 3043 is provided between the main tank 3041 and the auxiliary tank 3042 for communication;
the cathode 301 used in this embodiment is a conductive cathode 301 roller, which can rotate freely and is close to the deposition roller 305, the minimum distance between the conductive cathode 301 roller and the deposition roller 305, that is, the thickness of the conductive medium a, in the rotation direction of the deposition roller 305, the front end of the cathode 301 is provided with the pretreatment device 200, the pretreatment device 200 comprises a medium material spray head 204 and a cold air cylinder 205, the medium material spray head 204 sprays the conductive medium a material (molten PU master batch) on the surface of the deposition roller 305, the cold air cylinder 205 is blown and cured, then the cathode 301 presses and flattens to form a conductive medium a film, the conductive medium a film enters the electrolyte of the electrolytic cell 304 under the drive of the deposition roller 305, and the conductive medium a surface is subjected to electrodeposition to form a medium-foil B;
the scraper 306 is arranged at the rear end of the deposition roller 305 in the rotation direction, the blade part of the scraper abuts against the surface of the deposition roller 305, can be arranged symmetrically with the cathode 301, is arranged above the electrolyte and is used for scraping and separating the medium foil B and the deposition roller 305;
the separated medium foil B is driven by the conveying device 100 to be conveyed to the post-processing device 400;
in this embodiment, the post-treatment apparatus 400 is composed of an atmosphere treatment apparatus and a combustion apparatus, the atmosphere treatment apparatus is a box-type atmosphere furnace 402, the combustion apparatus is a flame nozzle 401, the flame nozzle 401 extends into the box-type atmosphere furnace 402, the box-type atmosphere furnace 402 is provided with an air inlet pipe 4021 and an air outlet pipe 4022, the air inlet pipe 4021 feeds low-oxygen partial pressure gas, the oxygen concentration in the gas is less than or equal to 14 vol%, the embodiment controls the oxygen concentration in the gas to be 12-14 vol%, the air outlet pipe 4022 is used for exhausting combustion gas, the air inlet pipe 4021 is arranged at the top end of the box-type atmosphere furnace 402, the air outlet pipe 4022 is arranged at the bottom end of the box-type atmosphere furnace 402 to form an environment more favorable for deoxidizing the electrolytic copper foil and avoiding oxidation, the flame nozzle 401 is aligned with the conductive medium a thin film layer of medium-foil B to perform continuous flame spraying, the PU thin film is burned and removed, the gas flow rate of the air inlet pipe 4021 and the air flow rate of the air outlet pipe 4022 are controlled, the exhaust gas is detected to ensure that the CO containing at least 2 vol is contained in the gas, so as CO, the CO is introduced into the box-type atmosphere furnace 402 to ensure that the PU thin film is burned in the oxygen-free atmosphere, but the PU foil is completely removed, the rolled product, and the rolled up by the copper foil is taken up into the copper foil roll, and the copper foil roll after the roll product is obtained by the copper foil treatment apparatus (the roll product 100) and the copper foil treatment apparatus, and the roll is obtained after the roll is completely removed, and the roll is obtained by the copper foil treatment apparatus 100).
The oxygen content of the oxygen-free copper foil product is characterized, and the characterization result shows that the oxygen content of the prepared product foil C is 2.8-3.0 ppm, the oxygen content accords with the oxygen-free copper foil standard, and the oxygen content is extremely low;
in addition, the oxygen content of the intermediate product, namely the medium-foil B is characterized by sampling and peeling the separated copper foil, and the characterization result shows that the oxygen content is 2.6-2.9, so that the oxygen content is not obviously increased in the subsequent post-treatment process.
In addition, the current density of the present example was controlled to be 3A/dm 2 The temperature of the electrolyte is 50 ℃, the loading time is calculated by controlling the conductive medium A through the conveying device 100 from the time when the conductive medium A enters the electrolyte to the time when the conductive medium A exits the electrolyte, the loading time is 4min in the embodiment, the thickness of the obtained product foil C is 3.0 μm, the tensile strength of the product foil C is represented, and the representation result shows that the tensile strength can reach 366MPa and the product foil C has excellent tensile property.
Therefore, the technical scheme of the invention can be directly, simply and effectively applied to the existing electrodeposition system, and the device matching and system can be formed by improving the electrodeposition system to a certain degree.
Claims (9)
1. A method for preparing zero-stress electrolytic metal foil is characterized in that,
the method comprises the following steps:
1) Arranging a movable conductive medium, wherein the conductive medium can dynamically pass through electrolyte, is electrically connected with an anode arranged in the electrolyte when in the electrolyte, and is used as a cathode to carry out electrodeposition preparation of metal foil on the conductive medium to obtain a conductive medium-metal foil;
2) And separating and removing the conductive medium component in the conductive medium-metal foil by a phase state change and/or chemical method and/or a dissolution and/or expansion and contraction method, namely completing the zero-stress preparation of the electrolytic metal foil.
2. The method of claim 1, wherein the step of preparing the electrolytic metal foil is further comprised of,
step 1), the movable conductive medium is put into the electrolyte in the form of a strip and/or a sheet of a target shape and/or a setting and curing slurry.
3. The method of claim 2, wherein the step of preparing the electrolytic metal foil is further comprised of,
and filling the sizing and curing slurry into a specific carrier, performing gravity leveling and/or shape pressing, and curing to obtain the conductive medium.
4. The method of claim 1, wherein the step of preparing the electrolytic metal foil is further comprised of,
step 1) the electrolyte contains soluble metal salt of a target metal foil component;
the anode in the step 1) is an insoluble anode.
5. A zero stress electrolytic metal foil system characterized in that,
the system is used for carrying out electrodeposition on a conductive medium and comprises a deposition device and a post-treatment device;
the deposition device comprises an electrolytic cell, a cathode, an anode and a power supply;
the cathode, the anode and the power supply are electrically connected;
the electrolytic cell is used for containing electrolyte, the anode is arranged in the electrolytic cell, the cathode is electrically connected with the conductive medium, and the conductive medium is used as an extension part of the cathode, so that the conductive medium exists as the cathode in the electrolytic cell for electrodeposition;
the post-treatment device is used for removing the conductive medium and comprises a solvent pool, a heating device, a refrigerating device, a combustion device, an atmosphere treatment device and a spraying device.
6. The zero-stress electrolytic metal foil system of claim 5,
the system further comprises a conveying device for enabling transport of the conductive medium.
7. The zero-stress electrolytic metal foil system of claim 6,
the system also comprises a pretreatment device;
the pretreatment device is used for loading a conductive medium on a carrier and/or performing surface treatment on the conductive medium;
the carrier moves under the drive of the conveying device, and the carrying conductive medium sequentially passes through the deposition device and the post-processing device.
8. The zero-stress electrolytic metal foil system of claim 7,
the pretreatment device comprises a spraying device and/or a brushing device and/or a solvent pool and/or a heating device and/or a refrigerating device and/or a UV curing device.
9. Use of the method according to claims 1 to 4,
the method is used for producing metal foils with the thickness dimension being more than or equal to 2 mu m, and/or is used for producing large-size metal foils with the length dimension specification being more than or equal to 3m and the width dimension specification being more than or equal to 1.2m, and/or is used for continuously producing metal foil rolls.
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