CN110894616B - High-density copper foil and preparation method thereof - Google Patents
High-density copper foil and preparation method thereof Download PDFInfo
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- CN110894616B CN110894616B CN201911388226.2A CN201911388226A CN110894616B CN 110894616 B CN110894616 B CN 110894616B CN 201911388226 A CN201911388226 A CN 201911388226A CN 110894616 B CN110894616 B CN 110894616B
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- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/38—Electroplating: Baths therefor from solutions of copper
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Abstract
The invention discloses a high-density copper foil and a preparation method thereof. The preparation method comprises the following steps: copper materials used as an anode, a cathode roller and electrolyte are used for jointly constructing an electrochemical reaction system, the electrolyte is a mixed solution containing copper ions and sulfate ions, and the concentration of the copper ions in the electrolyte is 0.1-0.5 mol.L‑1The concentration of sulfate ions is 1.20-6 mol.L‑1(ii) a Electrifying an electrochemical reaction system to perform an electrolytic reaction, so that copper ions in the electrolyte are deposited on the surface of the cathode roller to form a high-density copper foil, and adopting a cooling system to ensure that the temperature of the electrolyte is below 20 ℃ and the current density is 4000A/m during the electrolytic reaction2The circulation rate of the electrolyte is 0-2 L.min‑1. The invention adopts the cooling coil to cool the electrolyte, so that the electrolytic reaction is carried out at low temperature, and the high-density electrolytic copper foil product can be obtained without adding additives into the electrolyte.
Description
Technical Field
The invention relates to preparation of copper foil, in particular to high-density copper foil and a preparation method thereof, and belongs to the technical field of copper foil preparation.
Background
The high-density copper foil has the advantage of good conductivity and is a lithium ion battery cathode material with a very wide application range. In the conventional high-density electrolytic copper foil production process, various additives are generally required to be added to the electrolyte in order to reduce the size of the electro-crystallized particles in the copper foil, thereby obtaining a dense internal structure. And the used additives are usually high in cost and difficult to control, corrosion is often caused to groove body equipment, and the groove body equipment is easy to rot after standing for a long time, so that the production management difficulty is improved, and the manpower input and the equipment cost are increased.
Disclosure of Invention
The invention mainly aims to provide a high-density copper foil and a preparation method thereof, so that the defects of the prior art are overcome.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a high-density copper foil, which comprises the following steps:
at least enabling copper materials as an anode, a cathode roller and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte is a mixed solution containing copper ions and sulfate ions, and the concentration of the copper ions in the electrolyte is 0.1-0.5 mol.L-1The concentration of sulfate ions is 1.20-6 mol.L-1；
Electrifying the electrochemical reaction system to carry out electrolytic reaction, so that copper ions in the electrolyte are deposited on the surface of the cathode roller to form a high-density copper foil, and carrying out cooling treatment on the electrolyte by adopting a cooling system during the electrolytic reaction, so that the temperature of the electrolyte is always below 20 ℃, and the current density is 4000A/m2The circulation rate of the electrolyte is 0-2 L.min-1. In some preferred embodiments, the preparation method comprises: and during the electrolytic reaction, the distance between the cathode roller and the anode is 0.4-30 mm.
In some preferred embodiments, the preparation method comprises: during the electrolytic reaction, the rotating speed of the cathode roller is 0.5-15 r ·min-1。
Embodiments of the invention also provide high density copper foil prepared by the foregoing method having a density greater than 8.0 g-cm-3。
Compared with the traditional high-density electrolytic copper foil production process, the invention has the beneficial effects that:
the invention provides a method for preparing a high-density electrolytic copper foil without adding additives into electrolyte, which is characterized in that a cooling coil is adopted to cool the electrolyte, so that an electrolytic reaction is carried out at a low temperature, and a high-density electrolytic copper foil product is obtained by controlling the concentration of copper sulfate, the concentration of sulfuric acid, the current density and the circulation rate of the electrolyte.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a reaction scheme for preparing a high-density copper foil according to an exemplary embodiment of the present invention.
Fig. 2 is a load-displacement graph showing the nano-indentation test results of the high-density copper foil prepared under the conditions of example 1 of the present invention.
FIGS. 3a to 3c are SEM photographs of the surface of the high-density copper foil prepared under the conditions of example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made extensive research and practice to provide a technical scheme of the present invention, and provides a method for preparing a high-density copper foil without adding an additive to an electrolyte. The inventor of the present invention has found that when the concentration of copper ions in the electrolyte is low, the concentration of sulfuric acid is high, and the electrolyte is relatively static and the current density is low,can prepare the product with the density of more than 8.0g cm without adding any additive-3The copper foil product of (1). The metal copper is used as a consumable anode, the molar quantity of copper element consumed by the anode in the electrolysis process is equal to that of copper element electrodeposited at the cathode, and the concentration of copper ions in the electrolyte cannot be changed. In the reaction process, copper ions in the electrolyte can not be reduced due to consumption, and the copper anode can be oxidized to generate copper ions to be supplemented into the solution when the copper ions in the solution are consumed, so that the constancy of the copper ions in the solution is ensured, the concentration of the copper ions in the electrolyte can be prevented from fluctuating in a large range, and meanwhile, the obvious local concentration difference in the electrolyte can not be caused, and the reaction can be carried out under the condition of a low electrolyte circulation rate.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a high-density copper foil, including:
at least enabling copper materials as an anode, a cathode roller and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte is a mixed solution containing copper ions and sulfate ions, and the concentration of the copper ions in the electrolyte is 0.1-0.5 mol.L-1The concentration of sulfate ions is 1.20-6 mol.L-1；
Electrifying the electrochemical reaction system to carry out electrolytic reaction, so that copper ions in the electrolyte are deposited on the surface of the cathode roller to form a high-density copper foil, and carrying out cooling treatment on the electrolyte by adopting a cooling system during the electrolytic reaction, so that the temperature of the electrolyte is always below 20 ℃, and the current density is 4000A/m2The circulation rate of the electrolyte is 0-2 L.min-1Under the condition, a high-density electrolytic copper foil product is obtained.
In some preferred embodiments, the preparation method comprises: when the electrolysis reaction is carried out, the current density is 500-4000A/m2。
In some preferred embodiments, the preparation method comprises: during the electrolytic reaction, the temperature of the electrolyte is kept lower than 20 ℃, preferably 1-20 ℃.
In some preferred embodiments, the preparation method comprises: and during the electrolytic reaction, the distance between the cathode roller and the anode is 0.4-30 mm.
In some preferred embodiments, the preparation method comprises: the rotating speed of the cathode roller is 0.5-15 r.min during the electrolytic reaction-1。
In some preferred embodiments, the electrolyte is a mixed aqueous solution comprising copper sulfate and sulfuric acid.
Further, the time of the electrolytic reaction depends on the thickness of the copper foil formed by deposition, and is not limited herein.
FIG. 1 is a schematic diagram showing the reaction for preparing a high-density electrolytic copper foil. The invention is matched with a cooling system outside the electrolytic cell, a cooling coil is arranged in the same time slot, a refrigerant circulates through the cooling coil to cool the electrolyte, the temperature of the electrolyte is ensured not to rise due to the heating of a plate electrode, the temperature of the electrolyte is always lower than 20 ℃, and the reaction current density is controlled to be lower than 4000 A.m-2。
Further, the cathode roll is selected from a titanium shaft.
Further, the copper material includes a copper block or a copper sheet, but is not limited thereto.
Further, the shape of the anode may be various regular shapes such as a flat plate, an arc, a polygon, a sphere, and the like, and may also be other irregular shapes.
Further, the method further comprises: and stripping the high-density copper foil formed by deposition from the surface of the cathode roller, and performing the steps of cleaning, oxidation resistance treatment and collection.
In some more specific embodiments, the method for preparing the high-density copper foil specifically comprises the following steps:
step A, taking a mixed aqueous solution of copper sulfate and sulfuric acid as an electrolyte, and controlling the concentration of the copper sulfate to be 0.1 mol.L-1～0.5mol·L-1The sulfuric acid concentration is 1.20 mol.L-1～6mol·L-1In the meantime, no additional additive is added into the electrolyte;
step B, a refrigerating device is arranged outside the electrolytic cell, a cooling coil is arranged in the electrolytic cell, and the temperature of the electrolyte is ensured to be between 1 ℃ and 20 ℃ through refrigerant circulation;
step C, taking a metal titanium shaft as a cathode roller and a simple substance copper block or sheet as a consumable anode;
step D, the current density for electrolysis is between 500 A.m-2To 4000 A.m-2The distance between the cathode and the anode is between 0.4mm and 30mm, and the rotating speed of the cathode roller is 0.5 r.min-1To 15 r.min-1The circulation rate of the electrolyte in the electrolytic cell is 0 L.min-1To 2 L.min-1To (c) to (d);
and E, with the rotation of the cathode roller, stripping the high-density copper foil obtained by electrolysis from the surface of the cathode roller, and storing the high-density copper foil after surface cleaning, anti-oxidation treatment and cleaning and drying again.
Further, the density of the high-density copper foil is more than 8.0 g-cm-3。
By the technical scheme, the invention provides the method for preparing the high-density electrolytic copper foil without adding additives into the electrolyte, and the high-density electrolytic copper foil product is obtained by controlling the concentration of copper sulfate in the electrolyte, the concentration of sulfuric acid, the current density and the circulation rate of the electrolyte, and the additives are not required to be added, so that the process flow is simpler, and the production cost is lower.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in further detail below with reference to the accompanying drawings and several preferred embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying the specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The reagents used in the following examples were all of analytical purity.
Example 1
The mixed aqueous solution of copper sulfate and sulfuric acid is used as electrolyte, the concentration of copper sulfate is controlled to be stable at 0.1 mol.L-1The concentration of sulfuric acid is stabilized at 6 mol.L-1No additional additives are added to the electrolyte. The temperature of the electrolyte is 20 ℃, and the circulation rate of the electrolyte is 2L-min-1. The metal titanium shaft is used as a cathode roller, the metal copper block is used as a consumption anode, and the electrolytic current density is 500 A.m-2And the distance between the anode and the cathode is 30 mm. The rotating speed of the cathode roller is 0.5 r.min-1And the high-density copper foil obtained by electrolysis is stripped from the surface of the cathode roller along with the rotation of the cathode roller, and is stored after surface cleaning, anti-oxidation treatment, cleaning and drying again. The density of the copper foil product obtained in this example was measured to be 8.51g cm-3。
Fig. 2 shows the nano-indentation test result (load-displacement graph) of the high-density copper foil prepared in this example, which shows that the copper foil product has good hardness and elasticity. SEM photographs of the surface of the high-density copper foil prepared in this example are shown in fig. 3a to 3c, which show that the copper foil has a porous structure.
Example 2
The mixed aqueous solution of copper sulfate and sulfuric acid is used as electrolyte, the concentration of the copper sulfate is controlled to be stable at 0.5 mol.L-1The concentration of sulfuric acid is stabilized at 1.20 mol.L-1No additional additives are added to the electrolyte. The temperature of the electrolyte is 15 ℃, and the circulation rate of the electrolyte is 0L-min-1. The metal titanium shaft is used as a cathode roller, the metal copper block is used as a consumption anode, and the electrolytic current density is 4000 A.m-2And the distance between the anode and the cathode is 10 mm. The rotating speed of the cathode roller is 5 r.min-1And the high-density copper foil obtained by electrolysis is stripped from the surface of the cathode roller along with the rotation of the cathode roller, and is stored after surface cleaning, anti-oxidation treatment, cleaning and drying again. The density of the copper foil product obtained in this example was measured to be 8.31g cm-3。
Example 3
The mixed aqueous solution of copper sulfate and sulfuric acid is used as electrolyte, the concentration of the copper sulfate is controlled to be stable at 0.3 mol.L-1The concentration of sulfuric acid is stabilized at 3 mol.L-1No additional additives are added to the electrolyte. The temperature of the electrolyte is 1 ℃, and the circulation rate of the electrolyte is 1 L.min-1. The metal titanium shaft is used as a cathode roller, the metal copper block is used as a consumption anode, and the electrolytic current density is 2000 A.m-2And the distance between the anode and the cathode is 0.4 mm. The rotating speed of the cathode roller is 15 r.min-1And the high-density copper foil obtained by electrolysis is stripped from the surface of the cathode roller along with the rotation of the cathode roller, and is stored after surface cleaning, anti-oxidation treatment, cleaning and drying again. The density of the copper foil product obtained in this example was measured to be 8.41g cm-3。
Example 4
The mixed aqueous solution of copper sulfate and sulfuric acid is used as electrolyte, the concentration of copper sulfate is controlled to be stable at 0.1 mol.L-1The concentration of sulfuric acid is stabilized at 6 mol.L-1No additional additives are added to the electrolyte. The temperature of the electrolyte is 10 ℃, and the circulation rate of the electrolyte is 0L-min-1. The metal titanium shaft is used as a cathode roller, the metal copper plate is used as a consumption anode, and the electrolytic current density is 1000 A.m-2And the distance between the anode and the cathode is 8 mm. The rotating speed of the cathode roller is 10 r.min-1And the high-density copper foil obtained by electrolysis is stripped from the surface of the cathode roller along with the rotation of the cathode roller, and is stored after surface cleaning, anti-oxidation treatment, cleaning and drying again. The density of the copper foil product obtained in this example was measured to be 8.48g cm-3。
Comparative example 1
The comparative example differs from example 1 in that: the concentration of copper ions in the electrolyte is higher than 0.5 mol.L-1The density of the obtained copper foil product was 7.81g cm-3。
Comparative example 2
The comparative example differs from example 1 in that: the concentration of sulfate ions in the electrolyte is lower than 1.2 mol.L-1The density of the obtained copper foil product is 7.85 g-cm-3
Comparative example 3
The comparative example differs from example 1 in that: the current density is higher than 4000A/m2The density of the obtained copper foil product is 7.72g cm-3
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (7)
1. A method for preparing a high-density copper foil is characterized by comprising the following steps:
at least enabling copper materials as an anode, a cathode roller and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte is a mixed aqueous solution of copper sulfate and sulfuric acid, and the concentration of copper ions in the electrolyte is 0.1-0.5 mol.L-1The concentration of sulfate ions is 1.20-6 mol.L-1The distance between the cathode roller and the anode is 0.4-30 mm, and the rotating speed of the cathode roller is 0.5-15 r.min during the electrolytic reaction-1；
Electrifying the electrochemical reaction system for electrolytic reaction to enable copper ions in the electrolyte to deposit on the surface of the cathode roller to form a high-density copper foil, wherein a cooling system is adopted for cooling the electrolyte during the electrolytic reaction, so that the temperature of the electrolyte is always 1-15 ℃, and the current density is 4000A/m2The circulation rate of the electrolyte is 0-2 L.min-1The density of the high-density copper foil is more than 8.0 g-cm-3。
2. The production method according to claim 1, characterized by comprising: when the electrolysis reaction is carried out, the current density is 500-4000A/m2。
3. The method of claim 1, wherein: the cathode roll is selected from a titanium shaft.
4. The method of claim 1, wherein: the copper material is selected from a copper block or a copper sheet.
5. The method of claim 1, wherein: the shape of the anode is regular or irregular.
6. The method of claim 5, wherein: the anode is in a shape of a flat plate, an arc, a polygon or a sphere.
7. The method of claim 1, further comprising: and stripping the high-density copper foil formed by deposition from the surface of the cathode roller, and performing the steps of cleaning, oxidation resistance treatment and collection.
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