CN114540886A - Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition - Google Patents
Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition Download PDFInfo
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Abstract
The invention provides a method for preparing a copper foil based on copper-containing composite ionic liquid electrodeposition, which comprises the following steps: taking a raw material solution containing acid-soluble oil and copper-containing composite ionic liquid as an electrolyte, taking conductive glass as a cathode and taking an inert electrode as an anode, and carrying out electrodeposition treatment to form a copper foil on the surface of the conductive glass. The method can prepare the high-quality copper foil with the advantages of high copper content, fineness, flatness and the like, and realizes resource utilization of the copper-containing composite ionic liquid.
Description
Technical Field
The invention relates to recycling of copper-containing composite ionic liquid, in particular to a method for preparing copper foil based on electrodeposition of copper-containing composite ionic liquid.
Background
The copper-aluminum bimetal composite ionic liquid is an excellent catalyst for carbon tetra-alkylation, high-quality and high-yield alkylate oil can be obtained by catalyzing the carbon tetra-alkylation reaction with the copper-aluminum bimetal composite ionic liquid, however, a small amount of cyclic conjugated polyolefin (acid-soluble oil) can be generated by the carbon tetra-alkylation reaction process accompanied with side reactions such as olefin polymerization, hydrogen transfer, cracking, disproportionation and the like, the acid-soluble oil can greatly influence the catalytic effect along with the accumulation of time, so that the activity of the composite ionic liquid catalyst is gradually reduced and even loses activity, therefore, the waste copper-aluminum bimetal composite ionic liquid (or called composite ionic liquid waste liquid) produced by the industry contains the components of the copper-aluminum bimetal composite ionic liquid, acid-soluble oil, a complex compound of the copper-aluminum bimetal composite ionic liquid and the acid-soluble oil and the like, and along with the industrial application and popularization of the carbon tetra-alkylation technology, the resource utilization of the waste copper-aluminum bimetal composite ionic liquid plays a very important role in promoting the overall economic benefit.
In addition, copper has excellent electrical conductivity, thermal conductivity and mechanical properties, so that the copper is widely applied to the fields of microelectronic industry, automobile industry, building engineering and the like, and has high economic value, wherein the copper foil is used as one of important materials of products such as copper-clad plates, printed circuit boards, lithium ion batteries and the like, is widely applied to the fields of electrical and electronic industries and the like, and has wide market prospect.
Therefore, the process for preparing the copper foil by using the copper-containing composite ionic liquid is developed, and particularly the process for preparing the high-quality copper foil by using the copper-containing composite ionic liquid waste liquid is realized, so that the process has important significance for improving the utilization value of the copper-containing composite ionic liquid and efficiently utilizing and recovering copper resources.
Disclosure of Invention
The invention provides a method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition and a method for treating copper-containing composite ionic liquid waste liquid, which can be used for preparing high-quality copper foil with high copper content and fine and smooth and realizing resource utilization of copper-containing composite ionic liquid.
In one aspect of the invention, a method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition is provided, which comprises the following steps: taking a raw material solution containing acid-soluble oil and copper-containing composite ionic liquid as an electrolyte, taking conductive glass as a cathode and taking an inert electrode as an anode, and carrying out electrodeposition treatment to form a copper foil on the surface of the conductive glass.
According to one embodiment of the invention, the temperature of the electrodeposition treatment is 20 ℃ to 50 ℃; and/or the time of the electrodeposition treatment is 30-60 min; and/or the electrodeposition treatment is carried out under constant current or constant voltage, the constant current has a current density of 20 mA-cm-2～80mA·cm-2The voltage of the constant voltage is-1.2V to-3.0V; and/or the conductive glass comprises ITO conductive glass and/or FTO conductive glass; and/or the resistance of the conductive glass is 3-20 omega; and/or, the inert electrode comprises a platinum sheet; and/or the distance between the cathode and the anode is 0.5 cm-3.0 cm.
According to an embodiment of the present invention, the copper-containing composite ionic liquid comprises a copper-aluminum bimetal composite ionic liquid; and/or the copper-containing composite ionic liquid comprises at least one of quaternary ammonium salt ionic liquid, imidazolium salt ionic liquid, quaternary phosphonium salt ionic liquid and pyridinium salt ionic liquid.
According to an embodiment of the invention, in the copper-aluminum bimetal composite ionic liquid, the molar ratio of copper to aluminum is 3: 1-7: 1.
According to an embodiment of the invention, the source of anions of the copper-containing composite ionic liquid comprises AlCl3And CuCl; and/or, the quaternary ammonium salt ionic liquid comprises Et3NHCl-xAlCl3-yCuCl; and/or the imidazolium salt ionic liquid comprises [ Bmim ]]Cl-xAlCl3-yCuCl and/or [ Emim]Cl-xAlCl3-yCuCl。
According to an embodiment of the present invention, the content of the acid-soluble oil in the raw material liquid is in a range of 7.0 wt% to 15.0 wt%.
According to an embodiment of the invention, the acid-soluble oil comprises a cyclic conjugated polyolefin.
According to one embodiment of the invention, the raw material liquid comprises waste copper-aluminum bimetal composite ionic liquid discharged by a carbon four-alkylation process under catalysis of copper-aluminum bimetal composite ionic liquid.
In another aspect of the present invention, a method for treating a copper-containing composite ionic liquid waste liquid is provided, wherein the waste liquid comprises a copper-aluminum bimetal composite ionic liquid waste liquid discharged by a carbon tetra-alkylation process under catalysis of a copper-aluminum bimetal composite ionic liquid, and the treatment method comprises: and performing electrodeposition treatment by taking the copper-containing composite ionic liquid waste liquid as an electrolyte, conductive glass as a cathode and an inert electrode as an anode to form a copper foil on the surface of the conductive glass.
According to one embodiment of the invention, the temperature of the electrodeposition treatment is 20 ℃ to 50 ℃; and/or the time of the electrodeposition treatment is 30-60 min; and/or the electrodeposition treatment is carried out under constant current or constant voltage, the constant current has a current density of 20 mA-cm-2～80mA·cm-2The voltage of the constant voltage is-1.2V to-3.0V; and/or the conductive glass comprises ITO conductive glass and/or FTO conductive glass; and/or the resistance of the conductive glass is 3-20 omega; and/or, the inert electrode comprises a platinum sheet; and/or the distance between the cathode and the anode is 0.5 cm-3.0 cm.
According to the invention, the copper foil is prepared from the copper-containing composite ionic liquid by electrodeposition, and particularly the copper foil can be prepared from the waste liquid of the copper-aluminum bimetal composite ionic liquid discharged by the carbon tetra-alkylation process under the catalysis of the copper-aluminum bimetal composite ionic liquid by electrodeposition, the prepared copper foil has the advantages of high copper content, compactness and flatness, uniform copper element distribution, brightness and the like, researches show that the copper content (by mass) in the prepared copper foil is not lower than 95%, and the copper foil can be applied to the aspects of copper-clad plates, printed circuit boards, lithium ion batteries and the like, so that the resource utilization of the waste liquid of the copper-containing composite ionic liquid such as the waste liquid of the copper-aluminum bimetal composite ionic liquid is realized; in addition, the method provided by the invention has the advantages of stable product quality, no need of complex chemical treatment process, no need of additives, simplicity, convenience, easy operation, environmental protection, reusable conductive glass, low cost and the like, and is beneficial to actual industrial production and application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a copper foil product prepared in example 1;
FIG. 2 is an EDS profile of the copper foil product prepared in example 1 measured using an X-ray energy spectrometer (EDS);
FIG. 3 is an EDS profile of the copper foil product prepared in example 1 measured using an X-ray energy spectrometer (EDS).
Detailed Description
The present invention is described in further detail below in order to enable those skilled in the art to better understand the aspects of the present invention. The following detailed description is merely illustrative of the principles and features of the present invention, and the examples are intended to be illustrative of the invention and not limiting of the scope of the invention. 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 belong to the protection scope of the present invention.
In one aspect of the invention, a method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition is provided, which comprises the following steps: taking a raw material solution containing acid-soluble oil and copper-containing composite ionic liquid as an electrolyte, taking conductive glass as a cathode and taking an inert electrode as an anode, and carrying out electrodeposition treatment to form a copper foil on the surface of the conductive glass.
The inventor researches and discovers that under the preparation process system of the invention, a copper foil which is fine, flat and bright and consistent can be obtained by using a raw material liquid containing acid-soluble oil (such as copper-aluminum bimetal composite ionic liquid waste liquid discharged by a carbon four-alkylation process) as an electrolyte, and only loose copper powder can be obtained after electrodeposition treatment without obtaining the copper foil under the condition that the raw material liquid does not contain the acid-soluble oil (such as the freshly prepared copper-containing composite ionic liquid and no other components such as acid-soluble oil are introduced). The inventor considers through research and analysis that the conductive glass is used as a cathode (working electrode), and meanwhile, the raw material liquid containing acid-soluble oil is used as electrolyte, because of the existence of the acid-soluble oil in the raw material liquid, cathode polarization is accelerated, crystal grains are refined, the quality of an electrodeposition product can be greatly improved, and a compact, flat and uniform copper foil is prepared. Therefore, the method disclosed by the invention has the advantages of low requirement on equipment, greenness, safety, convenience in operation, rapidness, high efficiency, low cost, stable product quality and the like, and greatly improves the economic value of the copper-containing composite ionic liquid, especially the industrial waste copper-containing composite ionic liquid (such as the waste liquid of the copper-aluminum bimetal composite ionic liquid discharged by a carbon tetra-alkylation process catalyzed by the copper-aluminum bimetal composite ionic liquid).
The method provided by the invention also has the advantages of mild conditions, short time consumption and the like, can reduce energy consumption and improve the efficient treatment of the industrial waste copper-containing composite ionic liquid. In some embodiments, the temperature of the electrodeposition process is in the range of 20 ℃ to 50 ℃, such as 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or any two thereof, and the time of the electrodeposition process may be in the range of 30min to 60min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min or any two thereof.
Specifically, the electrodeposition treatment may be carried out under a constant current or a constant voltage, and the current density of the constant current may be 20mA · cm-2～80mA·cm-2E.g. 20mA cm-2、30mA·cm-2、40mA·cm-2、50mA·cm-2、60mA·cm-2、70mA·cm-2、80mA·cm-2Or any two of the above ranges, the constant voltage can be-1.2V-3.0V, such as-1.2V, -1.5V, -1.8V, -2.0V, -2.2V, -2.5V, -2.8V, -3.0V or any two of the above ranges, and the current density or voltage can be controlled to further improve the efficiency of the copper foil prepared by electrodeposition.
The conductive glass is plated with a conductive film on the surface, so that the conductive glass has conductive performance, and has higher mechanical strength and corrosion resistance. In some embodiments, the conductive glass may comprise ITO conductive glass (indium tin oxide conductive glass) and/or FTO conductive glass (fluorine-doped SnO)2Conductive glass)).
In addition, the resistance of the conductive glass may generally be in the range of 3 Ω to 20 Ω, such as 3 Ω, 5 Ω, 8 Ω, 10 Ω, 12 Ω, 15 Ω, 18 Ω, 20 Ω, or any two thereof. In some embodiments, the conductive glass used may include at least one of ITO conductive glass having a resistance of 3 Ω to 5 Ω, ITO conductive glass having a resistance of 7 Ω to 10 Ω, FTO conductive glass having a resistance of 7 Ω to 10 Ω, and FTO conductive glass having a resistance of 11 Ω to 20 Ω.
Further, the inert electrode may specifically include a platinum sheet (i.e., a platinum electrode), but is not limited thereto.
In general, the distance between the cathode and the anode may be 0.5cm to 3.0cm, for example, 0.5cm, 0.8cm, 1cm, 1.2cm, 1.5cm, 1.8cm, 2cm, 2.2cm, 2.5cm, 2.8cm, 3cm, or any two thereof.
In specific implementation, the raw material solution can be added into an electrolytic bath with a cathode (conductive glass) and an anode, electrolysis (namely electrodeposition treatment) is carried out in the electrolytic bath, copper is deposited on the surface of the conductive glass to form a copper foil in the electrolysis process, the conductive glass attached with the copper foil is taken out after the electrolysis is finished, the copper foil is physically stripped from the conductive glass after washing (for example, organic solvent and distilled water are sequentially adopted for cleaning) and drying, and a fine, flat and bright copper foil product is obtained, and the conductive glass after the copper foil is stripped can be reused after cleaning.
In general, the copper ion in the above copper-containing composite ionic liquid is a monovalent copper ion (i.e. cuprous ion, cu (i)), and the anion source thereof may include a metal halide, for example, cuprous halide, preferably a metal chloride, for example, cuprous chloride (CuCl). In some preferred embodiments, the copper-containing composite ionic liquid comprises a copper-aluminum bimetallic composite ionic liquid, and the anion source of the copper-aluminum bimetallic composite ionic liquid specifically comprises a copper halide and/or an aluminum halide, preferably AlCl3And/or CuCl.
In addition, the copper-containing composite ionic liquid can comprise at least one of quaternary ammonium salt ionic liquid, imidazole salt ionic liquid, quaternary phosphonium salt ionic liquid and pyridine salt ionic liquid, namely the cation source of the copper-containing composite ionic liquid can comprise quaternary ammonium compounds, imidazole compounds and quaternary phosphonium compoundsAt least one of phosphonium compounds and pyridines compounds, and illustratively, the quaternary ammonium ionic liquid comprises Et3NHCl-xAlCl3-yCuCl (in which [ Et ]3NH]Cl is triethylamine hydrochloride), and the imidazolium salt ionic liquid comprises [ Bmim ]]Cl-xAlCl3-yCuCl (of which [ Bmim ]]Cl is 1-butyl-3-methylimidazolium chloride) and/or [ Emim]Cl-xAlCl3-yCuCl (of which [ Emim [ ])]Cl is 1-ethyl-3-methylimidazolium chloride). In some preferred embodiments, the copper-containing composite ionic liquid comprises a quaternary ammonium salt ionic liquid and/or an imidazolium salt ionic liquid, and more preferably comprises Et3NHCl-xAlCl3-yCuCl、[Bmim]Cl-xAlCl3-yCuCl、[Emim]Cl-xAlCl3And at least one of-yCuCl is favorable for further improving the efficiency of preparing the copper foil by electrodeposition.
According to the research of the invention, the copper-aluminum bimetal composite ionic liquid has too small molar ratio of copper to aluminum and too large aluminum content, which is not beneficial to the formation of the copper foil, so that in order to further improve the preparation efficiency of the copper foil, the molar ratio of copper to aluminum in the copper-aluminum bimetal composite ionic liquid can be generally 3: 1-7: 1, such as 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1 or the range of any two of the two. Particularly, when the anion source is AlCl3With CuCl, AlCl3The molar ratio of the compound to CuCl is 3:1 to 7:1 (i.e., Et described above)3NHCl-xAlCl3-yCuCl、[Bmim]Cl-xAlCl3-yCuCl、[Emim]Cl-xAlCl3The ratio of x to y in the yCuCl is 3:1 to 7:1), such as 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, or any two thereof. Illustratively, Et described above3NHCl-xAlCl3-yCuCl、[Bmim]Cl-xAlCl3-yCuCl、[Emim]Cl-xAlCl3In yCuCl, 1.5. ltoreq. x.ltoreq.2, 0.3. ltoreq. y.ltoreq.0.5, x being, for example, in the range of 1.5, 1.6, 1.7, 1.8, 1.9, 2 or any two thereof, and y being, for example, in the range of 0.3, 0.35, 0.4, 0.45, 0.5 or any two thereof.
In the present invention, the copper-containing composite ionic liquid can be prepared according to conventional methods in the art, and illustratively, the anion source of the copper-containing composite ionic liquid comprises AlCl3And CuCl, the copper-containing composite ionic liquid can be prepared from quaternary ammonium compounds (such as Et)3NHCl), imidazoles (e.g., [ Bmim ]]Cl、[Emim]Cl, etc.), at least one of quaternary phosphonium compounds and pyridine compounds, and AlCl3And CuCl.
In the present invention, the raw material liquid generally contains a small amount of acid-soluble oil, and the content thereof may be measured by: firstly, hydrolyzing a raw material liquid, destroying the complexing action of acid-soluble oil and ionic liquid in the raw material liquid through hydrolysis, extracting and separating hydrocarbon to obtain the acid-soluble oil, and finally weighing to calculate the content of the acid-soluble oil in the raw material liquid. In some preferred embodiments, the acid-soluble oil is present in the feed solution in a range of 7.0 wt% to 15.0 wt%, such as 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, or any combination thereof. In the present invention, "wt%" represents a mass percentage.
The acid-soluble oil generally refers to an organic hydrocarbon, such as a heavy olefin, which is soluble in an acid solution, and specifically may include a polyolefin and/or a cycloolefin, and the like. In some preferred embodiments, the acid-soluble oil may include a cyclic conjugated polyolefin.
Specifically, in some embodiments, the raw material liquid may include a copper-aluminum bimetal composite ionic liquid waste liquid discharged from a carbon tetraalkylation process by catalysis of a copper-aluminum bimetal composite ionic liquid (i.e., a composite ionic liquid discharged from a carbon tetraalkylation industrial device), specifically, in a process of catalyzing carbon tetraalkylation by catalysis of a copper-aluminum bimetal composite ionic liquid, a carbon four raw material and a copper-aluminum bimetal composite ionic liquid are contacted in the carbon tetraalkylation industrial device, an alkylation reaction occurs under catalysis of the copper-aluminum bimetal composite ionic liquid, during the industrial production process, a reaction byproduct such as an acid-soluble oil such as cyclic conjugated polyolefin and a complex of the copper-aluminum bimetal composite ionic liquid and the acid-soluble oil reduces catalytic activity of the composite ionic liquid, thereby generating an inactivated composite ionic liquid, and the inactivated composite ionic liquid is discharged from the carbon tetraalkylation industrial device as a waste liquid, the above electrodeposition treatment may be carried out using the discharged waste liquid as an electrolytic solution, and in a specific operation, the discharged waste liquid may be subjected to a pretreatment including, for example, removal of solid impurities therefrom by filtration, and then subjected to the above electrodeposition treatment using the pretreated liquid as an electrolytic solution to prepare a copper foil. In the present invention, the carbon-tetralkylation process may be carried out according to a conventional method in the art, and is not particularly limited.
Therefore, the invention also provides a treatment method of the copper-containing composite ionic liquid waste liquid, the waste liquid comprises the copper-aluminum bimetal composite ionic liquid waste liquid discharged by adopting the copper-aluminum bimetal composite ionic liquid catalytic carbon tetra-alkylation process, and the treatment method comprises the following steps: and performing electrodeposition treatment by taking the copper-containing composite ionic liquid waste liquid as an electrolyte, conductive glass as a cathode and an inert electrode as an anode to form a copper foil on the surface of the conductive glass. For further research description, reference is made to the above contents, and repeated description is omitted here.
As mentioned above, by the electrodeposition process, the high-efficiency recovery of the copper-aluminum bimetal composite ionic liquid waste liquid can be realized, the discharge capacity is reduced, the copper recovery efficiency is improved, the high-quality copper foil with high copper content, fineness, flatness and brightness consistency is prepared, the resource utilization is realized, and the method also has the advantages of simple process, low cost, environmental protection and the like, and is beneficial to actual industrial production and application.
To make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the source of the starting solution is, unless otherwise specified: filtering the waste liquid of the copper-aluminum bimetal composite ionic liquid discharged from a carbon tetraalkylation industrial device catalyzed by the copper-aluminum bimetal composite ionic liquid to remove solid impurities in the waste liquid, and taking the obtained liquid as a raw material liquid; wherein, the copper-aluminum bimetal composite ionic liquid is shown in table 1; the raw material liquid contains acid-soluble oil, the acid-soluble oil is mainly cyclic conjugated polyolefin, and the content of the acid-soluble oil is shown in table 1.
In the following examples and comparative examples, after the electrodeposition was completed, the conductive glass was taken out, washed and dried, and then the copper content in the copper foil peeled off from the surface of the conductive glass was measured by an X-ray energy spectrometer (EDS).
Example 1
In this example, acid-containing soluble oil (12.0 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-2.0AlCl3-0.5CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) an ITO conductive glass sheet (with the resistance of 3-5 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) is used as a cathode, a platinum sheet is used as an anode, the distance between the anode and the cathode is 1.0cm, and the constant current (the current density is 40 mA/cm) is carried out at the temperature of 25 DEG C2) Performing electrodeposition for 30 min;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
Tests show that the average thickness of the copper foil product is 3.2 mu m, and the Cu content is up to 96 wt%.
Example 2
In this example, acid-containing soluble oil (content: 13.5 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-1.8AlCl3-0.5CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) taking an ITO conductive glass sheet (with the resistance of 3-5 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode, taking a platinum sheet as an anode, wherein the distance between the anode and the cathode is 0.5cm, and electrodepositing for 60min at a constant voltage (the voltage is-2.0V) at 50 ℃;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 6.7 mu m through testing, and the Cu content is up to 98 wt%.
Example 3
In this example, acid-containing soluble oil (content: 15.0 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-1.8AlCl3-0.4CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) performing electrodeposition for 60min at a constant voltage (voltage of-2.0V) at 40 ℃ by taking an ITO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode and a platinum sheet as an anode, wherein the distance between the anode and the cathode is 2.0 cm;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
Tests show that the average thickness of the copper foil product is 5.1 mu m, and the Cu content is up to 95 wt%.
Example 4
In this example, acid-containing soluble oil (content 7.2 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-1.6AlCl3-0.3CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) an ITO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) is used as a cathode, a platinum sheet is used as an anode, the distance between the anode and the cathode is 0.5cm, and the constant current (the current density is 30 mA/cm) is carried out at the temperature of 25 DEG C2) Performing electrodeposition for 60 min;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 4.6 mu m through testing, and the Cu content is up to 97 wt%.
Example 5
In this example, acid-containing soluble oil (12.0 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-2.0AlCl3-0.5CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) performing electrodeposition for 60min at a constant voltage (voltage of-2.0V) at 40 ℃ by using an FTO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode and a platinum sheet as an anode, wherein the distance between the anode and the cathode is 1.0 cm;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 4.9 mu m through testing, and the Cu content is up to 98 wt%.
Example 6
In this example, acid-containing soluble oil (content: 10.6 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-1.8AlCl3-0.5CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) an FTO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) is taken as a cathode, a platinum sheet is taken as an anode, the distance between the anode and the cathode is 3.0cm, and the constant current (the current density is 40 mA/cm) is carried out at the temperature of 25 DEG C2) Performing electrodeposition for 30 min;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 2.7 mu m through testing, and the Cu content is up to 96 wt%.
Example 7
In this example, acid-containing soluble oil (content 8.8 wt%) and copper-containing composite ionic liquid (Et) were used3NHCl-1.8AlCl3-0.4CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) performing electrodeposition for 60min at a constant voltage (voltage of-2.0V) at 25 ℃ by using an FTO conductive glass sheet (with the resistance of 11-20 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode and a platinum sheet as an anode, wherein the distance between the anode and the cathode is 0.5 cm;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 4.3 mu m through testing, and the Cu content is up to 97 wt%.
Example 8
In this example, acid-containing soluble oil (content 9.4 wt%) and copper-containing composite ionic liquid ([ Bmim [ ]]Cl-2.0AlCl3-0.5CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) taking an ITO conductive glass sheet (with the resistance of 3-5 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode, taking a platinum sheet as an anode, wherein the distance between the anode and the cathode is 1.0cm, and electrodepositing for 30min at a constant voltage (the voltage is-2.0V) at the temperature of 25 ℃;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 3.0 mu m through testing, and the Cu content is up to 97 wt%.
Example 9
In this example, acid-containing soluble oil (content 12.3 wt%) and copper-containing composite ionic liquid ([ Bmim [ ]]Cl-1.8AlCl3-0.3CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) performing electrodeposition for 60min at a constant voltage (voltage of-2.0V) at 25 ℃ by taking an ITO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode and a platinum sheet as an anode, wherein the distance between the anode and the cathode is 1.0 cm;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 4.7 mu m through testing, and the Cu content is up to 96 wt%.
Example 10
In this example, acid-containing soluble oil (content 10.8 wt%) and copper-containing composite ionic liquid ([ Emim [ ]) were used]Cl-1.8AlCl3-0.4CuCl) as an electrolyte, the copper foil being prepared as follows:
(1) an ITO conductive glass sheet (with the resistance of 3-5 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) is used as a cathode, a platinum sheet is used as an anode, and the distance between the anode and the cathode1.0cm, constant current (current density 40 mA/cm) at 25 deg.C2) Performing electrodeposition for 30 min;
(2) and after the electrodeposition is finished, taking out the conductive glass sheet, sequentially cleaning the conductive glass sheet by using an acetone-ethanol mixed solution and distilled water, drying, and then physically putting copper foil on the conductive glass to obtain a copper foil product.
The average thickness of the copper foil product is 2.9 mu m through testing, and the Cu content is up to 97 wt%.
Comparative example 1
In this comparative example 1, fresh copper-containing composite ionic liquid (Et) free of acid-soluble oil was used3NHCl-2.0AlCl30.5CuCl) was used directly as electrolyte and the electrodeposition process was as follows:
(1) an ITO conductive glass sheet (with the resistance of 3-5 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) is used as a cathode, a platinum sheet is used as an anode, the distance between the anode and the cathode is 1.0cm, and the constant current (the current density is 40 mA/cm) is carried out at the temperature of 25 DEG C2) Performing electrodeposition for 30 min;
(2) after the electrodeposition, the conductive glass sheet was taken out, washed with a mixed solution of acetone and ethanol, and distilled water in this order, and dried, and the deposition product was found to be loose copper powder without forming a copper foil, in which the copper content was 95 wt%.
Comparative example 2
In this comparative example 2, fresh copper-containing composite ionic liquid (Et) free of acid-soluble oil was used3NHCl-2.0AlCl30.5CuCl) was used directly as electrolyte and the electrodeposition process was as follows:
(1) performing electrodeposition for 60min at a constant voltage (voltage of-2.0V) at 40 ℃ by using an FTO conductive glass sheet (with the resistance of 7-10 omega and the specification of 2cm multiplied by 1cm multiplied by 0.1cm) as a cathode and a platinum sheet as an anode, wherein the distance between the anode and the cathode is 1.0 cm;
(2) after the electrodeposition was completed, the conductive glass sheet was taken out, washed with a mixed solution of acetone-ethanol and distilled water in this order, and dried, and it was found that the resulting deposition product was loose copper powder without forming a copper foil, the copper content of which was 95 wt%.
In the above examples and comparative examples, the composition of the copper-containing composite ionic liquid, the acid-soluble oil content in the raw material liquid, the conductive glass, the resistance of the conductive glass, the distance between the cathode and the anode (cathode-anode distance), the temperature and time of the electrodeposition treatment, the electrodeposition method (constant current/constant voltage), and the current density and voltage of the constant current, as well as the thickness of the resulting copper foil product and the copper content in the copper foil are summarized in table 1.
Further describing the properties of the obtained copper foil by taking example 1 as an example, the Scanning Electron Microscope (SEM) image of the copper foil product peeled from the surface of the conductive glass in example 1 is shown in fig. 1, and the microstructure of the copper foil appears as particles with uniform size; the EDS profile of the copper foil product measured by EDS is shown in FIG. 2, wherein the bright spots represent the distribution of copper elements, which indicates that the copper elements are uniformly distributed; an EDS profile of the copper foil product measured by EDS is shown in FIG. 3, and it is understood that the distribution of copper element in the copper foil is 96 wt%. The results of the tests of examples 2 to 10 are similar to those of example 1, and all show that the microstructure of the copper foil is granular with uniform size, the distribution of copper element is uniform, and the copper content is high.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition is characterized by comprising the following steps: taking a raw material solution containing acid-soluble oil and copper-containing composite ionic liquid as an electrolyte, taking conductive glass as a cathode and taking an inert electrode as an anode, and carrying out electrodeposition treatment to form a copper foil on the surface of the conductive glass.
2. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition according to claim 1,
the temperature of the electrodeposition treatment is 20-50 ℃; and/or the presence of a gas in the gas,
the time of the electrodeposition treatment is 30min to 60 min; and/or the presence of a gas in the gas,
the electrodeposition treatment is carried out under constant current or constant voltage, and the current density of the constant current is 20 mA-cm-2～80mA·cm-2The voltage of the constant voltage is-1.2V to-3.0V; and/or the presence of a gas in the gas,
the conductive glass comprises ITO conductive glass and/or FTO conductive glass; and/or the presence of a gas in the gas,
the resistance of the conductive glass is 3-20 omega; and/or the presence of a gas in the gas,
the inert electrode comprises a platinum sheet; and/or the presence of a gas in the gas,
the distance between the cathode and the anode is 0.5 cm-3.0 cm.
3. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition according to claim 1,
the copper-containing composite ionic liquid comprises copper-aluminum bimetal composite ionic liquid; and/or the presence of a gas in the gas,
the copper-containing composite ionic liquid comprises at least one of quaternary ammonium salt ionic liquid, imidazolium salt ionic liquid, quaternary phosphonium salt ionic liquid and pyridinium salt ionic liquid.
4. The method for preparing the copper foil based on the copper-containing composite ionic liquid electrodeposition as claimed in claim 3, wherein the molar ratio of copper to aluminum in the copper-aluminum bimetal composite ionic liquid is 3: 1-7: 1.
5. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition according to claim 3 or 4,
the anion source of the copper-containing composite ionic liquid comprises AlCl3And CuCl; and/or the presence of a gas in the gas,
the quaternary ammonium salt ionic liquid comprises Et3NHCl-xAlCl3-yCuCl; and/or the presence of a gas in the gas,
the imidazolium salt ionic liquid comprises [ Bmim ]]Cl-xAlCl3-yCuCl and/or [ Emim]Cl-xAlCl3-yCuCl。
6. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition as claimed in claim 1, wherein the acid-soluble oil is contained in the raw material liquid in a range of 7.0 wt% to 15.0 wt%.
7. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition according to claim 1 or 6, wherein the acid-soluble oil comprises cyclic conjugated polyolefin.
8. The method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition as claimed in claim 1 or 6, wherein the raw material liquid comprises copper-aluminum bimetal composite ionic liquid waste liquid discharged by a carbon tetra-alkylation process catalyzed by copper-aluminum bimetal composite ionic liquid.
9. A treatment method of copper-containing composite ionic liquid waste liquid is characterized in that the waste liquid comprises copper-aluminum bimetal composite ionic liquid waste liquid discharged by a carbon tetra-alkylation process under catalysis of copper-aluminum bimetal composite ionic liquid, and the treatment method comprises the following steps: and performing electrodeposition treatment by taking the copper-containing composite ionic liquid waste liquid as an electrolyte, conductive glass as a cathode and an inert electrode as an anode to form a copper foil on the surface of the conductive glass.
10. The method for treating the copper-containing composite ionic liquid waste liquid according to claim 9, wherein the temperature of the electrodeposition treatment is 20-50 ℃; and/or the presence of a gas in the gas,
the time of the electrodeposition treatment is 30min to 60 min; and/or the presence of a gas in the gas,
the electrodeposition treatment is carried out under constant current or constant voltage, and the current density of the constant current is 20 mA-cm-2～80mA·cm-2The voltage of the constant voltage is-1.2V to-3.0V; and/or the presence of a gas in the gas,
the conductive glass comprises ITO conductive glass and/or FTO conductive glass; and/or the presence of a gas in the gas,
the resistance of the conductive glass is 3-20 omega; and/or the presence of a gas in the gas,
the inert electrode comprises a platinum sheet; and/or the presence of a gas in the gas,
the distance between the cathode and the anode is 0.5 cm-3.0 cm.
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| CN101831677A (en) * | 2010-02-08 | 2010-09-15 | 哈尔滨工业大学 | Method for electrodepositing lithium-copper alloy in ionic liquid system |
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| CN104485459A (en) * | 2014-11-13 | 2015-04-01 | 昆明理工大学 | Method for preparing copper foil for lithium ion battery through low eutectic type ionic liquid electro-deposition |
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| CN101831677A (en) * | 2010-02-08 | 2010-09-15 | 哈尔滨工业大学 | Method for electrodepositing lithium-copper alloy in ionic liquid system |
| CN103639420A (en) * | 2013-11-27 | 2014-03-19 | 昆明理工大学 | Method for utilizing low co-fusion type ionic liquid electro-deposition to manufacture nanometer copper powder |
| CN104141151A (en) * | 2014-08-06 | 2014-11-12 | 哈尔滨工业大学 | Method for forming metal simple substance through ionic liquid in electrolytic deposition mode |
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