Copper-aluminum composite plate prepared by continuous casting with molten aluminum and its process

Abstract

The present invention proposes a copper-aluminum composite plate prepared by continuous casting with molten aluminum, and a process for producing the same, which belongs to the technical field of composite plates. The process includes the steps of (S1) heating an aluminum ingot to 700-800°C and smelting it for 1-3 hours, (S2) degassing the smelted molten aluminum and leaving it at that temperature, (S3) texturing and cleaning a copper strip, (S4) heating the pre-treated copper strip to 200-650°C, (S5) continuously casting the molten aluminum onto the treated copper strip under inert gas protection, quenching and crystallizing the copper-aluminum composite material, and performing oxygen-free continuous casting, and (S6) continuously rolling the continuously cast copper-aluminum composite material and continuously casting it with molten aluminum to obtain a copper-aluminum composite plate. The copper-aluminum composite plate prepared by the present invention, which is produced by continuous casting of molten aluminum, has improved wettability at the metal interface between aluminum and copper, high bonding strength, small interfacial thickness, high composite strength, good mechanical properties, low cost, high efficiency, and wide applicability.

Description

[Technical Field]

[0001] The present invention relates to the technical field of composite plates, and more particularly to a copper-aluminum composite plate prepared by continuous casting from molten aluminum and a process for producing the same. [Background technology]

[0002] Copper and aluminum are important non-ferrous metals, with copper having good electrical conductivity, thermal conductivity, and corrosion resistance, and aluminum having good electrical conductivity and thermal conductivity. Comparing copper and aluminum, copper resources are scarce, while aluminum resources are relatively abundant. Furthermore, aluminum has a low specific gravity and is inexpensive. Aluminum-copper composite metal strip is a bimetal in which aluminum is used as the outer layer of the matrix and copper is clad. It is a new conductor and decorative material that combines the high-quality electrical conductivity and low-cost resources of aluminum with the high chemical stability and low contact resistance of copper. Aluminum-copper composite metal strip combines the advantages of copper and aluminum. The use of aluminum-copper composite metal strip instead of copper strip is widely applied in high-tech fields such as the military industry, aerospace, electronic computers, electronic devices, etc., as well as in the power, high- and low-voltage electrical appliance, automation, and building industries, and is currently a focus of research on metallic materials.

[0003] The international standard composite strength of aluminum-copper composite materials is 12 kgf / cm or more, and the composite strength requirement for aluminum-copper composite materials in existing lithium batteries is 15 kgf / cm or more. With the continuous advancement of new energy technology, lithium batteries, as the core energy storage equipment of new energy, and aluminum-copper composite materials as the core component materials of lithium batteries, lithium battery manufacturers have higher requirements for the strength of aluminum-copper composite materials.

[0004] Currently, the methods for producing aluminum-copper composite strip mainly include solid-solid composite methods such as rolling composite, explosive composite, extrusion-pultrusion composite, and diffusion welding composite, and liquid-solid composite methods such as core-fill continuous casting and dual crystallizer continuous casting. Solid-solid composite processes are typically outdated, suffer from low yields and unstable quality, and are not suitable for continuous large-scale production. Therefore, liquid-solid composite methods have become a focus of research. However, when the liquid-solid composite method directly combines molten aluminum with copper plate, a thick bonding interface layer is formed. The thicker the bonding interface layer, the more intermetallic compounds there are, and the lower the strength of the composite strip. Therefore, the thicker the bonding interface layer formed when directly combining molten aluminum with copper plate, the lower the strength of the composite plate, and the lower the strength of the composite plate, which cannot meet the requirements for use.

[0005] Chinese invention patent CN101758071B discloses a method for producing aluminum-copper composite metal strip, which uses an oxygen-free continuous casting and rolling method to prepare the aluminum-copper composite strip. This method requires online polishing until there is no oxide layer before bonding the copper and aluminum, which makes the process relatively complicated and the bonding strength of the copper and aluminum is relatively low (about 100 MPa). Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is to provide a copper-aluminum composite plate prepared by continuous casting of molten aluminum, which can be used to prepare poles of new energy batteries, and a process for preparing the same, which improves the wettability of the aluminum-copper metal interface through the processes of continuous casting and multiple rolling, resulting in a composite plate with high bonding strength, small interfacial thickness, high composite strength, and good mechanical properties, and which is simple to prepare, low-cost, highly efficient, and widely applicable. [Means for solving the problem]

[0007] The technical solution of the present invention is realized as follows:

[0008] The present invention provides a process for preparing a copper-aluminum composite plate material by continuous casting of molten aluminum, comprising: A smelting step S1 in which an aluminum ingot is heated to 700 to 800 ° C and smelted for 1 to 3 hours; A still-standing step S2 in which the molten aluminum smelted in step S1 is degassed and left to stand for 10 to 30 minutes while keeping the temperature constant; a copper strip pretreatment step S3 in which the copper strip is embossed and washed; a copper strip heating step S4 in which the pretreated copper strip obtained in step S3 is heated to 200 to 650°C; a continuous casting step S5 in which the molten aluminum processed in step S2 is continuously cast onto the copper strip processed in step S4 under the protection of an inert gas, and the copper-aluminum composite material is rapidly cooled and crystallized, followed by oxygen-free continuous casting; and a continuous rolling step S6 of rolling the copper-aluminum composite material continuously cast in step S5 to obtain a copper-aluminum composite plate material continuously cast with molten aluminum.

[0009] As a further improvement of the present invention, the texturing treatment in step S3 comprises mechanical texturing using a steel brush or an abrasive tape, chemical texturing or laser texturing, and the cleaning is ultrasonic cleaning or laser cleaning. In a further improvement of the present invention, the casting speed in step S5 is 200-1200 mm / min, the casting width is 10-100 mm, the casting thickness is 3-20 mm, and the cooling rate of the rapid cooling crystallization is 100-150°C / min, and the specific method is as follows: under the protection of inert gas, the copper strip processed in step S4 is continuously passed through a crystallizer of a continuous casting facility, and the molten aluminum is continuously cast onto the copper strip through the casting system, and the crystallizer rapidly cools and crystallizes the copper-aluminum composite material, followed by oxygen-free continuous casting. 。

[0010] As a further improvement of the present invention, the thickness of the copper-aluminum composite plate material prepared by continuous casting the molten aluminum in step S6 is 2 to 12 mm, the rolling pressure is 5,000 to 5,000,000 N, the rolling speed is 300 to 1,500 mm / min, and the rolling tension is 10,000 to 200,000 N. 。

[0011] As a further improvement of the present invention, in step 2, Cu@Si@Al Janus nanosheets are added before degassing treatment, and the amount of the added Cu@Si@Al Janus nanosheets is 5-7 wt% of the molten aluminum, and the preparation method of the Cu@Si@Al Janus nanosheets is as follows: T1. Preparation of SiO2 nano-hollow microspheres: Dissolve tetraethyl orthosilicate in an organic solvent to obtain an oil phase; dissolve an emulsifier in water to obtain an aqueous phase; add the aqueous phase dropwise to the oil phase to emulsify; adjust the pH of the solution to 10-11; heat and stir to react; then centrifuge, wash, dry, and calcinate to prepare SiO2 nano-hollow microspheres. T2. Ball milling: The SiO2 nano hollow microspheres prepared in step T1 are ball milled to prepare SiO2 nanosheets. T3. Modification: Add the SiO2 nanosheets prepared in step T2 to ethanol, add a silane coupling agent, react with the mixture while heating and stirring, then centrifuge, wash, and dry to prepare modified SiO2 nanosheets. T4. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: Aluminum isopropoxide is dissolved in dichloromethane and allowed to stand. The modified SiO2 nanosheets prepared in step T3 are added and suspended at the interface. An aqueous solution containing copper salt is added dropwise, and citric acid is added. The mixture is allowed to stand, centrifuged, washed, dried, and calcined to prepare copper oxide@SiO2@aluminum oxide nanosheets. T5. Reduction: The copper oxide@SiO2@aluminum oxide nanosheets prepared in step T4 were mixed with magnesium powder, and then heated and reduced, followed by hydrogen gas reduction to prepare Cu@Si@Al Janus nanosheets.

[0012] As a further improvement of the present invention, the mass ratio of the tetraethyl orthosilicate, organic solvent, emulsifier, and water in step T1 is 12-15:100:0.5-1:30-50, the emulsifier is selected from at least one of polysorbate-20, polysorbate-40, polysorbate-60, and polysorbate-80, the heating and stirring reaction is carried out at a temperature of 50-60°C for a time of 10-12 hours, and the baking is carried out at a temperature of 300-500°C. The temperature of the heating and stirring reaction is 40 to 50°C and the time is 1 to 3 hours, the ball milling time in step T2 is 2 to 4 hours, the mass ratio of the SiO2 nanosheets to the silane coupling agent in step T3 is 100:22 to 25, the silane coupling agent is a silane coupling agent having an amino group and is selected from at least one of KH550, KH602, and KH792, and the heating and stirring reaction is carried out at a temperature of 40 to 50°C and for a time of 0.5 to 1 hour. 。

[0013] In a further improvement of the present invention, the mass ratio of the modified SiO2 nanosheet, aluminum isopropoxide, copper salt, and citric acid in step T4 is 50:12-15:7-12:3-5, the time of the static reaction is 30-50 min, the temperature of the calcination is 500-700°C and the time is 1-3 h, the copper salt is selected from at least one of copper chloride, copper sulfate, and copper nitrate, the mass ratio of the copper oxide@SiO2@aluminum oxide nanosheet and magnesium powder in step T5 is 100:7-12, the temperature of the thermal reduction reaction is 700-800°C and the time is 0.5-1 h, the temperature of the hydrogen gas reduction reaction is 600-800°C and the time is 1-2 h, and the amount of hydrogen gas flow is 20-30 mL / min. 。

[0014] As a further improvement of the present invention, after the cleaning treatment in step S3, a layer of ethylene glycol dimethyl ether solution of 11-mercaptoundecanoic acid having a concentration of 7 to 12 wt % is coated on the surface. 。

[0015] The present invention further protects a copper-aluminum composite plate material prepared by continuous casting of the molten aluminum prepared by the above-mentioned preparation process.

[0016] The present invention further provides that the copper-aluminum composite plate prepared by continuous casting of the above-mentioned molten aluminum is used to prepare poles of new energy batteries. [Effects of the Invention]

[0017] The present invention has the following beneficial effects.

[0018] If the wettability between the metal matrix is ​​poor, interface defects such as interfacial voids and cracks will occur between the metal matrix during the preparation process, and brittle phase compounds will form at the interface, reducing the bonding strength between the metals and thereby affecting the use performance of the alloy material.

[0019] In this invention, Cu@Si@Al Janus nanosheets are prepared by first preparing silicon dioxide nano-hollow microspheres by emulsion method, crushing them under the action of ball mill to form nanosheets, and then modifying the surface with a silane coupling agent having an amino group, which is then added to an organic solvent and an aqueous solution. The modified silicon dioxide nanosheets are dispersed at the oil-water interface, aluminum isopropoxide is dissolved in the organic solvent, and copper salt is dissolved in water. Under the action of the amino groups on the modified silicon dioxide nanosheets, aluminum isopropoxide is dissolved in the organic solvent, and copper salt is dissolved in water. The isopropoxide adheres to the surface of the nanosheet, and under the catalytic action of a small amount of water, a sol-gel reaction occurs, thereby forming aluminum oxide and fixing it to the oil layer side of the nanosheet. At the same time, under the complex action of the amino group, copper ions are fixed to the amino group on the water layer side of the nanosheet. After adding citric acid, a gel is formed. The nanosheet is separated and then calcined to prepare copper oxide@SiO2@aluminum oxide nanosheets. After magnesium thermal reduction and hydrogen gas reduction, Cu@Si@Al Janus nanosheets are prepared.

[0020] In the present invention, by adding Cu@Si@Al Janus nanosheets to molten aluminum, the nanosheets are automatically liberated at the aluminum-copper metal interface, and the aluminum metal-bearing layer on the nanosheets penetrates into the aluminum metal layer, and the copper metal-bearing layer penetrates into the copper metal layer. After rolling, the thickness of the interface layer is greatly reduced, and the voids and gas gaps at the interface are also reduced, thereby improving the bonding strength and composite strength and strengthening the mechanical properties of the prepared composite plate.

[0021] In this invention, a copper strip is textured to roughen its interface and increase the interfacial bonding strength. Then, a layer of 11-mercaptoundecanoic acid solution is coated on the surface. Because 11-mercaptoundecanoic acid contains thio and carboxyl groups in its molecular structure, it has good interfacial activity and forms an organic-inorganic composite layer through an in-situ reaction, improving the wettability and dispersibility of the metal interface. This significantly improves the wettability and composite properties between the copper matrix and the aluminum matrix, and enhances the interfacial bonding strength between the two.

[0022] The copper-aluminum composite plate material prepared by continuous casting of molten aluminum according to the present invention can be used to prepare pole posts of new energy batteries. The process of continuous casting and multiple rolling improves the wettability of the aluminum-copper metal interface, and the prepared composite plate material has high bonding strength, small interfacial thickness, high composite strength, good mechanical properties, a simple preparation method, low cost, high efficiency, and wide applicability. DETAILED DESCRIPTION OF THE INVENTION

[0023] The technical solutions in the embodiments of the present invention will be described below clearly and completely, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and are not all of the embodiments, and all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any creative work fall within the scope of protection of the present invention.

[0024] Preparation Example 1: Preparation of Cu@Si@Al Janus nanosheets The method is as follows: T1. Preparation of SiO2 nano-hollow microspheres: 12 parts by weight of tetraethyl orthosilicate was dissolved in 100 parts by weight of dichloromethane to obtain an oil phase, and 0.5 parts by weight of polysorbate-20 was dissolved in 30 parts by weight of water to obtain an aqueous phase. The aqueous phase was added dropwise to the oil phase and emulsified at 10,000 r / min for 15 minutes. The pH of the solution was adjusted to 10, heated to 50°C, stirred for 10 hours, centrifuged, washed, dried, and calcined at 300°C for 1 hour to prepare SiO2 nano-hollow microspheres.

[0025] T2. Ball milling: The SiO2 nano-hollow microspheres prepared in step T1 were ball milled for 2 h to prepare SiO2 nanosheets.

[0026] T3. Modification: 100 parts by weight of the SiO2 nanosheets prepared in step T2 were added to 200 parts by weight of ethanol, and 22 parts by weight of the silane coupling agent KH550 was added. The mixture was heated to 40°C, stirred for 0.5 hours, centrifuged, washed, and dried to prepare modified SiO2 nanosheets.

[0027] T4. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: 12 parts by weight of aluminum isopropoxide was dissolved in 100 parts by weight of dichloromethane, and the solution was allowed to stand. 50 parts by weight of the modified SiO2 nanosheets prepared in step T3 was added and suspended at the interface. 100 parts by weight of an aqueous solution containing 7 parts by weight of copper chloride was added dropwise, and 3 parts by weight of citric acid was added. The solution was allowed to stand for 30 minutes, centrifuged, washed, dried, and calcined at 500°C for 1 hour to prepare copper oxide@SiO2@aluminum oxide nanosheets.

[0028] T5. Reduction: 100 parts by weight of the copper oxide@SiO2@aluminum oxide nanosheets prepared in step T4 were mixed with 7 parts by weight of magnesium powder, heated to 700°C, and reduced for 0.5 h, and then reduced at 600°C for 1 h with hydrogen gas at a flow rate of 20 mL / min to prepare Cu@Si@Al Janus nanosheets.

[0029] Preparation Example 2: Preparation of Cu@Si@Al Janus nanosheets The method is as follows: T1. Preparation of SiO2 nano-hollow microspheres: 15 parts by weight of tetraethyl orthosilicate was dissolved in 100 parts by weight of dichloromethane to obtain an oil phase, and 1 part by weight of polysorbate-40 was dissolved in 50 parts by weight of water to obtain an aqueous phase. The aqueous phase was added dropwise to the oil phase and emulsified at 10,000 r / min for 15 minutes. The pH of the solution was adjusted to 11, heated to 60°C, stirred for 12 hours, centrifuged, washed, dried, and calcined at 500°C for 3 hours to prepare SiO2 nano-hollow microspheres.

[0030] T2. Ball milling: The SiO2 nano-hollow microspheres prepared in step T1 were ball milled for 4 h to prepare SiO2 nanosheets.

[0031] T3. Modification: 100 parts by weight of the SiO2 nanosheets prepared in step T2 were added to 200 parts by weight of ethanol, and 25 parts by weight of the silane coupling agent KH602 was added. The mixture was heated to 50°C, stirred for 1 hour, centrifuged, washed, and dried to prepare modified SiO2 nanosheets.

[0032] T4. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: 15 parts by weight of aluminum isopropoxide was dissolved in 100 parts by weight of dichloromethane and allowed to stand. 50 parts by weight of the modified SiO2 nanosheets prepared in step T3 was added and suspended at the interface. 100 parts by weight of an aqueous solution containing 12 parts by weight of copper sulfate was added dropwise, and 5 parts by weight of citric acid was added. The mixture was allowed to react for 50 minutes, centrifuged, washed, dried, and calcined at 700°C for 3 hours to prepare copper oxide@SiO2@aluminum oxide nanosheets.

[0033] T5. Reduction: 100 parts by weight of the copper oxide@SiO2@aluminum oxide nanosheets prepared in step T4 were mixed with 12 parts by weight of magnesium powder, heated to 800°C, and reduced for 1 hour. Then, the mixture was reduced with hydrogen gas at 800°C for 2 hours with a hydrogen gas flow rate of 30 mL / min to prepare Cu@Si@Al Janus nanosheets.

[0034] Preparation Example 3: Preparation of Cu@Si@Al Janus nanosheets The method is as follows: T1. Preparation of SiO2 nano-hollow microspheres: 13 parts by weight of tetraethyl orthosilicate was dissolved in 100 parts by weight of dichloromethane to obtain an oil phase, and 0.7 parts by weight of polysorbate-80 was dissolved in 40 parts by weight of water to obtain an aqueous phase. The aqueous phase was added dropwise to the oil phase and emulsified at 10,000 r / min for 15 minutes. The pH of the solution was adjusted to 10.5, heated to 55°C, stirred for 11 hours, centrifuged, washed, dried, and calcined at 400°C for 2 hours to prepare SiO2 nano-hollow microspheres.

[0035] T2. Ball milling: The SiO2 nano-hollow microspheres prepared in step T1 were ball milled for 3 h to prepare SiO2 nanosheets.

[0036] T3. Modification: 100 parts by weight of the step SiO2 nanosheets prepared in T2 was added to 200 parts by weight of ethanol, and 23 parts by weight of a silane coupling agent was added. The mixture was heated to 45°C, stirred for 1 hour, centrifuged, washed, and dried to prepare modified SiO2 nanosheets.

[0037] T4. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: 13 parts by weight of aluminum isopropoxide was dissolved in 100 parts by weight of dichloromethane, and the solution was allowed to stand. 50 parts by weight of the modified SiO2 nanosheets prepared in step T3 was added and suspended at the interface. 100 parts by weight of an aqueous solution containing 10 parts by weight of copper nitrate was added dropwise, and 4 parts by weight of citric acid was added. The solution was allowed to stand for 40 minutes, centrifuged, washed, dried, and calcined at 600°C for 2 hours to prepare copper oxide@SiO2@aluminum oxide nanosheets.

[0038] T5. Reduction: 100 parts by weight of the copper oxide@SiO2@aluminum oxide nanosheets prepared in step T4 were mixed with 10 parts by weight of magnesium powder, heated to 750°C, and reduced for 1 hour. Then, the mixture was reduced with hydrogen gas at 700°C for 1.5 hours with a hydrogen gas flow rate of 25 mL / min to prepare Cu@Si@Al Janus nanosheets.

[0039] Comparative Preparation Example 1 It differed from Preparation Example 3 in that step T3 was not performed.

[0040] The method is as follows: T1. Preparation of SiO2 nano-hollow microspheres: 13 parts by weight of tetraethyl orthosilicate was dissolved in 100 parts by weight of dichloromethane to obtain an oil phase, and 0.7 parts by weight of polysorbate-80 was dissolved in 40 parts by weight of water to obtain an aqueous phase. The aqueous phase was added dropwise to the oil phase and emulsified at 10,000 r / min for 15 minutes. The pH of the solution was adjusted to 10.5, heated to 55°C, stirred for 11 hours, centrifuged, washed, dried, and calcined at 400°C for 2 hours to prepare SiO2 nano-hollow microspheres.

[0041] T2. Ball milling: The SiO2 nano-hollow microspheres prepared in step T1 were ball milled for 3 h to prepare SiO2 nanosheets.

[0042] T3. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: 13 parts by weight of aluminum isopropoxide was dissolved in 100 parts by weight of dichloromethane and allowed to stand. 50 parts by weight of the SiO2 nanosheets prepared in step T2 was added and allowed to float at the interface. 100 parts by weight of an aqueous solution containing 10 parts by weight of copper nitrate was added dropwise, and 4 parts by weight of citric acid was added. The mixture was allowed to react for 40 minutes, centrifuged, washed, dried, and calcined at 600°C for 2 hours to prepare copper oxide@SiO2@aluminum oxide nanosheets.

[0043] T4. Reduction: 100 parts by weight of the copper oxide@SiO2@aluminum oxide nanosheets prepared in step T3 were mixed with 10 parts by weight of magnesium powder, heated to 750°C, and reduced for 1 hour. Then, the mixture was reduced with hydrogen gas at 700°C for 1.5 hours with a hydrogen gas flow rate of 25 mL / min to prepare Cu@Si@Al Janus nanosheets.

[0044] Comparative Preparation Example 2 It differed from Preparation Example 3 in that step T5 was not performed.

[0045] The method is as follows: T1. Preparation of SiO2 nano-hollow microspheres: 13 parts by weight of tetraethyl orthosilicate was dissolved in 100 parts by weight of dichloromethane to obtain an oil phase, and 0.7 parts by weight of polysorbate-80 was dissolved in 40 parts by weight of water to obtain an aqueous phase. The aqueous phase was added dropwise to the oil phase and emulsified at 10,000 r / min for 15 minutes. The pH of the solution was adjusted to 10.5, heated to 55°C, stirred for 11 hours, centrifuged, washed, dried, and calcined at 400°C for 2 hours to prepare SiO2 nano-hollow microspheres.

[0046] T2. Ball milling: The SiO2 nano-hollow microspheres prepared in step T1 were ball milled for 3 h to prepare SiO2 nanosheets.

[0047] T3. Modification: 100 parts by weight of the SiO2 nanosheets prepared in step T2 were added to 200 parts by weight of ethanol, and 23 parts by weight of a silane coupling agent was added. The mixture was heated to 45°C, stirred for 1 hour, centrifuged, washed, and dried to prepare modified SiO2 nanosheets.

[0048] T4. Preparation of copper oxide@SiO2@aluminum oxide nanosheets: 13 parts by weight of aluminum isopropoxide was dissolved in 100 parts by weight of dichloromethane, and the solution was allowed to stand. 50 parts by weight of the modified SiO2 nanosheets prepared in step T3 was added and suspended at the interface. 100 parts by weight of an aqueous solution containing 10 parts by weight of copper nitrate was added dropwise, and 4 parts by weight of citric acid was added. The solution was allowed to stand for 40 minutes, centrifuged, washed, dried, and calcined at 600°C for 2 hours to prepare copper oxide@SiO2@aluminum oxide nanosheets.

[0049] Example 1 This example provides a process for preparing a copper-aluminum composite plate by continuous casting with molten aluminum, and includes the following steps:

[0050] S1. Smelting: Industrial LF21 pure aluminum ingot was heated to 750℃ and smelted for 2 hours.

[0051] S2. Standing: The molten aluminum smelted in step S1 was degassed and left standing at room temperature for 20 minutes.

[0052] S3. Copper strip pretreatment: A 2 mm thick tough pitch copper T2 copper strip was textured with a steel brush and then ultrasonically cleaned for 10 minutes.

[0053] S4. Copper strip heating: The pretreated copper strip obtained in step S3 was heated to 350°C.

[0054] S5. Continuous casting: Under the protection of nitrogen gas, the copper strip processed in step S4 is continuously passed through the crystallizer of the continuous casting equipment, and the molten aluminum processed in step S2 is continuously cast onto the copper strip through the casting system. The crystallizer rapidly cools and crystallizes the copper-aluminum composite material, and oxygen-free continuous casting is performed.

[0055] The casting speed was 1000 mm / min, the casting width was 50 mm, the casting thickness was 10 mm, and the cooling rate for the rapid cooling crystallization was 120° C. / min.

[0056] S6. Continuous rolling: The copper-aluminum composite material continuously cast in step S5 was rolled and continuously cast with molten aluminum to obtain a copper-aluminum composite plate material.

[0057] The copper-aluminum composite plate material prepared by continuous casting the molten aluminum had a thickness of 7 mm, a rolling pressure of 1,000,000 N, a rolling speed of 1,000 mm / min, and a rolling tension of 100,000 N.

[0058] Example 2 This example provides a process for preparing a copper-aluminum composite plate by continuous casting with molten aluminum, and includes the following steps:

[0059] S1. Smelting: Industrial LF21 pure aluminum ingot was heated to 750℃ and smelted for 2 hours.

[0060] S2. Standing: The Cu@Si@Al Janus nanosheet produced in Production Example 1 was added to the molten aluminum smelted in step S1 in an amount of 6 wt% of the molten aluminum. The mixture was stirred and mixed for 30 min, degassed, and then left to stand for 20 min.

[0061] S3. Copper strip pretreatment: A 2 mm thick tough pitch copper T2 copper strip was textured with a steel brush and then ultrasonically cleaned for 10 minutes.

[0062] S4. Copper strip heating: The pretreated copper strip obtained in step S3 was heated to 300°C.

[0063] S5. Continuous casting: Under the protection of nitrogen gas, the copper strip processed in step S4 is continuously passed through the crystallizer of the continuous casting equipment, and the molten aluminum processed in step S2 is continuously cast onto the copper strip through the casting system. The crystallizer rapidly cools and crystallizes the copper-aluminum composite material, and oxygen-free continuous casting is performed.

[0064] The casting speed was 1000 mm / min, the casting width was 50 mm, the casting thickness was 10 mm, and the cooling rate for the rapid cooling crystallization was 120° C. / min.

[0065] S6. Continuous rolling: The copper-aluminum composite material continuously cast in step S5 was rolled and continuously cast with molten aluminum to obtain a copper-aluminum composite plate material.

[0066] The copper-aluminum composite plate material prepared by continuous casting the molten aluminum had a thickness of 7 mm, a rolling pressure of 1,000,000 N, a rolling speed of 1,000 mm / min, and a rolling tension of 100,000 N.

[0067] Example 3 This example provides a process for preparing a copper-aluminum composite plate by continuous casting with molten aluminum, and includes the following steps:

[0068] S1. Smelting: Industrial LF21 pure aluminum ingot was heated to 700℃ and smelted for 1 hour.

[0069] S2. Standing: The Cu@Si@Al Janus nanosheet prepared in Preparation Example 1 was added to the molten aluminum smelted in step S1 in an amount of 5 wt% of the molten aluminum. The mixture was stirred and mixed for 30 min, degassed, and then left to stand for 10 min.

[0070] S3. Copper strip pretreatment: A 2 mm thick tough pitch copper T2 copper strip was textured with a steel brush, ultrasonically cleaned for 10 minutes, and then coated with a layer of 7 wt% ethylene glycol dimethyl ether solution of 11-mercaptoundecanoic acid on the surface.

[0071] S4. Copper strip heating: The pretreated copper strip obtained in step S3 was heated to 350°C.

[0072] S5. Continuous casting: Under the protection of nitrogen gas, the copper strip processed in step S4 is continuously passed through the crystallizer of the continuous casting equipment, and the molten aluminum processed in step S2 is continuously cast onto the copper strip through the casting system. The crystallizer rapidly cools and crystallizes the copper-aluminum composite material, and oxygen-free continuous casting is performed.

[0073] The casting speed was 1000 mm / min, the casting width was 50 mm, the casting thickness was 10 mm, and the cooling rate for the rapid cooling crystallization was 100° C. / min.

[0074] S6. Continuous rolling: The copper-aluminum composite material continuously cast in step S5 was rolled and continuously cast with molten aluminum to obtain a copper-aluminum composite plate material.

[0075] The copper-aluminum composite plate material prepared by continuous casting the molten aluminum had a thickness of 7 mm, a rolling pressure of 1,000,000 N, a rolling speed of 1,000 mm / min, and a rolling tension of 100,000 N.

[0076] Example 4 This example provides a process for preparing a copper-aluminum composite plate by continuous casting with molten aluminum, and includes the following steps:

[0077] S1. Smelting: Aluminum ingot was heated to 800℃ and smelted for 3 hours.

[0078] S2. Standing: The Cu@Si@Al Janus nanosheet prepared in Preparation Example 2 was added to the molten aluminum smelted in step S1 in an amount of 7 wt% of the molten aluminum. The mixture was stirred and mixed for 30 min, degassed, and then left to stand for 30 min.

[0079] S3. Copper strip pretreatment: A 2 mm thick tough pitch copper T2 copper strip was textured with a steel brush, ultrasonically cleaned for 10 minutes, and then coated with a layer of 12 wt% ethylene glycol dimethyl ether solution of 11-mercaptoundecanoic acid on the surface.

[0080] S4. Copper strip heating: The pretreated copper strip obtained in step S3 was heated to 350°C.

[0081] S5. Continuous casting: Under the protection of nitrogen gas, the copper strip processed in step S4 is continuously passed through the crystallizer of the continuous casting equipment, and the molten aluminum processed in step S213 is continuously cast onto the copper strip through the casting system. The crystallizer rapidly cools and crystallizes the copper-aluminum composite material, and oxygen-free continuous casting is performed.

[0082] The casting speed was 1000 mm / min, the casting width was 50 mm, the casting thickness was 10 mm, and the cooling rate for the rapid cooling crystallization was 150° C. / min.

[0083] S6. Continuous rolling: The copper-aluminum composite material continuously cast in step S5 was rolled and continuously cast with molten aluminum to obtain a copper-aluminum composite plate material.

[0084] The copper-aluminum composite plate material prepared by continuous casting the molten aluminum had a thickness of 7 mm, a rolling pressure of 1,000,000 N, a rolling speed of 1,000 mm / min, and a rolling tension of 100,000 N.

[0085] Example 5 This example provides a process for preparing a copper-aluminum composite plate by continuous casting with molten aluminum, and includes the following steps:

[0086] S1. Smelting: Industrial LF21 pure aluminum ingot was heated to 750℃ and smelted for 2 hours.

[0087] S2. Standing: The Cu@Si@Al Janus nanosheet prepared in Preparation Example 3 was added to the molten aluminum smelted in step S1 in an amount of 6 wt% of the molten aluminum. The mixture was stirred and mixed for 30 min, degassed, and then left to stand for 20 min.

[0088] S3. Copper strip pretreatment: A 2 mm thick tough pitch copper T2 copper strip was textured with a steel brush, ultrasonically cleaned for 10 minutes, and then coated with a layer of 10 wt% ethylene glycol dimethyl ether solution of 11-mercaptoundecanoic acid on the surface.

[0089] S4. Copper strip heating: The pretreated copper strip obtained in step S3 was heated to 350°C.

[0090] S5. Continuous casting: Under the protection of nitrogen gas, the copper strip processed in step S4 is continuously passed through the crystallizer of the continuous casting equipment, and the molten aluminum processed in step S2 is continuously cast onto the copper strip through the casting system. The crystallizer rapidly cools and crystallizes the copper-aluminum composite material, and oxygen-free continuous casting is performed.

[0091] The casting speed was 1000 mm / min, the casting width was 50 mm, the casting thickness was 10 mm, and the cooling rate for the rapid cooling crystallization was 120° C. / min.

[0092] S6. Continuous rolling: The copper-aluminum composite material continuously cast in step S5 was rolled and continuously cast with molten aluminum to obtain a copper-aluminum composite plate material.

[0093] The copper-aluminum composite plate material prepared by continuous casting the molten aluminum had a thickness of 7 mm, a rolling pressure of 1,000,000 N, a rolling speed of 1,000 mm / min, and a rolling tension of 100,000 N.

[0094] Comparative Example 1 This example differed from Example 5 in that the Cu@Si@Al Janus nanosheets were prepared in Comparative Preparation Example 1.

[0095] Comparative Example 2 This example differed from Example 5 in that the Cu@Si@Al Janus nanosheets were prepared in Comparative Preparation Example 2.

[0096] Test Example 1 Performance tests were carried out on the copper-aluminum composite plates prepared by continuous casting of molten aluminum in Examples 1 to 5 of the present invention and Comparative Examples 1 and 2, as well as similar commercially available products. The results are shown in Table 1.

[0097] [Table 1]

[0098] From the above table, it can be seen that the copper aluminum composite plates prepared in Examples 2 to 5 of the present invention by continuous casting of molten aluminum have good bonding strength and composite strength, high shear strength, and small interfacial layer thickness.

[0099] The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for producing a copper-aluminum composite plate material by continuous casting with molten aluminum, A smelting step S1 in which an aluminum ingot is heated to 700 to 800 ° C. and smelted for 1 to 3 hours; The molten aluminum obtained in step S1 is degassed and left to stand for 10 to 30 minutes, and a Cu@Si@Al Janus nanosheet is added before the degassing treatment in an amount of 5 to 7 wt % of the molten aluminum in a standing step S2, and the Cu@Si@Al Janus nanosheet is prepared as follows: T1. SiO ２ Preparation of nano hollow microspheres: Tetraethyl orthosilicate is dissolved in an organic solvent to obtain an oil phase, an emulsifier is dissolved in water to obtain an aqueous phase, the aqueous phase is added dropwise to the oil phase to emulsify, the pH value of the solution is adjusted to 10-11, and the reaction is carried out under heating and stirring, followed by centrifugation, washing, drying, and calcination to obtain SiO ２ Preparing hollow nanospheres T2. Ball mill: SiO prepared in step T1 ２ The nano-hollow microspheres were ball-milled to form SiO ２ Preparing nanosheets T3. Modification: SiO prepared in step T2 ２ The nanosheets were added to ethanol, and a silane coupling agent was added. The mixture was reacted with heat and stirring, then centrifuged, washed, and dried to form a modified SiO ２ Preparing nanosheets T4. Copper oxide @SiO ２ @Preparation of aluminum oxide nanosheets: Aluminum isopropoxide was dissolved in dichloromethane and allowed to stand. The modified SiO prepared in step T3 was then added to the aluminum oxide nanosheets. ２ The nanosheets were added and suspended at the interface, and then an aqueous solution containing copper salt was added dropwise, followed by the addition of citric acid. The mixture was then left to react, centrifuged, washed, dried, and calcined to give copper oxide@SiO ２ @Preparing aluminum oxide nanosheets, T5. Reduction: copper oxide@SiO prepared in step T4 ２ a step S2 of mixing aluminum oxide nanosheets and magnesium powder, carrying out a heating reduction reaction, and then carrying out a hydrogen gas reduction reaction to prepare Cu@Si@Al Janus nanosheets; a copper strip pretreatment step S3 in which the copper strip is embossed and washed; a copper strip heating step S4 in which the pretreated copper strip obtained in step S3 is heated to 200 to 650°C; a continuous casting step S5 in which the molten aluminum processed in step S2 is continuously cast onto the copper strip processed in step S4 under the protection of an inert gas, and the copper-aluminum composite material is rapidly cooled and crystallized, followed by oxygen-free continuous casting; and a continuous rolling step S6 of rolling the copper-aluminum composite material continuously cast in step S5 to obtain a copper-aluminum composite plate prepared by continuous casting with molten aluminum.

2. 2. The process of claim 1, wherein the texturing in step S3 includes mechanical texturing using a steel brush or an abrasive tape, chemical texturing, or laser texturing, and the cleaning is ultrasonic cleaning or laser cleaning.

3. In step S5, the casting speed is 200 to 1200 mm / min, the casting width is 10 to 100 mm, the casting thickness is 3 to 20 mm, and the cooling rate of the rapid cooling crystallization is 100 to 150 ° C. / min; The specific method is as follows:

2. The process according to claim 1, wherein the copper strip treated in step S4 is continuously passed through a crystallizer of a continuous casting facility under the protection of an inert gas, and the molten aluminum is continuously cast onto the copper strip through a casting system, and the crystallizer rapidly cools and crystallizes the copper-aluminum composite material, resulting in oxygen-free continuous casting.

4. 2. The process according to claim 1, wherein the copper aluminum composite plate prepared by continuous casting from the molten aluminum in step S6 has a thickness of 2 to 12 mm, a rolling pressure of 5,000 to 5,000,000 N, a rolling speed of 300 to 1,500 mm / min, and a rolling tension of 10,000 to 200,000 N.

5. In step T1, the mass ratio of the tetraethyl orthosilicate, the organic solvent, the emulsifier, and the water is 12 to 15:100:0.5 to 1:30 to 50, the emulsifier is selected from at least one of polysorbate-20, polysorbate-40, polysorbate-60, and polysorbate-80, the heating and stirring reaction is carried out at a temperature of 50 to 60°C for 10 to 12 hours, the baking is carried out at a temperature of 300 to 500°C for 1 to 3 hours, the ball milling time in step T2 is 2 to 4 hours, and the SiO ２ The process according to claim 1, characterized in that the mass ratio of the nanosheet to the silane coupling agent is 100:22-25, the silane coupling agent is a silane coupling agent having an amino group and is selected from at least one of KH550, KH602, and KH792, and the reaction time of the heating and stirring is 0.5-1 hour at a temperature of 40-50°C.

6. The modified SiO ２ The mass ratio of the nanosheet, aluminum isopropoxide, copper salt, and citric acid is 50:12-15:7-12:3-5, the static reaction time is 30-50 min, the baking temperature is 500-700°C, and the baking time is 1-3 h, and the copper salt is selected from at least one of copper chloride, copper sulfate, and copper nitrate; The copper oxide@SiO in step T5 ２ The process according to claim 1, wherein the mass ratio of aluminum oxide nanosheets to magnesium powder is 100:7-12, the thermal reduction reaction is carried out at a temperature of 700-800°C for 0.5-1 hour, the hydrogen gas reduction reaction is carried out at a temperature of 600-800°C for 1-2 hours, and the hydrogen gas flow rate is 20-30 mL / min.

7. 2. The process according to claim 1, wherein after the cleaning treatment in step S3, the surface is coated with one layer of an ethylene glycol dimethyl ether solution of 11-mercaptoundecanoic acid with a concentration of 7-12 wt %.

8. A copper-aluminum composite plate material prepared by continuous casting of molten aluminum, prepared by the process according to any one of claims 1 to 7.

9. The copper-aluminum composite plate material prepared by continuous casting of the molten aluminum according to claim 8 is used in preparing pole posts of new energy batteries.

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