A method for preparing non-ferrous metal alloy by alloying waste solar cell silicon plate material

Abstract

This invention discloses a method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panels. The method uses waste silicon panels as a silicon source, directly refining them with magnesium, aluminum, and copper sources. Through the synergistic effect of thermodynamic phase equilibrium control and kinetic dissolution mechanisms in a multi-element alloy system, silicon melting is achieved within a temperature range of 900–1200°C, yielding a non-ferrous metal-magnesium-aluminum-copper-silicon alloy. This invention only requires crushing the recycled waste solar panels and then removing the debris and impurities through physical separation technology to obtain raw materials that meet the requirements of subsequent processes, eliminating the need for complex chemical treatment processes such as acid leaching purification.

Description

Technical Field

[0001] This invention relates to the reuse of waste solar cell silicon panel materials through alloying and the preparation of high-performance non-ferrous metal alloy materials through optimized processes. It is a method for high-performance regeneration of waste solar cell materials and improvement of the strength and toughness of magnesium, aluminum and copper alloys. Background Technology

[0002] Silicon solar cells, using silicon as their primary material, are widely used in solar power generation. They are devices that convert sunlight into electrical energy using the photoelectric effect, directly converting solar radiation into direct current. They were initially invented in the 1950s by Daryl Chapin and others at Bell Labs. With continuous technological advancements, the efficiency and manufacturing cost of silicon solar cells have significantly improved, and they now dominate the photovoltaic market. Silicon solar cells are widely used in rooftop solar systems, solar power plants, traffic lights, and energy storage. As their production capacity and application scope continue to expand, the recycling of waste silicon solar panels has become an urgent problem to be solved.

[0003] Patent CN 118745511 A discloses a method for preparing silicon-based high-entropy alloys from photovoltaic silicon waste using a compensation method. The method involves first pretreating the cutting slurry to obtain silicon wafer cutting waste, then refining it at high temperature and cooling it in the furnace to obtain refined silicon ingots. After crushing the silicon ingots, the waste is fused with solvent metals such as aluminum and tin, and first directionally solidified to obtain a precursor. Then, the silicon-rich regions are cut and separated, and the target metal is added according to a specific ratio. The alloy is then fused with the target metal, held at a certain temperature, and cast and cooled to obtain the final alloy. However, this method has a long directional solidification time (0.5~80h), low efficiency, and is sensitive to the impurity content of the raw materials, which may affect the stability of the alloy's properties. Meanwhile, in comparison with the method for recycling high-silicon aluminum alloy from waste crystalline silicon batteries disclosed in patent CN118109698 A, the method involves crushing and screening the battery cells, separating silver-rich slag from aluminum-silicon tailings by gravity separation, mixing the aluminum-silicon tailings with aluminum particles and flux in a certain proportion, and then smelting at high temperature to obtain a high-silicon aluminum alloy containing 17-30% silicon. However, the proportion of flux in this method needs to be precisely controlled, otherwise the purity of the alloy will be affected. Summary of the Invention

[0004] The purpose of this invention is to address the limitations of current technologies by providing a method for preparing non-ferrous metal alloys through alloying of waste solar cell silicon panels. This method uses waste silicon panels as a silicon source, directly refining them with magnesium, aluminum, and copper sources. Through the synergistic effect of thermodynamic phase equilibrium control and kinetic dissolution mechanisms in a multi-element alloy system, silicon melting is achieved within a temperature range of 900–1200°C, yielding a non-ferrous metal-magnesium-aluminum-copper-silicon alloy. This invention only requires crushing the recycled waste solar panels and then removing the debris and impurities through physical separation techniques to obtain raw materials that meet the requirements of subsequent processes, eliminating the need for complex chemical treatment processes such as acid leaching and purification.

[0005] The technical solution of this invention is as follows: A method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials includes the following steps: 1) Crush and process waste solar cells; 2) Remove the battery silicon plate material and clean and dry it to obtain the silicon source. The drying temperature is 400~500℃ and the holding time is 3~6h. 3) Preheat the metal raw materials to remove moisture. The preheating temperature is 200~300℃, and the holding time is 30 minutes. Then, according to the non-ferrous metal alloy composition M... x A a B b Si z N y The element mass ratio is determined by mixing the silicon source treated in step 2) with the metal raw materials to obtain a smelting mixture, which is then smelted to obtain a non-ferrous metal alloy. Among them, M x A a B b Si z N y In this context, M is a basic element, one of Mg, Al, and Cu; A and B are two other elements besides the basic elements of Mg, Al, and Cu; N is a dopant element, including one or more of Zn, Mn, or Cr; the subscript indicates the mass percentage of the relevant element in the alloy. x = 83.5 wt.%~95.0 wt.%, a = 0.5 wt.%~10.0 wt.%, b = 0.1 wt.%~2.0 wt.%; y = 0.0 wt.%~5.0 wt.%; z = 2.0 wt.%~10 wt.%; When the value is 0, it means that the element is not present. The metal raw materials include magnesium source, aluminum source and copper source; The magnesium source is pure magnesium or a magnesium alloy, wherein the magnesium alloy is AZ31, AZ61, AZ91, or MgCu50. The aluminum source is pure aluminum or an aluminum alloy, wherein the aluminum alloy is 6061; The copper source is pure copper or a copper alloy, and the copper alloy is QAl9-2 or CuMg50. When magnesium is the base element, the melting temperature is 900~1000℃, with stirring 2~3 times during the process, stirring time 3~5min, and a standing holding time of 15~30min before casting; when aluminum is the base element, the melting temperature is 1000~1100℃, with stirring 2~3 times during the process, stirring time 3~5min, and a standing holding time of 15~30min before casting; when copper is the base element, the melting temperature is 1100~1200℃, with stirring 2~3 times during the process, stirring time 3~5min, and a standing holding time of 15~30min before casting. When the doping element ratio is 0, the content of the basic elements is 87.0 wt.%~95.0 wt.%, with Mg, Al, Cu, and Si totaling 100%. When the raw material is an alloy, the content of the basic elements is 83.5 wt.%~92.0 wt.%, with Mg, Al, Cu, and Si accounting for 95.0 wt.%~99.5 wt.% of the non-ferrous metal alloy. When smelting based on different raw materials, the proportions of the four elements in the alloy are different, as follows: When the magnesium source is a magnesium alloy, the element content in the resulting alloy is: aluminum 3.0 wt.%~9.0 wt.%, copper 0.5 wt.%~1.0 wt.%, silicon 2.0 wt.%~4.0 wt.%, with the remainder being magnesium and elements contained in the raw materials; MgCu50 is not used as a source of magnesium or copper base elements, but only as element A or element B, providing Mg or Cu elements to the alloy during smelting; When the aluminum source is an aluminum alloy, the element content in the resulting alloy is: magnesium 0.8wt.%~1.5wt.%, copper 0.15wt.%~0.5wt.%, silicon 6.0wt.%~11.0wt.%, and the remainder is aluminum and elements contained in the raw materials; When the copper source is a copper alloy, magnesium is 0.8 wt.%~1.2 wt.%, aluminum is 8.0 wt.%~11.0 wt.%, silicon is 2.0 wt.%~6.0 wt.%, and the remainder is copper and elements contained in the raw materials; 4) Heat-treat the sample from step 3); According to the method provided by the present invention, the above-mentioned smelted sample is taken and subjected to heat treatment. When magnesium is the alloying element, the heat treatment temperature is 360~520℃ and the holding time is 6~10h; when aluminum is the alloying element, the heat treatment temperature is 360~520℃ and the holding time is 4~12h; when copper is the alloying element, the heat treatment temperature is 600~800℃ and the holding time is 6~16h. 5) After heat treatment, air cool to room temperature, and then perform machining to make the sample surface smooth; 6) Take the sample obtained in step 5) and perform hot extrusion; Where magnesium is the alloying element, the sample preheating temperature is 300~360℃, the holding time is 0.5~1h, the extrusion temperature is 300~360℃, the die holding temperature is 300~360℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50; where aluminum is the alloying element, the sample preheating temperature is 300~400℃, the holding time is 0.5~1h, the extrusion temperature is 300~400℃, the die holding temperature is 300~400℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50; where copper is the alloying element, the sample preheating temperature is 650~750℃, the holding time is 0.5~1h, the extrusion temperature is 650~750℃, the die holding temperature is 650~750℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50. The non-ferrous metal alloy is a magnesium-aluminum-copper-silicon alloy.

[0006] The essential features of this invention are: This invention overcomes the limitations of traditional silicon panel recycling methods, which require complex processes such as smelting, cutting, and acid leaching purification. It obtains silicon raw materials that meet the requirements of subsequent processes simply by crushing waste solar panels and using physical separation technology to remove debris and impurities, eliminating the need for complex chemical treatments. Furthermore, it innovatively introduces magnesium, aluminum, and copper alloying elements to construct a eutectic alloy system with silicon, effectively lowering the high melting point of pure silicon (approximately 1414℃). Specifically, the eutectic point of the aluminum-silicon system is approximately 577℃, the copper-silicon system is approximately 1085℃, and the magnesium-silicon system is approximately 637℃. This invention abandons the traditional method of smelting magnesium-silicon, aluminum-silicon, and copper-silicon alloys using pure metals or intermediate alloys. Instead, it uses waste solar cell silicon panels as the silicon source and smelts them in specific proportions with pure magnesium or magnesium alloys (such as AZ31, AZ61, etc.), pure aluminum or 6061 aluminum alloy, and pure copper or copper alloys such as QAl9-2. No flux is needed, avoiding the problem of alloy purity being affected by improper flux ratio control. This not only solves the problem of recycling waste silicon panels and reduces costs, but also precisely optimizes performance by leveraging the characteristics of silicon in different alloy systems. In magnesium alloys, it passivates iron and forms a Mg2Si strengthening phase; in aluminum alloys, it improves melt fluidity and balances strength and plasticity; and in copper alloys, it precipitates a Cu3Si phase and forms a stable oxide film, significantly improving the alloy's corrosion resistance, mechanical properties, and other comprehensive indicators.

[0007] In the smelting process of magnesium, aluminum, copper, and silicon quaternary alloys, the phenomenon that the actual smelting temperature of silicon and silicon alloys is lower than the melting point of pure silicon (1414℃) is essentially a manifestation of the synergistic effect of thermodynamic phase equilibrium regulation and kinetic dissolution mechanism in the multi-element alloy system. From a thermodynamic perspective, silicon can form binary eutectic phases of Mg-Si (637℃) and Al-Si (577℃) and ternary eutectic phases of Mg-Al-Si (approximately 564℃) with magnesium and aluminum matrix elements. When the alloy composition approaches the eutectic point, the system can achieve silicon participation in alloying as a eutectic phase component through eutectic transformation, without needing to reach the melting point of pure silicon itself. At the same time, silicon follows the thermodynamic law of solute dissolution in liquid magnesium and aluminum matrix. The energy provided by the thermal motion of liquid matrix atoms can overcome the binding energy between silicon atoms, allowing silicon atoms to dissolve in the matrix through diffusion. This process is similar to the dissolution of a solute in a solvent, without the need for direct melting of silicon. The smelting temperature only needs to be higher than the liquidus temperature of the matrix to meet the requirements. From the perspective of kinetics and multi-element regulation, aluminum can form a highly stable Al-Si eutectic phase to construct a melting "temperature anchor" for the system, while copper can reduce the energy barrier of the system by forming ternary intermetallic compounds such as Mg2CuSi after dissolution (forming compounds with negative enthalpy and thermodynamic stability), thus synergistically optimizing phase equilibrium. The small wetting angle (30°~40°) between liquid magnesium, aluminum and solid silicon can reduce the solid-liquid interface energy. Combined with mechanical stirring and inert gas protection during the melting process, this reduces silicon particle agglomeration and increases the solid-liquid contact area, further reducing the kinetic barrier of silicon dissolution and promoting efficient alloying of silicon at temperatures below its melting point.

[0008] The beneficial effects of this invention are as follows: After applying the research method, high-performance non-ferrous metal alloys were successfully prepared through simple alloying and process optimization, while simultaneously achieving low-cost recycling of waste solar cells. For example, Table 1 shows that the yield strength of Example 2 increased by 16 MPa and the tensile strength increased by 46 MPa compared to Comparative Example 2; similarly, in Table 2, the yield strength of Example 6 increased by 21 MPa and the tensile strength increased by 41 MPa compared to Comparative Example 6; and in Table 3, the relevant mechanical properties of Example 8 were also improved compared to Comparative Example 8. Attached Figure Description

[0009] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further illustrated below with reference to the accompanying drawings.

[0010] Figure 1 This is a flowchart illustrating the process for preparing high-performance non-ferrous metal alloys based on the alloying of waste solar cell silicon panels, as described in this invention. Detailed Implementation

[0011] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

[0012] Unless the context explicitly requires it, the words "comprising," "including," and similar terms throughout the specification and claims should be interpreted as encompassing rather than being exclusive or exhaustive; that is, meaning "including but not limited to."

[0013] Example 1: Mg 94 Preparation of Al3Cu1Si2 non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; The dried silicon plate material is based on a pure silicon source with a purity of 99.9%. The following examples are the same and will not be repeated. 2) Surface treatment: Use sandpaper to polish the surface of pure magnesium, pure aluminum, and MgCu50 alloy to remove the surface oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take the cleaned and dried waste solar cell silicon panel material, pure magnesium, pure aluminum, and MgCu50 alloy (the mass ratio of the four is 2:93:3:2 - that is, the mass percentage of the four elements is: Si:2.0wt.%, Al:3.0wt.%, Cu:1.0wt.%, Mg:94.0wt.%) and smelt them in the following proportions: smelting temperature 1000℃, mechanical stirring twice during the process, each stirring time is 5min, the total smelting time is 90min, the holding time before casting is 15min, and then casting is performed. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 400℃ for 6 hours. After that, air cool it to room temperature and machine the sample to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 300℃ for 0.5 hours, and then extruded in an extruder at 300℃, with the die held at 300℃, an extrusion speed of 0.3 mm / s, and an extrusion ratio of 30, to obtain Mg. 94 Al3Cu1Si2 non-ferrous metal alloy.

[0014] Example 2: Mg 91.9 Al3Cu 0.5 Si3Zn1Mn0.6 Preparation of non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of AZ31 and MgCu50 magnesium alloys to remove the surface oxide scale and machining marks, then clean and dry them at 200℃ for 30 minutes. 3) Smelting: Take the cleaned and dried waste solar cell silicon panel material, AZ31 magnesium alloy, and MgCu50 (the mass ratio of the three is 3:96:1, that is, the mass percentage of the six elements is: Si:3.0wt.%, Al:3.0wt.%, Cu:0.5wt.%, Mg:91.9wt.%, Zn:1.0wt.%, Mn:0.6wt.% (Zn and Mn are elements contained in AZ31 alloy)) and smelt them. The smelting temperature is 1000℃, and the mixture is mechanically stirred twice during the process, with each stirring time being 5 minutes. The total smelting time is 90 minutes. Before casting, the mixture is kept at the heat for 15 minutes and then cast. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 400℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 300℃ for 0.5 hours, and then extruded in an extruder at 300℃, with the die held at 300℃, an extrusion speed of 0.3 mm / s, and an extrusion ratio of 25, to obtain Mg. 91.9 Al3Cu 0.5 Si3Zn1Mn 0.6 Non-ferrous metal alloys.

[0015] When raw material metals are involved in alloys, the presence of other metallic elements does not significantly affect the properties of the final alloy.

[0016] Example 3: Mg 89.15 Al6Cu 0.5 Si3Zn1Mn 0.35 Preparation of non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of AZ61 and MgCu50 magnesium alloys to remove the surface oxide scale and machining marks, then clean and dry them at 200℃ for 30 minutes. 3) Smelting: Take the cleaned and dried waste solar cell silicon panel material, AZ61, and MgCu50 magnesium alloy (the mass ratio of the three is 3:96:1—that is, the mass percentage of the six elements is: Si:3.0wt.%, Al:6.0wt.%, Cu:0.5wt.%, Mg:89.15wt.%, Zn:1.0wt.%, Mn:0.35wt.% (Zn and Mn are elements contained in AZ61 alloy)) and smelt them in the following proportions: The smelting temperature is 1000℃, and mechanical stirring is performed twice during the process, with each stirring time being 5 minutes. The total smelting time is 90 minutes. Before casting, the material is kept at the heat for 15 minutes and then cast. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 420℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 320℃ for 0.5 hours, and then extruded in an extruder at 320℃, with the die held at 320℃, an extrusion speed of 0.2 mm / s, and an extrusion ratio of 25, to obtain Mg. 89.15 Al6Cu 0.5 Si3Zn1Mn 0.35 Non-ferrous metal alloys.

[0017] When raw material metals are involved in alloys, the presence of other metallic elements does not significantly affect the properties of the final alloy.

[0018] Example 4: Mg 84.7 Al9Cu1Si4Zn1Mn 0.3 Preparation of non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of AZ91 and MgCu50 magnesium alloys to remove the surface oxide scale and machining marks, then clean and dry them at 200℃ for 30 minutes. 3) Smelting: Take the cleaned and dried waste solar cell silicon panel material, AZ91 magnesium alloy, and MgCu50 (the mass ratio of the three is 2:47:1, that is, the mass percentage of the six elements is: Si: 4.0 wt.%, Al: 9.0 wt.%, Cu: 1.0 wt.%, Mg: 84.7 wt.%, Zn: 1.0 wt.%, Mn: 0.3 wt.% (Zn and Mn are elements contained in AZ91 alloy)) and smelt them in the following proportions: smelting temperature 1000℃, mechanical stirring twice during the process, each stirring time 5 min, total smelting time 90 min, heat preservation and standing time 15 min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 420℃ for 10 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 320℃ for 0.5 hours, and then extruded in an extruder at 320℃, with the die held at 320℃, an extrusion speed of 0.2 mm / s, and an extrusion ratio of 25, to obtain Mg. 84.7 Al9Cu1Si4Zn1Mn 0.3 Non-ferrous metal alloys.

[0019] When raw material metals are involved in alloys, the presence of other metallic elements does not significantly affect the properties of the final alloy.

[0020] Example 5: Al 92 Mg 1.5 Cu 0.5 Preparation of Si6 non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of pure aluminum, pure magnesium, and MgCu50 alloy to remove the surface oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take the cleaned and dried waste silicon solar cell silicon panel material, pure aluminum, pure magnesium, and MgCu50 alloy (the mass ratio of the four is 6:92:1:1—that is, the mass percentage of the four elements is: Si:6.0wt.%, Mg:1.5wt.%, Cu:0.5wt.%, Al:92.0wt.%) and smelt them in the following proportions: smelting temperature 1030℃, mechanical stirring twice during the process, each stirring time is 5min, the total smelting time is 80min, the holding time before casting is 15min, and then casting is performed. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 450℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Preheat the machined sample in an electric resistance furnace to 360℃ for 0.5 hours, then place it in an extruder for extrusion at 360℃, with the die maintained at 360℃, an extrusion speed of 0.5 mm / s, and an extrusion ratio of 20, to obtain Al. 92 Mg 1.5 Cu 0.5 Si6 non-ferrous metal alloy.

[0021] Example 6: Al 91.72 Mg 0.94 Cu 0.28 Si 6.56 Zn 0.15 Mn 0.1 Cr 0.25 Preparation of non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of 6061 aluminum alloy to remove the surface oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take the cleaned and dried waste silicon solar cell silicon panel material and 6061 aluminum alloy (the mass ratio of the two is 3:47 - that is, the mass percentage of the seven elements is: Si: 6.56wt.%, Mg: 0.94wt.%, Cu: 0.28wt.%, Al: 91.72wt.%, Zn: 0.15wt.%, Mn: 0.1wt.%, Cr: 0.25wt.% (Mg, Cu, Zn, Mn, and Cr are the elements contained in 6061 alloy, and also contain a small amount of Si element)) and smelt them in the following proportions: The smelting temperature is 1030℃, and mechanical stirring is performed twice during the process, with each stirring time being 5 minutes. The total smelting time is 80 minutes. Before casting, the material is kept at the heat for 15 minutes and then cast. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 480℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 360℃ for 0.5 hours, and then extruded in an extruder at 360℃, with the die held at 360℃, an extrusion speed of 0.4 mm / s, and an extrusion ratio of 15, to obtain Al. 91.72 Mg 0.94 Cu0.28 Si 6.56 Zn 0.15 Mn 0.1 Cr 0.25 Non-ferrous metal alloys.

[0022] When raw material metals are involved in alloys, the presence of other metallic elements does not significantly affect the properties of the final alloy.

[0023] Example 7: Cu 87 Preparation of Mg1Al8Si4 non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of pure copper, pure aluminum, and CuMg50 alloy to remove the surface oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take the cleaned and dried waste silicon solar cell silicon panel material, pure copper, pure aluminum, and CuMg50 alloy (the mass ratio of the four is 2:43:4:1 - that is, the mass percentage of the four elements is: Si:4.0wt.%, Mg:1.0wt.%, Al:8.0wt.%, Cu:87.0wt.%) and smelt them in the following proportions: smelting temperature 1150℃, mechanical stirring twice during the process, each stirring time is 5min, the total smelting time is 100min, the holding time before casting is 15min, and then casting is performed. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 750℃ for 10 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 700℃ for 0.5 hours, and then extruded in an extruder at 700℃, with the die held at 700℃, an extrusion speed of 0.5 mm / s, and an extrusion ratio of 20, to obtain Cu. 87 Mg1Al8Si4 is a non-ferrous metal alloy.

[0024] Example 8: Cu 83.5 Mg1Al9Si4Zn 0.5 Preparation of Mn2 non-ferrous alloys: 1) Material preparation: Prepare waste solar cells, crush them, and make the internal silicon plate material into squares with a diameter of no more than 60mm or a side length of no more than 50mm, and then dry them; 2) Surface treatment: Use sandpaper to polish the surface of QAl9-2 and CuMg50 copper alloys to remove the surface oxide scale and machining marks, then clean and dry. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take the cleaned and dried waste silicon solar cell silicon panel material, QAl9-2 copper alloy, and CuMg50 (the mass ratio of the three is 2:47:1—that is, the mass percentage of the six elements is: Si: 4.0wt.%, Mg: 1.0wt.%, Al: 9.0wt.%, Cu: 83.5wt.%, Zn: 0.5wt.%, Mn: 2.0wt.% (Zn and Mn elements are elements contained in QAl9-2 alloy)) and smelt them in the following proportions: The smelting temperature is 1150℃, and mechanical stirring is performed twice during the process, with each stirring time being 5 minutes. The total smelting time is 100 minutes. Before casting, the material is kept at the heat for 15 minutes and then cast. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at room temperature to 800℃ for 16 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) The machined sample was preheated in an electric resistance furnace at 750℃ for 0.5 hours, and then extruded in an extruder at 750℃, with the die held at 750℃, an extrusion speed of 0.3 mm / s, and an extrusion ratio of 25, to obtain Cu. 83.5 Mg1Al9Si4Zn 0.5 Mn2 non-ferrous metal alloy.

[0025] When raw material metals are involved in alloys, the presence of other metallic elements does not significantly affect the properties of the final alloy.

[0026] Comparative Example 1: 1) Material preparation: Prepare pure magnesium materials; 2) Surface treatment: Sand the magnesium surface with sandpaper to remove the oxide scale and machining marks, then clean and dry it at 200℃ for 30 minutes. 3) Smelting: Magnesium smelting: smelting temperature 750℃, mechanical stirring twice during the process, each stirring time 5min, holding at the temperature for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at room temperature to 300℃ for 6 hours. After that, air cool the sample to room temperature and machine it to make the surface smooth.

[0027] 5) Place the machined sample in an electric resistance furnace for preheating at 300°C for 0.5 hours. Then place it in an extruder for extrusion at 300°C, with the die holding temperature at 300°C, the extrusion speed at 0.3 mm / s, and the extrusion ratio at 30 to obtain a non-ferrous metal alloy.

[0028] 6) The composition of the obtained non-ferrous metal alloy is Mg: 100.0 wt.%.

[0029] Comparative Example 2: 1) Material preparation: Prepare AZ31 magnesium alloy material; 2) Surface treatment: Polish the prepared AZ31 magnesium alloy surface with sandpaper to remove the surface oxide scale and machining marks, and then dry it at 200℃ for 30 minutes. 3) Melting: Take AZ31 magnesium alloy for melting: melting temperature 750℃, mechanical stirring twice during the process, each stirring time 5min, holding the temperature and standing for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 400℃ for 6 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in an electric resistance furnace for preheating at 300°C for 0.5 hours. After preheating, place it in an extruder for extrusion at 300°C, with the die holding temperature at 300°C, the extrusion speed at 0.5 mm / s, and the extrusion ratio at 25 to obtain a non-ferrous metal alloy.

[0030] 6) The composition of the obtained non-ferrous metal alloy is Al: 3.0 wt.%, Mg: 95.4 wt.%, Zn: 1.0 wt.%, Mn: 0.6 wt.%.

[0031] Comparative Example 3: 1) Material preparation: Prepare AZ61 magnesium alloy material; 2) Surface treatment: Polish the prepared AZ61 magnesium alloy surface with sandpaper to remove the surface oxide scale and machining marks, and then dry it at 200℃ for 30 minutes. 3) Melting: Take AZ61 magnesium alloy for melting: melting temperature 750℃, mechanical stirring twice during the process, each stirring time 5min, holding at the temperature for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 420℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in an electric resistance furnace for preheating at 320°C for 0.5 hours. After preheating, place it in an extruder for extrusion at 320°C, with the die holding temperature at 320°C, an extrusion speed of 0.3 mm / s, and an extrusion ratio of 25 to obtain a non-ferrous metal alloy.

[0032] 6) The composition of the obtained non-ferrous metal alloy is Al: 6.0 wt.%, Mg: 92.65 wt.%, Zn: 1.0 wt.%, Mn: 0.35 wt.%.

[0033] Comparative Example 4: 1) Material preparation: Prepare AZ91 magnesium alloy material; 2) Surface treatment: Polish the prepared AZ91 magnesium alloy surface with sandpaper to remove the surface oxide scale and machining marks, and then dry it at 200℃ for 30 minutes. 3) Melting: Take AZ91 magnesium alloy for melting: melting temperature 750℃, mechanical stirring twice during the process, each stirring time 5min, holding at the temperature for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 420℃ for 10 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in an electric resistance furnace for preheating at 320°C for 0.5 hours. After preheating, place it in an extruder for extrusion at 320°C, with the die holding temperature at 320°C, an extrusion speed of 0.3 mm / s, and an extrusion ratio of 25 to obtain a non-ferrous metal alloy.

[0034] 6) The composition of the obtained non-ferrous metal alloy is Al: 9.0 wt.%, Mg: 89.7 wt.%, Zn: 1.0 wt.%, Mn: 0.3 wt.%.

[0035] Comparative Example 5: 1) Material preparation: Prepare pure aluminum materials; 2) Surface treatment: Sand the aluminum surface with sandpaper to remove the oxide scale and machining marks, then clean and dry it at 200℃ for 30 minutes. 3) Smelting: Aluminum is smelted at a temperature of 750℃, with mechanical stirring twice during the process, each stirring time being 5 minutes. Before casting, the aluminum is kept at the temperature for 15 minutes and then cast. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 450℃ for 8 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in an electric resistance furnace for preheating at 360°C for 0.5 hours. Then place it in an extruder for extrusion at 360°C, with the die temperature maintained at 360°C, the extrusion speed at 0.5 mm / s, and the extrusion ratio at 20 to obtain a non-ferrous metal alloy.

[0036] 6) The composition of the obtained non-ferrous metal alloy is Al: 100.0 wt.%.

[0037] Comparative Example 6: 1) Material preparation: Prepare 6061 aluminum alloy; 2) Surface treatment: Polish the prepared 6061 aluminum alloy surface with sandpaper to remove the surface oxide scale and machining marks, and then dry it at 200℃ for 30 minutes. 3) Melting: Take 6061 aluminum alloy for melting: melting temperature 750℃, mechanical stirring twice during the process, each stirring time 5min, holding the temperature and standing for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 450℃ for 10 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in a resistance furnace for preheating at 360°C for 0.5 hours. After preheating, place it in an extruder for extrusion at 360°C, with the die temperature maintained at 360°C, an extrusion speed of 0.4 mm / s, and an extrusion ratio of 15 to obtain a non-ferrous metal alloy.

[0038] 6) The composition of the obtained non-ferrous metal alloy is Si: 0.6 wt.%, Mg: 1.0 wt.%, Cu: 0.3 wt.%, Al: 97.6 wt.%, Zn: 0.15 wt.%, Mn: 0.1 wt.%, Cr: 0.25 wt.%.

[0039] Comparative Example 7: 1) Material preparation: Prepare pure copper material; 2) Surface treatment: Use sandpaper to polish the copper surface to remove the oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Smelting: Take copper for smelting: smelting temperature is 1100℃, mechanical stirring is carried out twice during the process, each stirring time is 5 minutes, and the copper is kept at the temperature for 15 minutes before casting. 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at 750℃ for 10 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in a resistance furnace for preheating at 700℃ for 0.5 hours, and then place it in an extruder for extrusion at 700℃, with the die holding temperature at 700℃, the extrusion speed at 0.5 mm / s, and the extrusion ratio at 20 to obtain a non-ferrous metal alloy.

[0040] 6) The composition of the obtained non-ferrous metal alloy is Cu: 100.0 wt.%.

[0041] Comparative Example 8: 1) Material preparation: Prepare QAl9-2 copper alloy; 2) Surface treatment: Use sandpaper to polish the surface of QAl9-2 copper alloy to remove the surface oxide scale and machining marks, then clean and dry it. The drying temperature is 200℃ and the holding time is 30min. 3) Melting: Take QAl9-2 copper alloy for melting: melting temperature 1100℃, mechanical stirring twice during the process, each stirring time 5min, holding at the temperature for 15min before casting; 4) Cool the smelted sample to room temperature and shape it. Then heat the sample at room temperature to 800℃ for 16 hours. Afterward, air cool the sample to room temperature and machine it to make the surface smooth. 5) Place the machined sample in an electric resistance furnace for preheating at 750°C for 0.5 hours. Then place it in an extruder for extrusion at 750°C, with the die holding temperature at 750°C, the extrusion speed at 0.4 mm / s, and the extrusion ratio at 25 to obtain a non-ferrous metal alloy.

[0042] 6) The composition of the obtained non-ferrous metal alloy is Al: 9.0 wt.%, Cu: 88.5 wt.%, Zn: 0.5 wt.%, Mn: 2.0 wt.%.

[0043] It will be readily understood by those skilled in the art that, without conflict, the above-mentioned preferred solutions can be freely combined and superimposed.

[0044] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. For those skilled in the art, the present invention can be modified and varied in various ways. Any modifications, equivalent substitutions, or improvements made within the spirit and principle of the present invention should be included within the scope of protection of the present invention.

[0045] To systematically characterize the mechanical properties of the alloy, the size design of the tensile specimens and the room temperature tensile testing procedure were strictly performed in accordance with the GB / T 228.1-2010 standard. A SUNS UTM5105G electronic universal testing machine was used for room temperature tensile testing, with a tensile rate set at 1.5 mm / min. Specimens were cut along the extrusion direction (ED). To eliminate the influence of experimental randomness, three parallel specimens were prepared for testing under each set of process parameters.

[0046] Table 1. Room temperature mechanical property test results of magnesium alloys in Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, and 4:

[0047] Table 2. Room temperature mechanical property test results of aluminum alloys in Examples 5, 6, and Comparative Examples 5 and 6:

[0048] Table 3. Room temperature mechanical property test results of copper alloys in Examples 7 and 8 and Comparative Examples 7 and 8:

[0049] In summary, this invention is based on the properties of silicon in magnesium, aluminum, and copper alloy systems, which can significantly improve alloy casting fluidity, promote the formation of strengthening phases, and enhance corrosion resistance. Through systematic research and optimization, it was determined that 2.0 wt.% to 10.0 wt.% of recycled silicon plate material from waste solar cells can be smelted with magnesium, aluminum, and copper-based raw material alloys in a preset ratio, and finally, a high-performance magnesium, aluminum, and copper recycled alloy was successfully prepared.

[0050] Matters not covered in this invention are common knowledge.

Claims

1. A method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials, characterized in that, The method includes the following steps: 1) Crush and process waste solar cells; 2) Remove the silicon plate material from the battery and clean and dry it to obtain the silicon source; drying temperature: 400~500℃, heat preservation time: 3~6h; 3) Preheat the metal raw materials to remove moisture; preheat temperature 200~300℃, hold for 30 minutes, then proceed according to the non-ferrous metal alloy composition M. x A a B b Si z N y The element mass ratio is determined by mixing the silicon source treated in step 2) with the metal raw materials to obtain a smelting mixture, which is then smelted to obtain a non-ferrous metal alloy. Among them, M x A a B b Si z N y In this context, M is a basic element, one of Mg, Al, and Cu; A and B are two other elements besides the basic elements of Mg, Al, and Cu; N is a dopant element, including one or more of Zn, Mn, or Cr; the subscript indicates the mass percentage of the relevant element in the alloy. x = 83.5 wt.%~95.0 wt.%, a = 0.5 wt.%~10.0 wt.%, b = 0.1 wt.%~2.0 wt.%; y = 0.0 wt.%~5.0 wt.%; z = 2.0 wt.%~10 wt.%; When the value is 0, it means that the component is not present. The metal raw materials mentioned are magnesium source, aluminum source and copper source; 4) Heat-treat the sample from step 3); When the magnesium source is the alloying base element, the heat treatment temperature is 360~520℃ and the holding time is 6~10h; when the aluminum source is the alloying base element, the heat treatment temperature is 360~520℃ and the holding time is 4~12h; when the copper source is the alloying base element, the heat treatment temperature is 600~800℃ and the holding time is 6~16h. 5) After heat treatment, air cool to room temperature, and then perform machining to make the sample surface smooth; 6) Take the sample obtained in step 5) and perform hot extrusion to obtain a magnesium-aluminum-copper-silicon non-ferrous metal alloy.

2. The method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials as described in claim 1, characterized in that, The magnesium source is pure magnesium or a magnesium alloy, wherein the magnesium alloy is AZ31, AZ61, AZ91, or MgCu50. The aluminum source is pure aluminum or an aluminum alloy, wherein the aluminum alloy is 6061; The copper source is pure copper or a copper alloy, and the copper alloy is QAl9-2 or CuMg50.

3. The method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials as described in claim 1, characterized in that, In step 3), when magnesium is the base element, the melting temperature is 900~1000℃, with stirring 2~3 times during the process, stirring time 3~5min, and standing time before casting 15~30min; when aluminum is the base element, the melting temperature is 1000~1100℃, with stirring 2~3 times during the process, stirring time 3~5min, and standing time before casting 15~30min; when copper is the base element, the melting temperature is 1100~1200℃, with stirring 2~3 times during the process, stirring time 3~5min, and standing time before casting 15~30min.

4. The method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials as described in claim 1, characterized in that, When the doping element ratio is 0, the content of the basic elements is 87.0 wt.%~95.0 wt.%, with the four elements Mg, Al, Cu and Si totaling 100%.

5. The method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials as described in claim 1, characterized in that, When the raw material is an alloy, the content of the basic elements is 83.5 wt.%~92.0 wt.%, with Mg, Al, Cu, and Si accounting for 95.0 wt.%~99.5 wt.% of the non-ferrous metal alloy. When smelting based on different raw materials, the proportions of the four elements in the alloy are different, as follows: When the magnesium source is a magnesium alloy, the element content in the resulting alloy is: aluminum 3.0 wt.%~9.0 wt.%, copper 0.5 wt.%~1.0 wt.%, silicon 2.0 wt.%~4.0 wt.%, and the remainder is magnesium and elements contained in the raw materials; When the aluminum source is an aluminum alloy, the element content in the resulting alloy is: magnesium 0.8wt.%~1.5wt.%, copper 0.15wt.%~0.5wt.%, silicon 6.0wt.%~11.0wt.%, and the remainder is aluminum and elements contained in the raw materials; When the copper source is a copper alloy, magnesium is 0.8 wt.%~1.2 wt.%, aluminum is 8.0 wt.%~11.0 wt.%, silicon is 2.0 wt.%~6.0 wt.%, and the remainder is copper and elements contained in the raw materials.

6. The method for preparing non-ferrous metal alloys by alloying waste solar cell silicon panel materials as described in claim 1, characterized in that, The hot extrusion parameters in step 6) are as follows: When magnesium is the alloying element, the sample preheating temperature is 300~360℃, the holding time is 0.5~1h, the extrusion temperature is 300~360℃, the die holding temperature is 300~360℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50; When aluminum is the alloying element, the sample preheating temperature is 300~400℃, the holding time is 0.5~1h, the extrusion temperature is 300~400℃, the die holding temperature is 300~400℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50; When copper is the alloying element, the sample preheating temperature is 650~750℃, the holding time is 0.5~1h, the extrusion temperature is 650~750℃, the die holding temperature is 650~750℃, the extrusion speed is 0.1~0.5mm / s, and the extrusion ratio is 4~50.

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