A continuous production method of metal-graphene composite material

Abstract

The present application relates to a kind of metal graphene composite continuous production method, belong to graphene composite technical field, to solve at least one of the problems such as existing method cannot continuous production, process is complex, cannot satisfy industrial production, production cost is high, etc..The method of the present application adds matrix metal and precursor slag with precursor after each casting, realizes at least 20 times of circulation production, the method of the present application has the advantages such as energy saving, simple operation, process stability, high production efficiency etc..And the graphene content, size, layer number and other properties of the metal graphene composite prepared by the method of the present application are stable.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of graphene composite materials, and particularly relates to a continuous production method of metal graphene composite materials. BACKGROUND

[0002] Graphene is one of the materials with the highest strength, and has good toughness and can be bent. The theoretical Young's modulus of graphene is 1.0 TPa, and the intrinsic tensile strength is 130 GPa. The carrier mobility of graphene at room temperature is about 15000 cm 2 / (V·s), which is more than 10 times of silicon material and more than twice of indium antimonide (InSb), which is the highest known carrier mobility. Under certain conditions such as low temperature, the carrier mobility of graphene can be as high as 250000 cm 2 / (V·s). Unlike many materials, the electron mobility of graphene is less affected by temperature change. The electron mobility of single-layer graphene is about 15000 cm 2 / (V·s) at any temperature between 50K and 500K.

[0003] Due to the numerous excellent properties of graphene, it is applied in more and more fields. In recent years, with the rapid development of new energy and energy storage fields, graphene is increasingly applied in the field of batteries. For example, graphene is directly added in active material as a battery additive to improve the porosity of active material, enhance the conductivity and charge acceptance of active material, and improve the anti-sulfuration performance and deep cycle performance of the battery. Graphene alloy prepared by adding graphene in the grid alloy can combine the conductivity and mechanical properties of the alloy, effectively solve the interface bonding problem between the active material and the grid, avoid premature capacity loss, greatly improve the corrosion resistance and creep resistance of the grid, and effectively prolong the service life of the battery. Due to the excellent properties of graphene alloy, graphene alloy has been widely used in the field of battery energy.

[0004] Currently, metal graphene is increasingly valued in the field of material application and has achieved wide application. By adding graphene material in metal material, the hardness, conductivity, corrosion resistance and other factors conducive to the performance improvement of the product can be changed.

[0005] However, the current metal graphene composite material has the problems of non-continuous production, complex process, inability to meet the industrial production, high production cost and the like. SUMMARY

[0006] In view of the above analysis, the present application aims to provide a metal graphene composite continuous production method to solve at least one of the problems of the prior art, such as non-continuous production, complex process, inability to meet industrial production, and high production cost.

[0007] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0008] A metal graphene composite continuous production method, comprising the following steps:

[0009] (1) Mix NaCl and KCl, melt, cool, crush, add boron carbide, and mix uniformly to obtain a precursor slag;

[0010] (2) Add a certain amount of metal and a certain amount of the precursor slag obtained in step (1) to a heating and stirring device with a discharge function at the bottom, melt and perform heat preservation treatment;

[0011] (3) Discharge a certain amount of melt from the bottom of the heating and stirring device, and pour the melt into a mold to obtain a metal graphene composite ingot;

[0012] (4) Add the same mass of metal as the melt discharged in step (3) and a certain amount of the precursor slag obtained in step (1) to the heating and stirring device, melt and perform heat preservation treatment;

[0013] (5) Repeat steps (3) and (4) to realize continuous production of the metal graphene composite.

[0014] Further, the molar ratio of NaCl to KCl in step (1) is 2:3 to 2:1, and preferably 2:3 to 3:2.

[0015] Further, in step (1), the melting temperature is 800-900℃, and the melting and dehydration time is 30-60min.

[0016] Further, in step (1), the mass of boron carbide is 4-10% of the total mass of NaCl and KCl, and preferably 5-10%.

[0017] Further, in step (2), the mass ratio of metal to precursor slag is 1:0.3-0.5, and preferably 1:0.3-0.4.

[0018] Further, in step (2), the melting temperature is 700-800℃, and the time is 0.5-2h.

[0019] Further, in step (3), the mass ratio of the melt to the metal in step (2) is 0.5-0.9:1, and preferably 0.8-0.9:1.

[0020] Further, in step (3), the mold needs to be preheated at a temperature of 150-300 DEG C for 1-2 hours.

[0021] Further, in step (4), the mass ratio of the metal to the precursor slag is 35-48:1, preferably 35-45:1.

[0022] Further, in step (5), steps (3) and (4) are repeated 4-20 times.

[0023] Further, the metal is at least one of lead, aluminum or zinc.

[0024] In a second aspect, the present application provides a metal-graphene composite material prepared by the above method.

[0025] In a third aspect, the present application provides an application of the above metal-graphene composite material in battery materials.

[0026] Compared with the prior art, the present application can achieve at least one of the following beneficial effects:

[0027] (1) The method of the present application melts NaCl and KCl, cools, and adds boron carbide, so that the salt can be fully dehydrated, the melting point of the mixed salt after melting is reduced, the temperature required for secondary melting is lower, which is more conducive to the reaction and further improves the content of graphene in the composite material; at the same time, it is also beneficial to reduce the size and number of layers of graphene, and improve the purity of the composite material;

[0028] (2) The method of the present application adds the base metal and the precursor slag with the precursor after each casting, realizes at least 20 times of cyclic production, and has the advantages of energy saving, simple operation, stable process, high production efficiency, etc. The metal-graphene composite material prepared by the method of the present application has stable performance such as graphene content, size and number of layers, wherein the graphene content is 0.005-0.01%, the graphene size is about (5-20) x (20-40) μm, and the number of layers is 2-3.

[0029] In the present application, the above technical solutions can be combined with each other to realize more preferred combination schemes. Other features and advantages of the present application will be described in the subsequent specification, and some advantages will become apparent from the specification, or will be understood by implementing the present application. The purpose and other advantages of the present application can be achieved and obtained from the contents specifically pointed out in the specification and the drawings. BRIEF DESCRIPTION OF DRAWINGS

[0030] The accompanying drawings are included to provide a further understanding of the application and are incorporated herein and constitute a part of the application. The drawings illustrate embodiments of the application and, together with the description, serve to explain the principles of the application.

[0031] Figure 1 The application discloses an induction furnace with a teapot spout pouring function.

[0032] Figure 2 The application discloses an induction furnace with a plug valve structure.

[0033] Figure 3 The application discloses an induction furnace with a specific slider valve structure.

[0034] Figure 4 The application discloses an induction furnace with a slider valve structure with a rotating furnace reactor.

[0035] Figure 5 The application discloses an induction furnace with a metal pump discharge function.

[0036] Figure 6 The Raman spectrum of the composite material prepared in Example 1 of the application. DETAILED DESCRIPTION

[0037] The preferred embodiments of the application will be described in detail below with reference to the drawings, which form a part of this application, and which illustrate preferred embodiments of the application. The embodiments of the application together with the drawings serve to explain the principles of the application, and do not limit the scope of the application.

[0038] One specific embodiment of the application discloses a continuous production method of metal graphene composite material, comprising the following steps:

[0039] (1) mixing NaCl and KCl, melting, cooling, crushing, adding boron carbide, and uniformly mixing to obtain a precursor slag;

[0040] (2) adding a certain amount of metal and a certain amount of the precursor slag obtained in step (1) into a heating and stirring device with a discharge function at the bottom, melting and performing heat preservation treatment;

[0041] (3) discharging a certain amount of melt from the bottom of the heating and stirring device, pouring the melt into a mold to obtain a metal graphene composite material ingot;

[0042] (4) adding metal with the same mass as the melt discharged in step (3) and a certain amount of the precursor slag obtained in step (1) into the heating and stirring device, melting and performing heat preservation treatment;

[0043] (5) repeating steps (3) and (4) to realize continuous production of the metal graphene composite material.

[0044] The method of the present application can fully dehydrate the salt after melting NaCl and KCl, cooling, and adding boron carbide, so that the melting point of the mixed salt after melting is reduced, and the temperature required in the secondary melting is lower, which is more conducive to the reaction and further improves the content of graphene in the composite material; at the same time, it is also conducive to reducing the size and number of layers of graphene, and improving the purity of the composite material.

[0045] The method of the present application realizes at least 20 cycles of production after each casting by adding base metal and precursor slag with precursor, and has the advantages of energy saving, simple operation, stable process, high production efficiency and the like. The metal graphene composite material prepared by the method of the present application has stable performances such as graphene content, size, and number of layers, wherein the graphene content is 0.005-0.01%, the graphene size is about (5-20) x (20-40) μm, and the number of layers is 2-3. It should be noted that the purity of lead in the present application is 99.99%, the purity of NaCl is 99.8%, and the purity of KCl is 99.8%; the mass fraction of boron carbide in the carbon-containing precursor boron carbide (B4C) is ≥96.0%, and the particle size is at least F220.

[0046] The carbon source in the method of the present application comes from boron carbide, which decomposes to form carbon atoms under certain conditions, enters the lead liquid, and recombines to form a graphene structure after reaching a certain concentration, so that the graphene in the composite material prepared by the method of the present application has better combination with lead and is more uniformly dispersed; secondly, graphene is expensive, and compared with the direct addition of graphene, the method of the present application has cost advantages.

[0047] Preferably, the heating and stirring device in the present application is an induction furnace, and the induction furnace with a discharging function at the bottom in the present application is an existing structure, for example, Figure 1 the teapot spout pouring, the melt at the bottom is discharged through the teapot spout; Figure 2 the plug valve structure, the melt at the bottom is discharged by taking out the plug; Figure 3 the slider valve structure, the melt at the bottom is pumped out by opening the valve; Figure 4 the slider valve structure with the rotating furnace reactor, the whole furnace can rotate, the discharge port is located at the upper part of the furnace body, the normal liquid is below the discharge port, when the furnace is rotated to a certain position, the liquid flows to the position of the discharge port, and then the liquid is discharged by opening the valve; Figure 5 metal pump discharge, the metal pump is arranged at the upper part of the furnace body, and the melt at the bottom is pumped out through a pipe.

[0048] In one specific embodiment, the molar ratio of NaCl to KCl in step (1) is 2:3-2:1, preferably 2:3-3:2, for example, 2:3, 5:6, 1:1, 7:6, 4:3, 3:2.

[0049] The purpose of using NaCl and KCl as mixed salt in the present application is that the mixed salt has a lower melting point than single salt. In the above-mentioned molar ratio range, the melting point is relatively low near the eutectic point of NaCl and KCl.

[0050] In one specific embodiment, in step (1), the melting temperature is 800-900℃, for example, 800℃, 810℃, 820℃, 830℃, 840℃, 850℃, 860℃, 870℃, 880℃, 890℃, 900℃, and the melting dehydration time is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min.

[0051] In the above-mentioned melting temperature and time, NaCl and KCl can be fully melted, and the energy consumption is low, which does not affect the service life of the equipment.

[0052] In one specific embodiment, in step (1), the particle size is <3mm, which is beneficial to uniform mixing with boron carbide.

[0053] In one specific embodiment, in step (1), the mass of boron carbide is 4-10% of the total mass of NaCl and KCl, preferably 5-10%, for example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%. Since boron carbide is a carbon source, it must be in excess to ensure sufficient graphene content in the product.

[0054] In one specific embodiment, in step (2), the mass ratio of metal to precursor slag is 1:0.3-0.5, preferably 1:0.3-0.4, for example, 1:0.31, 1:0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37, 1:0.38, 1:0.39, 1:0.4. Since the amount of precursor slag is responsible for providing the carbon source, too little will affect the final content of graphene in the product, or it will take longer to reach the target content; too much will cause unnecessary waste of resources.

[0055] In one specific embodiment, in step (2), the melting temperature is 700-800℃, for example, 700℃, 710℃, 720℃, 730℃, 740℃, 750℃, 760℃, 770℃, 780℃, 790℃, 800℃, and the time is 0.5-2h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h.

[0056] When the temperature is lower than the above range, the reaction is not conducive to proceed, and when the temperature is higher than 800℃, the salt volatilization loss is increased, and the energy consumption is also increased. The time is related to the content of graphene, and the longer the time is, the higher the content is.

[0057] In one specific embodiment, in step (3), the mass ratio of the melt to the metal in step (2) is 0.5-0.9:1, preferably 0.8-0.9:1, for example, 0.8:1, 0.81:1, 0.82:1, 0.83:1, 0.84:1, 0.85:1, 0.86:1, 0.87:1, 0.88:1, 0.89:1, 0.9:1. The melt discharged from the bottom is a metal-graphene composite material, and the total amount of the product is approximately equal to the amount of the metal. In order to ensure that the salt does not leak out, a small amount of metal should be left at the bottom, and it is safer to leave 10-20%.

[0058] In one specific embodiment, in step (3), the mold needs to be preheated at a temperature of 150-300℃ (for example, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃) for 1-2h (for example, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h).

[0059] If the mold temperature is too low, the cooling speed of the metal will be too fast, resulting in large shrinkage holes and affecting subsequent use. If the mold temperature is too high, the cooling speed of the metal will be too slow, which will cause composition segregation.

[0060] In one specific embodiment, in step (4), the mass ratio of the metal to the precursor slag is 35-48:1, preferably 35-45:1, for example, 35:1, 36:1, 37:1, 38:1, 39:1, 40:1, 41:1, 42:1, 43:1, 44:1, 45:1, 46:1, 47:1, 48:1.

[0061] In one specific embodiment, in step (4), the melting temperature is 700-800℃, for example, 700℃, 710℃, 720℃, 730℃, 740℃, 750℃, 760℃, 770℃, 780℃, 790℃, 800℃, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h.

[0062] The reaction is not conducive when the temperature is below 700 DEG C, and the salt volatilization loss and energy consumption are increased when the temperature is above 800 DEG C.

[0063] In one specific embodiment, in step (5), steps (3) and (4) are repeated ≤20 times, preferably 4-20 times.

[0064] The method of the present application adds precursor slag after each casting, and the maximum concentration of graphene in the composite material is achieved in the fourth cycle due to the increase of carbon ion concentration in the precursor slag, and the graphene content in the composite material begins to decrease after 20 cycles due to the accumulation of boron carbide decomposition products in the furnace, therefore, the optimal cycle number is 4-20 in the present application, and the graphene content is higher.

[0065] The present application is prepared in an induction furnace, and in the induction furnace, the convection of the metal melt is ensured due to the electric force, and the mixing of the metal melt is achieved. The molten salt has no conductivity, therefore, it can only heat the molten metal and will not move under the action of electromagnetic force. The convection in the molten salt is essentially only heat flow, and the salt heated by the metal rises from the molten metal-salt interface to the salt-atmosphere interface in the furnace and is replaced by the cooler salt, which ensures the continuous movement of the molten metal-salt interface. This is because the boron carbide and the salt are mixed together, and the salt at the metal-salt interface moves upward under the action of heat flow, and the cooler salt at the upper part sinks, and the boron carbide also moves in the same way, and the substances at the metal-salt interface are always changing, thereby playing a stirring role without additional mechanical stirring.

[0066] In one specific embodiment, the metal is at least one of lead, aluminum or zinc.

[0067] In another specific embodiment of the present application, a metal graphene composite material prepared by the above method is disclosed.

[0068] In another specific embodiment of the present application, the application of the above metal graphene composite material in battery materials is disclosed.

[0069] The technical solutions of the present application are further explained and described in combination with specific embodiments.

[0070] It should be noted that in the following embodiments, the purity of lead is 99.9%, the purity of NaCl is 99.8%, the purity of KCl is 99.8%, the mass fraction of boron carbide in boron carbide is ≥96.0%, and the particle size is F220.

[0071] Example 1

[0072] A continuous production method of a metal graphene composite material, comprising the following steps:

[0073] (1) NaCl and KCl are mixed in a molar ratio of 1:1, melted and dehydrated at a temperature of 900℃ for 40 min, cooled, the molten slag is ground and crushed in a porcelain mortar, boron carbide is added, the mass of boron carbide is 5% of the total mass of NaCl and KCl, and mixed uniformly to obtain a precursor slag;

[0074] (2) Lead and the precursor slag are added into an induction furnace with a bottom discharge function, the mass ratio of lead to the precursor slag is 1:0.3, melted at 800℃ and kept for 1 h;

[0075] (3) A certain amount of melt is discharged from the bottom of the induction furnace, the mass ratio of the melt to the lead in step (2) is 0.8:1, the melt is poured into a metal mold, the metal mold is preheated at 290℃ for 1 h, and a metal graphene composite ingot is obtained;

[0076] (4) A certain amount of the precursor slag obtained in step (1) and lead with the same mass of the discharged melt in step (3) are added into the induction furnace, the mass ratio of lead to the precursor slag is 35:1, melted at 800℃ and kept for 1 h;

[0077] (5) Steps (3) and (4) are repeated 20 times to realize continuous production of the metal graphene composite material.

[0078] Example 2

[0079] A continuous production method of a metal graphene composite material, comprising the following steps:

[0080] (1) NaCl and KCl are mixed in a molar ratio of 2:3, melted and dehydrated at a temperature of 800℃ for 60 min, cooled, the molten slag is ground and crushed in a porcelain mortar, boron carbide is added, the mass of boron carbide is 7.5% of the total mass of NaCl and KCl, and mixed uniformly to obtain a precursor slag;

[0081] (2) Lead and the precursor slag are added into an induction furnace with a bottom discharge function, the mass ratio of lead to the precursor slag is 1:0.35, melted at 750℃ and kept for 1.25 h;

[0082] (3) A certain amount of melt is discharged from the bottom of the induction furnace, the mass ratio of the melt to the lead in step (2) is 0.85:1, the melt is poured into a metal mold, the metal mold is preheated at 150℃ for 2 h, and a metal graphene composite ingot is obtained;

[0083] (4) A certain amount of the precursor slag obtained in step (1) and lead with the same mass of the discharged melt in step (3) are added into the induction furnace, the mass ratio of lead to the precursor slag is 40:1, melted at 750℃ and kept for 1.25 h;

[0084] (5) repeating steps (3) and (4) 20 times to realize continuous production of the metal graphene composite material.

[0085] Example 3

[0086] A method for continuous production of a metal graphene composite material, comprising the following steps:

[0087] (1) mixing NaCl and KCl in a molar ratio of 3:2, melting and dehydrating at a temperature of 850°C for 30 min, cooling, grinding the molten slag in a porcelain mortar, adding boron carbide with a mass of 10% of the total mass of NaCl and KCl, and mixing uniformly to obtain a precursor slag;

[0088] (2) adding lead and the precursor slag obtained in step (1) into an induction furnace with a bottom discharge function, wherein the mass ratio of lead to the precursor slag is 1:0.4, melting at 700°C and maintaining for 2 h;

[0089] (3) discharging a certain amount of melt from the bottom of the induction furnace, wherein the mass ratio of the melt to the lead in step (2) is 0.9:1, pouring the melt into a metal mold preheated at 230°C for 1.5 h to obtain a metal graphene composite material ingot;

[0090] (4) adding lead and a certain amount of the precursor slag obtained in step (1) into the induction furnace, wherein the mass ratio of lead to the precursor slag is 45:1, melting at 700°C and maintaining for 2 h;

[0091] (5) repeating steps (3) and (4) 20 times to realize continuous production of the metal graphene composite material.

[0092] Example 4

[0093] The preparation method of a metal graphene composite material in this example is the same as that in Example 1, except that in step (1), the molar ratio of NaCl to KCl is 2:1.

[0094] Example 5

[0095] The preparation method of a metal graphene composite material in this example is the same as that in Example 1, except that in step (1), the mass of boron carbide is 4% of the total mass of NaCl and KCl.

[0096] Example 6

[0097] The preparation method of a metal graphene composite material in this example is the same as that in Example 1, except that in step (2), the mass ratio of lead to the precursor slag is 1:0.5.

[0098] Example 7

[0099] The preparation method of the metal graphene composite material of the present comparative example is the same as that of Example 1, except that in step (3), the mass ratio of the melt to lead in step (2) is 0.5:1.

[0100] Example 8

[0101] The preparation method of the metal graphene composite material of the present comparative example is the same as that of Example 1, except that in step (4), the mass ratio of lead to precursor slag is 48:1.

[0102] Comparative Example 1

[0103] The preparation method of the metal graphene composite material of the present comparative example is the same as that of Example 1, except that in step (1), KCl, NaCl and boron carbide are directly mixed, without melting, cooling and crushing KCl and NaCl.

[0104] Test Example 1

[0105] The metal graphene composite material ingots prepared by Examples 1-8 and Comparative Example 1 for 1-20 cycles were respectively examined for carbon content on a Leco C744-MHC carbon analyzer, and for carbon modification on a Renishaw INVIA0820-04 confocal Raman scattering spectrometer, and the results are shown in Table 1.

[0106] The Raman spectrum of the composite material prepared in Example 1 is shown in Figure 6 From the intensity ratio I2D / IG of the 2D and G peaks equal to 0.61, it can be seen that two layers of graphene are formed, and the number of graphene layers of the products obtained in other examples or comparative examples is also tested by the same method.

[0107] Table 1

[0108]

[0109]

[0110] From Examples 1-3, the carbon content is higher when cycled 4-20 times, because the increase in carbon ion concentration in the precursor slag achieves the maximum concentration of graphene in the composite material in the 4th cycle, and after 20 cycles, the graphene content in the composite material begins to decrease due to the accumulation of boron carbide decomposition products in the furnace, therefore, the optimal cycle is 4-20 times in the present application, and the graphene content is higher.

[0111] Compared with Example 1, the graphene content in the composite material prepared in Examples 4-5 is significantly reduced.

[0112] Compared with Example 1, Example 6-7 increases the input of raw materials, reduces the output of composite materials, although the content of graphene in the composite materials is similar to that of Example 1, the production cost is increased and the production efficiency is reduced, and secondly, the number of graphene layers in Example 6 is also slightly increased.

[0113] Compared with Example 1, Example 8 reduces the input of carbon-containing agent in continuous production, and the content of graphene in the composite materials produced in the previous several cycles is similar to that of Example 1, and the content of graphene shows a downward trend due to the reduction of carbon source.

[0114] Compared with Example 1, Comparative Example 1 cancels the raw material pretreatment step, and the content of graphene in the composite materials is significantly reduced, and the number of graphene layers is increased.

[0115] Test Example 2

[0116] The metal graphene composite ingots prepared in the 10th cycle of Examples 1-8 and Comparative Examples 1-2 were taken respectively for corrosion weight loss test, and the corrosion weight loss of each material is shown in Table 2.

[0117] Corrosion weight loss test process: environmental temperature 25℃, current density 43mA / cm 2 , corrosion medium is 1.28g / cm 3 density of sulfuric acid aqueous solution, time 216h. After the test is completed, the surface corrosion layer is washed away with sugar alkali solution, and the weight change before and after corrosion is compared.

[0118] Table 2

[0119]

[0120]

[0121] Compared with Example 1, the corrosion weight loss of the composite materials of Examples 4-5 is significantly increased, and the corrosion resistance of the prepared composite materials is reduced.

[0122] Compared with Example 1, the corrosion weight loss of the composite materials of Examples 6-7 is similar, indicating that the corrosion resistance of the materials is similar, but Example 6 increases the production cost and Example 7 reduces the production efficiency.

[0123] Compared with Example 1, the corrosion weight loss of the composite materials of Example 8 is slightly increased, and the corrosion resistance of the prepared composite materials is reduced.

[0124] Compared with Example 1, the corrosion weight loss of the composite materials of Comparative Example 1 is significantly increased, indicating that the corrosion resistance of the composite materials prepared without using the raw material pretreatment process of the application is reduced.

[0125] The lead graphene composite material prepared by the method has high graphene content and uniform dispersion, and greatly improves the corrosion resistance of the lead material. The method realizes continuous production of the lead graphene composite material, batch quality is stable, realizes reuse of part of raw materials, reduces production cost, and improves production efficiency.

[0126] The inventors also conducted the above-mentioned test on other embodiments, and the results were basically consistent. Due to the limited space, the changes or replacements that can be easily thought of by those skilled in the art within the technical range disclosed by the present application are not listed one by one.

[0127] The above describes only the preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any changes or replacements that can be easily thought of by those skilled in the art within the technical range disclosed by the present application should be covered within the protection scope of the present application.

Claims

1. A continuous production method for metal-graphene composite materials, characterized in that, Includes the following steps: (1) Mix NaCl and KCl, melt them at a temperature of 800~900℃, dehydrate them for 30-60 minutes, cool them, crush them, add boron carbide, mix them evenly, and obtain the precursor slag. (2) Add the metal and the precursor slag described in step (1) into a heating and stirring device with a bottom discharge function. The mass ratio of the metal to the precursor slag is 1:0.3~0.

5. Melt and keep warm. The melting temperature is 700~800℃ and the time is 0.5~2h. (3) The melt is discharged from the bottom of the heating and stirring device and poured into the mold to obtain a metal graphene composite material ingot; (4) Add metal of the same mass as the melt discharged in step (3) and precursor slag obtained in step (1) to the heating and stirring device, melt and heat-preserve. (5) Repeat steps (3) and (4) to achieve continuous production of metal graphene composite materials.

2. The continuous production method of a metal graphene composite material according to claim 1, characterized in that, In step (1), the molar ratio of NaCl to KCl is 2:3 to 2:

1.

3. The continuous production method of a metal graphene composite material according to claim 1, characterized in that, In step (1), the melting temperature is 810~890℃, and the melting and dehydration time is 35-55 minutes.

4. A continuous production method for a metal graphene composite material according to any one of claims 1-3, characterized in that, In step (1), the mass of boron carbide is 4 to 10% of the total mass of NaCl and KCl.

5. A continuous production method for a metal graphene composite material according to any one of claims 1-3, characterized in that, In step (2), the mass ratio of metal to precursor slag is 1:0.3~0.4; The melting temperature is 710~790℃, and the time is 0.6~1.9h.

6. The continuous production method of a metal graphene composite material according to claim 1, characterized in that, In step (3), the mass ratio of the melt to the metal in step (2) is 0.5~0.9:1; The mold needs to be preheated at 150~300℃ for 1~2 hours.

7. The continuous production method of a metal graphene composite material according to claim 1, characterized in that, In step (4), the mass ratio of metal to precursor slag is 35~48:

1.

8. The continuous production method of metal graphene composite material according to any one of claims 1-3, characterized in that, The metal is at least one of lead, aluminum, or zinc.

9. A metal graphene composite material prepared by the method according to any one of claims 1-8.

10. The application of the metal graphene composite material according to claim 9 in battery materials.

Images