Metal matrix graphite composite and method of making same

Abstract

The application discloses a metal-based graphite composite material and a preparation method thereof, and belongs to the field of metal-based graphite composite materials. The metal-based graphite composite material is prepared by mixing an intercalation compound of graphite, a catalyst and a metal reducing agent, carrying out a reduction reaction to obtain an intermediate product, and removing impurities from the intermediate product. The intercalation compound of graphite contains an intercalation agent, and the intercalation agent contains a metal compound. The intercalation compound of graphite is not prone to agglomeration, and the intercalation agent in the intercalation compound of graphite is uniformly distributed between graphite layers. In-situ reduction of the metal compound in the intercalation agent by the metal reducing agent can make the metal source in the metal-based graphite intercalation composite material more uniformly distributed. In addition, the catalyst, especially the sodium metal catalyst, can promote the insertion of the metal reducing agent at a relatively low temperature, and the metal reducing agent can also complete the reduction of the intercalation agent to obtain the metal source at a relatively low temperature, so that the metal particles are not excessively grown due to excessively high temperature.

Description

Technical Field

[0001] This application relates to the field of metal-graphite composite materials, and more particularly to a metal-based graphite composite material and its preparation method. Background Technology

[0002] Metal-graphene composite materials have a wide range of applications. Their synthesis generally involves using graphene as the matrix, employing vapor deposition, hydrothermal processes, or mixing with metal precursors, followed by various treatments to ultimately obtain the metal / graphene composite material. However, using graphene as a raw material is prone to agglomeration, resulting in poor metal particle dispersion. Although extending the mixing time or using high-energy ball milling can effectively improve the uniformity of metal particles in graphene, the subsequent processing steps are cumbersome and unsuitable for large-scale production. Furthermore, researchers have synthesized metal / graphene composites by growing graphene on the surface of metal particles through vapor deposition. However, this method typically uses a gaseous carbon source and requires high temperatures (above 1000K) to achieve a high pyrolysis rate, making it unsuitable for some low-melting-point metal particles.

[0003] Compared to using graphene directly as a raw material or vapor-deposited graphene, using graphite particles as a precursor is the most ideal strategy. However, the challenge lies in how to uniformly disperse metal particles within the graphite interlayer. Currently, no effective method has been reported for uniformly dispersing metals within the graphite interlayer, especially high-melting-point metals. While it is difficult to insert metal particles into the graphite interlayer, metal chlorides can be easily inserted through molten salt reactions to form graphite interlayer compounds with a hierarchical structure. Reducing the chlorides to elemental form yields a metal / graphene composite material. However, currently reported methods for reducing graphite interlayer compounds suffer from poor efficiency, slow reaction rates, and hazards. For example, using hydrogen at high temperatures (around 1000K) to reduce chlorides in graphite interlayer compounds to elemental form, while avoiding the introduction of impurities, presents several drawbacks: first, the use of hydrogen poses a significant risk; second, the high temperature can cause metal particles to grow; and third, the steric hindrance within the graphite layers can lead to incomplete reduction reactions. In addition, hydrazine hydrate can be used to reduce chloride, which can be carried out at room temperature, but the reaction rate is slow (more than 24 hours). Sodium metal can also be used to reduce chloride, but this requires higher temperatures and poses a greater risk. Summary of the Invention

[0004] The main objective of this application is to provide a metal-based graphite composite material and its preparation method, thereby solving the technical problems that are easily encountered in the preparation of metal-based graphite composite materials in the prior art, such as uneven graphite dispersion, excessively large metal particles due to excessively high reaction temperature, and insufficient reduction reaction caused by the steric hindrance effect of graphite layer.

[0005] To achieve the above objectives, this application provides a method for preparing a metal-based graphite composite material, comprising the following steps:

[0006] The intermediate product is obtained by mixing graphite intercalation compounds, catalysts and metal reducing agents and carrying out a catalytic reduction reaction.

[0007] The intermediate product is purified to obtain the metal-based graphite composite material;

[0008] The graphite intercalation compound contains an intercalating agent, and the intercalating agent contains a metal compound.

[0009] In some embodiments of this application, the catalyst comprises metallic sodium.

[0010] In some embodiments of this application, the graphite interlayer compound is obtained by combining the intercalating agent and the graphite substrate, wherein the graphite substrate includes at least one of natural graphite, artificial graphite, microcrystalline graphite, expanded graphite, and multilayer graphene.

[0011] And / or, the metal compound includes at least one of metal halides and metal oxides.

[0012] In some embodiments of this application, the metal reducing agent includes at least one of lithium, potassium, calcium, strontium, and barium.

[0013] In some embodiments of this application, the reaction temperature of the catalytic reduction reaction is 0℃-300℃; and / or, the reaction time of the catalytic reduction reaction is ≤24h.

[0014] In some embodiments of this application, in the step of removing impurities from the intermediate product, the intermediate product is cleaned with a cleaning agent, the cleaning agent including at least one of deionized water, organic solvent and acid / base reagent.

[0015] In some embodiments of this application, the metal-based graphite composite material may also be modified, including oxidation, sulfidation, phosphating or selenization.

[0016] In some embodiments of this application, the oxidation process includes atmospheric oxidation or microwave oxidation;

[0017] In some embodiments of this application, the sulfidation treatment includes a sulfur source, which includes at least one of elemental sulfur, hydrogen sulfide, sulfur oxide, sodium sulfide, and thiourea.

[0018] In some embodiments of this application, the phosphating treatment includes a phosphorus source, which includes at least one of elemental phosphorus, phosphine, phosphoric acid, and sodium hypophosphite.

[0019] In some embodiments of this application, the metal-based graphite composite material includes elemental metal graphite composite material, metal compound graphite composite material, or metal alloy graphite composite material.

[0020] To achieve the above objectives, this application also provides a metal-based composite material prepared by the preparation method described above.

[0021] The beneficial effects that this application can achieve are:

[0022] This application uses a graphite intercalation compound as a precursor, and then uses a catalyst to induce a metal reducing agent to intercalate into the graphite intercalation compound, reducing the intercalating agent in the graphite intercalation compound to a metallic element, thus obtaining a metal-based graphite composite material. Compared with the existing technology that uses graphene as a precursor for the composite material and mixes it with a metal source, which easily leads to agglomeration and uneven distribution of the metal source in graphite, the graphite intercalation compound used in this application is less prone to agglomeration. Moreover, the intercalating agent in the graphite intercalation compound is more evenly distributed between the graphite layers. Using a metal reducing agent to reduce the metal compound in the intercalating agent in situ can make the metal source in the metal-based graphite intercalation composite material even more evenly distributed.

[0023] Catalysts, especially sodium metal catalysts, can promote the insertion of metal reducing agents at lower temperatures. Moreover, the metal reducing agents can also reduce the intercalating agent to obtain the metal source at lower temperatures. The reaction time is short, and the metal particles will not grow excessively due to excessive temperature, thus destroying the graphite structure.

[0024] The synthesis method described in this application is simple to operate, low in cost, high in yield, and high in product qualification rate. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0026] Figure 1 This is a schematic diagram of the preparation process of the metal-based graphite composite material of this application.

[0027] Figure 2 This is an EDS (energy dispersive spectroscopy) characterization image of the metal-based graphite composite material obtained in the embodiments of this application.

[0028] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0029] It should be understood that the specific embodiments described herein are merely illustrative of this application and are not intended to limit this application.

[0030] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0031] In this application, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. Furthermore, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. If the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed in this application.

[0032] This application provides a metal-based graphite composite material and its preparation method, referring to... Figure 1 The preparation method includes the following steps:

[0033] Step S10: Mix the graphite intercalation compound, catalyst and metal reducing agent, and carry out a catalytic reduction reaction to obtain the intermediate product;

[0034] Step S20: Remove impurities from the intermediate product to obtain a metal-based graphite composite material;

[0035] Among them, the graphite intercalation compound contains an intercalating agent, and the intercalating agent contains a metal compound.

[0036] This application uses a graphite intercalation compound as a precursor, and then uses a catalyst to induce a metal reducing agent to intercalate into the graphite intercalation compound, reducing the intercalating agent in the graphite intercalation compound to a metallic element, thus obtaining a metal-based graphite composite material. Compared with the existing technology that uses graphene as a precursor for the composite material and mixes it with a metal source, which easily leads to agglomeration and uneven distribution of the metal source in graphite, the graphite intercalation compound used in this application is less prone to agglomeration. Moreover, the intercalating agent in the graphite intercalation compound is more evenly distributed between the graphite layers. Using a metal reducing agent to reduce the metal compound in the intercalating agent in situ can make the metal source in the metal-based graphite intercalation composite material even more evenly distributed.

[0037] The catalyst in the preparation method of this application mainly promotes the metal reducing agent to enter the graphite intercalation compound and directly contact the intercalating agent. Then, under the catalytic reduction reaction conditions, the metal reducing agent can reduce the metal compound in the intercalating agent to the metal element in situ, thereby obtaining a metal-based graphite composite material with uniform metal source distribution. In addition, the metal reducing agent enters the graphite intercalation compound to directly reduce the intercalating agent, which can avoid the incomplete reduction reaction caused by the steric hindrance effect between graphite layers.

[0038] It is understood that the catalytic reduction reaction in this application includes both catalytic and reduction reactions. When the graphite intercalation compound, catalyst and metal reducing agent are mixed, the catalyst can catalyze the metal reducing agent to enter the graphite intercalation compound. The metal reducing agent reduces the metal compound in the graphite intercalation compound to obtain a metal-based graphite composite material containing elemental metal.

[0039] In some embodiments, the catalyst includes sodium metal, which can promote the insertion of the metal reducing agent into the graphite intercalation compound at a lower temperature, and is less likely to damage the structure of the graphite intercalation compound due to a higher catalytic temperature, thereby affecting the physicochemical properties of the metal-based graphite composite material.

[0040] In one embodiment, the sodium metal catalyst can promote the entry of the metal reducing agent into the graphite intercalation compound under catalytic temperature conditions of 0°C to 300°C. For example, the catalytic temperature can be any temperature value in the range of 0°C to 300°C, such as 0°C, 10°C, 20°C, 25°C, 30°C, 35°C, 45°C, 50°C, 100°C, 150°C, 200°C, 250°C, 260°C, 280°C, 290°C, 300°C, etc.

[0041] In some embodiments, the temperature of the catalytic reduction reaction is 0°C to 300°C. The catalyst can promote the entry of the metal reducing agent into the graphite intercalation compound at a lower temperature, and the metal reducing agent can also reduce the metal compound in the intercalating agent to obtain a metal-based graphite composite material containing elemental metals at a lower temperature, without causing excessive growth of metal particles due to excessively high temperatures. It is understood that the temperature of the above-mentioned catalytic reduction reaction can be any temperature value within the range of 0°C to 300°C, such as 0°C, 10°C, 20°C, 25°C, 30°C, 35°C, 45°C, 50°C, 100°C, 150°C, 200°C, 250°C, 260°C, 280°C, 290°C, and 300°C.

[0042] This application can catalytically reduce the metal compound of the intercalating agent in a relatively short time, and the time of the catalytic reduction reaction is not limited. In some embodiments, the reaction time of the catalytic reduction reaction is ≤24h. It is understood that the reaction time of the catalytic reduction reaction can be 0.5min, 0.6min, 0.8min, 1min, 2min, 5min, 8min, 10min, 15min, 20min, 30min, 40min, 50min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 15h, 18h, 19h, 20h, 22h, 23h, 24h, etc., ≤24h, and greater than 0h.

[0043] The graphite intercalation compound of this application is obtained by combining an intercalating agent and a graphite substrate.

[0044] This application does not limit the types of graphite substrates described above. In some embodiments, the graphite substrate includes at least one of natural graphite, artificial graphite, microcrystalline graphite, expanded graphite, and multilayer graphene. The above-mentioned types of graphite substrates have good dispersibility, are less prone to agglomeration, and are more likely to yield structurally complete graphite interlayer compounds.

[0045] The metal compound in the intercalating agent of this application can be at least one of a metal chloride or a metal oxide to provide a metal source. The metal compound in the intercalating agent can be reduced in situ to obtain an elemental metal under the reduction of a metal reducing agent.

[0046] This application does not limit the preparation method of the above-mentioned graphite intercalation compound, and it can be prepared by a method commonly used by those skilled in the art. For example, the graphite intercalation compound of this application can be obtained by combining the intercalating agent and the graphite substrate through a gas-phase constant pressure reaction method, a mixing method, an impregnation method, or an electrochemical method.

[0047] The metal reducing agent of this application can reduce the metal compound in the intercalating agent to a metal element. In some embodiments, the metal reducing agent includes at least one of lithium, potassium, calcium, strontium, and barium. The above-mentioned metal reducing agents have good reducing properties for metal compounds. Moreover, under the action of a catalyst, they can be catalyzed into the graphite intercalation compound and contact the intercalating agent at a lower temperature. They can also reduce the metal compound in the intercalating agent in situ at a lower temperature, without easily destroying the structure of the graphite intercalation compound.

[0048] In some embodiments, the graphite intercalation compound may be dried before mixing the graphite intercalation compound, the catalyst, and the metal reducing agent to prevent excessive moisture in the graphite intercalation compound from affecting the catalytic reduction reaction.

[0049] In some embodiments, the graphite intercalation compound can be vacuum dried at 80°C for 4 hours to obtain a dried graphite intercalation compound.

[0050] In some embodiments, after mixing graphite intercalation compounds, catalysts, and metal reducing agents to obtain a mixture, a catalytic reduction reaction can be completed during the grinding process. During the grinding process, the mixture heats up and agglomerates to obtain hard particles, which are the intermediate products.

[0051] The grinding process described above easily generates heat and raises the temperature. In some embodiments, the heat provided by grinding can complete the catalytic reduction reaction without the need for an additional heat source. However, it should be noted that if the heat generated by grinding is insufficient to promote the catalytic reduction reaction, further heating can be applied to reach the required reaction temperature.

[0052] In some embodiments, the graphite intercalation compound, catalyst, and metal reducing agent are mixed and then subjected to a catalytic reduction reaction in a glove box.

[0053] In some embodiments, the catalytic reduction reaction is carried out in an inert atmosphere, including an argon atmosphere.

[0054] In some embodiments, the catalytic reduction reaction is carried out under conditions where water and oxygen are less than or equal to 0.01 ppm, thereby reducing the influence of water and oxygen on the catalytic reduction reaction.

[0055] The intermediate products obtained from the catalytic reduction reaction usually contain impurities, such as chlorides of the reducing agent. These impurities can easily affect the physicochemical properties of metal-based graphite composites and hinder subsequent treatments such as oxidation, sulfidation, phosphating, and selenization, which are intended to enrich the variety of metal-based graphite composites. The presence of impurities can reduce the efficiency and effectiveness of oxidation, sulfidation, phosphating, and selenization. Therefore, it is necessary to remove impurities from the intermediate products.

[0056] This application does not limit the method for removing impurities from intermediate products. In some embodiments, the intermediate products can be cleaned with a cleaning agent to achieve the purpose of impurity removal. The cleaning agent includes at least one of deionized water, an organic solvent, and an acid-base reagent. Further, the organic solvent includes at least one of ethanol, methanol, and acetone, and the acid-base reagent includes hydrochloric acid. The above cleaning agents can remove impurities while retaining the metal source obtained from the reduction, and have little impact on the structural integrity of the graphite interlayer compound.

[0057] In some embodiments, the intermediate product can be immersed in a cleaning agent and allowed to stand for a period of time until the impurities are removed. Alternatively, the metal-based graphite composite material can be immersed in a cleaning agent to accelerate impurity removal through mechanical cleaning. Mechanical cleaning methods include ultrasonic cleaning or magnetic stirring cleaning.

[0058] In some embodiments, the intermediate product is immersed in a cleaning agent, and after no more bubbles are generated, it is ultrasonicated for 15 minutes, and then cleaned with deionized water, alcohol and acetone to obtain a metal-based graphite composite material.

[0059] In some embodiments, the metal matrix composite material obtained after impurity removal is dried by vacuum drying at 60°C to 80°C for 10 to 15 hours.

[0060] This application does not limit the time for the above-mentioned impurity removal. As long as the impurities are removed, it is acceptable. The standard for judgment is that no more bubbles are generated when the intermediate product is soaked in the cleaning agent. When no more bubbles are generated, the impurities can be considered to have been removed.

[0061] In some embodiments, the impurity removal time can be ≤24h and greater than 0h.

[0062] The metal source in the metal-based graphite composite material obtained through steps S10 to S20 is an elemental metal. In order to enrich the types of metal-based graphite composite materials in this application, the metal-based graphite composite material can also be modified. The modification treatment includes oxidation treatment, sulfidation treatment, phosphating treatment or selenization treatment.

[0063] This application does not limit the above-mentioned oxidation treatment, sulfidation treatment, phosphating treatment or refining treatment methods, and may refer to the technical means commonly used in the art.

[0064] When metal-based graphite composites are oxidized, the elemental metal source can be oxidized to a metal oxide, thus obtaining a metal compound graphite composite. In some embodiments, the oxidation process includes air oxidation, electromagnetic heating oxidation, or microwave oxidation.

[0065] When metal-based graphite composites are subjected to sulfidation treatment, the metal source element can be sulfided into metal sulfides, thereby obtaining metal compound graphite composites. In some embodiments, the sulfur source for sulfidation includes at least one of elemental sulfur, hydrogen sulfide, sulfur oxides, sodium sulfide, and thiourea, and the sulfidation treatment includes elemental sulfur sulfidation, carbon disulfide sulfidation, or sulfur-containing organic sulfidation, etc.

[0066] When metal-based graphite composites are phosphated, the elemental metal source can be phosphated into metal phosphides, thus obtaining a metal compound graphite composite. In some embodiments, the phosphorus source for phosphating includes at least one of elemental phosphorus, phosphine, phosphoric acid, and sodium hypophosphite, and the phosphating process includes elemental phosphorus phosphating or phosphorus-containing organic phosphating, etc.

[0067] The following embodiments further illustrate the content of this application, enabling those skilled in the art to easily understand other advantages and effects of this application. The application scope of the above-described subject matter is not limited to the following embodiments; all technologies implemented based on the above-described content of this application fall within the scope of this application.

[0068] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the reagents, methods and equipment used are conventional reagents, methods and equipment in this technical field.

[0069] Example 1

[0070] Step S10: After drying 1g of natural graphite with a particle size of 10μm at 120℃ for 4h, 3.4g of anhydrous ferric chloride was quickly added and mixed in air. After vacuum drying at 120℃ for 1h, the mixture was transferred to a reaction vessel. The reaction vessel was sealed in air and placed in a heating furnace to be heated to 450℃ and kept at that temperature for 48h to obtain the product. The obtained product was washed with deionized water, alcohol and acetone and then dried at 80℃ for 12h to obtain a first-order FeCl3-graphite interlayer compound.

[0071] Step S20: After vacuum drying 0.46g of the graphite interlayer compound obtained in step S10 at 80°C for 4 hours, the mixture is transferred to a glove box with an argon atmosphere. The mixture is then placed in a dry mortar along with 0.03g of lithium metal reducing agent and 0.05g of sodium catalyst, which are weighed in the glove box. The mixture is ground until the product slightly heats up and agglomerates. A catalytic reduction reaction is then carried out at 50°C to 100°C for 15 minutes, resulting in hard particles, which is the intermediate product.

[0072] Step S30: Transfer the intermediate product from step S20 to a dry, sealed container and then to a glove box. Dissolve the intermediate product with 99.9% alcohol. After no more bubbles are generated, sonicate for 15 minutes and continue to clean with deionized water, alcohol, and acetone. Then, vacuum dry at 80°C for 12 hours to obtain a metal-based graphite composite material, wherein the metal-based graphite composite material is an iron / graphite composite material.

[0073] Example 2

[0074] Step S10: 1g of natural graphite with a particle size of 10μm was dried at 120℃ for 4h, and then 1g of anhydrous ferric chloride was quickly added and stirred in air. The mixture was then vacuum dried at 120℃ for 1h and transferred to a reaction vessel. The reaction vessel was sealed in air and placed in a furnace to be heated to 450℃ and held at that temperature for 48h to obtain the product. The obtained product was washed with deionized water, alcohol, and acetone, and then dried at 80℃ for 12h to obtain a higher-order FeCl3-graphite intercalation compound.

[0075] Step S20: After vacuum drying 0.46g of the graphite interlayer compound obtained in step S10 at 80°C for 4 hours, the mixture is transferred to a glove box with an argon atmosphere. The mixture is then placed in a dry mortar along with 0.03g of potassium metal reducing agent and 0.05g of sodium catalyst sheet weighed in the glove box to obtain a mixture. The mixture is ground until the product slightly heats up and agglomerates under conditions where the water and oxygen concentrations in the glove box are below 0.01ppm. A catalytic reduction reaction is then carried out at 100°C to 300°C for 3 minutes to completely transform the product into hard particles, thus obtaining the intermediate product.

[0076] Step S30: Transfer the intermediate product from step S20 to a dry, sealed container and then to a glove box. Dissolve the intermediate product with 99.9% alcohol. After no more bubbles are generated, sonicate for 15 minutes and continue to clean with deionized water, alcohol, and acetone. Then, vacuum dry at 80°C for 12 hours to obtain a metal-based graphite composite material, wherein the metal-based graphite composite material is an iron / graphite composite material.

[0077] Example 3

[0078] Step S10: 1g of natural graphite with a particle size of 10μm was dried at 120℃ for 4h, and then 9g of anhydrous aluminum chloride was quickly added and stirred in air. The mixture was then vacuum dried at 120℃ for 1h and transferred to a reaction vessel. The reaction vessel was sealed in air and placed in a furnace to be heated to 200℃ and held at that temperature for 12h to obtain the product. The obtained product was washed with deionized water, alcohol, and acetone, and then dried at 100℃ for 12h to obtain a first-order AlCl3-graphite intercalation compound.

[0079] Step S20: After vacuum drying 0.40g of the graphite intercalation compound obtained in step S10 at 80°C for 4 hours, the mixture is transferred to a glove box with an argon atmosphere. The mixture is then placed in a dry mortar along with 0.03g of strontium metal reducing agent and 0.05g of sodium flakes weighed in the glove box to obtain a mixture. The mixture is ground in the glove box with water and oxygen concentrations below 0.01ppm until the product slightly heats up and agglomerates. A catalytic reduction reaction is then carried out at 50°C to 100°C for 12 hours until the product is completely transformed into hard particles, thus obtaining the intermediate product.

[0080] Step S30: Transfer the intermediate product from step S20 to a dry, sealed container and remove it from the glove box. Dissolve the mixed product in 99.9% alcohol, and after no more bubbles are generated, sonicate for 15 minutes. Continue to wash with deionized water, alcohol, and acetone, and then vacuum dry at 80°C for 12 hours to obtain a metal-based graphite composite material, wherein the metal-based graphite composite material is an aluminum / graphite composite material.

[0081] Example 4

[0082] Step S10: 1g of natural graphite with a particle size of 20μm was dried at 120℃ for 4h. Then, it was mixed with a mixture of 4.5g of anhydrous ferric chloride and 9g of anhydrous aluminum chloride in air and stirred. After vacuum drying at 80℃ for 5h, it was transferred to a reaction vessel. The reaction vessel was sealed in air and placed in a heating furnace and heated to 650℃ for 36h to obtain the product. The obtained product was washed with deionized water, alcohol and acetone and then dried at 80℃ for 12h to obtain a FeCl3-AlCl3-graphite interlayer compound composed of second, third and fourth order mixtures.

[0083] Step S20: After vacuum drying 0.50g of the graphite intercalation compound at 80°C for 4 hours, transfer it to a glove box with an argon atmosphere. Then, place it together with 0.03g of calcium metal reducing agent and 0.05g of sodium catalyst sheet weighed in the glove box into a dry mortar to obtain a mixture. Under the condition that the water and oxygen in the glove box are below 0.01ppm, grind the mixture until the product slightly heats up and agglomerates. Then, carry out a catalytic reduction reaction at 50°C to 100°C for 20 hours until it completely turns into hard particles to obtain the intermediate product.

[0084] Step S30: Transfer the intermediate product from step S20 to a dry, sealed container and then to a glove box. Dissolve the intermediate product with 99.9% alcohol. After no more bubbles are generated, sonicate for 15 minutes and continue to clean with deionized water, alcohol, and acetone. Then, vacuum dry at 80°C for 12 hours to obtain a metal-based graphite composite material, wherein the metal-based graphite composite material is an aluminum-iron / graphite composite material.

[0085] The aluminum-iron / graphite composite material obtained in Example 4 contains ferric chloride intercalation and aluminum chloride intercalation, making it a bimetallic / graphite composite material. The aluminum chloride intercalation is dominant, resulting in a higher aluminum content in the obtained product. Furthermore, the metal content in the bimetallic / graphite composite material can be controlled by adjusting the composition of the FeCl3-AlCl3-graphite interlayer compound.

[0086] Performance testing

[0087] (1) The metal-based / graphite composite material obtained in Example 1 was characterized by energy dispersive spectroscopy (EDS). The characterization results are shown in the figure below. Figure 2 Example 1 (Part 1). From... Figure 2 It can be clearly seen that Fe is evenly distributed in the region where the graphite host is located, which proves that Fe is uniformly and stably dispersed in the graphite layers in the form of extremely small particles or even atoms.

[0088] (2) The metal-based / graphite composite material obtained in Example 2 was characterized by energy dispersive spectroscopy (EDS). The characterization results are shown in the figure below. Figure 2 Example 2, Part 2. From... Figure 2It is evident that Fe is uniformly distributed throughout the graphite host, demonstrating that Fe is uniformly and stably dispersed in the graphite interlayer in the form of extremely small particles or even atoms. The distribution of Fe in the product of Example 2 is completely different from that in the product of Example 1, proving that the mass fraction of iron in graphite can be controlled by using graphite interlayer compound reactants of different orders.

[0089] (3) The metal-based / graphite composite material obtained in Example 3 was characterized by energy dispersive spectroscopy (EDS). The characterization results are shown in the figure below. Figure 2 Example 3, Part 3. (By...) Figure 2 It can be clearly seen that the Al element is evenly distributed in the region where the graphite host is located, which proves that Al is uniformly and stably dispersed in the graphite layers in the form of extremely small particles or even atoms.

[0090] (4) The metal-based / graphite composite material obtained in Example 4 was characterized using an energy dispersive spectroscopy (EDS) instrument. The characterization results are shown in the figures below. Figure 2 Example 4, by Figure 2 It can be clearly seen that Fe and Al elements are uniformly distributed in the region where the graphite host is located, which proves that the method of this application can prepare metal-based / graphite composite materials doped with bimetallic elements.

[0091] The above are merely preferred embodiments of this application and do not limit the patent scope of this application. Any equivalent structural or procedural transformations made using the content of this application's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of this application.

Claims

1. A method of producing a metal matrix graphite composite material, characterized by, The method comprises the following steps: mixing a graphite intercalation compound, a catalyst and a metal reducing agent to perform a catalytic reduction reaction to obtain an intermediate product; removing impurities from the intermediate product to obtain the metal-based graphite composite material; The graphite intercalation compound contains an intercalation agent, and the intercalation agent contains a metal compound. The catalyst comprises metallic sodium. The graphite intercalation compound is obtained by compounding the intercalation agent and a graphite substrate, and the graphite substrate comprises at least one of natural graphite, artificial graphite, microcrystalline graphite, expanded graphite and multi-layer graphene. The metal compound comprises at least one of a metal halide and a metal oxide. The metal reducing agent comprises at least one of lithium, potassium, calcium, strontium and barium. The catalytic reduction reaction is performed at a temperature of 0-300℃, and / or the reaction time is less than or equal to 24 hours.

2. The method of claim 1, wherein the metal matrix graphite composite is prepared by a process comprising: In the step of removing impurities from the intermediate product, the intermediate product is cleaned with a cleaning agent, and the cleaning agent comprises at least one of deionized water, an organic solvent and an acid-base reagent.

3. The method of claim 1, wherein the metal matrix graphite composite is prepared by a process comprising: The metal-based graphite composite material is further subjected to a modification treatment, and the modification treatment comprises oxidation treatment, sulfidation treatment, phosphidation treatment or selenidation treatment.

4. The method of claim 3, wherein the metal matrix graphite composite is prepared by a process comprising: The oxidation treatment comprises atmospheric oxidation or microwave oxidation. The sulfidation treatment comprises a sulfur source, and the sulfur source comprises at least one of elemental sulfur, hydrogen sulfide, sulfur oxide, sodium sulfide and thiourea. The phosphidation treatment comprises a phosphorus source, and the phosphorus source comprises at least one of elemental phosphorus, phosphine, phosphoric acid and sodium hypophosphite.

5. The method of claim 1, wherein the metal matrix graphite composite is prepared by a process comprising: The metal-based graphite composite material comprises a metal element graphite composite material, a metal compound graphite composite material or a metal alloy graphite composite material.

6. A metal-based graphite composite material prepared by the preparation method of any one of claims 1-5.

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