阅读说明：本技术 一种石墨烯基高熵合金材料的制备方法 (Preparation method of graphene-based high-entropy alloy material ) 是由 罗翔远 陈云 贺梓霖 吴然皓 肖嘉薇 高增光 谢斌 丁树权 唐建伟 陈新 高健 于 2021-08-30 设计创作，主要内容包括：本发明涉及高熵合金材料制备技术领域,尤其涉及一种石墨烯基高熵合金材料的制备方法。一种石墨烯基高熵合金材料的制备方法,包括以下步骤：S1.取纤维素分散在去离子水中,得到纤维素分散液,取五种金属盐粉末分散在去离子水中,得到金属盐分散液；S2.将步骤S1制得的所述纤维素分散液和所述金属盐分散液混合后得到混合液,然后对混合液进行干燥,得到纤维素与金属盐的混合粉末。所述石墨烯基高熵合金材料的制备方法,能够快速、大面积地制备石墨烯基高熵合金材料,有助于高熵合金在冷却结晶时细化晶粒,改善了石墨烯基高熵合金材料的结构,性能稳定,解决了现有石墨烯基高熵合金材料生产方法生产效率低、稳定性差和应用局限性的问题。(The invention relates to the technical field of preparation of high-entropy alloy materials, in particular to a preparation method of a graphene-based high-entropy alloy material. A preparation method of a graphene-based high-entropy alloy material comprises the following steps: s1, taking cellulose to disperse in deionized water to obtain cellulose dispersion liquid, and taking five kinds of metal salt powder to disperse in deionized water to obtain metal salt dispersion liquid; s2, mixing the cellulose dispersion liquid prepared in the step S1 with the metal salt dispersion liquid to obtain a mixed liquid, and then drying the mixed liquid to obtain mixed powder of cellulose and metal salt. The preparation method of the graphene-based high-entropy alloy material can be used for quickly preparing the graphene-based high-entropy alloy material in a large area, is beneficial to refining grains of the high-entropy alloy during cooling crystallization, improves the structure of the graphene-based high-entropy alloy material, has stable performance, and solves the problems of low production efficiency, poor stability and application limitation of the existing production method of the graphene-based high-entropy alloy material.)

1. A preparation method of a graphene-based high-entropy alloy material is characterized by comprising the following steps:

s1, taking cellulose to disperse in deionized water to obtain cellulose dispersion liquid, and taking five kinds of metal salt powder to disperse in deionized water to obtain metal salt dispersion liquid;

s2, mixing the cellulose dispersion liquid prepared in the step S1 with the metal salt dispersion liquid to obtain a mixed liquid, and then drying the mixed liquid to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 to prepare the graphene-based high-entropy alloy material.

2. The preparation method of the graphene-based high-entropy alloy material according to claim 1, wherein in the mixed solution in the step S2, the mass ratio of cellulose to metal salt is (2-5): 1.

3. the method for preparing the graphene-based high-entropy alloy material of claim 1, wherein in step S1, five metal salt powders are dispersed in deionized water, and the five metal salt powders are ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride.

4. The method for preparing the graphene-based high-entropy alloy material according to claim 3, wherein the concentration of any two metal salts in the metal salt dispersion liquid is higher than the concentration of the remaining three metal salts.

5. The method for preparing the graphene-based high-entropy alloy material according to claim 1, wherein in step S1, the concentration of cellulose in the cellulose dispersion liquid is 1 to 5mg/mL, the concentration of ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of cobalt chloride is 0.15mg/mL, the concentration of nickel chloride is 0.15mg/mL, the concentration of copper chloride is 0.25mg/mL, and the concentration of zinc chloride is 0.25 mg/mL;

in the step S2, the cellulose dispersion liquid and the metal salt dispersion liquid prepared in the step S1 are mixed in a volume ratio of 1: 1 to obtain a mixed solution.

6. The method for preparing the graphene-based high-entropy alloy material according to claim 1, wherein in step S3, the mixed powder of the cellulose and the metal salt obtained in step S2 is subjected to electric discharge machining in a nitrogen atmosphere, wherein the electric discharge machining has a discharge voltage of 100-300V and a discharge capacitance of 100-300 mF.

7. The method for preparing the graphene-based high-entropy alloy material according to claim 1, wherein in step S2, the drying temperature for drying the mixed solution is 50-70 ℃, and the drying time is 110-130 min.

Technical Field

The invention relates to the technical field of preparation of high-entropy alloy materials, in particular to a preparation method of a graphene-based high-entropy alloy material.

Background

High entropy alloys are considered to be of considerable interest in material science and engineering, since they may have many desirable properties. The high-entropy alloy is an alloy formed of five or more metals in equal or approximately equal amounts. The high-entropy alloy has the excellent properties of high strength, good wear resistance, oxidation resistance, corrosion resistance and the like. In the carbon material, the graphene has a very high melting point, so that the structure of the graphene can be still maintained at the high temperature of smelting the high-entropy alloy, the graphene has good heat-conducting property, and the heat-conducting coefficient of the graphene can reach 5300W/mK, so that the graphene can quickly dissipate heat in the hot processing process.

However, the existing preparation method of the high-entropy alloy has a plurality of defects, and the ideal performance of the high-entropy alloy material cannot be fully exerted by simple stacking and mixing of the graphene and the high-entropy alloy material. The preparation method of the existing high-entropy alloy material mainly comprises the following steps: (1) the method is a vacuum melting method, which cannot melt high-melting-point metals, and the application of the high-entropy alloy is limited because the main element selection of the high-entropy alloy generally contains one or more high-melting-point elements; (2) a mechanized method, which uses a high-energy ball mill or a grinder to violently impact alloy powder particles for a long time to cause atomic diffusion in the powder particles, but the method has a low production efficiency and a wide selection range of high-entropy alloy elements; (3) the electrochemical deposition method utilizes ions to perform redox reaction on the surface of a base material to obtain a high-entropy alloy material, but most of compound films prepared by the method are polycrystalline or amorphous, and the performance is poor. Therefore, it is urgently needed to develop a fast, large-area and low-cost preparation method of a high-entropy alloy material, and apply the method to the performance reinforcement of graphene polymers.

Disclosure of Invention

The invention aims to provide a preparation method of a graphene-based high-entropy alloy material, which can be used for quickly preparing the graphene-based high-entropy alloy material in a large area, is beneficial to refining grains of the high-entropy alloy during cooling crystallization, improves the structure and the performance of the graphene-based high-entropy alloy material, and solves the problems of low production efficiency, poor stability and application limitation of the conventional production method of the graphene-based high-entropy alloy material.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, taking cellulose to disperse in deionized water to obtain cellulose dispersion liquid, and taking five kinds of metal salt powder to disperse in deionized water to obtain metal salt dispersion liquid;

s2, mixing the cellulose dispersion liquid prepared in the step S1 with the metal salt dispersion liquid to obtain a mixed liquid, and then drying the mixed liquid to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 to prepare the graphene-based high-entropy alloy material.

In the mixed solution of step S2, the mass ratio of the cellulose to the metal salt is (2-5): 1.

in step S1, five metal salt powders, namely, ferric chloride, cobalt chloride, nickel chloride, copper chloride, and zinc chloride, are dispersed in deionized water.

Further, in the metal salt dispersion, the concentration of any two metal salts is higher than the concentration of the remaining three metal salts.

In step S1, the cellulose concentration in the cellulose dispersion is 1 to 5mg/mL, the ferric chloride concentration in the metal salt dispersion is 0.2mg/mL, the cobalt chloride concentration is 0.15mg/mL, the nickel chloride concentration is 0.15mg/mL, the copper chloride concentration is 0.25mg/mL, and the zinc chloride concentration is 0.25 mg/mL;

in the step S2, the cellulose dispersion liquid and the metal salt dispersion liquid prepared in the step S1 are mixed in a volume ratio of 1: 1 to obtain a mixed solution.

In step S3, the mixed powder of cellulose and metal salt obtained in step S2 is subjected to electric discharge machining in a nitrogen atmosphere, wherein the electric discharge machining has a discharge voltage of 100 to 300V and a discharge capacitance of 100 to 300 mF.

In step S2, the drying temperature for drying the mixed solution is 50 to 70 ℃, and the drying time is 110 to 130 min.

Compared with the prior art, the invention has the following beneficial effects:

1. the mixture of the cellulose and the metal salt powder is prepared firstly, and then the mixed powder of the cellulose and the metal salt is subjected to discharge machining, so that the solid metal salt can be directly converted into the high-entropy alloy material in a short time, the process is simple, the efficiency is high, the efficiency for preparing the graphene-based high-entropy alloy material by the discharge machining is high, and a large batch of products can be produced in a short time;

2. in the preparation process, cellulose is converted into graphene nanosheets under the conditions of high temperature and high pressure, molten metal is crystallized by taking the graphene nanosheets as crystal nuclei, and is attached to the graphene nanosheets to form a high-entropy alloy through crystallization, and at the moment, the graphene nanosheets are wrapped inside the solidified high-entropy alloy as the crystal nuclei and cannot be agglomerated into graphite, so that graphene in the prepared graphene-based high-entropy alloy material is not easy to agglomerate (single graphene can be agglomerated into graphite under the discharge condition, the structure of the graphene is lost after agglomeration, excellent properties are lost), and the performance is stable;

3. in the graphene-based high-entropy alloy material, the graphene component provides good heat-conducting property, and the mechanical property of the graphene-based high-entropy alloy material is enhanced;

4. the highest temperature in the discharge machining process exceeds 3000K, is higher than the melting point of most high-entropy alloys, but is lower than the melting point of graphene, so that the graphene can still keep the structure of the graphene at the high temperature for smelting the high-entropy alloys, and the preparation method greatly expands the machining range of the high-entropy alloys while ensuring the structure of the graphene nanosheets;

5. the cellulose used in the preparation method can be derived from agricultural products or waste materials containing cellulose, such as corn straws, corn cob meal and the like, and in the discharge processing process, impurity elements in the cellulose are instantaneously volatilized at extremely high temperature, so that the purpose of waste utilization can be achieved, and the production cost is effectively reduced.

Detailed Description

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, taking cellulose to disperse in deionized water to obtain cellulose dispersion liquid, and taking five kinds of metal salt powder to disperse in deionized water to obtain metal salt dispersion liquid;

s2, mixing the cellulose dispersion liquid prepared in the step S1 with the metal salt dispersion liquid to obtain a mixed liquid, and then drying the mixed liquid to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 to prepare the graphene-based high-entropy alloy material.

The high-entropy alloy has the excellent properties of high strength, good wear resistance, oxidation resistance, corrosion resistance and the like. In the carbon material, the graphene has an extremely high melting point, so that the graphene can still maintain a self-structure at a high temperature for smelting the high-entropy alloy. And the graphene has good heat-conducting property, and the heat-conducting coefficient of the graphene can reach 5300W/mK, so that the aim of quickly radiating heat in the hot processing process of the graphene can be fulfilled. The ideal performance of the composite material cannot be fully exerted by simple stacking and mixing of the graphene material and the high-entropy alloy material. According to the invention, the mixture of the cellulose and the metal salt powder is prepared firstly, then the mixed powder of the cellulose and the metal salt is subjected to discharge processing, so that the solid metal salt can be directly converted into the high-entropy alloy material in a short time, the process is simple, the efficiency is high, in the preparation process, the cellulose is converted into the graphene nanosheets under the conditions of high temperature and high pressure, the molten metal is crystallized by taking the graphene nanosheets as crystal nuclei, the graphene nanosheets are attached to the graphene nanosheets, the high-entropy alloy is formed by crystallization, and the graphene nanosheets are wrapped in the solidified high-entropy alloy as the crystal nuclei and cannot be agglomerated into graphite, so that the graphene in the prepared graphene-based high-entropy alloy material is not easy to agglomerate (single graphene can be agglomerated into graphite under the discharge condition, loses the structure of the graphene after agglomeration, loses excellent properties), and the performance is stable. In addition, in the graphene-based high-entropy alloy material, the graphene component provides good heat conduction performance, and the mechanical properties of the graphene-based high-entropy alloy material are enhanced. The highest temperature in the discharge machining process exceeds 3000K, is higher than the melting point of most high-entropy alloys, but is lower than the melting point of graphene, so that the graphene can still keep the structure of the graphene at the high temperature of smelting the high-entropy alloys, and the preparation method greatly expands the machining range of the high-entropy alloys while ensuring the structure of the graphene nanosheets. The graphene-based high-entropy alloy material prepared by the discharge machining has high efficiency, and can produce a large batch of products in a short time.

Furthermore, the cellulose used in the preparation method can be derived from agricultural products or waste materials containing cellulose, such as corn straws, corn cob meal and the like, and in the discharge processing process, impurity elements in the cellulose are instantaneously volatilized at extremely high temperature, so that the purpose of waste utilization can be achieved, and the production cost is effectively reduced.

The ideal effect of graphene on dispersing high-entropy alloy is fully exerted, the high-entropy alloy is crystallized by taking the graphene nanosheets as the cores to form the graphene-based high-entropy alloy material, the graphene component provides good heat conduction performance, the high-entropy alloy is beneficial to refining crystal grains during cooling crystallization, the structure of the graphene-based high-entropy alloy material is improved, and a solution is provided for the rapid preparation of the graphene-based high-entropy alloy material and the prevention of agglomeration of the graphene nanosheets in the composite material through an electric discharge machining process which is high in energy density and can complete machining instantly.

According to the invention, the mixed powder of cellulose and metal salt is subjected to accurate discharge processing, so that the graphene-based high-entropy alloy material can be prepared rapidly in a large area, the full combination of graphene sheets and the high-entropy alloy is effectively realized, the agglomeration of graphene nanosheets in the mixture of graphene and molten high-entropy alloy is prevented, the high-entropy alloy is beneficial to refining grains during cooling crystallization, the structure of the graphene-based high-entropy alloy material is improved, the requirements of high efficiency, low cost, high stability, simple process, no secondary pollution and the like in the preparation process of the graphene-based high-entropy alloy material are met, and the problems of low production efficiency, poor stability and application limitation of the existing production method of the graphene-based high-entropy alloy material are solved.

In the mixed solution of step S2, the mass ratio of the cellulose to the metal salt is (2-5): 1.

the mass ratio of cellulose to metal salt is limited to (2-5): 1, the quality ratio of cellulose to metal salt can influence the structure and purity of the composite material if being too high or too low, if the amount of cellulose is too large, namely the content of cellulose in the obtained mixed powder of cellulose and metal salt is too much, the cellulose is easily influenced to be converted into graphene in discharge machining, impurities are easily introduced, since the graphene serves as a crystal nucleus in the crystallization process of the high-entropy alloy, the molten high-entropy alloy is crystallized around the graphene, if the addition amount of the cellulose is too little, the graphene nanosheet obtained through conversion is too little, the crystal nucleus is insufficient, the crystallization process of the high-entropy alloy is influenced, and the structure of the composite material after crystallization is not uniform.

In step S1, five metal salt powders, namely, ferric chloride, cobalt chloride, nickel chloride, copper chloride, and zinc chloride, are dispersed in deionized water.

By using five metal salt powders, and the five metal salt powders adopt ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride, the preparation method firstly prepares a mixture of cellulose and the metal salt powders, then carries out discharge processing on the mixed powder of the cellulose and the metal salt, can directly convert five solid metal salts into a high-entropy alloy material in a short time, the cellulose is converted into graphene nanosheets under the conditions of high temperature and high pressure, the five molten metals use the graphene nanosheets as attachments, and are crystallized to form a high-entropy alloy, the high-entropy alloy has fine crystal grains and uniform components. In the present production method, the high-entropy alloy element may be selected from Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W, and the raw material metal salt may be selected from these elements.

Preferably, the concentration of any two metal salts in the metal salt dispersion is higher than the concentration of the remaining three metal salts.

When the concentration of metal salt in the metal salt dispersion liquid is changed and other conditions are not changed, the size of the high-entropy alloy particles is changed along with the change of the concentration of the salt, and when the concentration of any two metal salts in the metal salt dispersion liquid is higher than the concentration of the rest three metal salts, namely when a certain two metal elements are used as main element elements of the high-entropy alloy, the metal atoms with higher content cannot be separated out by simple substances in the crystallization process and are forced to be mixed with other atoms, so that more lattice distortion is generated, the components of the high-entropy alloy are more uniform, and the grains of the prepared graphene-based high-entropy alloy material are smaller.

Preferably, in the step S1, the concentration of cellulose in the cellulose dispersion liquid is 1 to 5mg/mL, the concentration of ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of cobalt chloride is 0.15mg/mL, the concentration of nickel chloride is 0.15mg/mL, the concentration of copper chloride is 0.25mg/mL, and the concentration of zinc chloride is 0.25 mg/mL;

in the step S2, the cellulose dispersion liquid and the metal salt dispersion liquid prepared in the step S1 are mixed in a volume ratio of 1: 1 to obtain a mixed solution.

By limiting the concentration of cellulose in the cellulose dispersion liquid and the concentration of each metal salt in the metal salt dispersion liquid, the graphene nanosheet obtained by cellulose conversion can be controlled to be in a proper concentration, the dispersibility of the graphene nanosheet is good, the graphene nanosheet is used as a crystal nucleus and wrapped in the solidified high-entropy alloy and cannot be agglomerated into graphite, if the addition amount of the cellulose is too small, the converted graphene nanosheet is too small, the crystal nucleus is insufficient, the crystallization process of the high-entropy alloy is influenced, and the structure of the crystallized composite material is uneven.

In step S3, the mixed powder of cellulose and metal salt obtained in step S2 is subjected to electric discharge machining in a nitrogen atmosphere, wherein the electric discharge machining has a discharge voltage of 100 to 300V and a discharge capacitance of 100 to 300 mF.

Through the discharge voltage and the discharge capacitance who prescribe a limit to carry out discharge machining in step S3, if discharge voltage and discharge capacitance are too low, the material is on-conductive, then can't carry out discharge machining, even electrically conductive, also can lead to the cellulose can not fully turn into graphite alkene, thereby introduce impurity, if discharge voltage and discharge capacitance are too high, probably puncture the raw materials in the minizone, lead to discharging inhomogeneous (the electric current passes through whole cylinder cross section under the normal condition), seriously influenced the quality of the composite material who obtains of preparation, even puncture the area of raw materials when great, can make unable preparation composite material, in addition, too high capacitance voltage has a higher requirement to discharge device, discharge device' S cost has been increased.

Specifically, in step S3 of the present invention, a discharge device is used to perform discharge machining on the prepared mixed powder of cellulose and metal salt, the device includes a discharge chamber, an electrical cabinet and a controller, a quartz tube is disposed in the discharge chamber, electrodes are disposed at two ends of the quartz tube, and the discharge chamber is connected to a vacuum pump and an air supply device;

a charging power supply and a capacitor bank are arranged in the electric cabinet, the capacitor bank is electrically connected with the electrode, the charging power supply is electrically connected with the capacitor bank, and the controller is electrically connected with the charging power supply.

Specifically, the charging power supply is used for charging the capacitor bank, the controller is specifically a computer, the controller is used for controlling starting and stopping of charging action of the charging power supply and discharging voltage and current, the vacuum pump is used for vacuumizing the discharging chamber, the gas supply device is specifically a gas cylinder, and the gas supply device is used for supplying process gas to the discharging chamber.

Specifically, in step S3, the specific steps of performing the electric discharge machining are: placing mixed powder of cellulose and metal salt into a discharge cavity of the quartz tube, filling the discharge cavity of the quartz tube, clamping the quartz tube by using the electrode, installing the quartz tube into the discharge chamber, opening the vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening the gas supply device 5 to fill nitrogen, and starting to perform discharge machining.

Preferably, in the step S2, the drying temperature for drying the mixed solution is 50 to 70 ℃, and the drying time is 110 to 130 min.

By limiting the drying temperature and the drying time for drying the mixed solution in the step S2, the mixed solution is ensured to be completely dried, incomplete evaporation of water in the obtained mixed powder of cellulose and metal salt does not occur, and the drying speed is high at the temperature, so that the graphene-based high-entropy alloy material is effectively improved.

In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Example 1

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 2

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 4mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 4: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 3

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 3mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 3: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 4

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 2mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 2: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 5

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain a cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 1mg/mL, and dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain a metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 1: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 6

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, and dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.2mg/mL, the concentration of the nickel chloride is 0.2mg/mL, the concentration of the copper chloride is 0.2mg/mL and the concentration of the zinc chloride is 0.2 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 7

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 100V, and the discharge capacitance is 100mF, so that the graphene-based high-entropy alloy material is prepared.

Example 8

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting discharge machining, wherein the discharge voltage for the discharge machining is 200V, and the discharge capacitance is 200mF, so that the graphene-based high-entropy alloy material is prepared.

Example 9

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 240V, and the discharge capacitance is 240mF, so that the graphene-based high-entropy alloy material is prepared.

Example 10

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 300V, and the discharge capacitance is 300mF, so that the graphene-based high-entropy alloy material is prepared.

Example 11

A preparation method of a graphene-based high-entropy alloy material comprises the following steps:

s1, dispersing cellulose in deionized water to obtain cellulose dispersion liquid, wherein the concentration of the cellulose in the cellulose dispersion liquid is 5mg/mL, dispersing ferric chloride, cobalt chloride, nickel chloride, copper chloride and zinc chloride in the deionized water to obtain metal salt dispersion liquid, wherein the concentration of the ferric chloride in the metal salt dispersion liquid is 0.2mg/mL, the concentration of the cobalt chloride is 0.15mg/mL, the concentration of the nickel chloride is 0.15mg/mL, the concentration of the copper chloride is 0.25mg/mL and the concentration of the zinc chloride is 0.25 mg/mL;

s2, mixing the cellulose dispersion liquid prepared in the step S1 and the metal salt dispersion liquid according to the volume ratio of 1: 1 to obtain a mixed solution, wherein the mass ratio of cellulose to metal salt in the mixed solution is 5: 1, drying the mixed solution at the drying temperature of 60 ℃ for 120min to obtain mixed powder of cellulose and metal salt;

and S3, performing discharge machining on the mixed powder of the cellulose and the metal salt prepared in the step S2 by using a discharge device, placing the mixed powder of the cellulose and the metal salt into a discharge cavity of a quartz tube of the discharge device, filling the discharge cavity of the quartz tube, clamping the mixed powder by using an electrode, installing the mixed powder into a discharge chamber, opening a vacuum pump to vacuumize the inside of the discharge chamber (to below 5 Pa), opening a gas supply device to fill nitrogen, starting the discharge machining, wherein the discharge voltage for the discharge machining is 400V, and the discharge capacitance is 300mF, so that the graphene-based high-entropy alloy material is prepared.

Comparative example 1

In comparison with example 1, in step S1 of this comparative example, cellulose was dispersed in deionized water to obtain a cellulose dispersion liquid in which the concentration of cellulose was 0.5mg/mL, and the mass ratio of cellulose to metal salt in the mixed solution of step S2 was 0.5: 1, the other raw materials and the preparation method are consistent with those of the embodiment 1, and the graphene-based high-entropy alloy material is prepared.

Comparative example 2

In comparison with example 1, in step S1 of this comparative example, cellulose was dispersed in deionized water to obtain a cellulose dispersion liquid in which the concentration of cellulose was 6mg/mL, and the mass ratio of cellulose to metal salt in the mixed solution of step S2 was 6: 1, the other raw materials and the preparation method are consistent with those of the embodiment 1, and the graphene-based high-entropy alloy material is prepared.

In the high-entropy alloy material, the grain size is one of important parameters for measuring the performance of the high-entropy alloy material, and the grain refining function is to increase the tensile strength and improve the mechanical properties such as toughness, so that the grain size of the graphene-based high-entropy alloy material prepared in examples 1-8 and comparative examples 1-2 is measured, and the grain size of the graphene-based high-entropy alloy material is characterized by using a Japanese Hitach SU8220 Scanning Electron Microscope (SEM) in an experiment, and the test results are shown in the following table:

from the test results of examples 1 to 5, it can be seen that when the concentration of cellulose in the deionized water dispersion is changed and other conditions are not changed, the grain size of the graphene-based high-entropy alloy material changes with the change of the cellulose concentration, and when the mass ratio of cellulose to metal salt in the mixed solution is 5: the grain size of the prepared graphene-based high-entropy alloy material is minimum, the preparation process for preparing the graphene-based high-entropy alloy material through discharge machining is simple, the preparation efficiency is high, and the graphene-based high-entropy alloy material can be quickly prepared;

as can be seen from examples 1 and 6, when the concentration of the metal salt in the metal salt dispersion is changed and other conditions are not changed, the size of the crystal grains of the graphene-based high-entropy alloy material changes with the change of the concentration of the metal salt, and the concentrations of two metal salts in the metal salt dispersion in example 1 are higher than those of the other three metal salts, so that the two metal elements are used as the main elements of the high-entropy alloy, the composition of the high-entropy alloy is more uniform, the crystal grains of the prepared graphene-based high-entropy alloy material are smaller, and when the concentrations of the metal salts in the metal salt dispersion in example 6 are the same, the crystal grains of the prepared graphene-based high-entropy alloy material are larger than those of the graphene-based high-entropy alloy material prepared in example 1;

as can be seen from example 1 and examples 7 to 11, the grain sizes of the graphene-based high-entropy alloy materials prepared by changing the discharge voltage and the discharge capacitance in step S3 are different. When the voltage and capacitance parameters are selected to be smaller, the cellulose cannot be fully converted into graphene, and impurities are introduced, so that the crystal grains of the prepared composite material become larger; when the voltage and capacitance parameters are selected to be larger, the raw materials are broken down in a small range by the current, so that the discharge is uneven, and the crystal grains of the prepared composite material become larger. When the voltage is 100-300V and the discharge capacitance is 100-300 mF, the minimum crystal grain is present;

in comparative example 1, the concentration of cellulose in the cellulose dispersion liquid is too low, and insufficient cellulose is not converted into graphene nanosheets in the discharge machining process, so that the amount of the graphene nanosheets is insufficient, and the graphene nanosheets are taken as crystal nuclei, so that the crystal nuclei are insufficient, the crystallization process of the high-entropy alloy is influenced, the more crystal nuclei are in unit volume during crystallization, the smaller the crystal grain diameter is, the less crystal nuclei are in unit volume when the crystal nuclei are small, the fewer crystal grains are, and the larger the crystal grain diameter is, so that the crystal grain diameter of the prepared graphene-based high-entropy alloy material is increased;

in the comparative example 2, the concentration of cellulose in the cellulose dispersion liquid is too high, so that the content of cellulose is too high, the conversion of cellulose into graphene in electric discharge machining is influenced, impurities are introduced, the crystallization process of the high-entropy alloy and the quality of the high-entropy alloy are influenced, and the grain diameter of the prepared graphene-based high-entropy alloy material is increased.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.