CN106670501B - Preparation method of graphene-metal matrix composite powder - Google Patents
Preparation method of graphene-metal matrix composite powder Download PDFInfo
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- CN106670501B CN106670501B CN201611241794.6A CN201611241794A CN106670501B CN 106670501 B CN106670501 B CN 106670501B CN 201611241794 A CN201611241794 A CN 201611241794A CN 106670501 B CN106670501 B CN 106670501B
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention discloses a preparation method of graphene-metal matrix composite powder, which comprises the steps of mixing graphene oxide and deionized water, and ultrasonically dispersing the mixture uniformly; at the same time, carrying out ultrasonic treatment on silver nitrate or copper sulfate in absolute ethyl alcohol; then pouring silver nitrate or copper sulfate solution into the graphene dispersion liquid, stirring under the water bath condition, adding hydrazine hydrate for reaction, and washing, filtering and drying after the reaction is finished to obtain graphene-loaded metal composite powder; and mixing the graphene-loaded metal composite powder with absolute ethyl alcohol, dispersing, homogenizing, adding silver powder or copper powder, ultrasonically mixing, and drying to obtain the graphene-loaded metal composite powder. The graphene-metal matrix composite powder obtained by the invention has the advantages of less graphene agglomeration, no oxidation, short powder mixing time and high efficiency, can be directly used for preparing the bulk graphene-metal matrix composite powder, and provides raw materials for subsequent processes.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials, and particularly relates to a preparation method of graphene-metal matrix composite powder.
Background
Graphene is a polymer made of carbon atoms in sp2The hybrid orbitals are arranged like a honeycomb two-dimensional lattice plane film. The thickness of about 0.335nm is the thinnest material in the world, with an ultra-large specific surface area. Each C atom of the composite material has four valence electrons, each carbon atom is connected with each other through a sigma bond with strong polarity, each carbon atom has one non-bonded pi electron after the sigma bond is formed, and the electrons can freely move in the crystal, so that the composite material has super conductivity and can be introduced into the composite material as a good carrier.
The copper metal and the silver metal have high heat conduction, electric conduction and forming performance, are important base materials for preparing the composite material, in the reports of related documents related to the preparation of the graphene copper-based or silver-based composite powder material at present, the direct addition of the graphene into the copper powder or the silver powder is mostly limited, the powder mixing is mostly carried out by adopting a high-energy ball ink method, a homogenizer and the like, the agglomeration phenomenon of the graphene in the powder is easy to occur after the mixing, and the performance of the material is greatly reduced.
Disclosure of Invention
The invention aims to provide a preparation method of graphene-metal matrix composite powder, which solves the problem that graphene is easy to agglomerate in powder in the existing preparation method.
The technical scheme adopted by the invention is that the preparation method of the graphene-metal matrix composite powder is implemented according to the following steps:
step 2, pouring a silver nitrate solution or a copper sulfate solution into the graphene dispersion liquid, stirring under a water bath condition, adding hydrazine hydrate for reaction, and washing, filtering and drying after the reaction is finished to obtain graphene-loaded silver composite powder or graphene-loaded copper composite powder;
and 3, dispersing the composite powder obtained in the step 2 in absolute ethyl alcohol, carrying out crushing and dispersion treatment in a cell crusher with ultrasonic power of 1800 plus 2500W for 10-30 minutes, then adding silver powder or copper powder with the mass of 50-100 times that of the composite powder, continuing ultrasonic dispersion for 10-30 minutes, and drying to obtain the graphene-silver-based composite powder or the graphene-copper-based composite powder.
The present invention is also characterized in that,
in the step 2, the mass ratio of the oxidized graphene to the silver nitrate in the silver nitrate solution and the graphene dispersion liquid is 1: 2.5-16, 1ml of hydrazine hydrate is used for every 5-16mg of silver nitrate.
In the step 2, the mass ratio of the copper sulfate solution to the graphene oxide dispersion liquid to the copper sulfate is 1: 1.5-5, 1ml hydrazine hydrate is used per 15-25mg copper sulfate.
In the step 2, the temperature of the water bath is 70-90 ℃, and hydrazine hydrate is added for reaction for 1-2 h.
The grain diameter of the silver powder or the copper powder in the step 3 is 200-500 nm.
The preparation method of the graphene-metal-based composite powder has the beneficial effects that the graphene oxide, the silver nitrate or the copper sulfate are used as raw materials, the reducing agent hydrazine hydrate is added for reduction reaction to prepare the graphene-metal-based composite material loaded with metal ions, the graphene-metal-based composite powder with little agglomeration and no agglomeration is mixed by utilizing the ultrasonic dispersion principle, the phenomena of non-uniform agglomeration and dispersion of the graphene in the powder mixing process in the existing research are greatly improved, and meanwhile, the simplest drying method is adopted, so that the cost is reduced, and the oxidation is prevented. The process is stable, well solves the problem that graphene is easy to agglomerate, is simple to operate, low in equipment investment and reliable in quality, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image with a microscopic scale of 1 μm of the graphene-silver-based composite powder prepared in example 3;
fig. 2 is a spectrum of the graphene-silver based composite powder prepared in example 3;
FIG. 3 is a transmission electron microscope image of 100nm at a microscopic scale of the graphene-silver-based composite powder prepared in example 3;
FIG. 4 is an X-ray diffraction pattern of the graphene-silver-based composite powder prepared in example 3;
FIG. 5 is a scanning electron micrograph of the graphene-copper-based composite powder obtained in example 4, with a microscopic scale of 2 μm;
FIG. 6 is a spectrum of the graphene-copper-based composite powder obtained in example 4;
FIG. 7 is an X-ray diffraction chart of the graphene-copper-based composite powder obtained in example 4.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The preparation method of the graphene-metal matrix composite powder is implemented according to the following steps:
step 2, according to the mass ratio of the graphene oxide to the copper sulfate being 1: 2.5-16, mixing the graphene oxide solution and the copper sulfate solution, or mixing the graphene oxide solution and the copper sulfate solution according to the mass ratio of 1: 1.5-5, mixing the graphene oxide solution and the copper sulfate solution, stirring and adding hydrazine hydrate for reaction under the condition of 70-90 ℃ water bath (1 ml of hydrazine hydrate is used for every 5-16mg of silver nitrate or 1ml of hydrazine hydrate is used for every 15-25mg of copper sulfate), and washing, filtering and drying after the reaction is finished to obtain graphene-loaded silver composite powder or graphene-loaded copper composite powder;
and 3, dispersing the composite powder obtained in the step 2 in absolute ethyl alcohol, crushing and dispersing for 10-30 minutes in a cell crusher with ultrasonic power of 1800 plus 2500W, then adding silver powder or copper powder (the particle size of the silver powder or the copper powder is 200 plus 500nm) which is 50-100 times of the mass of the composite powder, continuing to disperse for 10-30 minutes by ultrasonic, and drying to obtain the graphene-silver-based composite powder or the graphene-copper-based composite powder.
The invention mainly utilizes ultrasound to achieve the purposes of uniformly dispersing graphene and reducing the thickness of a graphene layer. Ultrasonic pulverization is that when ultrasonic vibration is transmitted into liquid, strong cavitation effect is excited in the liquid due to high sound intensity, so that a large amount of cavitation bubbles are generated in the liquid. As these cavitation bubbles are generated and burst, micro-jets will be generated, breaking up solid particles in the liquid. Meanwhile, due to the vibration of ultrasonic waves, solid and liquid are more fully dispersed and uniformly mixed. Copper ions and silver ions enter the graphene layers when the graphene layers are separated through ultrasonic blasting, so that the distance between the graphene layers can be pulled, and the purposes of uniformly dispersing graphene and loading the copper ions and the silver ions are achieved.
Compared with the existing high-energy ball milling mixed powder, the graphene-metal matrix composite powder obtained by the invention has the advantages of less graphene agglomeration, no oxidation, short powder mixing time and high efficiency, can be directly used for preparing the bulk graphene-metal matrix composite powder, and provides raw materials for subsequent processes. The process is stable, well solves the problem that graphene is easy to agglomerate, is simple to operate, low in equipment investment and reliable in powder quality, and is suitable for industrial large-scale production.
Example 1
step 2, pouring a silver nitrate solution into the graphene dispersion liquid, transferring the graphene dispersion liquid into a constant-temperature water bath kettle at 80 ℃ for electromagnetic stirring, simultaneously adding 5ml of hydrazine hydrate with the concentration of 75% for reaction for 2 hours, cooling to room temperature, respectively centrifuging for 3 times by using deionized water and absolute ethyl alcohol, and drying the centrifuged precipitate at the temperature lower than 60 ℃ by using an electric heating sleeve to obtain non-oxidized graphene silver-loaded composite powder;
and 4, drying the graphene-silver-based composite material obtained in the step 3 at 60 ℃ by using an electric heating sleeve to obtain the graphene-silver-based composite powder directly used for preparing the block.
Example 2
step 2, pouring a silver nitrate solution into the graphene dispersion liquid, transferring the graphene dispersion liquid into a constant-temperature water bath kettle at 70 ℃ for electromagnetic stirring, simultaneously adding 5ml of hydrazine hydrate with the concentration of 75% for reaction for 1.5h, cooling to room temperature, respectively centrifuging for 3 times by using deionized water and absolute ethyl alcohol, drying the centrifuged precipitate at the temperature lower than 60 ℃ by using an electric heating sleeve, and obtaining non-oxidized graphene silver-loaded composite powder;
and 4, drying the graphene-silver-based composite material obtained in the step 3 at 60 ℃ by using an electric heating sleeve to obtain the graphene-silver-based composite powder directly used for preparing the block.
Example 3
step 2, pouring a silver nitrate solution into the graphene dispersion liquid, transferring the graphene dispersion liquid into a constant-temperature water bath kettle at 90 ℃ for electromagnetic stirring, simultaneously adding 5ml of hydrazine hydrate with the concentration of 75% for reaction for 1 hour, cooling to room temperature, respectively carrying out centrifugal treatment for 3 times by using deionized water and absolute ethyl alcohol, and drying at the temperature lower than 60 ℃ by using an electric heating sleeve to obtain non-oxidized graphene silver-loaded composite powder;
and 4, drying the graphene-silver-based composite material obtained in the step 3 at 60 ℃ by using an electric heating sleeve to obtain the graphene-silver-based composite powder directly used for preparing the block.
The structure and performance of the graphene-silver-based composite powder obtained in example 3 are detected, the morphology is shown in fig. 1, it is obvious from fig. 1 that the thin graphene is wrapped and wound between silver particles, fig. 2 shows the content of the selected region of the graphene-silver-based composite powder, and it is obvious that the components are basically carbon and silver, which indicates that the prepared powder is not oxidized. Fig. 3 illustrates that the graphene layer is relatively thin. As is clear from the XRD chart of fig. 4, four diffraction peaks (111), (200), (220), and (311) of silver were observed in the composite powder, and no diffraction peaks other than these four diffraction peaks were observed, indicating that silver in the mixed powder was not oxidized; since the amount of graphene added in the mixed powder was small, no diffraction peak of carbon could be observed.
Example 4
And 2, mixing the copper sulfate solution and the graphene oxide solution, transferring the mixture into a constant-temperature water bath kettle at 90 ℃ for electromagnetic stirring, simultaneously adding 5ml of hydrazine hydrate (the mass ratio is 75%), reacting for 1 hour, cooling to room temperature, sequentially centrifuging the solid product for three times by using deionized water and absolute ethyl alcohol respectively, and drying the centrifuged precipitate at the temperature lower than 60 ℃ by using an electric heating sleeve to obtain the non-oxidized graphene copper-loaded composite powder.
And 3, mixing 0.5g of the prepared graphene-loaded copper composite powder with 300ml of absolute ethyl alcohol in a 500ml beaker, crushing and dispersing the mixture in a cell crusher with ultrasonic power of 2200W for 20 minutes, adding 30g of copper powder (with the particle size of 500nm), and performing ultrasonic crushing, dispersing and mixing for 20 minutes under the same ultrasonic condition to obtain the graphene-copper-based composite material with a thin layer and uniform dispersion.
And 4, drying the dispersed powder at 60 ℃ by adopting an electric heating sleeve.
The structure and performance of the graphene-copper-based composite powder obtained in example 4 are detected, the morphology is shown in fig. 5, it is obvious from fig. 5 that the thin graphene is wrapped and wound between copper particles, fig. 6 shows the content of the selected region of the graphene-copper-based composite body, it is obvious that the components are basically carbon, copper and a very small amount of oxygen, the content of oxygen can be almost ignored, and it indicates that the prepared powder is hardly oxidized. As is clear from the XRD chart of fig. 7, three diffraction peaks (111), (200), and (220) of copper were observed in the composite powder, and no diffraction peaks other than these three diffraction peaks were observed, indicating that copper in the mixed powder was not oxidized; since the amount of graphene added in the mixed powder was small, no diffraction peak of carbon could be observed.
Example 5
And 2, mixing the copper sulfate solution and the graphene oxide solution, transferring the mixture into a constant-temperature water bath kettle at 80 ℃ for electromagnetic stirring, simultaneously adding 6ml of hydrazine hydrate (the mass ratio is 75%), reacting for 2 hours, cooling to room temperature, sequentially centrifuging the solid product for three times by using deionized water and absolute ethyl alcohol respectively, and drying the solid product at the temperature lower than 60 ℃ by using an electric heating sleeve to obtain the composite powder of the graphene-loaded copper without the oxide.
And 3, mixing 0.3g of the graphene-loaded copper composite powder prepared in the step 2 with 300ml of absolute ethyl alcohol in a 500ml beaker, crushing and dispersing the mixture in a cell crusher with ultrasonic power of 1800W for 30 minutes, adding 30g of copper powder (with the particle size of 200nm), and further performing ultrasonic crushing, dispersing and mixing for 30 minutes under the same ultrasonic condition to obtain the graphene-copper-based composite material with a thin layer and uniform dispersion.
And 4, drying the dispersed powder at 60 ℃ by adopting an electric heating sleeve.
Example 6
And 2, mixing the copper sulfate solution and the graphene oxide solution, transferring the mixture into a constant-temperature water bath kettle at 60 ℃ for electromagnetic stirring, simultaneously adding 8ml of hydrazine hydrate (the mass ratio is 75%), reacting for 3 hours, cooling to room temperature, sequentially centrifuging the solid product for three times by using deionized water and absolute ethyl alcohol respectively, and drying the solid product at the temperature lower than 60 ℃ by using an electric heating sleeve to obtain the composite powder of the graphene-loaded copper without the oxide.
And 3, mixing 0.6g of the graphene-loaded copper composite powder prepared in the step 2 with 300ml of absolute ethyl alcohol in a 500ml beaker, crushing and dispersing the mixture in a cell crusher with the ultrasonic power of 2500W for 10 minutes, adding 30g of copper powder (the particle size is 300nm), and performing ultrasonic crushing, dispersing and mixing for 10 minutes under the same ultrasonic condition to obtain the graphene-copper-based composite material with a thin layer and uniform dispersion.
And 4, drying the dispersed powder at 60 ℃ by adopting an electric heating sleeve.
Claims (3)
1. The preparation method of the graphene-metal matrix composite powder is characterized by comprising the following steps:
step 1, mixing graphene oxide and deionized water, and performing ultrasonic dispersion uniformly to obtain a graphene oxide dispersion liquid; carrying out ultrasonic treatment on silver nitrate or copper sulfate in absolute ethyl alcohol to obtain a silver nitrate solution or a copper sulfate solution;
step 2, pouring a silver nitrate solution or a copper sulfate solution into the graphene oxide dispersion liquid, stirring under a water bath condition, adding hydrazine hydrate for reaction, and washing, filtering and drying after the reaction is finished to obtain graphene-supported silver composite powder or graphene-supported copper composite powder;
the mass ratio of the graphene oxide to the silver nitrate in the silver nitrate solution and the graphene oxide dispersion liquid is 1: 2.5-16, using 1ml hydrazine hydrate for every 5-16mg silver nitrate;
the mass ratio of graphene oxide to copper sulfate in the copper sulfate solution to the graphene oxide dispersion liquid is 1: 1.5-5, using 1ml hydrazine hydrate for every 15-25mg copper sulfate;
step 3, dispersing the composite powder obtained in the step 2 in absolute ethyl alcohol, carrying out crushing and dispersion treatment in a cell crusher with ultrasonic power of 1800 plus 2500W for 10-30 minutes, then adding silver powder or copper powder with the mass of 50-100 times of that of the composite powder, continuing ultrasonic dispersion for 10-30 minutes, and drying to obtain graphene-silver-based composite powder or graphene-copper-based composite powder;
the drying is realized by adopting an electric heating sleeve at the temperature of lower than 60 ℃.
2. The method for preparing the graphene-metal matrix composite powder according to claim 1, wherein the temperature of the water bath in the step 2 is 70 ℃ to 90 ℃, and hydrazine hydrate is added for reaction for 1 to 2 hours.
3. The method for preparing the graphene-metal-based composite powder according to claim 1, wherein the particle size of the silver powder or the copper powder in the step 3 is 200-500 nm.
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