CN113333773B - Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock - Google Patents

Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock Download PDF

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CN113333773B
CN113333773B CN202110704558.8A CN202110704558A CN113333773B CN 113333773 B CN113333773 B CN 113333773B CN 202110704558 A CN202110704558 A CN 202110704558A CN 113333773 B CN113333773 B CN 113333773B
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朱荣涛
黄鹏飞
章新喜
张文军
刘壮
朱海洋
廖云天
吴雨
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China University of Mining and Technology CUMT
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Abstract

The disclosure provides a method for preparing metal particle loaded coal-based graphene through high-temperature thermal shock, which introduces nano metal particles into a carbon source through a dipping reduction method. According to the method, the carbon sources such as coal, coal pitch, coke and coal-based graphite are subjected to high-temperature thermal shock graphitization and metal salt thermal reduction by using the joule heat generated by capacitive discharge, and the coal-based graphene-loaded metal particles are generated in a short time. The metal used in the process of loading the metal nanoparticles is transition metal such as Fe, co, ni, cu and the like, and the metal salt is chloride or hydrate thereof, acetate or hydrate thereof. The preparation method is simple, low in cost, high in product graphitization degree, excellent in performance, suitable for large-scale production and important in application value.

Description

Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock
Technical Field
The disclosure relates to the field of material preparation, in particular to a method for preparing coal-based graphene loaded metal particles through high-temperature thermal shock.
Background
Supercapacitors have a high power density, but they typically have a lower energy density than rechargeable batteries. Supercapacitors with higher operating voltages and higher energy densities have therefore been developed to meet the high-speed growing energy storage demands without sacrificing power transfer and cycle life.
The pseudocapacitance can fully utilize different potential windows of the two electrodes to provide the maximum working voltage in a battery system, thereby greatly improving the specific capacitance and obviously improving the energy density. Due to the outstanding theoretical capacitance and the abundant and non-toxic elemental transition metal oxides, metal hydroxides and conducting polymer materials are excellent electrode materials for pseudocapacitance.
In the last decades, carbon materials, such as activated carbon, carbon nanotubes and graphene, have proven to be the most promising electrode materials for electrochemical double layer capacitors. Among various carbon materials, graphene is highly specific surface area
Figure BDA0003131681240000011
And high conductivity (2X 10) 5 cm 2 V -1 s -1 ) Graphene can be used as a substrate, and not only can well disperse transition metal oxides, but also can be used as a direct conduction path for rapid electron transport.
Although lattice atom close packing of graphite is highly stable, when it is smaller than 20 nm in size, it is thermodynamically very unstable except for some specific conditions, which is one of the reasons why the conversion of graphite into graphene is extremely difficult to manufacture.
At present, the graphene oxide and the carbon nanotube loaded with metal particles are used as electrode materials of a super capacitor to show excellent performance. However, all these methods use expensive graphene oxide or reduced graphene oxide as a precursor, and the solvothermal reaction has high energy consumption and long reaction time, and these synthesis techniques require two or more complicated synthesis steps [ CN201611108184.9], and the process is complicated.
At present, a method for preparing coal-based graphene loaded with metal nanoparticles by a one-step high-temperature thermal shock method is not reported. Therefore, the development of a method for preparing graphene loaded with metal nanoparticles, which has the advantages of low cost, simple equipment and rapid production, undoubtedly has very important application in the field of energy storage.
Disclosure of Invention
Based on the above-mentioned cost and process problems, the high-performance low-cost metal particle-loaded coal-based graphene is prepared by introducing a capacitance discharge-based joule heating impact method. In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of metal nanoparticle-loaded coal-based graphene comprises the following steps: weighing excessive metal salt by using an analytical balance, dissolving the excessive metal salt in a small amount of water to prepare an over-saturated metal salt solution, adding a coal-based carbon material into the over-saturated metal salt solution, uniformly mixing the solution, standing, filtering, drying, loading a sample, and thermally shocking at high temperature to obtain the metal nanoparticle-loaded graphene composite material.
In the above scheme, the metal salt solution is one or more of chlorides or chlorohydrates of gold, silver, platinum, palladium, ruthenium, rhodium, iron, cobalt, nickel, manganese, zinc, copper, titanium, tin, molybdenum, cadmium, tungsten, bismuth, and cerium, and acetic acid or acetic acid hydrate.
In the scheme, the coal-based carbon material is one or more of anthracite, bituminous coal, coal tar pitch, coke and/or coal-based graphite and other carbon sources.
In the scheme, the mass ratio of the coal-based carbon material to the metal salt solution is 1:0.001-1.
In the above scheme, the high temperature thermal shock is obtained by joule heat generated by directly discharging the sample by the capacitor.
In the scheme, the applied voltage is 100V-200V, the applied voltage time is 50 ms-500 ms, the applied voltage energy is 5-20kJ/g, and the peak temperature of the applied voltage is 2500-3000 ℃. .
Compared with the prior art, the invention has the following beneficial effects: the raw materials needed are cheap and the cost is low; (2) The reaction is quick, the process is simple, and a complex post-treatment process is not needed; (3) Compared with the traditional radiation heating, the material is directly electrified and acted by utilizing the self-conductive and resistance characteristics of the material, so that the energy consumption is lower.
Drawings
Fig. 1 is a comparison graph of raman spectra of coal-based graphene loaded with metal Ni nanoparticles before and after high temperature thermal shock in examples 1 and 2;
FIG. 2 is a scanning electron microscope image of the coal-based graphene loaded with metallic Ni nanoparticles after thermal shock at high temperature in example 1;
FIG. 3 is a scanning electron microscope image and an energy spectrum of the coal-based graphene loaded with the metallic Ni nanoparticles after high-temperature thermal shock in example 1;
FIG. 4 is a scanning electron microscope image of the coal-based graphene loaded with metallic Co nanoparticles after thermal shock at high temperature in example 3;
FIG. 5 is a scanning electron microscope image of the coal-based graphene loaded with metallic Cu nanoparticles after thermal shock at high temperature in example 7;
fig. 6 is a schematic structural view of a high-temperature thermal shock device.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
In some embodiments, the applied voltage is 20-300V, e.g., 20V, 50V, 100V,130V, 150V, 200V, 230V, 250V, 300V, etc., preferably 130V-200V, and the discharge time is 20-2000ms, e.g., 20ms, 50ms, 100ms, 150ms, 200ms, 300ms, 500ms, 1000ms, 2000ms, etc., preferably 100-200ms, to achieve a high temperature of about 2500-3000 ℃.
The high-temperature thermal shock device used in the invention comprises a quartz tube 1, wherein a conductive metal salt @ carbon source precursor 2 is contained in the quartz tube 1; two ends of the quartz tube 1 are sealed by graphite blocks 3, and electrode rods 9 are symmetrically arranged; the electrode bar 9 is a copper electrode which is tightly contacted with the graphite block; the electrode rods 9 are respectively installed with the rubber plate 7 in a sliding fit mode, the gaskets 5 are respectively fixedly installed on the two sides, located on the rubber plate 7, of the electrode rods 9 through limiting nuts 8, and a spring 6 structure is arranged between the gasket and the rubber plate 7, and the gasket is close to one side of the quartz tube 1; the electrode bar 9 is connected with a capacitor 10; when the capacitor 10 is charged and discharged, and the conductive metal salt @ carbon source precursor in the quartz tube 1 is subjected to thermal shock, the generated high-heat gas impacts the graphite block 3, the electrode rod 9 slides to two sides along the rubber plate 7 in a micro-scale manner, the gas is allowed to escape during the high-temperature thermal shock, and the pretightening force is changed by compressing the spring 6 to increase the conductivity of the sample 2. The quartz tube 1 can also be replaced by insulating high-temperature-resistant materials such as mica and ceramic.
A sealed reaction chamber can be arranged outside the high-temperature thermal shock device, and the reaction chamber is connected with a vacuum pump and a gas bottle and is used for forming a vacuum or inert gas protection environment. The apparatus used in the present invention is not limited thereto, and any apparatus capable of providing the production conditions for the present invention may be used.
Example 1
High-temperature thermal shock of the coal-based graphene loaded metal Ni under different discharge voltages:
step 1) preparation excess nickel chloride hexahydrate NiCl is weighed by an analytical balance 2 · 6 H 2 O,20g dissolved in a small amount of water H 2 In 5mL of O, supersaturated NiCl is prepared 2 An aqueous solution;
step 2) adding 1g of coal tar pitch with 200 meshes, uniformly mixing the solution, standing, filtering and drying to obtain the conductive NiCl 2 @ coal pitch precursor;
step 3) accurately weighing 120mg of dried NiCl 2 The @ coal pitch precursor is loaded in a quartz tube with the inner diameter of 6mm, and the quartz tube loaded with the sample is fixed at the two ends of the capacitance electrode;
and 4) setting inert gas protection, vacuumizing the reaction chamber by using a vacuum pump, filling nitrogen, repeating for three times, and replacing oxygen in the reaction chamber to ensure that the materials are not oxidized in the reaction process.
And 5) applying high voltage, selecting a capacitor of 60mF, selecting 100V,130V,160V and 200V for voltage respectively, and sieving to obtain the coal-based graphene material loaded with the metal nanoparticles, wherein the electrifying time is 200ms, and the mesh size is less than 200 meshes.
For the coal sample with the resistance of more than 100 ohms, the coal sample is placed in a tube furnace under the protection of argon gas and the temperature of 800 ℃ is kept for 2 hours or 5% -10% of conductive carbon black is doped to ensure that the resistance of the coal sample reaches within 100 ohms.
Example 2
High-temperature thermal shock of the coal-based graphene loaded metal Ni under different discharge times:
steps 1) to 4) were the same as in example 1;
and 5) applying high voltage, selecting a capacitor of 60mF, selecting a voltage of 200V, electrifying for 50ms, 100ms, 150ms, 200ms and 300ms, and screening out the coal-based graphene material loaded with the metal nanoparticles with a size of less than 200 meshes.
Fig. 1 is a graph comparing raman spectra of the coal-based graphene loaded with the metal Ni nanoparticles before and after the thermal shock at high temperature in examples 1 and 2. Wherein (a) is NiCl before flash evaporation 2 The Raman spectra of the coal pitch precursor, (b) - (e) are the comparison graphs of the Raman spectra of the coal-based graphene loaded with the metal Ni nanoparticles in example 1 after different voltage treatments, and (f) is I under different voltages D /I G And I 2D /I G The ratio of (A) to (B); (g) - (k) is a comparative graph of Raman spectra of the metal Ni nanoparticle-loaded coal-based graphene of example 2 treated at different times, and (l) is I at different times D /I G And I 2D /I G Is measured in the measurement. The sample shows three typical peaks: the D peak (1350 cm) -1 ) G peak (1582 cm) -1 ) And 2D peak (2700 cm) -1 ) The D peak represents a defect of a carbon atom lattice, and the G peak represents in-plane stretching vibration of sp2 hybridization of a carbon atom. I is D /I G The larger the value of the intensity ratio of the D peak to the G peak, the more defects in the carbon atom crystal are. The 2D peak is a diphone resonance second-order Raman peak, is used for representing the interlaminar stacking mode of carbon atoms in the graphene sample, and I thereof 2D /I G A larger value indicates a smaller number of graphene layers.
As can be seen from FIG. 1 (f), as the voltage increases, it receives more Joule heat energy, and I D /I G The increase indicates a significant reduction of defects in the lattice of carbon atoms compared to the original precursor, its I 2D /I G The decrease in value indicates a thinning of the carbon sheet layer after graphitization. As can be seen from FIG. 1 (l), as the discharge proceedsExtension of time, also I D /I G The increase indicates a significant reduction of defects in the lattice of carbon atoms, I 2D /I G The decrease in value indicates a reduction in the thickness of the carbon sheet after graphitization. As can be seen from fig. 1, graphene grows in the precursor after the high-temperature thermal shock treatment.
As shown in fig. 2, which is a scanning electron microscope image of the coal-based graphene loaded with the metal Ni nanoparticles after the high-temperature thermal shock in example 1, a lamellar structure after the high-temperature thermal shock treatment can be observed, and a large number of spherical particles grow on the lamellar structure; fig. 3 is a scanning electron microscope image and an energy spectrum of the coal-based graphene loaded with the metal Ni nanoparticles after thermal shock at a high temperature in example 1, and it can be seen from the image that the spherical particles loaded in the middle of the graphene sheet layer are metal Ni. As can be seen from fig. 2-3, the metallic Ni particles were successfully loaded in the graphite sheet layer after the thermal shock at high temperature.
Example 3
High-temperature thermal shock of metal Co loaded by coal-based graphene:
step 1) preparation excess cobalt chloride hexahydrate CoCl is weighed by an analytical balance 2 · 6 H 2 O,20g in a small amount of water H 2 O,5mL, to make supersaturated CoCl 2 An aqueous solution;
steps 2 to 4 are the same as in example 1;
and 5) applying high voltage, selecting a capacitor of 60mF, selecting the voltage to be 200V respectively, electrifying for 200ms, and screening out the coal-based graphene material loaded with the metal nanoparticles with the particle size less than 200 meshes to obtain the coal-based graphene material loaded with the metal nanoparticles.
As shown in fig. 4, which is a scanning electron microscope image of the coal-based graphene loaded with the metallic Co nanoparticles after the high-temperature thermal shock in example 3, it can be seen that the metallic Co particles are successfully loaded on the graphite sheet layer after the high-temperature thermal shock.
Example 4
High-temperature thermal shock of the coal-based graphene loaded metal Cu under different discharge times:
step 1) preparation excess cobalt chloride hexahydrate CoCl is weighed by an analytical balance 2 · 6 H 2 O,20g dissolved in a small amount of water H 2 In 5mL of O, to prepare supersaturatedCoCl 2 An aqueous solution;
step 2-4 the same as in example 1;
and 5) applying high voltage, selecting a capacitor of 60mF, selecting the voltage of 200V respectively, and sieving to obtain the coal-based graphene material loaded with the metal nanoparticles, wherein the voltage is 200ms, and the electrifying time is 200 ms.
As shown in fig. 5, which is a scanning electron microscope image of the coal-based graphene loaded with the metal Cu nanoparticles after the high-temperature thermal shock in example 4, it can be seen that the metal Cu particles are successfully loaded on the graphite sheet layer after the high-temperature thermal shock.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. Accordingly, the above-described embodiments of the present invention are to be considered as illustrative only and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and any changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (6)

1. The method for preparing the metal nanoparticle-loaded coal-based graphene through high-temperature thermal shock is characterized in that voltage is applied to a conductive metal salt @ carbon source precursor, the particle size of the conductive metal salt @ carbon source precursor is smaller than 200 meshes, and the carbon source comprises one or more of anthracite, bituminous coal, coal pitch, coke and/or coal-based graphite; the metal salt solution is one or more of transition state metals of Fe, co, ni and/or Cu; the applied voltage is 20-300V, the discharge time is 20-2000ms, the peak temperature of the applied voltage is 2500-3000 ℃, the energy of the applied voltage is 5-20kJ/g, joule thermal shock is generated to graphitize the carbon source, and the conductive metal salt is thermally reduced to a metal simple substance, so that the coal-based graphene material loaded with the nano metal particles is obtained.
2. The method for preparing the metal nanoparticle-loaded coal-based graphene by high-temperature thermal shock according to claim 1, which comprises a step of preparing a conductive metal salt @ carbon source precursor, and specifically comprises the following steps: and (3) dipping the carbon source, centrifuging and drying to obtain the conductive metal salt @ carbon source precursor which is less than 200 meshes and loaded with the metal salt solution.
3. The method for preparing the metal nanoparticle-loaded coal-based graphene by high-temperature thermal shock according to claim 1 or 2, comprising the step of pre-carbonizing the conductive metal salt @ carbon source precursor, specifically: for the coal sample with larger resistance, the coal sample is placed in a tube furnace under the protection of argon gas and kept at 800 ℃ for 2h.
4. The method for preparing the metal nanoparticle-loaded coal-based graphene according to claim 2, wherein the metal salt solution is one or more of high-concentration or saturated chloride or chloride hydrate, acetate or acetate hydrate.
5. The method for preparing the metal nanoparticle-loaded coal-based graphene through high-temperature thermal shock according to claim 1, wherein the resistance of the conductive metal salt @ carbon source precursor at two ends of the electrode is less than 10 Ω.
6. The method for preparing the metal nanoparticle-supported coal-based graphene by high-temperature thermal shock according to claim 1, wherein the voltage is applied under the protection of an inert gas, wherein the inert gas used for applying the high-temperature thermal shock is selected from one or more of nitrogen and argon.
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