CN108083266B - Method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder - Google Patents
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Abstract
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps: 1) mixing natural crystalline flake graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid with the mass concentration of 98%, and reacting in a constant-temperature water bath; filtering, drying and grinding to obtain a pre-oxidized graphite precursor; 2) mixing a pre-oxidized graphite precursor with concentrated sulfuric acid with the mass concentration of 98% in an ice water bath, adding potassium permanganate, and fully reacting in a constant temperature environment to obtain dark green viscous liquid; when the temperature is less than or equal to 45 ℃, adding deionized water for a period of time, and then adding ionized water and hydrogen peroxide to obtain a bright yellow solution; washing until the pH value is 6-6.8 to obtain a mixed solution; drying and grinding to obtain a graphite oxide reaction precursor; 3) fully mixing a graphite oxide reaction precursor with deionized water to obtain brown turbid liquid; carrying out ultrasonic oscillation to obtain a graphene oxide dispersion liquid; 4) performing constant-temperature water bath, and adding zinc powder into the graphene oxide dispersion liquid to obtain a mixture with black precipitates; and (4) carrying out suction filtration, drying and grinding to obtain the graphene with the wave absorption performance.
Description
Technical Field
The invention belongs to the field of novel wave-absorbing nano-material manufacturing, and particularly relates to a method for preparing graphene with wave-absorbing performance by reducing graphene oxide with zinc powder.
Background
Graphene is a novel carbonaceous material with a two-dimensional honeycomb crystal structure formed by close packing of single-layer carbon atoms and is the thinnest material in the known materials in the nature. The two-dimensional material keeps nearly perfect crystal structure and excellent crystallographic properties, contains rich and novel physical phenomena, and has important theoretical research and application value. Because of its excellent strength, flexibility, electric conduction, heat conduction and optical characteristics, it has been developed in the fields of physics, materials science, electronic information, computer, aerospace and the like.
The traditional chemical reduction method adopts a chemical reagent, namely hydrazine hydrate (N)2H4·H2O) and the like are reducing agents which are toxic and cause harm to human bodies, and the waste water after reaction can cause pollution to the environment. The zinc powder is reduced to the graphene oxide, so that the body is not damaged, the environment is not polluted, the zinc element attached to the graphene after reduction has the effect of enhancing the wave absorption performance, and the wave absorption performance of the whole material is effectively improved.
The main methods for preparing graphene at present are as follows: micro mechanical lift-off, chemical vapor deposition, solvent lift-off, solvothermal, and the like. These methods are complex, environmentally demanding and costly, and are not conducive to large-scale industrial production. The method for preparing the graphene by adopting the oxidation-reduction method has feasible process and low preparation cost, obtains stable graphene suspension, and solves the problem that the graphene is not easy to disperse. The oxidation-reduction method is to react natural graphite with strong acid and strong oxidizing substances to generate Graphite Oxide (GO), prepare graphene oxide (single-layer graphite oxide) through ultrasonic dispersion, and add a reducing agent to remove oxygen-containing groups on the surface of the graphite oxide, such as carboxyl, epoxy and hydroxyl, to obtain the graphene. And zinc powder is used as a reducing agent, so that the wave absorbing performance of the graphene is enhanced. Defects generated during the redox process may generate polarization relaxation of defects and group electron dipole relaxation, which may increase penetration and absorption of electromagnetic waves, turning disadvantages into advantages. The method is simple, low in cost, mild in reaction condition and easy to control.
At present, most of wave-absorbing property researches on graphene tend to compound graphene with other materials, such as ferrite and the like. The prepared wave-absorbing material has high production cost and is not beneficial to industrial popularization in daily life. The wave absorbing material has wave absorbing performance in low, medium and high frequency bands, wherein the peak value of the wave absorbing material reaches-12.13 dB in a range of 2-6 GHz.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing graphene with wave-absorbing performance by reducing graphene oxide with zinc powder, which realizes the wave-absorbing performance of graphene in a multi-frequency band, and is a preparation method of graphene with the advantages of simple method, low cost, easily-controlled reaction conditions, environmental protection, energy conservation and good wave-absorbing performance in a multi-frequency band (2-18 GHz).
The method for preparing the graphene with the wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) according to the stoichiometric ratio, natural crystalline flake graphite (C) and potassium persulfate (K)2S2O8) Phosphorus pentoxide (P)2O5) Concentrated sulfuric acid (H) with the mass fraction of 98%2SO4) Weighing the 4 raw materials respectively in a ratio of (8-10) to (4-6) to (3-5) to (38-40);
(2) mixing the 4 raw materials, placing the mixture in a constant-temperature water bath at the temperature of 60-80 ℃ under the stirring condition, and reacting for 6-8 hours;
(3) diluting with deionized water, washing to neutrality, vacuum filtering, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) respectively weighing or weighing 3 raw materials according to the mass fraction of 98% concentrated sulfuric acid (mL) to 98% potassium permanganate (g) in the pre-oxidized graphite precursor (g), wherein the mass fraction of the concentrated sulfuric acid (mL) to the pre-oxidized graphite precursor (1-3) to (13-15) to (4-8), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding the potassium permanganate while stirring to obtain a mixture;
(2) placing the mixture in a constant temperature environment of 30-40 ℃ for full reaction for 2-4 h to prepare dark green viscous liquid;
(3) measuring a first part of deionized water according to the volume ratio of 98% concentrated sulfuric acid to a first part of deionized water (1-3) to (2-4) in the raw material mass fraction in step 2(1), and measuring a second part of deionized water and hydrogen peroxide according to the volume ratio of 98% concentrated sulfuric acid to a second part of deionized water to (28-30) to (1-3) in the raw material mass fraction in step 2 (1);
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and adding a second part of deionized water and hydrogen peroxide after 12-18 min to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing with dilute hydrochloric acid, and washing with deionized water until the pH value is 6-6.8 to obtain a mixed solution;
(4) and drying and grinding the mixed solution to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) fully mixing a graphite oxide reaction precursor (g) and deionized water (mL) at 30-50 ℃ according to the ratio of (1-3) to (2000-5000) of the graphite oxide reaction precursor to the deionized water to prepare brown turbid liquid;
(2) ultrasonically oscillating the brown turbid liquid to fully disperse the brown turbid liquid to prepare a brown graphene oxide dispersion liquid;
(1) weighing or weighing the graphene oxide dispersion liquid and zinc powder respectively according to the ratio of the graphene oxide dispersion liquid (mL) to the zinc powder (g) to (190-210) to (0.5-2), adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 30-50 ℃, and fully mixing to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying and grinding to obtain the graphene with the wave absorption performance.
The method for preparing the graphene with the wave-absorbing property by reducing graphene oxide with the zinc powder comprises the following steps:
in the step 1(1), the potassium persulfate, the phosphorus pentoxide and the concentrated sulfuric acid are analytically pure.
In the step 1(2), the stirring speed is 150-270 r/min.
In the step 1(2), the reaction is carried out in a four-neck flask.
In the step 2(1), the ice water bath is adopted to prevent potassium permanganate from exploding due to thermal decomposition.
In the step 2(1), the slow adding speed is 0.5-1 g/min.
In the step 2(2), the constant temperature environment is a constant temperature water bath. The constant-temperature water bath is carried out in a constant-temperature water bath kettle.
In the step 2(2), the method for fully reacting is to assist electric stirring of the mixture.
In the step 2(3), the mass concentration of the dilute hydrochloric acid is 5-15%.
In the step 2(3), metal ions are washed away by dilute hydrochloric acid washing.
In the step 2(4), drying is carried out by adopting an air-blast drying oven.
In the step 3(1), the sufficient mixing method is to adopt electric stirring.
In the step 3(2), the ultrasonic oscillation is performed in an ultrasonic oscillator.
In the step 3(2), ultrasonic oscillation is carried out for 4-6 hours.
In the step 4(1), the method of thorough mixing is electric stirring.
In the step 4(2), drying is performed by adopting an air-blast drying oven.
The wave-absorbing reflectivity of the graphene with the wave-absorbing performance prepared by the preparation method is-36.2 dB.
Compared with the prior art, the method for preparing the graphene with the wave-absorbing property by reducing the graphene oxide with the zinc powder has the advantages that:
under mild conditions, water is used as a solvent, and metal zinc is used as a reducing agent, so that the cost is reduced. Because the ingredients are few and easy to obtain, the cost is low and the environment is not polluted while other impurities are not introduced. The graphene nano material with good electromagnetic performance is prepared by controlling conditions such as oxidant, intercalation agent, reaction time, reaction temperature and the like. Since graphene is prepared by a redox method, a polarization relaxation of a defect and a group electron dipole relaxation may be generated by a defect generated during a redox process, which may increase penetration and absorption of electromagnetic waves. The preparation method is simple, low in cost, easy to control reaction conditions, environment-friendly, energy-saving, light in product weight, good in dielectric loss and hysteresis loss and suitable for industrial production. The analysis of morphology requires the preparation of a sample and then the detection of an electron scanning microscope, and the analysis of the absorption performance requires the preparation of a sample and then the detection of a network vector analyzer.
Drawings
FIG. 1 is a process flow diagram of a method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder in embodiments 1-6 of the present invention;
FIG. 2 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 1 of the invention;
FIG. 3 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 2 of the invention;
FIG. 4 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 3 of the invention;
FIG. 5 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 4 of the invention;
FIG. 6 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 5 of the present invention;
FIG. 7 is a scanning electron microscope picture of the graphene with wave-absorbing property prepared in embodiment 6 of the invention;
FIG. 8 is a graph of the reflectivity loss of graphene with wave-absorbing properties prepared in example 1 of the present invention;
FIG. 9 is a graph of reflectivity loss of graphene with wave-absorbing properties prepared in example 2 of the present invention;
FIG. 10 is a graph of the reflectivity loss of graphene with wave-absorbing properties prepared in example 3 of the present invention;
FIG. 11 is a graph of the reflectivity loss of graphene with wave-absorbing properties prepared in example 4 of the present invention;
FIG. 12 is a graph of reflectivity loss of graphene with wave-absorbing properties prepared in example 5 of the present invention;
fig. 13 is a graph of the reflectivity loss of the graphene with wave-absorbing property prepared in embodiment 6 of the present invention;
the specific implementation mode is as follows:
the process flow chart of the method for preparing the graphene with the wave-absorbing property by reducing graphene oxide with zinc powder in the following embodiments 1-6 is shown in attached figure 1.
In the following examples, in the step 1(1), potassium persulfate, phosphorus pentoxide, and concentrated sulfuric acid were analytically pure.
Example 1
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 16g of natural crystalline flake graphite (C) and 8g of potassium persulfate (K) were weighed in a stoichiometric ratio of 8: 4: 3: 38, respectively2S2O8) 6g of phosphorus pentoxide (P)2O5) And 76mL of 98% concentrated sulfuric acid with mass concentration, and 4 raw materials are used together;
(2) mixing the 4 raw materials in a four-neck flask, placing the mixture in a constant-temperature water bath at 70 ℃ under the stirring condition, and reacting for 6 hours at the stirring speed of 150 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 2g of pre-oxidized graphite precursor (g), 26mL of 98% concentrated sulfuric acid (mL) and 4g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for fully reacting for 2 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 8g of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.1g of graphite oxide reaction precursor and deionized water at 30 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) being 1: 2000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 4 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 0.5g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at the temperature of 30-50 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 2 and the reflectivity loss picture shown in the figure 8 are shown, the real part of the magnetic conductivity of the graphene at a frequency point of 4.57GHz is 0.63, and the imaginary part of the graphene is 0.09; the real part of the dielectric constant is 123.69 and the imaginary part is 77.24.
Example 2
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 18g of natural crystalline flake graphite (C) and 10g of potassium persulfate (K) were weighed in a stoichiometric ratio of 9: 5: 4: 39, respectively2S2O8) 8g of phosphorus pentoxide (P)2O5) 78mL of 98% concentrated sulfuric acid with mass concentration, and 4 raw materials；
(2) Mixing the 4 raw materials in a four-neck flask, placing the mixture in a constant-temperature water bath at 70 ℃ under the stirring condition, and reacting for 7 hours at the stirring speed of 270 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 2g of pre-oxidized graphite precursor (g), 28mL of 98% concentrated sulfuric acid (mL) and 6g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for full reaction for 3 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 9mL of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.1g of graphite oxide reaction precursor and deionized water at 30 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) being 1: 2000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 5 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 1g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 30 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 3 and the reflectivity loss picture shown in the figure 9 are shown, and the real part of the magnetic permeability of the graphene at a frequency point of 17.49GHz is 0.75, and the imaginary part of the graphene is 0.24; the real part of the dielectric constant is-12.77 and the imaginary part is 88.65.
Example 3
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 20g of natural crystalline flake graphite (C) and 12g of potassium persulfate (K) were weighed in a stoichiometric ratio of 10: 6: 5: 40, respectively2S2O8) 10g of phosphorus pentoxide (P)2O5) And 80mL of 98% concentrated sulfuric acid by mass concentration, and 4 raw materials are used in total;
(2) mixing the 4 raw materials in a four-neck flask, placing the mixture in a constant-temperature water bath at 80 ℃ under the stirring condition, and reacting for 8 hours at the stirring speed of 180 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 6g of pre-oxidized graphite precursor (g), 30mL of 98% concentrated sulfuric acid (mL) and 8g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for fully reacting for 4 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 10mL of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.3g of graphite oxide reaction precursor and deionized water at 50 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) of 3: 5000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 6 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 2g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 30 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 4 and the reflectivity loss picture shown in the figure 10 are shown, the real part of the magnetic permeability of the graphene at a frequency point of 17.49GHz is 0.93 DEG, and the imaginary part of the graphene is 0.29; the real part of the dielectric constant is-17.43 and the imaginary part is 87.35.
Example 4
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 16g of natural crystalline flake graphite (C) and 8g of potassium persulfate (K) were weighed in a stoichiometric ratio of 8: 4: 3: 38, respectively2S2O8) 6g of phosphorus pentoxide (P)2O5) And 76mL of 98% concentrated sulfuric acid with mass concentration, and 4 raw materials are used together;
(2) mixing 4 raw materials in a four-neck flask, placing in a constant-temperature water bath at 60 ℃ under the stirring condition, and reacting for 6 hours at the stirring speed of 150 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 2g of pre-oxidized graphite precursor (g), 26mL of 98% concentrated sulfuric acid (mL) and 4g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for fully reacting for 2 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 8mL of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.3g of graphite oxide reaction precursor and deionized water at 30 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) of 3: 5000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 4 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 0.5g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 50 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 5 and the reflectivity loss picture shown in the figure 11 are shown, the real part of the magnetic permeability of the graphene at a 17.49GHz frequency point is 0.52, and the imaginary part of the graphene is 0.34; the real part of the dielectric constant is-4.93 and the imaginary part is 70.40.
Example 5
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 18g of natural crystalline flake graphite (C) and 10g of potassium persulfate (K) were weighed in a stoichiometric ratio of 9: 5: 4: 39, respectively2S2O8) 8g of phosphorus pentoxide (P)2O5) And 78mL of 98% concentrated sulfuric acid by mass concentration to obtain 4 raw materials;
(2) mixing the 4 raw materials in a four-neck flask, placing the mixture in a constant-temperature water bath at 70 ℃ under the stirring condition, and reacting for 7 hours at the stirring speed of 270 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 2g of pre-oxidized graphite precursor (g), 28mL of 98% concentrated sulfuric acid (mL) and 6g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for full reaction for 3 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 9mL of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.2g of graphite oxide reaction precursor and deionized water at 40 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) of 2: 4000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 4 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 1g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 50 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 6 and the reflectivity loss picture shown in the figure 12 are shown, the real part of the magnetic permeability of the graphene at a frequency point of 17.49GHz is 0.55, and the imaginary part of the graphene is 0.17; the real part of the dielectric constant is-15.66 and the imaginary part is 103.44.
Example 6
A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder comprises the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) 20g of natural crystalline flake graphite (C) and 12g of potassium persulfate (K) were weighed in a stoichiometric ratio of 10: 6: 5: 40, respectively2S2O8) 10g of phosphorus pentoxide (P)2O5) And 80mL of 98% concentrated sulfuric acid by mass concentration, and 4 raw materials are used in total;
(2) mixing the 4 raw materials in a four-neck flask, placing the mixture in a constant-temperature water bath at 80 ℃ under the stirring condition, and reacting for 8 hours at the stirring speed of 180 r/min;
(3) diluting with deionized water, washing to neutrality, vacuum-filtering with a vacuum pump, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
(1) weighing 2g of pre-oxidized graphite precursor (g), 30mL of 98% concentrated sulfuric acid (mL) and 8g of potassium permanganate (g), mixing the pre-oxidized graphite precursor and the 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate at the speed of 1g/min while stirring to obtain a mixture;
(2) placing the mixture in a constant-temperature water bath at 35 ℃, and electrically stirring for fully reacting for 4 hours to prepare dark green viscous liquid;
(3) measuring 92mL of first deionized water, 280mL of second deionized water and 10mL of hydrogen peroxide;
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and after 15min, adding a second part of deionized water and hydrogen peroxide to prepare a bright yellow solution;
(3) filtering the bright yellow solution, washing the bright yellow solution by using dilute hydrochloric acid with the mass concentration of 10%, and washing the bright yellow solution by using deionized water until the pH value is 6.5 to obtain a mixed solution;
(4) and drying the mixed solution in a blast drying oven, and grinding to obtain the graphite oxide reaction precursor.
Step 3, preparing a graphene oxide dispersion liquid:
(1) mixing 0.3g of graphite oxide reaction precursor and deionized water at 50 ℃ under the condition of electric stirring according to the ratio of the graphite oxide reaction precursor (g) to the deionized water (mL) of 3: 5000 to prepare brown turbid liquid;
(2) carrying out ultrasonic oscillation on the brown turbid liquid in an ultrasonic oscillator for 6 hours to fully disperse the brown turbid liquid to prepare brown graphene oxide dispersion liquid;
(1) respectively measuring or weighing 200mL of graphene oxide dispersion liquid and 2g of zinc powder, adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 50 ℃, and fully mixing under electric stirring to obtain a mixture with black precipitates;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying in a forced air drying oven, and then grinding to obtain the graphene with the wave absorption performance.
The scanning electron microscope picture of the graphene with the wave absorbing property shown in the figure 7 and the reflectivity loss picture shown in the figure 13 are shown, the real part of the magnetic permeability of the graphene at a frequency point of 5.08GHz is 0.35, and the imaginary part of the graphene is 0.04; the real part of the dielectric constant is 178.26 and the imaginary part is 102.53.
Claims (7)
1. A method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder is characterized by comprising the following steps:
step 1, generating a reaction pre-oxidized graphite precursor:
(1) according to the stoichiometric ratio, natural crystalline flake graphite (C) and potassium persulfate (K)2S2O8) Phosphorus pentoxide (P)2O5) Concentrated sulfuric acid (H) with the mass fraction of 98%2SO4) Weighing the 4 raw materials respectively in a ratio of (8-10) to (4-6) to (3-5) to (38-40);
(2) mixing the 4 raw materials, placing the mixture in a constant-temperature water bath at the temperature of 60-80 ℃ under the stirring condition, and reacting for 6-8 hours;
(3) diluting with deionized water, washing to neutrality, vacuum filtering, drying at room temperature, and grinding to obtain pre-oxidized graphite precursor;
step 2, preparing graphite oxide through secondary oxidation:
(1) respectively weighing or weighing the 3 raw materials according to the mass fraction of a pre-oxidized graphite precursor g, 98% concentrated sulfuric acid mL and potassium permanganate g being (1-3) to (13-15) to (4-8), mixing the pre-oxidized graphite precursor and 98% concentrated sulfuric acid in an ice-water bath, and slowly adding potassium permanganate while stirring to obtain a mixture;
(2) placing the mixture in a constant temperature environment of 30-40 ℃ for full reaction for 2-4 hours to prepare dark green viscous liquid, wherein the full reaction method is to assist electric stirring of the mixture;
(3) measuring a first part of deionized water according to the volume ratio of the concentrated sulfuric acid with the mass fraction of 98% in the step 2(1) to the first part of deionized water (1-3) to (2-4), and measuring the concentrated sulfuric acid with the mass fraction of 98% in the step 2 (1): measuring a second part of deionized water and hydrogen peroxide (28-30) to (1-3);
controlling the temperature of the dark green viscous liquid to be less than or equal to 45 ℃, adding a first part of deionized water, and adding a second part of deionized water and hydrogen peroxide after 12-18 min to prepare a bright yellow solution;
(4) filtering the bright yellow solution, washing with dilute hydrochloric acid, and washing with deionized water until the pH value is 6-6.8 to obtain a mixed solution;
(5) drying the mixed solution, and grinding to obtain a graphite oxide reaction precursor;
step 3, preparing a graphene oxide dispersion liquid:
(1) fully mixing a graphite oxide reaction precursor and deionized water at 30-50 ℃ according to the ratio of the graphite oxide reaction precursor to the deionized water (1-3) to (2000-5000) of mL to prepare brown turbid liquid, wherein the fully mixing method is that electric stirring is adopted;
(2) ultrasonically oscillating the brown turbid liquid to fully disperse the brown turbid liquid to prepare a brown graphene oxide dispersion liquid;
step 4, reducing graphene oxide by zinc powder to prepare graphene:
(1) weighing or weighing the graphene oxide dispersion liquid and zinc powder respectively according to the ratio of the graphene oxide dispersion liquid mL to the zinc powder g (190-210) to (0.5-2), adding the zinc powder into the graphene oxide dispersion liquid in a constant-temperature water bath at 30-50 ℃, and fully mixing to obtain a mixture with black precipitates, wherein the fully mixing method is electric stirring;
(2) and (3) carrying out suction filtration on the mixture with the black precipitate to obtain a filter cake, drying and grinding to obtain the graphene with the wave absorption performance.
2. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in step 1(1), potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid are analytically pure.
3. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in the step 1(2), the stirring speed is 150-270 r/min.
4. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in the step 1(2), the reaction is carried out in a four-neck flask; in the step 2(2), the constant temperature environment is constant temperature water bath; in the step 2(4), drying is carried out by adopting a blast drying oven; in the step 3(2), the ultrasonic oscillation is performed in an ultrasonic oscillator; in the step 4(2), drying is performed by adopting an air-blast drying oven.
5. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in the step 2(1), the slow adding speed is 0.5-1 g/min.
6. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in the step 2(4), the mass concentration of dilute hydrochloric acid is 5-15%.
7. The method for preparing graphene with wave-absorbing property by reducing graphene oxide with zinc powder according to claim 1, wherein in the step 3(2), ultrasonic oscillation is carried out for 4-6 h.
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