CN111099584A - Graphene uniformly coated with nano ferroferric oxide magnetic particles and preparation method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000006249 magnetic particle Substances 0.000 title claims abstract description 48
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 230000009471 action Effects 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 11
- 239000011358 absorbing material Substances 0.000 abstract description 10
- 238000011160 research Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 238000007619 statistical method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention discloses graphene uniformly coated with nano ferroferric oxide magnetic particles and a preparation method thereof. The ferroferric oxide coated on the surface of the graphene, which is obtained by the method, is very uniform, and the method is simple in process, low in cost and beneficial to realization of industrial production. Meanwhile, the invention mainly discusses the microwave absorption performance of the coating material, researches the relationship between the performance and different coating structures, provides a performance-structure relationship theory and provides a reference basis for preparing the wave-absorbing material with more excellent performance by subsequent design.
Description
Technical Field
The invention belongs to the technical field of preparation of nano composite materials, and particularly relates to a method for uniformly coating nano ferroferric oxide magnetic particles with graphene and establishment of a relation between coating structure and performance of a wave-absorbing material.
Background
Graphene is a research hotspot due to excellent mechanical, electrical, thermal, high specific surface area and other properties. The modification of graphene is also widely studied by more and more scholars. The modified graphene can overcome defects such as difficult dispersion and endow the modified graphene with new properties such as magnetism, electricity, optics and the like. The graphene coated by the magnetic particles can show more excellent characteristics of magnetism, electromagnetic wave absorption and the like. However, despite various reports and attempts, none of these coatings are particularly uniform, even with many agglomerates. The performance stability and the use of the ferroferric oxide coated graphene material are seriously influenced, and the performance stability and the use are uncontrollable and have no repeatability.
In addition, most of the current work is focused on improving the wave absorbing performance of the wave absorbing material, but neglects the discussion of the wave absorbing influence factors. In fact, the shape, size and microstructure of the material all play a crucial role in the wave-absorbing performance. At present, reports on the influence of the coating structure on the wave absorption performance are still less, and the mechanism is not clear yet. Therefore, the research on the relationship between the two has important reference significance.
Disclosure of Invention
In order to overcome the defects of non-uniformity and uncontrollable of ferroferric oxide coated graphene prepared by the existing method, the invention aims to provide a method for uniformly coating graphene with nano ferroferric oxide magnetic particles which are uniformly coated and have magnetic performance and better electromagnetic absorption performance. The method is prepared by adopting a polyol method, takes graphene and ferric salt as raw materials, and synthesizes ferroferric oxide coated graphene under an alkaline environment through the reduction action of an alcohol solvent. The preparation method is simple and easy to implement, and the result repeatability is good and easy to control.
In addition, the preparation method is changed, two different coating structure materials are prepared under the condition of controlling the same coating proportion, the wave absorbing performance of the materials is researched, and the wave absorbing performance of the coating material with uniform and compact coating is found to be better. Further, on the basis of a compact coating structure, the coating proportion is improved, and a coating material with more excellent comprehensive performance is obtained.
In order to achieve the purpose, the technical scheme of the invention is as follows:
graphene uniformly coated with nano ferroferric oxide magnetic particles is carboxylated reduced graphene oxide, the sheet size of the graphene is 0.5-3 mu m, the thickness of each single sheet is 0.55-3.74nm, and the number of the sheet layers is less than 10; the ferroferric oxide magnetic particles coated on the surface are granular, the particle size range is 5-12nm, the coating is uniform and compact, no impurities exist, and the coating rate is more than 95%.
A method for uniformly coating graphene with nano ferroferric oxide magnetic particles comprises the following steps:
1) according to the graphene: adding graphene into an alcoholic solution with the mass-to-volume ratio (g: mL) of the alcoholic solution being 1: 100-500, and stirring to obtain a graphene dispersion solution;
2) according to the iron salt: adding iron salt into a graphene dispersion solution according to the mass ratio of 1: 1-5: 1 of graphene, and carrying out cell crushing and ultrasonic treatment to obtain a mixed solution containing the iron salt and the graphene;
3) according to the alkaline solution (6 mol/L): dispersing an alkali solution into the alcohol solution at a volume ratio of 1-4: 10, and uniformly stirring to obtain an alkali alcohol solution;
4) adding an alkaline alcohol solution into a mixed solution containing ferric salt and graphene, performing cell crushing and ultrasonic treatment, transferring the obtained solution into a reaction kettle, and reacting at 180-240 ℃ for 2-4 hours;
5) and after the reaction is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, washing to be neutral under the centrifugal action, and drying in vacuum to obtain the graphene powder coated by the nano ferroferric oxide magnetic particles.
The graphene coated by the nano ferroferric oxide magnetic particles is Fe prepared in the atmospheric environment3O4The magnetic nano-particle coated graphene is characterized in that the ferroferric oxide magnetic nano-particles are uniformly coated, and the particle size of the magnetic nano-particle coated graphene is 5-12 nm.
The graphene is carboxylated reduced graphene oxide, the flake size of the graphene is 0.5-3 mu m, the thickness of each single flake is 0.55-3.74nm, and the number of the flakes is less than 10.
The iron salt is any one of ferric acetylacetonate, ferrous acetylacetonate and ferrous sulfate.
The alkali solution is sodium hydroxide solution or ammonia water.
The alcohol solution is triethylene glycol, ethylene glycol or diethylene glycol.
Fe of the invention3O4The graphene coated by the nano magnetic particles has the structural characteristics that: the ferroferric oxide magnetic particles on the surface are granular, the size range is 5-12nm, the average particle size is 7.81nm, the coating is uniform and compact, no impurities exist, and the coating rate can reach more than 95%.
Fe of the invention3O4One of the excellent properties of the magnetic nanoparticle-coated graphene is: through carrying out magnetic particle cladding to graphite alkene, effectively improved its electromagnetic absorption efficiency, and its inhale the wave efficiency and be adjustable according to the change of cladding structure.
According to the change, the comparison with the material coated with the sparse structure shows that the wave absorbing performance corresponding to different coating structures is quite different. Namely, under the condition that the coating proportion of the two is the same, when the coating structure is denser, the integral wave-absorbing efficiency is higher, thereby establishing the theoretical basis of structure-performance. When the coating proportion is adjusted subsequently, the wave-absorbing material with more excellent wave-absorbing performance is obtained according to a more excellent coating structure (namely, the coating rate is more than 95%, the coating is compact, uniform and free of impurities, and the average particle size of the coated particles is 7.81 nm).
According to the prepared different coating structures, the invention discovers that when the coating proportion is the same, the coating particles are uniform and compact, and the wave-absorbing valley value and the effective wave-absorbing bandwidth in the microwave absorption performance are more excellent. According to the deduction, the wave-absorbing material with excellent wave-absorbing comprehensive performance is obtained by improving the coating proportion on the basis of a compact coating structure, and the wave-absorbing valley value of the wave-absorbing material can reach-40.07 dB when the wave-absorbing material is 2mm thick.
Compared with a patent of coating the carbon nanotube, the carbon nanotube is a one-dimensional material, the graphene is a two-dimensional material, and differences of structures, specific surface areas and surface defects can cause differences of distribution of iron ions in the carbon nanotube, so that different coating structures are caused. So how to obtain a uniformly coated structure is the focus. Since graphene has a large specific surface area and is easily agglomerated, and thus, the coating is not uniform, the difficulty of non-uniform dispersion needs to be overcome. The invention just overcomes the technical problem that the graphene coating is easy to disperse and uneven, and the coating structure can be more uniform and compact by adopting the coating method.
In addition, the patent relates to the research on the relation between the coating structure and the wave-absorbing performance, and the performance of the coating sample related to the graphene is improved according to the theoretical basis, so that the obtained compact coating structure is more favorable for microwave absorption, and the technical effect which cannot be achieved by carbon nanotube coating is achieved.
The method is based on graphene, and adopts a polyol method to coat the graphene to prepare uniform Fe-coated film3O4Graphene coated with nano-magnetic particles; compared with the prior art, the invention has the following advantages:
1. fe of the invention3O4The graphene coated by the nano magnetic particles is very uniform, has no impurities and has a controllable structure.
2. The preparation method of the invention has simple process and low cost, and is easy to realize industrial production.
3. The invention provides Fe3O4The graphene uniformly coated with the nano magnetic particles has greatly improved electromagnetic absorption efficiency, and can be used in the fields of electromagnetic absorption and the like.
4. The invention can correspondingly adjust the wave-absorbing performance by adjusting the cladding structure and establish a structure-performance theoretical model to provide a basis for preparing the wave-absorbing material with excellent performance by subsequent design.
Drawings
FIG. 1 shows the nano Fe obtained in example 13O4Scanning electron microscopy of magnetic particle coated graphene;
FIG. 2 shows the nano-Fe obtained in example 13O4Transmission electron microscopy of magnetic particle coated graphene;
FIG. 3 shows the nano-Fe obtained in example 13O4A particle size distribution statistical histogram of ferroferric oxide particles coated on graphene coated with magnetic particles;
FIG. 4 shows the nano-Fe obtained in example 13O4The electromagnetic absorption efficiency of the magnetic particle coated graphene under different wave bands and different thicknesses is improved;
FIG. 5 shows the nano Fe obtained in example 23O4Transmission electron microscopy of magnetic particle coated graphene;
FIG. 6 shows the nano Fe obtained in example 23O4The electromagnetic absorption efficiency of the magnetic particle coated graphene under different wave bands and different thicknesses is improved;
FIG. 7 shows the nano-Fe obtained in example 33O4Transmission electron microscopy of magnetic particle coated graphene;
FIG. 8 shows the nano-Fe obtained in example 43O4The electromagnetic absorption efficiency of the magnetic particle coated graphene under different wave bands and different thicknesses is improved.
Detailed Description
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
1) Placing 20mL of triethylene glycol into a dry and clean 100mL beaker, adding 0.1g of graphene, and stirring to obtain a graphene dispersion solution;
2) adding 0.1g of ferric acetylacetonate into the dispersion solution, and carrying out cell crushing and ultrasonic treatment for 5min to obtain a mixed solution containing ferric salt and graphene;
3) preparing 6mol/L aqueous solution of sodium hydroxide;
4) taking another dry and clean 50mL beaker, adding 10mL of triethylene glycol, adding 2mL of the sodium hydroxide solution, and uniformly stirring to obtain an alkaline alcohol solution;
5) adding an alkaline alcohol solution into a mixed solution containing ferric salt and graphene, and then carrying out cell crushing and ultrasonic treatment for 5 min;
6) transferring the solution obtained in the step 5) into a reaction kettle, putting the reaction kettle into an oven, and reacting for 2 hours at 200 ℃;
7) and after the reaction in the step 6) is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, repeatedly washing under the centrifugal action until the pH value is 6-8, and drying in vacuum to obtain graphene powder uniformly coated with the nano ferroferric oxide magnetic particles. Wherein, the Fe3O4Fe in nano-magnetic particle coated graphene3O4The particle diameter of the nano magnetic particle is 5-12 nm.
The scanning electron microscope, the transmission electron microscope and the statistical analysis of the particle size of the coated particles were performed on the graphene powder uniformly coated with the nano ferroferric oxide magnetic particles obtained in this example, and the results are shown in fig. 1, fig. 2 and fig. 3. As can be seen from fig. 1 and 2, the ferroferric oxide is coated on the surface of the graphene uniformly, and has no agglomeration (high rate, fig. 2) or excessive impurities (low rate, fig. 1), and the coating rate can reach more than 95%. As can be seen from FIG. 3, the ferroferric oxide coated on the surface of the graphene has small particle size which is distributed between 5 nm and 12nm, and the average particle size is 7.81 nm.
The electromagnetic absorption efficiency analysis of the graphene powder uniformly coated with nano-ferroferric oxide magnetic particles obtained in the present example was performed, and the results are shown in fig. 4, in which the sample had a low overall attenuation valley value and a sharp attenuation peak, and the wave absorption attenuation valley values at 1.5, 2, 2.5, 3, 3.5, and 4mm were-12.86 dB (11.3GHz), -13.65dB (8.2GHz), -14.02dB (6.4GHz), -13.61dB (5.3GHz), -12.15dB (4.4GHz), and-11.54 dB (3.8GHz), respectively.
Example 2 (comparative example)
1) Placing 50mL of triethylene glycol into a dry and clean 100mL beaker, adding 0.1g of graphene, and stirring to obtain a graphene dispersion solution;
2) adding 0.1g of ferrous acetylacetonate into the dispersion solution, and performing cell crushing and ultrasonic treatment for 10min to obtain a mixed solution containing iron salt and graphene (the step ensures that the coating proportion is the same as that of the embodiment 1);
3) transferring the solution obtained in the step 2) into a reaction kettle, putting the reaction kettle into an oven, and reacting for 4 hours at 200 ℃;
4) after the reaction in the step 3) is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, repeatedly washing under the centrifugal action until the pH value is 6-8, and performing vacuum drying to obtain the graphene powder control group uniformly coated with the nano ferroferric oxide magnetic particles.
The transmission electron microscope analysis of the graphene powder uniformly coated with the nano ferroferric oxide magnetic particles obtained in this example is performed, and the result is shown in fig. 5. As can be seen from FIG. 5, the ferroferric oxide is sparsely and unevenly coated on the surface of the graphene, and the coating rate is low.
The electromagnetic absorption efficiency analysis of the graphene powder uniformly coated with the nano ferroferric oxide magnetic particles obtained in this example is performed, and the result is shown in fig. 6. As can be seen from FIG. 6, the wave-absorbing attenuation valleys at 2, 2.5, 3, 3.5 and 4mm are-6.63 dB (17.7GHz), -6dB (14.1GHz), -5.16dB (11.2GHz), -4.92dB (9.4GHz) and-4.7 dB (8.6GHz), respectively, which is significantly worse than the absorption efficiency in example 1. The result shows that even under the same coating proportion, the wave absorbing materials with different coating structures have obvious difference in wave absorbing efficiency. Wherein, the material with uniform and compact coating structure has better wave-absorbing performance.
Example 3
1) Putting 50mL of ethylene glycol into a dry and clean 100mL beaker, adding 0.1g of graphene, and stirring to obtain a graphene dispersion solution;
2) adding 0.4g of ferrous acetylacetonate into the dispersion solution, and carrying out cell crushing and ultrasonic treatment for 5min to obtain a mixed solution containing ferric salt and graphene;
3) preparing ammonia water into 6mol/L aqueous solution;
4) adding 10mL of glycol into another dry and clean 50mL beaker, adding 4mL of the ammonia water solution, and uniformly stirring to obtain an alkaline alcohol solution;
5) adding an alkaline alcohol solution into a mixed solution containing ferric salt and graphene, and then carrying out cell crushing and ultrasonic treatment for 5 min;
6) transferring the solution obtained in the step 5) into a reaction kettle, putting the reaction kettle into an oven, and reacting for 2 hours at 240 ℃;
7) and after the reaction in the step 6) is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, repeatedly washing under the centrifugal action until the pH value is 6-8, and drying in vacuum to obtain graphene powder uniformly coated with the nano ferroferric oxide magnetic particles.
The transmission electron microscope analysis of the graphene powder uniformly coated with the nano ferroferric oxide magnetic particles obtained in this example is performed, and the result is shown in fig. 7. As can be seen from FIG. 7, the ferroferric oxide is coated on the surface of the graphene to be compact, uniform and impurity-free.
Example 4
1) Putting 10mL of diethylene glycol into a dry and clean 100mL beaker, adding 0.1g of graphene, and stirring to obtain a graphene dispersion solution;
2) adding 0.5g of ferrous sulfate into the dispersion solution, and carrying out cell crushing and ultrasonic treatment for 5min to obtain a mixed solution containing iron salt and graphene;
3) preparing 6mol/L aqueous solution of sodium hydroxide;
4) taking another dry and clean 50mL beaker, adding 10mL of diglycol, adding 1mL of the sodium hydroxide solution, and uniformly stirring to obtain an alkaline alcohol solution;
5) adding an alkaline alcohol solution into a mixed solution containing ferric salt and graphene, and then carrying out cell crushing and ultrasonic treatment for 5 min;
6) transferring the solution obtained in the step 5) into a reaction kettle, putting the reaction kettle into a drying oven, and reacting for 4 hours at 180 ℃;
7) and after the reaction in the step 6) is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, repeatedly washing under the centrifugal action until the pH value is 6-8, and drying in vacuum to obtain graphene powder uniformly coated with the nano ferroferric oxide magnetic particles.
The electromagnetic absorption efficiency analysis of the graphene powder uniformly coated with the nano ferroferric oxide magnetic particles obtained in this example is performed, and the result is shown in fig. 8. As can be seen from FIG. 8, the valley of the wave absorption is lower at thicknesses of 2.0, 3.5 and 4.0mm, wherein the valley of the wave absorption at thickness of 2.0mm can be as low as-40.07 dB, and the corresponding valleys at other thicknesses of 1.5, 2.5, 3, 3.5 and 4mm are-14.64, -17.17, -25.8, -37.22 and-30.37 dB, respectively. In addition, the effective wave-absorbing bandwidth (< -10dB) gradually increases along with the thinning of the thickness, and when the thickness is 1.75mm, the effective wave-absorbing bandwidth area reaches 5.5GHz at most. The result shows that according to the structure-performance relation model, the wave-absorbing material with more excellent wave-absorbing performance can be obtained through design, and the effectiveness of the relation model is laterally proved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. Graphene uniformly coated with nano ferroferric oxide magnetic particles is characterized in that the graphene is carboxylated reduced graphene oxide, the size of a sheet is 0.5-3 mu m, the thickness of a single sheet is 0.55-3.74nm, and the number of the sheets is less than 10; the ferroferric oxide magnetic particles coated on the surface are granular, the particle size range is 5-12nm, the coating is uniform and compact, no impurities exist, and the coating rate is more than 95%.
2. A method for uniformly coating graphene with nano ferroferric oxide magnetic particles comprises the following steps:
1) according to the graphene: adding graphene into an alcohol solution at a mass-to-volume ratio of 1: 100-500, and stirring to obtain a graphene dispersion solution;
2) according to the iron salt: adding iron salt into a graphene dispersion solution according to the mass ratio of 1: 1-5: 1 of graphene, and performing crushing and ultrasonic treatment to obtain a mixed solution containing the iron salt and the graphene;
3) according to the alkaline solution: the volume ratio of the alcoholic solution is 1-4: 10 dispersing an alkali solution into an alcohol solution, and uniformly stirring to obtain an alkali alcohol solution;
4) adding an alkaline alcohol solution into a mixed solution containing ferric salt and graphene, performing cell crushing and ultrasonic treatment, transferring the obtained solution into a reaction kettle, and reacting at 180-240 ℃ for 2-4 hours;
5) and after the reaction is finished and the temperature is reduced to room temperature, filtering under the action of a magnet, washing to be neutral under the centrifugal action, and drying in vacuum to obtain the graphene powder coated by the nano ferroferric oxide magnetic particles.
3. The method for uniformly coating graphene with nano ferroferric oxide magnetic particles according to claim 2, wherein the graphene is carboxylated reduced graphene oxide, the sheet size of the graphene is 0.5-3 μm, the thickness of each single sheet is 0.55-3.74nm, and the number of the sheets is less than 10.
4. The method for uniformly coating graphene with nano ferroferric oxide magnetic particles according to claim 2, wherein the alcoholic solution is triethylene glycol, ethylene glycol or diethylene glycol.
5. The method for uniformly coating graphene with nano ferroferric oxide magnetic particles according to claim 2, wherein the iron salt is any one of ferric acetylacetonate, ferrous acetylacetonate and ferrous sulfate.
6. The method for uniformly coating graphene with nano ferroferric oxide magnetic particles according to claim 2, wherein the alkali solution is sodium hydroxide solution or ammonia water.
7. The method for uniformly coating graphene with nano ferroferric oxide magnetic particles according to claim 2, wherein the particle size of the nano ferroferric oxide magnetic particles coated on the graphene powder coated with the nano ferroferric oxide magnetic particles is 5-12nm, and the coated particles are uniform and compact.
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| CN112003026A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院兰州化学物理研究所 | Reduced graphene oxide/ferroferric oxide/aluminum nitride composite material wave absorbing agent, preparation method thereof and wave absorbing material |
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| CN112003026A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院兰州化学物理研究所 | Reduced graphene oxide/ferroferric oxide/aluminum nitride composite material wave absorbing agent, preparation method thereof and wave absorbing material |
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