CN113329604B - Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material - Google Patents
Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material Download PDFInfo
- Publication number
- CN113329604B CN113329604B CN202110542484.2A CN202110542484A CN113329604B CN 113329604 B CN113329604 B CN 113329604B CN 202110542484 A CN202110542484 A CN 202110542484A CN 113329604 B CN113329604 B CN 113329604B
- Authority
- CN
- China
- Prior art keywords
- electromagnetic wave
- composite material
- wave absorption
- absorption composite
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/007—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems with means for controlling the absorption
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/008—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems with a particular shape
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention provides a preparation method of a manganese sulfide and graphene electromagnetic wave absorption composite material, and belongs to the field of electromagnetic wave absorption material preparation and electromagnetic wave protection technologies. The invention adopts a hydrothermal and heat treatment two-step method for synthesis, and Mn (NO) is mixed according to a certain proportion 3 ) 2 、C 3 H 7 NO 2 S and urea are sequentially added into GO dispersion liquid, then constant temperature reaction is carried out for 18-28 hours at 140-180 ℃, and after freeze drying, reaction is carried out in argon at 1-5 ℃ for min ‑1 Heating at a heating rate, carrying out heat treatment at the temperature of 400-600 ℃ for 2-6 hours, and cooling to room temperature under the protection of argon after the heat treatment is finished, thus finally obtaining the shell-shaped MnS @ rGO electromagnetic wave absorption composite material. The electromagnetic wave absorption composite material prepared by the invention has the advantages of ultrathin and light weight, simple preparation process and low cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of electromagnetic wave absorbing materials and electromagnetic wave protection, and particularly relates to preparation of a shell-shaped manganese sulfide and graphene nanocomposite material designed as an electromagnetic wave absorber.
Background
With the intensive research of the 5G technology, the applications of various intelligent electronic devices become common, and a large amount of redundant electromagnetic radiation is generated, so that the electromagnetic interference caused by the electromagnetic radiation is increasingly serious, which becomes an important cause of the failure of the electronic devices. In addition, electromagnetic leakage and contamination from electromagnetic radiation can cause serious damage to the health of humans or other living organisms. In the military field, electromagnetic warfare has become a conventional means of modern combat, and highly information-based high-precision weapon systems face severe electromagnetic threats during service. In conclusion, the electromagnetic wave absorbing and protecting material has great application requirements in civil use and military use, and the development technology of the electromagnetic wave absorbing material is the key of the national civilization.
The ideal wave-absorbing material has the advantages of thickness, light weight, wide frequency band and strong absorption, the thin thickness and the light weight are two important indexes in the design process of the electromagnetic wave-absorbing material, and the thin and light electromagnetic wave-absorbing material has important application requirements. According to different wave-absorbing mechanisms, wave-absorbing materials can be divided into dielectric loss, magnetic loss and dielectric-magnetic synergistic loss wave-absorbing materials. Carbon materials, conductive ceramics, conductive polymers, and the like absorb electromagnetic waves mainly through dielectric loss and conductive loss. The dielectric loss mainly arises from dipole polarization, interface polarization, alternating induced micro-current, and the like. The magnetic materials include conventional ferrite, magnetic metal powder and carbonyl iron, and absorption of electromagnetic waves is mainly accomplished by magnetic resonance loss and eddy current loss.
The MnS @ rGO composite material is widely reported and is mainly used for preparing high-efficiency energy storage and conversion devices, including battery electrode materials and catalytic materials. For example, xu Xijun et al prepared high capacity and long life lithium and sodium ion battery anode materials using mns @ rgo composites (see ACS appl. Mater. Interfaces 2015,7,20957-20964). Gao Xu et al synthesized alpha-MnS/graphene foam composites and designed as battery electrode materials. (see Energy Storage Materials 2019,16,46-55). These work designs MnS @ rgo composites as electrodes can be used as substitutes for traditional graphite-based negative electrode materials mainly because MnS has high reversible capacity. The main consideration of the electrode material in the battery is the energy density and stability of the material, while the mns @ rgo composite material has relatively few studies on the loss and absorption of electromagnetic waves. Chen Dezhi and the like research the electromagnetic wave absorption performance of the hollow alpha-MnS/rGO composite material, however, the designed and prepared hollow alpha-MnS/rGO electromagnetic wave absorption composite material has the defects of high addition amount and large thickness, and cannot meet the application requirement of the thin and light electromagnetic wave absorption material. Therefore, it is necessary to design a thin and light MnS/rGO electromagnetic absorption composite material with low addition and small thickness by regulating and controlling the structure and the loading amount.
Disclosure of Invention
The invention provides a design and preparation method of a shell-shaped MnS @ rGO electromagnetic wave absorption composite material aiming at the defects of high additive amount and large thickness of the existing MnS/rGO electromagnetic wave absorption composite material. The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material not only has the advantages of ultrathin and light weight, but also has the advantages of simple preparation process and low cost, does not need to use highly toxic chemical reagents in the preparation process, and is suitable for large-scale industrial production.
The invention relates to a preparation method of a shell-shaped MnS @ rGO electromagnetic wave absorption composite material, which comprises the following steps:
(1) Under the condition of magnetic stirring, mn (NO) is added according to a certain proportion 3 ) 2 、C 3 H 7 NO 2 And S and urea are sequentially added into the GO (graphene oxide) dispersion liquid, and are strongly stirred for 20-40 minutes to obtain a uniformly mixed solution.
(2) Transferring the mixed solution obtained in the step (1) into a Teflon lining, then sealing the Teflon lining into a stainless steel reaction kettle, and carrying out constant temperature reaction at 140-180 ℃ for 18-28 hours.
(3) After the reaction in the step (2) is finished, cooling to room temperature in a fume hood, centrifugally cleaning the reaction product by using deionized water and absolute ethyl alcohol, freezing the obtained reaction product at-10 to-20 ℃, and freeze-drying in a vacuum freeze dryer at-40 to-60 ℃ to obtain a primary reaction product.
(4) Finally, the primary reaction product is put in argon at 1-5 ℃ min -1 Heating at a heating rate, carrying out heat treatment at the temperature of 400-600 ℃ for 2-6 hours, and cooling to room temperature under the protection of argon after the heat treatment is finished, thus finally obtaining the nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material.
A certain proportion of Mn (NO) as described in step (1) 3 ) 2 、C 3 H 7 NO 2 S and urea, is Mn (NO) 3 ) 2 、C 3 H 7 NO 2 The molar mass ratio of S to urea is 1:1 (1-3), mn (NO) 3 ) 2 The mass concentration of the solution was 50wt.%.
The GO dispersion liquid in the step (1) is obtained by uniformly dispersing GO powder in deionized water through a high-frequency ultrasonic cleaning machine and continuously performing ultrasonic dispersion for 1-3 hours, wherein the concentration of the GO dispersion liquid is 0.5-3 mg/mL.
The centrifugal cleaning in the step (3) is carried out for 1-3 times, the obtained reaction product is frozen for 2-5 hours at the temperature of-10 to-20 ℃, and the freeze drying is carried out for 12-48 hours in a vacuum freeze dryer at the temperature of-40 to-60 ℃.
The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material is applied to electromagnetic wave absorption or electromagnetic protection facilities.
The invention adopts a hydrothermal and heat treatment two-step method for synthesis, perfects the research of MnS @ rGO nano composite material as a high-performance electromagnetic wave absorption material, provides a new selection and direction for a new generation of applicable electromagnetic wave absorption material, and has the following beneficial effects compared with the prior art:
(1) The graphene has the characteristics of large specific surface area, small density and the like, the conductivity of the graphene is reduced by the generation of the shell-shaped manganese sulfide between graphene layers, the impedance matching of the electromagnetic wave absorption composite material is regulated and controlled through the synergistic effect of the two materials, and the fact that most of electromagnetic waves can be incident into the material and are converted into heat energy to be dissipated is ensured. In addition, because the shell-shaped manganese sulfide is provided with the cavity, incident electromagnetic waves can be reflected and scattered for many times in the cavity, and the loss path of the electromagnetic waves is prolonged, so that the wave absorbing capacity of the composite wave absorbing material is greatly improved.
(2) The shell-shaped MnS @ rGO electromagnetic wave absorption composite material prepared by the invention has the advantages of thinness and lightness, wide wave absorption frequency band and high absorption strength, and the preparation process is simple, does not need a template and complex hardware equipment, and has lower manufacturing cost.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the reaction-synthesized nutshell MnS/rGO electromagnetic wave absorption composite material of example 1;
FIG. 2 is an X-ray diffraction pattern of the fructiform MnS/rGO of example 1;
FIG. 3 is a reflection loss curve of a sample of example 1 added at 30%;
FIG. 4 is a reflection loss curve of the sample of example 2 added at 30%;
FIG. 5 is a reflection loss curve of the sample of example 3 added in an amount of 40%;
FIG. 6 is a reflection loss curve of a sample of example 4 added at 30%.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description will be given with reference to the accompanying drawings and specific examples and comparative examples. The examples and comparative examples are only to aid understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
(1) 1.432g of Mn (NO) with a mass concentration of 50wt.% is measured 3 ) 2 Solution, 0.968g of L-cysteine (C) was weighed 3 H 7 NO 2 S) and 0.24g of urea, and standing for later use. Wherein Mn (NO) 3 ) 2 、C 3 H 7 NO 2 The molar mass ratio of S to urea is 1.
(2) Weighing 120mg of GO powder, uniformly dispersing the weighed GO powder in 60mL of deionized water, and dispersing for 2 hours in a high-frequency ultrasonic cleaning machine to obtain a GO dispersion liquid with the concentration of 2 mg/mL.
(3) Under the condition of magnetic stirring, weighing Mn (NO) 3 ) 2 、C 3 H 7 NO 2 And S and urea are sequentially added into the GO dispersion liquid and stirred for 30 minutes to obtain 60mL of uniform mixed solution.
(4) The homogeneous mixed solution was poured into a Teflon liner, followed by enclosing in a stainless steel autoclave and reacting at a constant temperature of 160 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature in a fume hood, and the reaction products were each centrifugally washed three times with deionized water and anhydrous ethanol.
(5) The resulting reaction product was frozen at-20 ℃ for 3 hours, and then the reaction product was put into a freeze dryer and vacuum dried at-50 ℃ for 24 hours. A pure and dry preliminary reaction product is obtained.
(6) Most preferablyThen, the preliminary reaction product after vacuum drying was put in argon at 3 ℃ for min -1 Is heated to 500 c for 4 hours. And after the heat treatment is finished, cooling to room temperature under the protection of argon to obtain the nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material. Fig. 1 is an SEM image of a nutshell MnS/rGO electromagnetic wave absorption composite material, and it can be observed that the nutshell MnS half microspheres are partially coated by rGO nanosheets. The unique half-coated fruit-shell structure can regulate and control impedance matching, prolong the transmission path of electromagnetic waves and greatly promote the loss absorption of the electromagnetic waves. FIG. 2 is an X-ray diffraction spectrum of a nutshell MnS @ rGO electromagnetic wave absorption composite material, and it can be concluded that no impurities are introduced in the preparation process of the composite material, and the prepared sample has high purity.
(7) The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material is uniformly mixed with paraffin to prepare a coaxial sample. The inner diameter of the sample was 3.0mm, the outer diameter was 7.0mm, and the thickness was 2.0mm. Three groups of different samples are obtained according to different addition amounts of the shell-shaped MnS @ rGO electromagnetic wave absorption composite material in paraffin, the filling amount of the paraffin is fixed to be 0.5g and is unchanged, and the addition proportions of the composite material in each group are respectively 20%,30% and 40%, so that the total mass of the samples is determined. Then, the electromagnetic parameters of the three groups of samples are measured by a full-automatic vector network parameter sweep frequency measuring system (HP-8722 ES) by adopting a coaxial reflection-transmission network method.
FIG. 3 is the electromagnetic wave absorption performance of the eggshell-like MnS @ rGO with an addition amount of 30 wt.%. The MnS @ rGO120-30% has the best electromagnetic wave absorption performance in the frequency range of 2-18GHz, and the full absorption of the electromagnetic wave in the frequency range of 8-18GHz can be realized by regulating and controlling the thickness at 2.2 mm; the effective wave-absorbing bandwidth can reach 3.9GHz under the ultrathin thickness of 1.3mm, and the maximum reflection loss peak value can reach-39.5 dB.
Example 2
(1) 1.432g of Mn (NO) with a mass concentration of 50wt.% is measured 3 ) 2 Solution, 0.968g of L-cysteine (C) was weighed 3 H 7 NO 2 S) and 0.72g of urea, standing for later use. Wherein Mn (NO) 3 ) 2 、C 3 H 7 NO 2 The molar mass ratio of S to urea is 1:1:3.
(2) Weighing 120mg of GO powder, uniformly dispersing the weighed GO powder in 60mL of deionized water, and dispersing in a high-frequency ultrasonic cleaning machine to obtain GO dispersion liquid with the concentration of 2 mg/mL.
(3) Weighing Mn (NO) under the condition of magnetic stirring 3 ) 2 、C 3 H 7 NO 2 And S and urea are sequentially added into the GO dispersion liquid, and stirred for 30 minutes to obtain 60mL of uniform mixed solution.
(4) The homogeneous mixed solution was poured into a Teflon liner, followed by enclosing in a stainless steel autoclave and reacting at a constant temperature of 160 ℃ for 24 hours. After the reaction was complete, it was cooled to room temperature in a fume hood. The products of the reaction were each washed three times centrifugally with deionized water and absolute ethanol.
(5) The resulting hydrothermal reaction product was frozen at-20 ℃ for 3 hours, and then the reaction product was put into a freeze dryer and vacuum dried at-50 ℃ for 24 hours. A pure and dry preliminary reaction product is obtained.
(6) Finally, the preliminary reaction product after vacuum drying is put in argon at 3 ℃ for min -1 Is heated to 500 c for 4 hours. And after the heat treatment is finished, cooling to room temperature under the protection of argon to obtain the nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material.
(7) The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material is uniformly mixed with paraffin to prepare a coaxial sample. The inner diameter of the specimen was 3.0mm, the outer diameter was 7.0mm, and the thickness was 2.0mm. Three groups of different samples are obtained according to different addition amounts of the shell-shaped MnS @ rGO electromagnetic wave absorption composite material in paraffin, the filling amount of the paraffin is fixed to be 0.5g and is unchanged, and the addition proportions of the composite material in each group are respectively 20%,30% and 40%, so that the total mass of the samples is determined. And then measuring the electromagnetic parameters of the three groups of samples by a full-automatic vector network parameter sweep frequency measuring system (HP-8722 ES) by adopting a coaxial reflection-transmission network method. FIG. 4 shows the electromagnetic wave absorption performance of the nutshell-like MnS @ rGO added in an amount of 30 wt.%. The peak value of the maximum reflection loss of the MnS microsphere does not exceed-10 dB in the thickness range of 2mm, and the reason that the wave absorbing performance is poor is probably that the concentration of urea is too high, the formation of the MnS microsphere with the core-shell structure is inhibited, multiple reflection can not be caused to incident electromagnetic waves, and the absorption and loss of the electromagnetic waves are not facilitated.
Example 3
(1) 1.432g of Mn (NO) with the mass concentration of 50wt.% is measured 3 ) 2 Solution, 0.968g of L-cysteine (C) was weighed 3 H 7 NO 2 S) and 0.24g of urea, and standing for later use. Wherein Mn (NO) 3 ) 2 、C 3 H 7 NO 2 The molar mass ratio of S to urea is 1.
(2) Weighing 60mg of GO powder, uniformly dispersing the weighed GO powder in 60mL of deionized water, and dispersing in a high-frequency ultrasonic cleaning machine to obtain 1mg/mL GO dispersion liquid.
(3) Under the condition of magnetic stirring, weighing Mn (NO) 3 ) 2 、C 3 H 7 NO 2 And S and urea are sequentially added into the GO dispersion liquid, and 60mL of uniform mixed solution is obtained after stirring for 30 minutes.
(4) The homogeneous mixed solution was poured into a Teflon liner, followed by enclosing in a stainless steel autoclave and reacting at a constant temperature of 160 ℃ for 24 hours. After the reaction was complete, it was cooled to room temperature in a fume hood. The products of the reaction were each washed three times by centrifugation with deionized water and absolute ethanol.
(5) The resulting product was frozen at-20 ℃ for 3 hours, and the reaction product was then placed in a lyophilizer and dried under vacuum at-50 ℃ for 24 hours. A pure and dry preliminary reaction product is obtained.
(6) Finally, the primary reaction product after vacuum drying is carried out at 3 ℃ min in argon -1 Is heated to 500 c for 4 hours. And cooling to room temperature under the protection of argon after the heat treatment is finished to obtain the shell-shaped MnS @ rGO electromagnetic wave absorption composite material.
(7) The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material is uniformly mixed with paraffin to prepare a coaxial sample. The inner diameter of the sample was 3.0mm, the outer diameter was 7.0mm, and the thickness was 2.0mm. Three groups of different samples are obtained according to different addition amounts of the shell-shaped MnS @ rGO electromagnetic wave absorption composite material in paraffin, the filling amount of the paraffin is fixed to be 0.5g and is unchanged, and the addition proportions of the composite material in each group are respectively 20%,30% and 40%, so that the total mass of the samples is determined. Then, the electromagnetic parameters of the three groups of samples are measured by a full-automatic vector network parameter sweep frequency measuring system (HP-8722 ES) by adopting a coaxial reflection-transmission network method.
Fig. 5 is a reflection loss curve of the shelly mns @ rgo electromagnetic wave absorption composite prepared in this example at an addition amount of 40 wt.%. When the thickness is 1.4mm, the effective wave-absorbing bandwidth of the shell-shaped MnS @ rGO electromagnetic wave absorption composite material is increased to 4.3GHz; when the thickness is 1.5mm, the effective reflection loss bandwidth of the shelly MnS @ rGO electromagnetic wave absorption composite material can reach 4.8GHz, and the maximum reflection loss peak value can also reach-36.3 dB.
Example 4
(1) 1.432g of Mn (NO) with the mass concentration of 50wt.% is measured 3 ) 2 Solution, 0.968g of L-cysteine (C) was weighed 3 H 7 NO 2 S) and 0.24g of urea, and standing for later use. Wherein Mn (NO) 3 ) 2 、C 3 H 7 NO 2 The molar mass ratio of S to urea is 1.
(2) Weighing 120mg of GO powder, uniformly dispersing the weighed GO powder in 60mL of deionized water, and dispersing in a high-frequency ultrasonic cleaning machine to obtain a GO dispersion liquid with the concentration of 2 mg/mL.
(3) Under the condition of magnetic stirring, weighing Mn (NO) 3 ) 2 、C 3 H 7 NO 2 And S and urea are sequentially added into the GO dispersion liquid, and stirred for 30 minutes to obtain 60mL of uniform mixed solution.
(4) The uniform mixed solution was poured into a Teflon liner, followed by sealing in a stainless steel autoclave and reacting at a constant temperature of 160 ℃ for 24 hours. After the reaction was complete, it was cooled to room temperature in a fume hood. The products of the reaction were each washed three times centrifugally with deionized water and absolute ethanol.
(5) The resulting product was frozen at-20 ℃ for 3 hours, and the reaction product was then placed in a lyophilizer and dried under vacuum at-50 ℃ for 24 hours. A pure and dry preliminary reaction product is obtained.
(6) Finally, the primary reaction product after vacuum drying is put into argon at 5 ℃ min -1 Is heated to 500 c for 4 hours. And after the heat treatment is finished, cooling to room temperature under the protection of argon to obtain the nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material.
(7) The prepared nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material is uniformly mixed with paraffin to prepare a coaxial sample. The inner diameter of the sample was 3.0mm, the outer diameter was 7.0mm, and the thickness was 2.0mm. Three groups of different samples are obtained according to different addition amounts of the shell-shaped MnS @ rGO electromagnetic wave absorption composite material in paraffin, the filling amount of the paraffin is fixed to be 0.5g and is unchanged, and the addition proportions of the composite material in each group are respectively 20%,30% and 40%, so that the total mass of the samples is determined. And then measuring the electromagnetic parameters of the three groups of samples by a full-automatic vector network parameter sweep frequency measuring system (HP-8722 ES) by adopting a coaxial reflection-transmission network method.
Fig. 6 is a reflection loss curve of the nutshell-shaped mns @ rgo electromagnetic wave absorption composite prepared under this example at an addition amount of 30 wt.%. It can be seen that the nutshell-shaped MnS/rGO electromagnetic wave absorption composite material prepared in the embodiment has poor wave absorption performance in a high-frequency band, and the maximum reflection loss is less than-5 dB; the microwave-absorbing material has relatively good high-frequency wave-absorbing performance in an intermediate frequency wave band, and the maximum reflection loss exceeds-5 dB. The reason that the shell-shaped MnS/rGO composite material has poor electromagnetic wave absorption performance is that the shell-shaped semi-microsphere structure formed in the hydrothermal process is damaged due to too fast temperature rise during annealing, so that the impedance matching and multiple reflection loss capability of the composite material are weakened, and finally the electromagnetic wave absorption performance of the composite material is reduced.
Claims (5)
1. A preparation method of a manganese sulfide and graphene electromagnetic wave absorption composite material is characterized by comprising the following specific preparation steps:
(1) Under the condition of magnetic stirring, mn (NO) is added according to a certain proportion 3 ) 2 、 C 3 H 7 NO 2 S, adding GO and graphene oxide dispersion liquid into urea in sequence, and stirring strongly for 20-40 minutes to obtain a uniformly mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a Teflon lining, then sealing the Teflon lining into a stainless steel reaction kettle, and reacting for 18 to 28 hours at a constant temperature of between 140 and 180 ℃;
(3) After the reaction in the step (2) is finished, cooling to room temperature in a fume hood, centrifugally cleaning the reaction product by using deionized water and absolute ethyl alcohol, freezing the obtained reaction product for 2-5 hours at-10 to-20 ℃, and then freeze-drying the reaction product for 12-48 hours in a vacuum freeze dryer at-40 to-60 ℃ to obtain a primary reaction product;
(4) Finally, the primary reaction product is put in argon at 1-5 ℃ min -1 Heating at a heating rate, carrying out heat treatment at the temperature of 400-600 ℃ for 2-6 hours, and cooling to room temperature under the protection of argon after the heat treatment is finished, thus finally obtaining the nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material.
2. The method for preparing the manganese sulfide and graphene electromagnetic wave absorption composite material according to claim 1, wherein the certain proportion of Mn (NO) in the step (1) 3 ) 2 、 C 3 H 7 NO 2 S, urea is Mn (NO) 3 ) 2 、 C 3 H 7 NO 2 The molar mass ratio of S to urea is 1:1 (1-3), mn (NO) 3 ) 2 The mass concentration of the solution was 50wt.%.
3. The preparation method of the manganese sulfide and graphene electromagnetic wave absorption composite material as claimed in claim 1, wherein the GO dispersion liquid in step (1) is a GO dispersion liquid with a concentration of 0.5-3mg/mL obtained by uniformly dispersing GO powder in deionized water through a high-frequency ultrasonic cleaner and continuously performing ultrasonic dispersion for 1-3 hours.
4. The method for preparing the manganese sulfide and graphene electromagnetic wave absorption composite material according to claim 1, wherein the centrifugal cleaning in the step (3) is performed for 1 to 3 times.
5. The nutshell-shaped MnS @ rGO electromagnetic wave absorption composite material prepared by the method for preparing the manganese sulfide and graphene electromagnetic wave absorption composite material according to any one of claims 1 to 4 is applied to electromagnetic protection facilities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110542484.2A CN113329604B (en) | 2021-05-18 | 2021-05-18 | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110542484.2A CN113329604B (en) | 2021-05-18 | 2021-05-18 | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113329604A CN113329604A (en) | 2021-08-31 |
| CN113329604B true CN113329604B (en) | 2022-10-14 |
Family
ID=77415909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110542484.2A Active CN113329604B (en) | 2021-05-18 | 2021-05-18 | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113329604B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634795B (en) * | 2022-03-25 | 2023-07-18 | 哈尔滨师范大学 | Preparation method of vanadium diselenide/CNTs composite material with full-band and multiband electromagnetic wave absorption performance |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163919A (en) * | 2014-07-25 | 2014-11-26 | 北京科技大学 | Polyaniline/oxidized graphene/ferriferrous oxide absorbing material and preparation method |
| CN105670560A (en) * | 2016-01-08 | 2016-06-15 | 北京科技大学 | Preparation method of nano-cobalt oxide/graphene composite wave-absorbing coating |
| CN108559445A (en) * | 2018-05-24 | 2018-09-21 | 安徽理工大学 | A kind of preparation method of the nano combined absorbing material of redox graphene/Mn ferrite |
| CN109264697A (en) * | 2018-09-30 | 2019-01-25 | 广州特种承压设备检测研究院 | A kind of high thermal conductivity of PI film preparation inhales wave graphene composite film and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760877B (en) * | 2012-07-23 | 2014-08-27 | 浙江大学 | Transition metal sulfide/graphene composite material, and preparation method and application thereof |
| CN102910617A (en) * | 2012-09-24 | 2013-02-06 | 同济大学 | Chemical preparation method of graphene-bismuth sulfide nanocomposite material |
| US9833522B2 (en) * | 2013-12-23 | 2017-12-05 | The Research Foundation For The State University Of New York | Graphene-based contrast agents for photoacoustic and thermoacoustic tomography and method of use |
| CN108365185A (en) * | 2018-01-09 | 2018-08-03 | 上海大学 | The preparation method of porous manganese sulfide and graphene composite material |
| CN109755535B (en) * | 2019-01-25 | 2021-08-27 | 中南大学 | Tin-manganese sulfide/carbon composite material and preparation method and application thereof |
| CN110070996A (en) * | 2019-05-28 | 2019-07-30 | 中山大学 | Nickel sulfide/graphene composite material preparation method and application |
-
2021
- 2021-05-18 CN CN202110542484.2A patent/CN113329604B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163919A (en) * | 2014-07-25 | 2014-11-26 | 北京科技大学 | Polyaniline/oxidized graphene/ferriferrous oxide absorbing material and preparation method |
| CN105670560A (en) * | 2016-01-08 | 2016-06-15 | 北京科技大学 | Preparation method of nano-cobalt oxide/graphene composite wave-absorbing coating |
| CN108559445A (en) * | 2018-05-24 | 2018-09-21 | 安徽理工大学 | A kind of preparation method of the nano combined absorbing material of redox graphene/Mn ferrite |
| CN109264697A (en) * | 2018-09-30 | 2019-01-25 | 广州特种承压设备检测研究院 | A kind of high thermal conductivity of PI film preparation inhales wave graphene composite film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《氧化还原石墨烯支撑的硫化锰负极材料》;张星和，杨晓娜;《电源技术研究与涉及》;20190430;第43卷(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113329604A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110012656B (en) | Preparation method of nano composite wave-absorbing material | |
| CN113025271B (en) | Ti 3 C 2 T x Preparation method of MXene @ ZnO composite wave-absorbing material | |
| CN109233740B (en) | Method for preparing Fe/Co/C composite wave-absorbing material based on modified MOF material pyrolysis | |
| CN102533216B (en) | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method | |
| CN110079271B (en) | Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof | |
| CN111454691B (en) | Graphene/amorphous titanium dioxide nanorod composite material, preparation method and application thereof | |
| Yu et al. | Unique electromagnetic wave absorber for three-dimensional framework engineering with copious heterostructures | |
| CN105950112B (en) | A kind of nano combined absorbing material and preparation method thereof | |
| CN113329604B (en) | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material | |
| CN114195197A (en) | Magnetic porous carbon composite and preparation method and application thereof | |
| Heng et al. | Microwave absorption enhancement of Fe/C core–shell hybrid derived from a metal-organic framework | |
| CN108847478A (en) | A kind of lithium battery silicon-carbon nano composite anode material and preparation method thereof | |
| CN105018029A (en) | Metallic nickel/graphene composite wave-absorbing material and preparation method thereof | |
| CN115843172B (en) | Hollow carbon supported metal nickel particles, preparation method and application of microwave absorption | |
| Meng et al. | Fabrication of core-shell Co@ HCN@ PANI composite material with enhanced electromagnetic wave absorption | |
| CN110699039A (en) | Porous Co/Nb2O5Carbon fiber aerogel composite wave-absorbing material and preparation method thereof | |
| Du et al. | Heterostructured C@ Fe3O4@ FeSiCr composite absorbing material derived from MIL-88 (Fe)@ FeSiCr | |
| Liang et al. | Fabrication of in-situ Ti-Cx-N1− x phase enhanced porous Si3N4 absorbing composites by gel casting | |
| CN111874888B (en) | Preparation method of ultra-wideband wave absorber of micron-scale square carbon material | |
| CN114058328A (en) | Wave-absorbing composite material and preparation method thereof | |
| CN116462965B (en) | Preparation method and application of polyaniline hybrid wave-absorbing material | |
| Xiong et al. | Metal-oxide doping enhances electromagnetic wave absorption performance of BaFe12O19 glass-ceramics | |
| CN117446792A (en) | Fe/N co-doped hollow carbonaceous nanosphere-loaded graphene aerogel surface wave-absorbing material and preparation method thereof | |
| CN113563842B (en) | Preparation method of tremella-shaped iron-based complex converted electromagnetic wave absorbent | |
| CN108165008A (en) | 1,1- diacetyl ferrocene chirality polyShiff bases salt/graphene composite wave-suction material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |