CN114752351B - Multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material and preparation method thereof - Google Patents
Multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material and preparation method thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 72
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011358 absorbing material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
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- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
Abstract
The invention discloses a multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material and a preparation method thereof, wherein a porous carbon sheet matrix is obtained by a high-temperature pyrolysis method by taking kilopaper as a precursor, and then a magnetic component of cobaltosic oxide with adjustable morphology is loaded on a porous carbon sheet by a method combining hydrothermal treatment and heat treatment, so that a series of multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material is finally obtained.
Description
Technical Field
The invention relates to an electromagnetic absorbing material in the field of functional materials, in particular to a multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave absorbing material and a preparation method thereof.
Background
In recent years, the rapid development of wireless electronic communication technology and equipment brings convenience to human beings, and meanwhile, the following problems of electromagnetic wave interference and pollution also seriously affect the operation and human health of surrounding precision equipment. Therefore, there is an urgent need for a wave-absorbing material that is lightweight, broadband, strongly absorbing, and thin in thickness to solve these problems. Such materials that can effectively attenuate electromagnetic waves can be classified into dielectric loss type wave absorbing materials and magnetic loss type wave absorbing materials according to their loss mechanisms. However, the above-mentioned type materials with single components do not have the disadvantages of poor impedance matching or weak attenuation capability, so that the requirements of light, thin, strong and wide cannot be met, and therefore, the construction of the composite wave-absorbing material with both magnetic loss and electric loss becomes a current research hot spot. Research shows that the effective combination of the two can solve the problem of impedance mismatch on one hand, so that more electromagnetic waves can enter the composite material, on the other hand, under the control of various loss mechanisms and interface effects, the electromagnetic waves can be rapidly lost and converted into other forms of energy, and the wave absorbing performance of the composite material is greatly improved. Unfortunately, most of the preparation processes of the composite materials are relatively complex, high in cost and low in yield, and cannot meet the actual demands. Meanwhile, how to design the microstructure of the material and regulate the proportion of components so as to avoid the phenomena of uneven distribution, agglomeration, excessive occupation ratio and the like of magnetic particles on a carbon matrix, and the like, which cause the overlarge density and poor performance of the final composite material, is also a problem which needs to be solved urgently at present.
Compared with the traditional carbon material, biomass carbon is used as a novel material with low cost, reproducibility and environmental friendliness, and is strongly touted in the field of electromagnetic absorption. In particular, most biomasses have unique microstructures such as porous structures, lamellar structures, hollow tubular structures and the like, the structural diversity can be maintained through simple high-temperature carbonization, and simultaneously the surfaces of the biomasses often contain a large amount of oxygen-containing functional groups, which is beneficial to attracting metal ions, so that the magnetic carbon-based composite material is successfully formed. The research shows that the biomass carbon material with the porous structure is not only beneficial to the multiple reflection of electromagnetic waves and the improvement of impedance matching, but also can reduce the overall density of the material. Currently, there are still significant challenges in developing magnetic biomass-based carbon composites.
Disclosure of Invention
Aiming at the technical state, the invention provides a multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material and a preparation method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material is composed of a multi-dimensional cobaltosic oxide array and a biomass-derived porous carbon sheet, wherein the morphology of the multi-dimensional cobaltosic oxide array unit is one of needle-shaped, sheet-shaped and sea urchin-shaped, and the biomass source of the porous carbon sheet is thousand sheets of paper.
The preparation method of the multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material provided by the invention comprises the following steps:
step 1, preparing a biomass-based porous carbon sheet material: cleaning, drying and calcining the biomass sheet paper under the protection gas, and cooling to obtain carbonized biomass;
step 2, preparing a multi-dimensional cobaltosic oxide array/biomass-derived porous carbon sheet composite wave-absorbing material: dissolving cobalt nitrate hexahydrate, urea and ammonium fluoride in a certain proportion into deionized water, and magnetically stirring to obtain pink transparent solution; immersing the porous carbon sheet prepared in the step 1 into the solution to perform hydrothermal reaction, and performing suction filtration after the reaction is finished to obtain a light pink precursor; finally, calcining the precursor under air, and cooling to obtain a series of multi-dimensional cobaltosic oxide array/biomass-derived porous carbon sheet composite wave-absorbing materials.
Wherein the temperature rising rate of the calcination in the step 1 is 1-10 ℃/min, the calcination temperature is 600-800 ℃, the calcination time is 90-180 min, and the protective atmosphere is one or more selected from argon and nitrogen.
Wherein, in the step 2, the mass ratio of the porous carbon sheet, the cobalt nitrate hexahydrate, the urea, the ammonium fluoride and the deionized water is 1: (0.72-2.18): (0.75-2.25): (0.38-1.13): (100-300); the hydrothermal reaction temperature is 100-130 ℃, and the reaction time is 360-720 min; the calcination temperature is 300-450 ℃, and the calcination time is 120-240 min.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the method adopts the multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material through high-temperature pyrolysis and hydrothermal reaction, and is simple and safe to operate, low in cost and environment-friendly.
2. According to the invention, the transformation of the morphology of the cobaltosic oxide array from the sea urchin sphere shape to the sheet shape and the needle shape can be realized by simply changing the hydrothermal reaction condition, so that the effective regulation and control of electromagnetic parameters and wave absorbing performance are realized.
3. The needle-shaped cobaltosic oxide/biomass-based porous carbon sheet composite material prepared by the invention has excellent electromagnetic absorption performance. Under the magneto-electric co-loss mechanism, rich interface effect and optimized impedance matching effect, the minimum reflection loss value of the absorber reaches-60.5 dB, and the effective absorption bandwidth reaches 6.8GHz.
Drawings
FIG. 1 XRD patterns of examples 1-3 and comparative examples;
FIG. 2 SEM (upper) and TEM (lower) images of examples 1-3 and comparative examples;
fig. 3. Wave absorbing properties of examples 1 to 3 and comparative examples.
Detailed Description
The invention will be described in further detail below with reference to the embodiments of the accompanying drawings, it being noted that the embodiments described below are intended to facilitate the understanding of the invention and are not meant to be limiting in any way.
The invention provides the following specific embodiments, discloses the performance of various combination examples, and analyzes the effect of each experimental parameter in the system. Accordingly, this patent should be considered to disclose all possible combinations of the described technical solutions in particular.
Example 1:
in the embodiment, the prepared product is sea urchin spherical cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material.
The preparation method of the sea urchin spherical cobaltosic oxide array/biomass-based porous carbon sheet composite material comprises the following steps:
step 1, ultrasonically cleaning the thousand sheets of paper with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the paper in an oven at 60 ℃ for 12 hours; heating the dried thousand sheets of paper to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, calcining for 120 min, and cooling to room temperature along with a furnace to obtain the biomass-based porous carbon sheet material.
Step 2, adding 291.5 mg cobalt nitrate hexahydrate, 300.3 mg urea and 74.1 mg ammonium fluoride into 40 ml deionized water, adding 200mg of the porous carbon sheet obtained in the step 1 after magnetic stirring until the porous carbon sheet is completely dissolved, and continuously stirring for 120 min; transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 50 mL, performing hydrothermal reaction at 120 ℃ to obtain 9 h, performing suction filtration on the obtained solid product with ethanol and deionized water for three times, and drying to obtain a light pink precursor; finally, calcining the precursor for 120 min at 350 ℃ in air, and cooling to obtain the sea urchin spherical cobaltosic oxide array/biomass derived porous carbon sheet composite wave-absorbing material.
The following tests were carried out on the product obtained above:
(A) The irradiation source is Cu-K alphaλX-ray diffraction (XRD for short, the same applies below) of =1.54 a) to determine the crystal structure of the sample.
(B) The microscopic morphology of the sample was observed using a scanning electron microscope (SEM for short, hereinafter the same) and a transmission electron microscope (TEM for short).
(C) Electromagnetic parameters (complex permittivity and complex permeability) of the material were measured by a cellular 3672B-S vector network analyzer in the frequency range of 2-18 GHz. Test sample preparation: by uniformly mixing the product with paraffin wax, which accounts for 35% of the total weight, then pressing into a ring-shaped member (outer diameter: 7.0 mm, inner diameter 3.04 mm).
Example 2:
in the embodiment, the prepared product is a flaky cobaltosic oxide array/biomass-based porous carbon plate composite wave-absorbing material.
The preparation method of the flaky cobaltosic oxide array/biomass-based porous carbon sheet composite material comprises the following steps:
step 1, ultrasonically cleaning the thousand sheets of paper with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the paper in an oven at 60 ℃ for 12 hours; heating the dried thousand sheets of paper to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, calcining for 120 min, and cooling to room temperature along with a furnace to obtain the biomass-based porous carbon sheet material.
Step 2, adding 291.5 mg cobalt nitrate hexahydrate, 300.3 mg urea and 109.8mg of ammonium fluoride into 40 ml deionized water, adding 200mg of the porous carbon sheet obtained in the step 1 after magnetic stirring until the porous carbon sheet is completely dissolved, and continuously stirring for 120 min; transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 50 mL, performing hydrothermal reaction at 120 ℃ to obtain 9 h, performing suction filtration on the obtained solid product with ethanol and deionized water for three times, and drying to obtain a light pink precursor; and finally, calcining the precursor at 350 ℃ for 120 min under air, and cooling to obtain the flaky cobaltosic oxide array/biomass derived porous carbon composite wave-absorbing material. The above-obtained product was examined, and the examination method and examination content were the same as in example 1.
Example 3:
in the embodiment, the prepared product is a needle-shaped cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material.
The preparation method of the flaky cobaltosic oxide array/biomass-based porous carbon sheet composite material comprises the following steps:
step 1, ultrasonically cleaning the thousand sheets of paper with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the paper in an oven at 60 ℃ for 12 hours; heating the dried thousand sheets of paper to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, calcining for 120 min, and cooling to room temperature along with a furnace to obtain the biomass-based porous carbon sheet material.
Step 2, adding 291.5 mg cobalt nitrate hexahydrate, 300.3 mg urea and 148.2 mg ammonium fluoride into 40 ml deionized water, adding 200mg of the porous carbon sheet obtained in the step 1 after magnetic stirring until the porous carbon sheet is completely dissolved, and continuously stirring for 120 min; transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 50 mL, performing hydrothermal reaction at 120 ℃ to obtain 9 h, performing suction filtration on the obtained solid product with ethanol and deionized water for three times, and drying to obtain a light pink precursor; finally, calcining the precursor at 350 ℃ for 120 min under air, and cooling to obtain the acicular cobaltosic oxide array/biomass-derived porous carbon sheet composite wave-absorbing material. The above-obtained product was examined, and the examination method and examination content were the same as in example 1.
Comparative examples:
this example is a comparative example of examples 1,2,3 described above.
In this example, the product produced is a biomass-based porous carbon sheet material.
The preparation method of the biomass-based porous carbon sheet material comprises the following steps:
ultrasonically cleaning the thousand sheets of paper with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the paper in an oven at 60 ℃ for 12 hours; heating the dried thousand sheets of paper to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, calcining for 120 min, and cooling to room temperature along with a furnace to obtain the biomass-based porous carbon sheet material.
The products obtained above were examined, and XRD and SEM/TEM examination methods were exactly the same as in example 1.
The phase changes of the materials prepared in examples 1 to 3 and comparative examples are shown in FIG. 1, the microscopic morphologies of the materials prepared in examples 1 to 3 and comparative examples are shown in FIG. 2, and the wave absorbing properties of the materials prepared in examples 1 to 3 and comparative examples are shown in Table 1 below, and the results are shown in FIG. 3.
Table 1: reflection loss and absorption performance tables in examples 1 to 3 and comparative example
The symbols in table 1 have the following meanings:
RL-reflection losses;RL min minimal reflection losses.
And (3) phase analysis: as shown in FIG. 1, the samples prepared in examples 1-3 were each composed of two phases, tricobalt tetraoxide and graphitized carbon, whereas the comparative examples exhibited only typical graphite diffraction peaks.
And (3) microscopic morphology change analysis: as shown in FIG. 2, along with the change of the hydrothermal reaction time and the ammonium fluoride concentration, the cobaltosic oxide array units in examples 1-3 respectively show sea urchin ball, flake-shaped and needle-shaped forms and uniformly cover the surface of the porous carbon sheet matrix, which shows that the change of hydrothermal conditions in the invention can realize the regulation and control of the microscopic morphology of the product. Wherein the average diameter of the sea urchin spherical cobaltosic oxide is 8-12 mu m, the thickness of the flaky cobaltosic oxide is 80-100 nm, and the length of the needle-shaped cobaltosic oxide is 4-6 mu m; the porous carbon sheet prepared in the comparative example is in a shape of cicada wing and microcosmic flat, the surface of the porous carbon sheet is provided with folds and holes, and the aperture range is 20-60 mu m.
Analysis of wave absorbing performance: as can be seen from table 1 and fig. 3, the wave absorbing performance of the sample, especially the range of effective absorption bandwidth, is significantly improved when the load is 35%, i.e. the mass of the wave absorbing composite material of the present invention is 35%, and the mass of the binder is 65%, wherein the binder is one of epoxy or paraffin wax, and the surface tricobalt tetraoxide is converted from sea urchin spherical shape into flaky shape and needle shape. In the frequency range measured, the RLmin value of the sample prepared in example 1 at 3.5 and mm is only-12.5 and dB, and the effective absorption bandwidth is only 1 GHz, which indicates that the sample does not have good wave absorbing performance; at a coating thickness of 2.5 mm, the effective absorption bandwidth of the sample prepared in example 2 reached 5.7 GHz, but the reflection RLmin value at 4mm was only-17.9 dB; in contrast, the sample prepared in example 3 exhibited excellent reflection loss (-60.5 dB) at a matching thickness of 2.44 mm, while the absorption bandwidth was increased to 6.8GHz. From this, the product obtained in example 3 shows excellent wave-absorbing performance in the C-Ku frequency band (4-18 Ghz), when the mass ratio of the ammonium fluoride content to the porous carbon exceeds 1.13, the obtained cobaltosic oxide is unevenly distributed in the porous carbon, and agglomeration occurs, so that the wave-absorbing performance is deteriorated, meanwhile, the components and the structure designed by the invention can realize the controllability of electromagnetic parameters and wave-absorbing characteristics, and have great application potential, and the sample prepared in the comparative example has reflection loss (-53.5 dB) and wave-absorbing bandwidth of 4.4GHz under the condition of matching thickness of 2 mm.
In conclusion, the multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material can be prepared through simple heat treatment and hydrothermal reaction, and especially the technological parameters can effectively adjust the microstructure of the system, so that the magneto-electric loss synergistic effect can be realized, the impedance matching can be optimized, and the final wave-absorbing performance can be improved. Among them, the excellent electromagnetic wave absorption characteristics exhibited by the needle-like tricobalt tetraoxide array/biomass-based porous carbon sheet composite material can be attributed to its specific microstructure and proper component ratio. Therefore, the composite material is an ideal wave-absorbing material and can be applied practically.
The foregoing embodiments have described the technical solutions of the present invention in detail, and it should be understood that the foregoing examples are only specific embodiments of the present invention and are not intended to limit the present invention. Any modification, supplement, or equivalent replacement made within the principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A multi-dimensional cobaltosic oxide array/biomass-based porous carbon sheet composite wave-absorbing material is characterized in that the multi-dimensional cobaltosic oxide array is uniformly distributed on the surface of a biomass-derived porous carbon sheet, wherein the appearance of the multi-dimensional cobaltosic oxide array is one of needle-shaped, sheet-shaped and sea urchin ball-shaped, and the biomass source of the porous carbon sheet is thousand sheets of paper;
the preparation method of the composite wave-absorbing material comprises the following steps:
step 1, preparing a biomass-based porous carbon sheet material: cleaning, drying and calcining the biomass paper sheet under a protective atmosphere, and cooling to obtain carbonized biomass, wherein the temperature rising rate of calcination is 1-10 ℃/min, the calcination temperature is 600-800 ℃, the calcination time is 90-180 min, and the protective atmosphere is one or more selected from argon and nitrogen;
step 2, preparing a multi-dimensional cobaltosic oxide array/biomass-derived porous carbon sheet composite wave-absorbing material: dissolving cobalt nitrate hexahydrate, urea and ammonium fluoride in a certain proportion into deionized water, and magnetically stirring to obtain pink transparent solution; immersing the porous carbon sheet prepared in the step 1 into the solution to perform hydrothermal reaction, and performing suction filtration after the reaction is finished to obtain a light pink precursor; finally, calcining the precursor under air, and cooling to obtain a series of multi-dimensional cobaltosic oxide array/biomass derived porous carbon sheet composite wave-absorbing materials; the mass ratio of the porous carbon sheet to the cobalt nitrate hexahydrate to the urea to the ammonium fluoride to the deionized water is 1: (0.72-2.18): (0.75-2.25): (0.38-1.13): (100-300); the hydrothermal reaction temperature is 100-130 ℃, and the reaction time is 360-720 min; the calcination temperature is 300-450 ℃ and the calcination time is 120-240 min.
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CN104263317A (en) * | 2014-09-26 | 2015-01-07 | 厦门大学 | Method for synthesizing cobalt oxide/graphene composite wave-absorbing material |
CN109494038A (en) * | 2018-11-06 | 2019-03-19 | 同济大学 | Ferroso-ferric oxide-nanoporous carbon nano-composite material and the preparation method and application thereof |
CN111019603A (en) * | 2019-11-20 | 2020-04-17 | 中车青岛四方机车车辆股份有限公司 | Cobaltosic oxide/carbon fiber composite material and preparation method and application thereof |
CN114068166A (en) * | 2021-11-09 | 2022-02-18 | 同济大学 | Hierarchical pore structure carbon-based magnetic composite material and preparation method and application thereof |
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CN104263317A (en) * | 2014-09-26 | 2015-01-07 | 厦门大学 | Method for synthesizing cobalt oxide/graphene composite wave-absorbing material |
CN109494038A (en) * | 2018-11-06 | 2019-03-19 | 同济大学 | Ferroso-ferric oxide-nanoporous carbon nano-composite material and the preparation method and application thereof |
CN111019603A (en) * | 2019-11-20 | 2020-04-17 | 中车青岛四方机车车辆股份有限公司 | Cobaltosic oxide/carbon fiber composite material and preparation method and application thereof |
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