CN111874888B - Preparation method of ultra-wideband wave absorber of micron-scale square carbon material - Google Patents

Preparation method of ultra-wideband wave absorber of micron-scale square carbon material Download PDF

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CN111874888B
CN111874888B CN202010786230.0A CN202010786230A CN111874888B CN 111874888 B CN111874888 B CN 111874888B CN 202010786230 A CN202010786230 A CN 202010786230A CN 111874888 B CN111874888 B CN 111874888B
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carbon material
micron
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wave absorber
square
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CN111874888A (en
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薛卫东
叶伟平
高小洪
赵睿
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University of Electronic Science and Technology of China
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    • 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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    • 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
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    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

Abstract

The invention relates to the technical field of electromagnetic wave absorbing materials, and provides a preparation method of an ultra-wideband wave absorber of a micron-scale square carbon material, which aims to solve the problem that the existing carbon material cannot have a wider frequency band absorption characteristic below 2.5mm, and the main scheme of the invention comprises the following steps: (1) sequentially adding barium chloride, potassium nitrate and absolute ethyl alcohol into 5, 10, 15, 20-tetra (4-pyridyl) porphyrin, and stirring at high temperature until the barium chloride, the potassium nitrate and the absolute ethyl alcohol are uniformly mixed; (2) putting the mixture prepared in the step (1) into a porcelain boat, and drying the mixture in vacuum; placing the dried mixture in argon gas for calcination treatment; (3) and (3) placing the calcined product obtained in the step (2) in deionized water, boiling, performing suction filtration and separation, and collecting the product after suction filtration. The square carbon material prepared by the method has high absorption strength and wide absorption frequency band under low thickness, and the size of the square and the number of the graphene laminated layers can be adjusted, so that the electromagnetic wave absorption performance of the material is controllable.

Description

Preparation method of ultra-wideband wave absorber of micron-scale square carbon material
Technical Field
The invention relates to a preparation method of an ultra-wideband wave absorber of a micron-scale cubic carbon material, belonging to the technical field of electromagnetic wave absorbing materials.
Technical Field
With the technological progress, electromagnetic waves bring great convenience to human beings in communication, industry and daily life, and also bring serious problems of mutual interference between electronic equipment, harm to human health and the like. The electromagnetic wave absorbing material provides a very effective way to solve this problem by converting electromagnetic wave energy into heat energy.
Microwave absorption means that the wave-absorbing material can effectively absorb incident electromagnetic waves and convert electromagnetic energy into heat energy or other forms of energy to be consumed, the electromagnetic loss capacity of the wave-absorbing agent directly determines the performance of the wave-absorbing material,
the 'light, thin, wide and strong' has become the evaluation standard of high-performance wave absorbing agents, and the development of high-performance electromagnetic shielding and absorbing materials is extremely important.
The wave absorbing agent reported at present, such as carbon nanotubes and nano porous carbon materials, has been widely applied. For example, a polyvinylidene fluoride-based wave-absorbing material of zinc ferrite @ carbon nano tubes is prepared by an inert group of great university of Beijing chemical industry, and researches show that when the thickness of the material is 2.42mm, the lowest reflection loss reaches nearly-55 dB, and the effective absorption frequency band is 8.9-11.0 GHz. (Suibi-rigid, Li Fei, Yunjie, Zhu Li.) A polyvinylidene fluoride-based wave-absorbing material and a preparation method [ P ] CN110527224A, 2019-12-03 ] Liang et al prepared a selective nanoporous carbon material with ZnO/NPC as a core and highly graphitized Co/NPC as a shell, and a sample with 50 wt% of the filling amount of the composite material had a maximum Reflection Loss (RL) of-28.8 dB at a thickness of 1.9mm and an effective absorption band of 13.8-18 GHz. (Xiaohui Liang, Bin Quan, Guingbin Ji, Wei Liu, Yan Cheng, Baoshan Zhang and Youwei Du, Novel nanoporus carbon derivative from metal-organic frames with a porous electromagnetic wave absorption capabilities, orange. front., 2016, 3, 1516-. As described above, the carbon material has good electromagnetic wave absorption properties, but there are several prominent problems in general: (1) a single carbon material generally has no magnetic loss, and the wave absorbing performance is weaker than that of a magnetic material (2). the common carbon material cannot have a wider frequency band absorption characteristic in a thinner thickness (such as below 2.5 mm); (3) the process is complex, the cost is high, and the large-scale production is not facilitated.
Disclosure of Invention
The invention aims to provide a preparation method of a micron-scale square carbon material ultra-wideband wave absorbing agent, which can be used for obtaining a graphene material with adjustable square block size and lamination quantity, and the electromagnetic wave absorbing material can show excellent absorption strength and absorption bandwidth in low thickness (2.0 mm).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a micron-scale square carbon material ultra-wideband wave absorber comprises the following steps:
sequentially adding barium chloride, potassium nitrate and absolute ethyl alcohol into 5, 10, 15, 20-tetra (4-pyridyl) porphyrin, and stirring at high temperature until the barium chloride, the potassium nitrate and the absolute ethyl alcohol are uniformly mixed;
step (2) placing the mixture prepared in the step (1) into a porcelain boat, and drying the mixture in vacuum; placing the dried mixture in argon gas for calcination treatment;
and (3) soaking the calcined product obtained in the step (2) in a dilute hydrochloric acid solution, adding deionized water after soaking, boiling, performing suction filtration and separation after boiling, and collecting the product after suction filtration.
Wherein the side length of the obtained square is less than 1.5 micrometers, the area of the carrier graphene is not more than 16 square micrometers, and the number of the laminated layers is at least two.
Wherein in the step (1), the adding amount of the 5, 10, 15, 20-tetra (4-pyridyl) porphyrin is 1.2-3.2 g, and the relative molecular weight range of the 5, 10, 15, 20-tetra (4-pyridyl) porphyrin is 618.69 mBarium chloride+mPotassium nitrate＝300g，VAnhydrous ethanol＝20mL。
Wherein, in the step (1), the mixture is stirred at the temperature of 60-75 ℃ until the mixture is uniformly mixed.
Wherein in the step (2), the calcining temperature is 650-950 ℃, the heat preservation time is 6-10 h, and the heating rate is 3.5-5.5 ℃/min
Wherein in the step (3), the mass fraction of the dilute hydrochloric acid is 2-7 wt%, and the soaking time is 1.5-2.5 h.
Has the advantages that: the square carbon material prepared by the method has high absorption strength and wide absorption frequency band under low thickness, and the size of the square and the number of the graphene laminated layers can be adjusted, so that the electromagnetic wave absorption performance of the material is controllable; finally, the preparation method has simple process, the condition equipment is easy to obtain, and the large-scale mass production can be realized.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1 of the present invention;
FIG. 2 is a TEM photograph of a square bulk carbon material obtained in example 1 of the present invention;
FIG. 3 is a TEM photograph of a square bulk carbon material obtained in example 2 of the present invention;
FIG. 4 is a reflection loss spectrum of a carbon material in a square block form obtained in example 1 of the present invention;
FIG. 5 shows the mixing ratio of raw materials adjusted to m in example 2Barium chloride∶mPotassium nitrate1: and 2, reflection loss spectrum of the prepared cube-shaped carbon material.
In fig. 4 and 5, the curves correspond to 1mm, 2mm, 3mm, 4mm and 5mm from top to bottom in sequence.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Example 1:
the invention relates to a preparation method of a micron-scale square carbon material ultra-wideband wave absorber, which comprises the following steps:
step 1: adding 150g of barium chloride, 150g of potassium nitrate and 20mL of absolute ethyl alcohol into 2g of 5, 10, 15, 20-tetra (4-pyridyl) porphyrin in sequence, and stirring at 70 ℃ until the mixture is uniformly mixed;
step 2: putting the mixture prepared in the step 1 into a porcelain boat with the size of 100mm multiplied by 40mm multiplied by 20mm, and drying the mixture in a vacuum drying oven for 6 hours; placing the dried mixture into argon gas for calcination treatment, wherein the calcination temperature is 800 ℃, the heat preservation time is 7h, and the heating rate is 4 ℃/min;
and step 3: and (3) placing the calcined product obtained in the step (2) in a dilute hydrochloric acid solution with the mass fraction of 5 wt% for soaking for 2 hours, adding deionized water after soaking, boiling, performing suction filtration separation after boiling, and collecting the product after suction filtration, namely the square graphene laminated material.
The side length of the square block of the square carbon material prepared by the embodiment is 0.8 micrometer, the area of the carrier graphene film is about 4 square micrometers, and the number of layers is two to four.
Example 2:
step 1: adjusting the mixing ratio of the raw materials to mBarium chloride∶mPotassium nitrateWhen the ratio of barium chloride to potassium nitrate is 1: 2, namely 100g of barium chloride and 200g of potassium nitrate, the side length of the square carbon material is 1.2 mu m, the area of the carrier graphene film is about 9 square microns, and the number of stacked layers is two.
Step 2: putting the mixture prepared in the step 1 into a porcelain boat with the size of 100mm multiplied by 40mm multiplied by 20mm, and drying the mixture in a vacuum drying oven for 6 hours; placing the dried mixture into argon gas for calcination treatment, wherein the calcination temperature is 700 ℃, the heat preservation time is 10h, and the heating rate is 5 ℃/min;
and step 3: and (3) placing the calcined product obtained in the step (2) into a dilute hydrochloric acid solution with the mass fraction of 6 wt% for soaking for 2 hours, adding deionized water after soaking, boiling, performing suction filtration separation after boiling, and collecting the product after suction filtration, namely the square graphene laminated material, as shown in figure 3.
When the mixing ratio of the raw materials is adjusted, the size of the square block, the membrane area and the number of the graphene lamination layers of the obtained product are correspondingly changed, so that the final wave absorbing performance of the product is influenced, and as can be seen from fig. 5, the reflection loss of the product is more than-7.5 dB under the condition of larger thickness such as 5mm, but the requirement of high loss under the condition of low thickness cannot be met.
Fig. 1 is an XRD pattern of the cubic carbon materials obtained in examples 1 and 2 of the present invention, which is a typical XRD pattern of carbon as can be seen from fig. 1.
Fig. 2 is a TEM photograph of the carbon material in a block form obtained in example 1 of the present invention, and it can be seen from fig. 2 that the size of the block is 0.8 μm, the area of the graphene film is about 1 μm by 4 μm, and the number of stacked layers is two to four.
FIGS. 4 and 5 are reflection loss maps of the cubic carbon materials obtained in examples 1 and 2. As can be seen from FIG. 4, the product of example 1 shows excellent wave-absorbing performance, the reflection loss is as high as-21.05 dB under the condition of the thickness of 2.0mm, and the bandwidth is 8.47 GHz. The mixing ratio of the raw materials is adjusted to mBarium chloride∶mPotassium nitrateWhen the ratio is 1: 2, the formula is shown in figure 5It can be seen that the reflection loss of the obtained product is above-10.0 dB in the full frequency band and in the larger thickness.
The square block-shaped carbon material is prepared by high-temperature calcination, the performance is improved by virtue of a solid-void interface brought by the unique structure of lamination of the square block and the carrier graphene, and a polarization center of the electron gathering capability is enhanced. In addition, the thick lamination of the carbon material in a block shape and the graphene as a support plays an important role in the multilayer permeation absorption and multilayer reflection of electromagnetic waves. Therefore, the invention has good wave-absorbing performance under low thickness.

Claims (6)

1. A preparation method of an ultra-wideband wave absorber of a micron-scale square carbon material is characterized by comprising the following steps:
sequentially adding barium chloride, potassium nitrate and absolute ethyl alcohol into 5, 10, 15, 20-tetra (4-pyridyl) porphyrin, and stirring at a high temperature of 60-75 ℃ until the barium chloride, the potassium nitrate and the absolute ethyl alcohol are uniformly mixed;
step (2), putting the mixture prepared in the step (1) into a porcelain boat, and drying the mixture in vacuum; placing the dried mixture in argon gas for calcination treatment;
and (3) soaking the calcined product obtained in the step (2) in a dilute hydrochloric acid solution, adding deionized water after soaking, boiling, performing suction filtration and separation after boiling, and collecting the product after suction filtration to obtain the wave absorbing agent of the square carbon material.
2. The method for preparing an ultra-wideband wave absorber of a micron-scale cubic carbon material as claimed in claim 1, wherein: the side length of the obtained square carbon material is less than 1.5 micrometers, the area of the loaded carrier graphene is not more than 16 square micrometers, and the number of stacked layers is at least two.
3. The method for preparing an ultra-wideband wave absorber of a micron-scale cubic carbon material as claimed in claim 1, wherein: in the step (1), the addition amount of 5, 10, 15, 20-tetra (4-pyridyl) porphyrin is 1.2-3.2 g, and 5, 10, 15, 20-tetra (4-pyridyl) porphyrin is added) The relative molecular weight of the porphyrin was 618.69, mBarium chloride+mPotassium nitrate=300g，VAnhydrous ethanol=20mL。
4. The method for preparing an ultra-wideband wave absorber of a micron-scale cubic carbon material as claimed in claim 1, wherein: in the step (2), the calcining temperature is 650-950 ℃, the heat preservation time is 6-10 h, and the heating rate is 3.5-5.5 ℃/min.
5. The method for preparing an ultra-wideband wave absorber of a micron-scale cubic carbon material as claimed in claim 1, wherein: the mass fraction of the dilute hydrochloric acid is 2-7 wt%, and the soaking time is 1.5-2.5 h.
6. A method for adjusting the number of stacked layers of carbon block materials prepared by the method for preparing an ultra-wideband wave absorber for a micron-sized carbon block material according to claim 3, wherein m is adjustedBarium chloride：mPotassium nitrateThe ratio of the carbon material to be processed is adjusted.
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