Composite wave-absorbing material of metal cation hybridized natural molybdenite and preparation method of composite wave-absorbing material

Abstract

The invention discloses a composite wave-absorbing material of metal cation hybridized natural molybdenite and a preparation method of the composite wave-absorbing material, and relates to the technical field of preparation of wave-absorbing materials. The preparation method comprises the following steps: firstly, adding molybdenite powder and ferric trichloride hexahydrate powder into deionized water, uniformly stirring and mixing, putting the mixture into a drying box at 75-90 DEG C, and staying overnight until the mixture is dried; and putting the mixed powder into a small porcelain boat, carrying out heat treatment in a tubular furnace in an argon atmosphere at the heat treatment temperature of 700-900 DEG C, the heating rate of 5-10 DEG C / min and the heat preservation time of 5-6 hours, and cooling the natural furnace to room temperature to obtain the composite wave-absorbing material of the metal cation hybridized natural molybdenite. Natural molybdenite is used as a raw material, FeCl3. 6H2O is used as a doping substance to be subjected to a hybridization reaction with MoS2 in a heat treatment environment, preparation of the (Mo, Fe < 3 + >) S composite wave-absorbing material is realized, the composite material belongs to an electromagnetic wave absorbing material, and the method solves the problem of complicated preparation process, reduces the cost, improves the preparation efficiency and also avoids environmental pollution.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of wave-absorbing materials, and in particular to a composite wave-absorbing material of metal cation hybrid natural molybdenite and a preparation method thereof. Background Art

[0002] In recent years, with the development of microwave communication technology, the use of communication equipment such as mobile phones, satellite broadcasting systems, and local area network systems within the microwave range has become more and more frequent. These devices have facilitated our daily lives, but the electromagnetic pollution problem that comes with it has also become more serious. The electromagnetic waves generated by mobile phone networks have a great impact on the human body; flights at airports may not be able to take off due to electromagnetic wave interference; in hospitals, mobile phones often interfere with the normal operation of various electronic diagnostic and treatment instruments. At the same time, in the military field, with the rapid development of modern military technology and the extensive use of centimeter-wave radars, the survivability of military targets and the penetration capability of weapon systems have been seriously challenged.

[0003] As a new type of electromagnetic absorbing material, molybdenum disulfide has great application potential in the field of electromagnetic wave absorption due to its unique two-dimensional layered structure, semiconductor properties and excellent microwave loss performance. Through the microstructure design, crystal phase regulation and multi-composite of molybdenum disulfide, its absorbing performance can be significantly improved to meet the needs of modern electronic products for lightweight, efficient and broadband absorbing materials. In the future, molybdenum disulfide and its composite materials will play an important role in many fields such as electromagnetic shielding, stealth materials, and environmental governance.

[0004] Patent CN118215279A discloses a NiCo 2-x Fe x S4@MoS2 electromagnetic wave absorbing material and its preparation method, the patent provides a hydrothermal synthesis method of MoS2, NiCo2S4 and CoS2 phases and complex yolk-shell heterogeneous structures, and NiCo 2- x Fe xS4@MoS2 electromagnetic wave absorption material has excellent wave absorption performance. However, the patent has the following shortcomings: First, the raw materials prepared are all metal salts obtained after metallurgy, which are relatively expensive; second, the preparation process adopts a multi-step hydrothermal method, which is cumbersome and cannot guarantee the uniformity of the sample. Patent CN115594222A discloses a two-dimensional FeNi@MoS2 nanostructure electromagnetic wave absorption material and its preparation method. The patent uses ion intercalation to peel molybdenite into single-layer or several-layer nanosheets, and then composites it with FeNi alloy particles to obtain a two-dimensional FeNi@MoS2 nanostructure material and exhibits excellent electromagnetic wave absorption performance. However, the patent has the following shortcomings: First, the raw materials prepared are nanosheets after molybdenite peeling, and the peeling process is complex, energy-consuming, and costly; second, the preparation process adopts a hydrothermal method, which is time-consuming and cannot guarantee the uniformity of the sample.

[0005] Therefore, there is an urgent need for a composite absorbing material of metal cation hybrid natural molybdenite and a preparation method thereof to solve the above problems. Summary of the invention

[0006] The purpose of the present invention is to provide a composite absorbing material of metal cation hybrid natural molybdenite and a preparation method thereof, so as to solve the complicated process of preparing raw materials, reduce costs, improve preparation efficiency, and also avoid environmental pollution.

[0007] The scheme of the present invention is:

[0008] A method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite comprises the following steps:

[0009] 1) adding molybdenite powder and ferric chloride hexahydrate powder into deionized water, stirring and mixing to obtain a mixture;

[0010] 2) placing the mixture in 1) in a drying oven at 75-90° C. overnight until dry to obtain a mixed powder;

[0011] 3) placing the mixed powder described in 2) in a small porcelain boat, and subjecting it to heat treatment in a tube furnace in an argon atmosphere, wherein the heat treatment temperature is 700 to 900° C., the heating rate is 5 to 10° C. / min, and the holding time is 5 to 6 h, to obtain a sample;

[0012] 4) The sample described in 3) is naturally cooled to room temperature in a furnace, and the sample is collected and marked to obtain a composite absorbing material of metal cation hybrid natural molybdenite.

[0013] As a preferred technical solution, the molar mass ratio of molybdenite powder to ferric chloride hexahydrate powder in 1) is 2:1-3, and the stirring is magnetic stirring for 30-60 minutes.

[0014] As a preferred technical solution, the molybdenite powder in 1) is added to the deionized water, and then the ferric chloride hexahydrate powder is added to the deionized water.

[0015] As a preferred technical solution, in said 3), the temperature is increased to the heat treatment temperature at a heating rate of 5°C / min.

[0016] As a preferred technical solution, the particle size of the molybdenite powder is ≤0.25 mm.

[0017] The present invention also discloses a composite absorbing material of metal cation hybrid natural molybdenite prepared by a method for preparing a composite absorbing material of metal cation hybrid natural molybdenite. The composite absorbing material of metal cation hybrid natural molybdenite comprises MoS2 and FeCl3·6H2O. FeCl3·6H2O is mixed with MoS2 in natural molybdenite as a doping substance to generate a hybridization reaction in a heat treatment environment.

[0018] The invention also discloses the application of a composite wave absorbing material of metal cation hybrid natural molybdenite as an electromagnetic wave absorbing material.

[0019] Advantages of the present invention:

[0020] (1) The present invention is prepared using natural raw materials, molybdenite powder (MoS2) and ferric chloride hexahydrate (FeCl3·6H2O), and has excellent electromagnetic wave absorption characteristics. It can be used as an electromagnetic wave absorption material and is widely used in the corresponding electromagnetic protection and microwave stealth fields.

[0021] (2) The present invention uses natural raw materials molybdenite powder (MoS2) and ferric chloride hexahydrate (FeCl3·6H2O) as raw materials, and makes FeCl3·6H2O as a doping material to undergo hybridization reaction with MoS2 in a heat treatment environment to achieve (Mo, Fe 3+ )S composite absorbing material preparation. The preparation process is simple, environmental pollution is reduced, and product consistency is good. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 900(Mo,Fe) prepared in Example 2 of the present invention 3+ )XRD pattern of S-1.0;

[0023] Figure 2 900 (Mo, Fe 3+ ) Raman spectrum of S-1.0 sample;

[0024] Figure 3 900 (Mo, Fe 3+ ) Wave absorption performance diagram of S-0.5 sample;

[0025] Figure 4 900 (Mo, Fe 3+ ) Wave absorption performance diagram of S-1.0 sample;

[0026] Figure 5 900 (Mo, Fe 3+ ) Wave absorption performance diagram of S-1.5 sample;

[0027] Figure 6 700 (Mo, Fe 3+ ) Wave absorption performance diagram of S-1.0 sample;

[0028] Figure 7 800 (Mo, Fe 3+ ) Wave absorption performance diagram of S-1.0 sample. DETAILED DESCRIPTION

[0029] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0030] The following examples are only used to further illustrate the present invention, but do not constitute any limitation to the present invention; the materials used in the following examples, molybdenite origin: Xumu Mountain, Myanmar; molybdenite purity: ≥96.00%. Other materials, unless otherwise specified, were purchased from conventional chemical reagent companies and raw material suppliers.

[0031] Embodiment 1:

[0032] A metal cation hybrid natural molybdenite (Mo,Fe 3+ )S composite absorbing material and a preparation method thereof, comprising the following steps:

[0033] 1) Weigh 10 mmol of molybdenite powder and 5 mmol of ferric chloride hexahydrate using an analytical balance;

[0034] 1) Add molybdenite powder to 10 ml of deionized water, then add ferric chloride hexahydrate powder, stir with electromagnetic stirring for 30 min at a stirring speed of 200 rpm, and mix well;

[0035] 2) Place the mixture obtained in 1) in a drying oven at 80°C overnight until dry;

[0036] 3) placing the mixed powder obtained in 2) in a small porcelain boat and performing heat treatment in a tubular furnace in an Ar atmosphere at a heat treatment temperature of 900° C., a heating rate of 5° C. / min, and a holding time of 6 h;

[0037] 4) Collect the samples obtained in 3), label the samples, and label the calcined products as 900 (Mo, Fe 3+ )S-0.5 sample.

[0038] Embodiment 2:

[0039] The difference from Example 1 is that the amount of ferric chloride hexahydrate in step 1) is changed to 10 mmol, and the calcined product is labeled as 900 (Mo, Fe 3+ )S-1.0 sample; the rest are the same as Example 1.

[0040] Embodiment 3:

[0041] The difference from Example 1 is that the amount of ferric chloride hexahydrate in step 1) is changed to 15 mmol, and the calcined product is labeled as 900 (Mo, Fe 3+ )S-1.5 sample; the rest are the same as in Example 1.

[0042] Figure 1 900(Mo,Fe 3+ )XRD pattern of S-1.0 sample. Figure 1 It can be seen that: 900 (Mo, Fe 3+ )S-1.0 material shows that MoS2 exists as the main phase, and no other compounds are generated.

[0043] Figure 2 900 (Mo, Fe 3+ ) Raman spectrum of S-1.0 sample. The product obtained by the present invention maintains the typical structure of MoS2 1 2g and A 1g .

[0044] Comparative Example 1:

[0045] The difference from Example 2 is that the calcination temperature in step 3) is 700°C; the rest is the same as Example 1. Comparative Example 2:

[0046] The difference from Example 2 is that the calcination temperature in step 3) is 800°C; the rest is the same as Example 1. Electromagnetic absorption property test:

[0047] Take the obtained (Mo,Fe 3+)S composite materials were used as samples, and the dielectric and electromagnetic properties of the materials were analyzed using a vector network analyzer (VNA, Agilent N5234A). The specific method is: paraffin and samples are mixed in a mass ratio of 3:7, and pressed into 22.86×10.16mm block and 15.8×7.9mm block samples for testing, and the vector network analyzer is used to simulate the microwave absorption performance of samples with different thicknesses.

[0048] (Mo,Fe 3+ )S composite material exhibits good wave absorbing performance in both X and Ku bands, among which Example 1 has good wave absorbing performance in X band RL min Reached -19.15dB (9.88GHz, d is 2.4mm), in the Ku band RL min It reaches -23.76dB (at 17.10GHz, d is 1.5mm), such as Figure 3 Example 2: X-band RL min Reached -47.98dB (9.96GHz, d is 2.4mm), in Ku band RL min It reaches -35.24dB (13.41GHz, d is 1.9mm), and the maximum EAB is 5.18GHz (12.15-17.33GHz, d is 1.8mm). As d changes, its EAB can cover the entire X and Ku bands. Figure 4 As shown. With the change of d, (Mo,Fe 3+ )S composite material EAB can also cover the entire X and Ku bands. RL of Example 3 min In the Ku band, the signal reaches -21.42dB at 1.4mm. Figure 5 The above results show that RL min and EAB are affected by the amount of FeCl3·6H2O, while RL min At 900(Mo,Fe 3+ )S-1.0 performed best.

[0049] The (Mo,Fe) with electromagnetic wave absorption performance obtained in Comparative Example 1 3+ )S composite material absorption performance curve is as follows Figure 6 As shown. The (Mo,Fe) with electromagnetic wave absorption performance obtained in Comparative Example 2 3+ )S composite material absorption performance curve is as follows Figure 7 As shown. Figure 6 Figure 7 It can be seen that compared with the sample prepared in Example 2, the sample prepared in the control example has poorer wave absorption performance, which indicates that the temperature causes (Mo, Fe 3+ )The microwave absorption performance of S composite materials is weakened.

[0050] Therefore, in (Mo,Fe 3+ The )S composite material has the best wave absorption performance at 900℃, 10mmol of molybdenite and 10mmol of ferric chloride hexahydrate, showing excellent electromagnetic wave absorption performance, and can be widely used as an electromagnetic wave absorption material in the corresponding electromagnetic protection field.

[0051] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite, It is characterized in that The following steps are involved: 1) adding molybdenite powder and ferric chloride hexahydrate powder into deionized water, stirring and mixing to obtain a mixture; 2) placing the mixture in 1) in a drying oven at 75-90° C. overnight until dry to obtain a mixed powder; 3) placing the mixed powder described in 2) in a small porcelain boat, and subjecting it to heat treatment in a tubular furnace in an argon atmosphere, wherein the heat treatment temperature is 700 to 900° C., the heating rate is 5 to 10° C. / min, and the holding time is 5 to 6 h, to obtain a sample; 4) The sample described in 3) is naturally furnace cooled to room temperature, and the sample is collected and marked to obtain a composite absorbing material of metal cation hybrid natural molybdenite.

2. A method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 1, Features: The molar mass ratio of the molybdenite powder to the ferric chloride hexahydrate powder in 1) is 2:1-3, and the stirring is magnetic stirring for 30-60 minutes.

3. A method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 1 or 2, Features: In 1), the molybdenite powder is first added into the deionized water, and then the ferric chloride hexahydrate powder is added into the deionized water.

4. The method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 1, Features: In the step 3), the temperature is increased to the heat treatment temperature at a heating rate of 5°C / min.

5. The method for preparing a composite wave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 1, Features: The particle size of the molybdenite powder is ≤0.25 mm.

6. A composite microwave absorbing material of metal cation hybrid natural molybdenite prepared by the method for preparing the composite microwave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 1, Features: The composite wave absorbing material of metal cation hybrid natural molybdenite includes MoS 2 With FeCl 3 6H 2 O,FeCl 3 6H 2 O as a doping substance is mixed with natural molybdenite to undergo hybridization reaction in a heat treatment environment.

7. Use of the composite wave absorbing material of metal cation hybrid natural molybdenite as claimed in claim 6 as an electromagnetic wave absorbing material.

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