Carbon and non-stoichiometric carbide hole coated multi-shell porous cobalt material and preparation method thereof
Carbon and non-stoichiometric carbide porous cobalt shell material were prepared by arc smelting and chemical dealloyment methods, which solved the problem of insufficient preparation of nano-scale porous cobalt nanoparticle composite materials, and achieved excellent electromagnetic wave absorption performance under low filling ratio.
Patent Information
- Application Number
- CN202510657859.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-21
- Publication Date
- 2025-08-12
AI Technical Summary
In the prior art, the preparation and microwave absorption performance of nano-scale porous cobalt nanoparticles and their composite materials have not been fully studied, and the lack of surface protection components leads to insufficient performance, and the dielectric components have problems with impedance mismatch and high density. No literature reports have been reported in the systematic study of Ni3ZnC0.7 on the surface of metal substrates and forming a continuous cladding layer.
Carbon and non-stoichiometric carbide pore-cobalt multi-shell material were prepared by arc smelting technology, chemical dealloyment method and solution precipitation method. By controlling the molar ratio of nickel and zinc, Ni3ZnC0.7 precursor was formed, and black nanoparticles were wrapped on the top of the carbon nanotube to form a multi-shell structure.
Excellent electromagnetic wave absorption performance under low filling ratio is achieved. The minimum reflection loss of Co@Ni3ZnC0.7@C material at m(Co@Ni3ZnC0.7@C):m(paraffin)=10% is -51.75dB, and the effective absorption bandwidth is 5.64GHz. The synergistic effect of multiple loss mechanisms improves the electromagnetic wave absorption performance of the material.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of wave absorbing materials, and in particular to a carbon and non-stoichiometric carbide pore-coated multi-shell porous cobalt material and a preparation method thereof. Background Art
[0002] With the development of communication technology and modern science and technology, constructing absorbing materials with light weight, strong absorption, thin thickness and wide frequency characteristics is of great significance to weakening the impact of electromagnetic radiation.
[0003] Magnetic materials such as cobalt (Co), iron (Fe), and nickel (Ni) are promising candidates for high-performance electromagnetic wave absorption due to their unique ferromagnetic properties and significant magnetic loss capabilities. To date, considerable attention has been devoted to alloy precursors in micron-scale particle form. However, the preparation and microwave absorption properties of nanoporous cobalt nanoparticles and their composites remain largely unknown. Liu et al. synthesized 31 nm nanoporous Co NPs (Co@CoO) via a chemical dealloying method, which has many potential applications. Through a passivation process, surface oxidation of Co resulted in the formation of CoO-coated (Co@CoO) microporous Co nanoparticles (10.1039 / c3nr05238a). However, the lack of a protective component inevitably results in the formation of CoO on the surface, and the dielectric component suffers from impedance mismatch and high density, leaving much room for improvement. A common strategy is to combine other dielectric lossy materials, such as carbides, with magnetic metals to design high-performance, low-density composites for electromagnetic wave absorption.
[0004] In recent years, metal carbides with multiple loss mechanisms such as dielectric loss and magnetic loss have emerged as non-stoichiometric bimetallic carbides Ni3ZnC 0.7 It has the advantages of precise control of composition, low synthesis cost, and easier formation of defects, so it has great development potential in the field of microwave absorption. Some researchers have combined it with various carbon materials to enhance dielectric properties and obtain excellent microwave absorption performance. However, there is no literature report on the use of in-situ generation technology to make Ni3ZnC 0.7 Systematic research on the directional growth and formation of continuous coating layers on metal substrates, as for Ni3ZnC 0.7 and carbon-coated porous metal to form many Shell Structural materials are even more of a blank area. Summary of the Invention
[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a carbon and non-stoichiometric carbide pore-coated multi-shell porous cobalt material and a preparation method thereof, wherein the preparation method of the material has the characteristics of strong feasibility and excellent process stability.
[0006] The technical solution adopted in the present invention is:
[0007] The porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores is prepared by arc melting and dealloying Co and Al to obtain porous Co, and then the porous Co, Ni(CH3COO)2·4H2O, Zn(CH3COO)2·2H2O and PTA and TEA are dissolved respectively and mixed for reaction, and then filtered and calcined to obtain the material after the reaction.
[0008] Co@Ni3ZnC 0.7 The average particle size of @C particles is 15-60nm, and a large number of rich and clear CNTs are derived. The irregularly curved tubular carbon nanotubes are intertwined with each other, forming a network structure that promotes conductive loss;
[0009] A large number of black nanoparticles are wrapped on the top of the carbon nanotubes, and the porous Co and Ni3ZnC 0.7 Numerous heterogeneous interfaces are formed between the nanoparticles and between the graphite carbon layers, and the material has a multi-shell structure.
[0010] The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores specifically comprises the following steps:
[0011] (1) Arc melting Co and Al in an argon atmosphere to obtain a Co-Al alloy ingot;
[0012] (2) arc melting the alloy ingot obtained in step (1) in an argon-hydrogen mixed atmosphere, and collecting a first-level nanopowder after reaction passivation;
[0013] (3) adding the primary nanopowder obtained in step (2) to a NaOH solution, chemically dealloying the powder using an ultrasonic cleaner, and vacuum drying the powder to obtain a porous nanoscale Co powder;
[0014] (4) dispersing the porous nanoscale Co powder, Ni(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O obtained in step (3) into DMF, and mechanically stirring to obtain liquid A;
[0015] (5) PTA and TEA were dispersed in DMF and magnetically stirred to obtain Liquid B;
[0016] (6) Pour liquid B into liquid A and continue mechanical stirring to obtain pore-coated Co@Ni3ZnC 0.7 Precursor solution;
[0017] (7) placing the solution obtained in step (6) into a circulating water filter and filtering to obtain a gel sample;
[0018] (8) Take the sample obtained in step (7), calcine it under nitrogen atmosphere, and naturally cool it to room temperature to obtain the pore-coated Co@Ni3ZnC 0.7 @CMulti-shell particles.
[0019] The primary nano powder in step (2) After plasma arc reaction It is obtained by deposition and collection on the inner wall of the reaction chamber cavity; the first-level nanopowder can be divided into ultrafine nanopowder and conventional nanopowder, and their particle sizes are 1-20nm and 20-100nm respectively.
[0020] The primary nanopowder in step (3) is added to a 20 wt% NaOH solution. The amount of NaOH added is calculated based on the Al content and the reaction formula 2Al+2NaOH+6H2O→2Na[Al(OH)4]+3H2. The ultrasonic time and temperature are selected to be 10-30 min and 30-80°C, respectively, to accelerate the reaction rate of Al and NaOH and make the reaction more complete.
[0021] The porous nanoscale Co powder has a spherical shape with numerous pores uniformly dispersed in each nanoparticle. The average diameter of the particles decreases due to the elimination of alumina in the particle shell and aluminum atoms in the particle core during the dealloying process.
[0022] In the step (4), Co powder, 11.25 mmol Ni(CH3COO)2·4H2O and 3.75 mmol Zn(CH3COO)2·2H2O are dispersed in 125-300 mL DMF; wherein the molar ratio of Co powder, Ni(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O is n:3:1 (n=1, 2, 3...).
[0023] By precisely controlling the molar ratio of nickel (Ni) and zinc (Zn), it is possible to ensure that Ni3ZnC with a specific chemical composition is formed in the subsequent reaction. 0.7 Precursor. During the synthesis process, DMF serves as a solvent, facilitating the dissolution and mixing of the metal salts Ni(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O, providing a homogeneous reaction environment for the subsequent coordination reaction. Furthermore, the proportions of Ni(CH3COO)2·4H2O, Zn(CH3COO)2·2H2O, and DMF can be increased or decreased according to experimental needs.
[0024] In the step (4), the mechanical stirring is performed for 0.5-1 h.
[0025] In step (5), 7-10 mmol of PTA and 2-4 ml of TEA are dispersed in 100-300 ml of DMF. PTA, as an organic acid, can participate in the reaction as a ligand or auxiliary ligand during the synthesis process, helping to form a stable metal complex; while TEA, as an alkaline source in the reaction, is used to adjust the pH value of the reaction system. This ratio is more conducive to the complexation and stability of the product. In addition, the proportions of PTA, TEA, and DMF can be increased or decreased according to experimental needs.
[0026] In the step (5), magnetic stirring is performed for 0.5 h to 1 h; and the molar ratio of PTA to TEA is 1:1.4 to 1:4.1.
[0027] In the step (6), the mechanical stirring is performed for 1 h to 20 h.
[0028] In the step (8), the sample obtained in the step (7) is heated to 700-1000° C. at a heating rate of 5° C. / min under a nitrogen atmosphere and kept warm for 10-12 hours.
[0029] The step (8) prepares the porous coated Co@Ni3ZnC 0.7 @CMulti-shell materials are used in the field of wave absorption.
[0030] Beneficial effects of the present invention:
[0031] The outstanding essential feature of the present invention is that it is the first time to use arc melting technology, chemical dealloying method and solution precipitation method to prepare carbon and Ni3ZnC 0.7 The porous cobalt multi-shell material was coated with pores and its electromagnetic parameters and wave absorption performance were tested. Combined with the density of the material, it was found that in m(Co@Ni3ZnC 0.7 @C): m(paraffin) = 10% low filling ratio, Co@Ni3ZnC 0.7 The minimum reflection loss of Co@Ni3ZnC is -51.75dB and the effective absorption bandwidth is 5.64GHz, which confirms that Co@Ni3ZnC 0.7 @C has great development potential in the field of wave absorption.
[0032] The excellent wave absorbing performance is mainly attributed to the following aspects: First, it is mainly composed of Ni3ZnC 0.7 The rich three-dimensional conductive network composed of CNTs catalyzed by Co extends the microcurrent transmission path, thereby promoting conduction loss. The hollow structure inside the CNTs optimizes impedance matching and provides a large contact area, which can enhance multiple reflections and scattering, further improving energy dissipation efficiency. Secondly, the high specific surface area provided by porous Co increases the contact area with Ni3ZnC 0.7 interface, so Co and Ni3ZnC 0.7 、Ni3ZnC 0.7The change in electronegativity at the interface with the graphite carbon layer contributes to the space charge polarization and enhances the dielectric loss. 0.7 The magnetic coupling between Co and the divergent magnetic flux lines build a multi-dimensional magnetic response network, which improves the magnetic loss of the material. 0.7 @C has achieved excellent electromagnetic wave absorption performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1 Co, Ni3ZnC obtained in Example 1 0.7 Co@Ni3ZnC at a molar ratio of 1.5:1 0.7 @X-ray diffraction spectrum of C material.
[0034] Figure 2 Co, Ni3ZnC obtained in Example 1 0.7 Co@Ni3ZnC at a molar ratio of 1.5:1 0.7 @Scanning electron microscope image of C material.
[0035] Figure 3 In Example 2, when m(Co@Ni3ZnC 0.7 @C): When m(paraffin)=10%, Co, Ni3ZnC 0.7 Co@Ni3ZnC at a molar ratio of 1.5:1 0.7 @C material performance diagram.
[0036] Figure 4 In Example 3, when m(Co@Ni3ZnC 0.7 @C): When m(paraffin)=10%, Co, Ni3ZnC 0.7 Co@Ni3ZnC at a molar ratio of 1:1 0.7 @C material performance diagram. DETAILED DESCRIPTION
[0037] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0038] Example 1
[0039] (1) 34.297 g of Co and 15.703 g of Al were weighed separately, placed on A4 paper, transferred to a copper crucible, and prepared into a Co-Al ingot in an argon atmosphere;
[0040] (2) arc melting the alloy ingot obtained in step (1) in an argon-hydrogen mixed atmosphere, and collecting the primary nanopowder on the inner wall of the reaction chamber after reaction passivation;
[0041] (3) adding the powder obtained in step (2) to a 20 wt% NaOH solution (100 mL) and chemically dealloying the solution using an ultrasonic cleaner and vacuum drying the solution. The ultrasonic time and temperature were set to 10 min and 50° C., respectively, to obtain a porous nanoscale Co powder.
[0042] (4) 0.0828 g of the powder obtained in step (3), 1.875 mmol of Ni(CH3COO)2·4H2O, and 1.875 mmol of Zn(CH3COO)2·2H2O were dispersed in 20.834 mL of DMF and mechanically stirred for 0.5 h to obtain liquid A;
[0043] (5) 1.5 mmol PTA and 0.354 mL TEA were dispersed in 16.667 mL DMF and magnetically stirred for 0.5 h to obtain Liquid B;
[0044] (6) Pour liquid B into liquid A and continue mechanical stirring for 1 hour to obtain Co / Ni3ZnC 0.7 Precursor solution;
[0045] (7) placing the solution obtained in step (6) into a circulating water filter and filtering to obtain a gel sample;
[0046] (8) Take the sample obtained in step (7), directly heat it to 700℃ under 5℃ / min nitrogen atmosphere and anneal it for 10h, and then cool it to room temperature naturally to obtain Co@Ni3ZnC 0.7 @C.
[0047] The prepared Co@Ni3ZnC 0.7 The @C material was characterized by X-ray diffractometer, and the results were as follows Figure 1 As shown in Figure 2, the broad peak at 26° corresponds to the peak of amorphous carbon (JCPDS 41-1487). Meanwhile, the peaks at 42.97°, 50.08°, and 73.34° correspond to the peaks of Ni3ZnC 0.7 The (111), (200) and (220) planes of Co@Ni3ZnC are in good agreement with the (111), (200) and (220) planes of Co@Ni3ZnC (JCPDS28-0713). The diffraction peaks of (110), (200) and (220) planes of Co@Ni3ZnC are located at 44.10°, 51.65° and 75.84°, respectively (JCPDS15-0806). The absence of other impurity peaks proves the successful chemical dealloying and the successful preparation of Co@Ni3ZnC. 0.7 @C composite materials. Then the Co@Ni3ZnC 0.7 @C was characterized by morphology, such as Figure 2As shown in Figure 2, there is no obvious agglomeration of black particles, and the average particle size is mainly concentrated at 24.87 nm (a). 0.7 @C particles derive a large number of rich and clear CNTs. Irregularly curved tubular carbon nanotubes intertwine with each other to form a network structure that promotes conductive loss. The enlarged view further shows that a large number of black nanoparticles are wrapped around the top of the carbon nanotubes (b). High-resolution transmission electron microscopy images show that the diameter of the magnetic nanoparticles is only about 27.10 nanometers, and the porous Co and Ni3ZnC inside the nanoparticles are 0.7 Numerous heterogeneous interfaces are formed between the nanoparticles and the graphite carbon layer, which also confirms the core-shell structure of the material. In addition, according to the energy dispersive spectrum results, the distribution of C, Co, Ni, and Zn elements further confirms that Ni3ZnC 0.7 It was successfully in situ generated inside and on the surface of porous Co and catalyzed the formation of graphite carbon layers on the particle surface to form a core-shell structure, which is consistent with the high-resolution transmission results.
[0048] Example 2
[0049] Preparation of Co and Ni3ZnC 0.7 Co@Ni3ZnC at a molar ratio of 1.5:1 0.7 @C material and prepare a test ring with a paraffin wax filling ratio of 10%. The specific steps are as follows:
[0050] (1) 34.297 g of Co and 15.703 g of Al were weighed separately, placed on A4 paper, transferred to a copper crucible, and prepared into a Co-Al ingot in an argon atmosphere;
[0051] (2) arc melting the alloy ingot obtained in step (1) in an argon-hydrogen mixed atmosphere, and collecting the primary nanopowder on the inner wall of the reaction chamber after reaction passivation;
[0052] (3) adding the powder obtained in step (2) to a 20 wt% NaOH solution (100 mL) and chemically dealloying the solution using an ultrasonic cleaner and vacuum drying the solution. The ultrasonic time and temperature were set to 10 min and 50° C., respectively, to obtain a porous nanoscale Co powder.
[0053] (4) 0.0828 g of the powder obtained in step (3), 1.875 mmol of Ni(CH3COO)2·4H2O, and 1.875 mmol of Zn(CH3COO)2·2H2O were dispersed in 20.834 mL of DMF and mechanically stirred for 0.5 h to obtain liquid A;
[0054] (5) 1.5 mmol PTA and 0.354 mL TEA were dispersed in 16.667 mL DMF and magnetically stirred for 0.5 h to obtain Liquid B;
[0055] (6) Pour liquid B into liquid A and continue mechanical stirring for 1 h to obtain Co@Ni3ZnC 0.7 Precursor solution;
[0056] (7) placing the solution obtained in step (6) into a circulating water filter and filtering to obtain a gel sample;
[0057] (8) Take the sample obtained in step (7), directly heat it to 700℃ under 5℃ / min nitrogen atmosphere and anneal it for 10h, and then cool it to room temperature naturally to obtain Co@Ni3ZnC 0.7 @C.
[0058] (9) Weigh 0.01g Co@Ni3ZnC 0.7 @C powder and 0.09g paraffin (m(Co@Ni3ZnC 0.7 @C):m (paraffin wax) = 10%) and mix them. Place the mixture in a container and melt the paraffin wax using the heating function of a constant temperature magnetic stirrer. Stir gently with a spatula until the mixture is evenly mixed. Place it in a mold and apply pressure to prepare a paraffin-filled Co@Ni3ZnC with an outer diameter of 7mm and an inner diameter of 3.04mm with a filling ratio of 10%. 0.7 @C Test loop.
[0059] The paraffin filling ratio 10% Co@Ni3ZnC prepared in Example 2 was analyzed by vector network analyzer (3656D). 0.7 @C test ring to test the absorption performance. Figure 3 Display, Ni3InC 0.5 The minimum reflection loss is -51.75dB and the effective absorption bandwidth is 5.64GHz.
[0060] Example 3
[0061] Preparation of Co and Ni3ZnC 0.7 When the molar ratio is 1:1, Co@Ni3ZnC 0.7 @C material and prepare a test ring with a paraffin wax filling ratio of 10%. The specific steps are as follows:
[0062] (1) 34.297 g of Co and 15.703 g of Al were weighed separately, placed on A4 paper, transferred to a copper crucible, and prepared into a Co-Al ingot in an argon atmosphere;
[0063] (2) arc melting the alloy ingot obtained in step (1) in an argon-hydrogen mixed atmosphere, and collecting the primary nanopowder on the inner wall of the reaction chamber after reaction passivation;
[0064] (3) adding the powder obtained in step (2) to a 20 wt% NaOH solution (100 mL) and chemically dealloying the solution using an ultrasonic cleaner and vacuum drying the solution. The ultrasonic time and temperature were set to 10 min and 50° C., respectively, to obtain a porous nanoscale Co powder.
[0065] (4) 0.0552 g of the powder obtained in step (3), 1.875 mmol of Ni(CH3COO)2·4H2O, and 1.875 mmol of Zn(CH3COO)2·2H2O were dispersed in 20.834 mL of DMF and mechanically stirred for 0.5 h to obtain liquid A;
[0066] (5) 1.5 mmol PTA and 0.354 mL TEA were dispersed in 16.667 mL DMF and magnetically stirred for 0.5 h to obtain Liquid B;
[0067] (6) Pour liquid B into liquid A and continue mechanical stirring for 1 h to obtain Co@Ni3ZnC 0.7 Precursor solution;
[0068] (7) placing the solution obtained in step (6) into a circulating water filter and filtering to obtain a gel sample;
[0069] (8) Take the sample obtained in step (7), directly heat it to 700℃ under 5℃ / min nitrogen atmosphere and anneal it for 10h, and then cool it to room temperature naturally to obtain Co@Ni3ZnC 0.7 @C.
[0070] (9) Weigh 0.01g Co@Ni3ZnC 0.7 @C powder and 0.09g paraffin (m(Co@Ni3ZnC 0.7 @C):m (paraffin wax) = 10%) and mix them. Place the mixture in a container and melt the paraffin wax using the heating function of a constant temperature magnetic stirrer. Stir gently with a spatula until the mixture is evenly mixed. Place it in a mold and apply pressure to prepare a paraffin-filled Co@Ni3ZnC with an outer diameter of 7mm and an inner diameter of 3.04mm with a filling ratio of 10%. 0.7 @C Test loop.
[0071] The paraffin filling ratio 10% Co@Ni3ZnC prepared in Example 3 was measured by vector network analyzer (3656D). 0.7 @C test ring to test the absorption performance. Figure 4 Display, Ni3InC 0.5 The minimum reflection loss is -44.89dB and the effective absorption bandwidth is 5.60GHz.
[0072] In summary, the above are merely embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.
Claims
1. A porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores, characterized in that: Co@Ni3ZnC 0.7 The average particle size of @C particles is 15-60 nm, and a large number of rich and clear CNTs are derived. The irregularly curved tubular carbon nanotubes are intertwined with each other, forming a network structure that promotes conductive loss; A large number of black nanoparticles are wrapped on the top of the carbon nanotubes, and the porous Co and Ni3ZnC 0.7 Numerous heterogeneous interfaces are formed between the nanoparticles and between the graphite carbon layers, and the material has a multi-shell structure.
2. A method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores, characterized in that: The specific steps include: (1) Arc melting Co and Al in an argon atmosphere to obtain a Co-Al alloy ingot; (2) arc melting the alloy ingot obtained in step (1) in an argon-hydrogen mixed atmosphere, and collecting a first-level nanopowder after reaction passivation; (3) adding the primary nanopowder obtained in step (2) to a NaOH solution, chemically dealloying the powder using an ultrasonic cleaner, and vacuum drying the powder to obtain a porous nanoscale Co powder; (4) The porous nanoscale Co powder, Ni(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O obtained in step (3) were dispersed in DMF and mechanically stirred to obtain liquid A; (5) PTA and TEA were dispersed in DMF and magnetically stirred to obtain liquid B; (6) Pour liquid B into liquid A and continue mechanical stirring to obtain pore-coated Co@Ni3ZnC 0.7 Precursor solution; (7) The solution obtained in step (6) is placed in a circulating water filter and filtered to obtain a gel sample; (8) The sample obtained in step (7) was calcined under nitrogen atmosphere and naturally cooled to room temperature to obtain the pore-coated Co@Ni3ZnC 0.7 @CMulti-shell particles.
3. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: The first-level nanopowder in step (2) is obtained by being deposited and collected on the inner wall of the reaction chamber after the plasma arc reaction; the first-level nanopowder can be divided into ultrafine nanopowder and conventional nanopowder, and their particle sizes are 1-20 nm and 20-100 nm, respectively.
4. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: The first-level nanopowder in step (3) is added to a 20 wt% NaOH solution. The amount of NaOH added should be based on the Al content and The reaction formula showed that the selected ultrasonic time and temperature were 10-30 min and 30-80 ℃, respectively.
5. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In the step (4), Co powder, 11.25 mmol Ni(CH3COO)2·4H2O and 3.75 mmol Zn(CH3COO)2·2H2O are dispersed in 125-300 mL DMF; wherein the molar ratio of Co powder, Ni(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O is n:3:1 (n=1, 2, 3...).
6. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In the step (4), the mechanical stirring is performed for 0.5-1 h.
7. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In the step (5), 7-10 mmol PTA and 2-4 ml TEA are dispersed in 100-300 ml DMF.
8. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In step (5), magnetic stirring is performed for 0.5 h to 1 h; The molar ratio between PTA and TEA is 1:1.4-1:4.
1.
9. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In the step (6), the mechanical stirring is performed for 1 h to 20 h.
10. The method for preparing a porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide pores according to claim 2, characterized in that: In the step (8), the sample obtained in the step (7) is heated to 700-1000°C at a heating rate of 5°C / min under a nitrogen atmosphere and kept at that temperature for 10-12 hours.
11. The use of the porous cobalt multi-shell material coated with carbon and non-stoichiometric carbide according to any one of claims 1 to 10, characterized in that: The step (8) prepares the porous coated Co@Ni3ZnC 0.7 @CMulti-shell materials are used in the field of wave absorption.