Method for preparing magnetic metal or alloy-coated two-dimensional basalt microparticle composite

Abstract

The application relates to a preparation method of a two-dimensional basalt microparticle composite material coated with a magnetic metal or alloy, and belongs to the field of microwave absorbing materials. In order to solve the problem that the existing basalt matrix coated with a metal or alloy layer causes great reduction of magnetic loss capacity and electric conduction loss, the method comprises the following steps: S10, attaching trace palladium (Pd) particles to basalt; S20, attaching magnetic metal nanoparticles to the basalt with the trace palladium (Pd) particles obtained in the step S10; and S30, coating a magnetic metal layer on the basalt with the magnetic metal nanoparticles obtained in the step S20. The method has the effects of realizing uniform coating of the metal or alloy layer, improving the electric conduction loss, and not introducing B impurities and weakening the magnetic loss capacity.

Description

Technical Field

[0001] This invention belongs to the field of microwave absorbing materials, specifically relating to a material composed of two-dimensional basalt microsheets and magnetic metals, bicomponent magnetic alloys, or multicomponent FeCoNi alloys, and a method for preparing the material. Background Technology

[0002] With the continuous promotion and application of electronic mobile communication devices, wireless networks, and electronic devices, electromagnetic pollution and the harm of electromagnetic waves to human health are increasingly attracting attention. Electromagnetic absorbing materials absorb and reduce the electromagnetic waves that cause pollution without causing secondary pollution. Therefore, research on electromagnetic waves is becoming an increasingly important focus. Fe, Co, and Ni are common magnetic loss-type absorbing materials. In particular, the composite of magnetic metals with dielectric substrates, such as carbon materials, SiO2, metal oxides, and metal sulfides, does not inhibit the coupling between magnetic particles due to the magnetic material being covered by the dielectric material. Furthermore, the rearrangement of the magnetic metals can adjust and optimize the dielectric loss, making it a potential class of microwave absorbing composite materials. Chemical plating is a common method for composites of magnetic metals or alloys onto dielectric substrates. This method is environmentally friendly, energy-saving, and simple.

[0003] For example, Pan F et al. [Pan F, Cai L, Shi Y, et al. Phase engineering reinforced multiple loss network in apple tree-like liquid metal / Ni-Ni3P / N-doped carbon fiber composites for high-performance microwave absorption[J]. Chemical Engineering Journal, 2022, 435: 135009] constructed a composite material of metallic nickel and carbon fiber for use as an electromagnetic microwave absorbing material. Similarly, Najim M et al. [Najim M, Modi G, Mishra YK, et al. Ultra-widebandwidth with enhanced microwave absorption of electroless Ni–P coated tetrapod-shaped ZnO nano-and microstructures[J]. Physical Chemistry Chemical Physics, 2015, 17(35): 22923-22933.] coated zinc oxide with metallic nickel. Compared to carbon fiber and zinc oxide alone, nickel-coated carbon fiber and zinc oxide exhibited superior electromagnetic loss capability and microwave absorption performance.

[0004] However, in current electroless plating processes for coating metal layers onto substrates, dimethylamine borane (DMAB) is often used as a reducing agent to directly form the metal coating. While this method offers slightly better coating uniformity, the resulting metal layer is often amorphous and introduces impurities such as phosphorus, significantly weakening magnetic loss capability. Using hydrazine hydrate as a reducing agent can form highly crystalline metal elements free of any impurities, but hydrazine's strong reducing power is difficult to control, and the resulting magnetic metal tends to self-aggregate during reduction, making it difficult to recombine with the substrate. This is especially true for basalt substrates, which are inert materials. The substrate surface contains only a small number of hydroxyl groups and no other functional groups, further hindering the catalytic recombination with magnetic metal particles. Even after activation and sensitization, preferably using micron-sized flaky basalt as a substrate, immersing it in a solution of magnetic metals such as Ni and Co using hydrazine as a reducing agent results in a composite of magnetic metal and basalt with a morphology resembling a mixture of magnetic metal and basalt. Only a very small number of magnetic particles adhere to the basalt surface. Figure 3This type of magnetic metal combined with basalt has poor conductivity and polarization loss performance, and cannot simultaneously improve magnetic loss and dielectric loss capabilities. Summary of the Invention

[0005] To address the issue of simultaneously improving the magnetic and electrical losses of existing basalt-matrix-coated metal or alloy-coated microwave absorbing materials, and to achieve uniform metal or alloy coating, increased electrical losses, and the absence of impurities such as boron introduced into the metal or alloy layer to avoid weakening the magnetic loss capability, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material according to some embodiments of this application is provided, in a first aspect, comprising:

[0006] S10. Attach trace amounts of palladium (Pd) particles to basalt;

[0007] S20. Attach magnetic metal nanoparticles to the basalt with trace amounts of palladium (Pd) particles obtained in step S10.

[0008] S30. Coat the basalt with attached magnetic metal nanoparticles obtained in step S20 with a magnetic metal layer.

[0009] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described. Step S10 specifically includes repeatedly sensitizing and activating basalt. After repeated sensitization and activation, the resulting product is vacuum dried for 3-12 hours at a temperature of 55-65°C. The product obtained after drying is basalt with trace amounts of palladium (Pd) particles attached. The sensitization process includes immersing the basalt in a hydrochloric acid solution with a concentration of 0.05-0.5 mol / L and a concentration of 0.1-1 mol / L stannous chloride, and stirring at room temperature for 60 minutes. The activation process includes filtering and washing the product obtained from the sensitization process with deionized water, then adding it to a hydrochloric acid solution with a concentration of 0.1-2 g / L and a concentration of 0.1-1 mol / L palladium chloride, and stirring at room temperature for 60 minutes.

[0010] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described, wherein step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution includes one of nickel sulfate hexahydrate (NiSO4·6H2O) and cobalt sulfate heptahydrate (CoSO4·7H2O), and also includes one or a combination of two of sodium citrate dihydrate (Na3C6H5O7·2H2O) and sodium succinate (C4H4Na2O4). The reaction solution also includes dimethylamine borane (DMAB) and water (H2O).

[0011] Step S30 includes adding basalt with attached magnetic metal nanoparticles to a reaction solution. The reaction solution includes one of nickel sulfate hexahydrate (NiSO4·6H2O) and cobalt sulfate heptahydrate (CoSO4·7H2O). The reaction solution also includes one or two of sodium citrate dihydrate (Na3C6H5O7·2H2O) and potassium sodium tartrate (NaKC4H4O6). The reaction solution also includes sodium hydroxide (NaOH), hydrazine hydrate (N2H4·H2O, 80%), and water (H2O).

[0012] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described. In step S20, the magnetic metal nanoparticles include Co(B) nanoparticles. Step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution contains cobalt sulfate heptahydrate (CoSO4·7H2O): sodium succinate (C4H4Na2O4): dimethylamine borane (DMAB): water (H2O) = 0.281–0.843 g: 0.486–0.81 g: 0.177–0.471 g: 30–60 ml. The reaction temperature is 10–30°C, and the reaction time is 30–120 min. After the reaction, the product is filtered and washed with deionized water, and then vacuum dried at 55–65°C to obtain basalt with attached magnetic metal nanoparticles.

[0013] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described. In step S30, the magnetic metal layer comprises a Co metal layer. Step S30 includes adding basalt with attached magnetic metal nanoparticles to a reaction solution. The reaction solution contains cobalt sulfate heptahydrate (CoSO4·7H2O): potassium sodium tartrate (NaKC4H4O6): sodium hydroxide (NaOH): hydrazine hydrate (N2H4·H2O): water (H2O) in the following proportions: 1.686–2.81 g: 1.892–3.153 g: 0.45 g–1.6 g: 1–6 ml: 100–200 ml. The reaction is carried out in an oil bath at a temperature of 50–60°C for 30–120 min. The product obtained after the reaction is washed with deionized water and dried under vacuum at 55–65°C to obtain basalt coated with a magnetic metal layer.

[0014] In a second aspect, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material according to some embodiments of this application includes:

[0015] S10. Attach trace amounts of palladium (Pd) particles to basalt;

[0016] S20. Attach magnetic metal nanoparticles to the basalt with trace amounts of palladium (Pd) particles obtained in step S10.

[0017] S30. Coat the basalt with magnetic metal nanoparticles obtained in step S20 with an alloy layer.

[0018] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described. Step S10 specifically includes repeatedly sensitizing and activating basalt. After repeated sensitization and activation, the resulting product is vacuum dried for 3-12 hours at a temperature of 55-65°C. The product obtained after drying is basalt with trace amounts of palladium (Pd) particles attached. The sensitization process includes immersing the basalt in a hydrochloric acid solution with a concentration of 0.05-0.5 mol / L and a concentration of 0.1-1 mol / L stannous chloride, and stirring at room temperature for 60 minutes. The activation process includes filtering and washing the product obtained from the sensitization process with deionized water, then adding it to a hydrochloric acid solution with a concentration of 0.1-2 g / L and a concentration of 0.1-1 mol / L palladium chloride, and stirring at room temperature for 60 minutes.

[0019] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described, wherein step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution includes one or more of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), and ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O). The reaction solution also includes one or more of sodium citrate dihydrate (Na3C6H5O7·2H2O) and sodium succinate (C4H4Na2O4). The reaction solution also includes dimethylamine borane (DMAB) and water (H2O).

[0020] Step S30 includes adding basalt with trace amounts of palladium (Pd) particles to a reaction solution. The reaction solution contains two or more of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), and ferrous sulfate heptahydrate (FeSO4·7H2O). The reaction solution also contains one or two of sodium citrate dihydrate (Na3C6H5O7·2H2O) and potassium sodium tartrate (NaKC4H4O6). The reaction solution also contains sodium hydroxide (NaOH), hydrazine hydrate (N2H4·H2O, 80%), and water (H2O).

[0021] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described. In step S20, the magnetic metal nanoparticles include magnetic CoNi(B) nanoparticles. Step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution contains nickel sulfate hexahydrate (NiSO4·6H2O): cobalt sulfate heptahydrate (CoSO4·7H2O): sodium citrate dihydrate (Na3C6H2O). The reaction mixture of dimethylamine borane (DMAB) and water (H2O) was 0.263–1.051 g, 0.281–1.124 g, 0.588–1.47 g, and 0.294–0.885 g, with a total volume of 30–60 ml. The reaction temperature was 10–30 °C, and the reaction time was 30–120 min. The product obtained after the reaction was filtered and washed with deionized water, and then dried under vacuum at 55–65 °C to obtain basalt with attached magnetic metal nanoparticles.

[0022] According to some embodiments of this application, a method for preparing a magnetic metal-coated two-dimensional basalt microsheet composite material is described, wherein the alloy layer in step S30 comprises a multi-component FeCoNi alloy, and step S30 includes adding basalt with attached magnetic metal nanoparticles to a reaction solution, wherein the reaction solution contains nickel sulfate hexahydrate (NiSO4·6H2O): cobalt sulfate heptahydrate (CoSO4·7H2O): ferrous sulfate heptahydrate (FeSO4·7H2O): sodium citrate dihydrate (Na3C6H5O7·2H2O). Sodium hydroxide (NaOH): hydrazine hydrate (N2H·H2O): water (H2O) = 0.784~1.573g: 0.562~1.407g: 0.556~1.390g: 2.941~4.705g: 0.45~1.6g: 1~6ml: 100~200ml. The reaction was carried out in an oil bath at a temperature of 70~90℃ for 30~120min. The product obtained after the reaction was washed with deionized water and dried under vacuum at 55~65℃ to obtain basalt with an alloy coating.

[0023] The beneficial effects of this invention are:

[0024] In the first aspect, the present invention optimizes the electroless plating process. In step S10, basalt is successively immersed in hydrochloric acid solution of stannous chloride and hydrochloric acid solution of palladium chloride, and the sites and quantities of Pd on the basalt surface are controlled by repeated cycles. In step (2), Pd particles on the basalt surface catalyze the composite of magnetic metal nanoparticles with the basalt surface. In step (3), the magnetic metal nanoparticles on the basalt surface further catalyze the composite of magnetic metal, bicomponent magnetic alloy or multicomponent FeCoNi alloy with hydrazine as a reducing agent and basalt, and finally obtain a basalt composite with a uniform and tight coating of metal or alloy layer.

[0025] Secondly, this invention enables the uniform deposition of monocomponent magnetic metals, bicomponent or ternary magnetic alloys onto the surface of a ceramic basalt matrix, yielding various magnetic metal-basalt composites for use as microwave absorbing materials. This invention first attaches trace amounts of palladium (Pd) particles to basalt, then attaches magnetic metal nanoparticles, further forming a magnetic alloy coated with monocomponent, bicomponent, or ternary magnetic metals. While this approach directly coats the basalt surface with magnetic particles, and although dimethylamine borane (DMAB) introduces impurity B, it is understood that the significant reduction in magnetic loss capability is only due to the introduction of impurity B into the final metal layer used for coating. Firstly, the magnetic particles formed in this step of the invention possess inherent magnetic properties, thus not leading to a reduction in overall magnetic loss performance. Secondly, this step does not form the final metal layer used for coating, but rather for attaching the magnetic particles. The metal layer formed in step S30 of the invention does not contain impurity B, thus not significantly weakening the magnetic loss capability. Furthermore, the direct coupling between the magnetic particles formed in step S30 is more conducive to improving magnetic loss. On the other hand, in step S30 of forming the coating layer, the reducing agent hydrazine hydrate can still be used. The resulting magnetic metal, bicomponent magnetic alloy, or multicomponent FeCoNi alloy is uniformly free of impurities such as B, and will not form phosphides or borides that reduce magnetic loss performance. However, by forming a coating layer on top of the magnetic metal nanoparticles in step S20, the metal layer is no longer difficult to combine with the substrate. The metal or alloy layer can be uniformly and densely coated on the surface of the ceramic substrate, thereby not hindering electron migration and contributing to the improvement of conductivity loss. The large heterogeneous interface formed between the metal layer and the ceramic substrate helps to improve dielectric loss capability, and the direct coupling between the magnetic particles in the metal layer helps to improve magnetic loss performance.

[0026] In a third aspect, Embodiment 1 of the present invention is a prior art example. In Embodiment 1, the magnetic Co particles obtained by immersing basalt in a composite solution of Co with hydrazine as a reducing agent mostly agglomerated and grew on their own, with only a small portion growing on the surface of the basalt (e.g., Figure 3 (As shown). In this invention, activated and sensitized basalt is reduced and grown with dimethylamine borane (DMAB) to form magnetic nanoparticles on its surface. The basalt with the magnetic nanoparticles can catalyze the reduction of magnetic metals by hydrazine, and magnetic alloy layers can grow uniformly on the basalt surface (e.g., ...). Figure 5 , Figure 12 and Figure 13 As shown, this method achieves uniform coating of a magnetic metal or alloy layer without non-metallic impurities on the surface of basalt. Attached image description:

[0027] Figure 1 This is a flowchart of a basalt composite monocomponent magnetic metal, a bicomponent or ternary magnetic alloy.

[0028] Figure 2 This is a SEM image of basalt.

[0029] Figure 3 SEM images of basalt composite Co particles.

[0030] Figure 4 The image shows a SEM image of a composite Co(B) nanolayer on a basalt surface. Co(B) indicates that the cobalt nanoparticles contain boron.

[0031] Figure 5 SEM images of the composite Co metal layer on the surface of basalt.

[0032] Figure 6 The image shows the SEM pattern of CoNi(B) nanoparticles on the surface of basalt. CoNi(B) indicates that the cobalt-nickel nanoparticles contain boron.

[0033] Figure 7 The XRD pattern of the basalt composite FeCoNi alloy.

[0034] Figure 8 This is a SEM image of a basalt-FeCoNi composite alloy.

[0035] Figure 9 This is a SEM image of a basalt-FeCoNi composite alloy.

[0036] Figure 10 for Figure 9 EDS energy dispersive spectroscopy (EDS) spectrum of the medium basalt composite FeCoNi alloy.

[0037] Figure 11 SEM image of CoNi(B) nanoparticles composited on basalt surface.

[0038] Figure 12 This is a SEM image of a FeCoNi alloy composite on a basalt surface.

[0039] Figure 13 This is a SEM image of a FeCoNi alloy composite on a basalt surface.

[0040] Figure 14 for Figure 13EDS energy dispersive spectroscopy (EDS) spectrum of FeCoNi alloy composite on medium basalt surface.

[0041] Figure 15 This is a SEM image of NiFe(B) nanoparticles composited on a basalt surface.

[0042] Figure 16 This is a SEM image of a NiFe(B) nanolayer composite on a basalt surface. Detailed Implementation

[0043] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The described embodiments are only possible technical implementations of the present invention and not all possible implementations. Those skilled in the art can obtain other embodiments in conjunction with the embodiments of the present invention without creative effort, and these embodiments are also within the protection scope of the present invention.

[0044] In some embodiments, the present invention aims to address the shortcomings of current electroless plating methods in composite bonding between metal layers and basalt substrates, and provides a material and its preparation method that is a composite of two-dimensional basalt microsheets with magnetic metals, bicomponent magnetic alloys, or multicomponent FeCoNi alloys. Figure 1 As shown, the preparation method of the magnetic metal or alloy-coated two-dimensional basalt microsheet composite material includes:

[0045] (1) Preparation of basalt with trace Pd particles attached: Basalt was immersed in hydrochloric acid solution of stannous chloride for sensitization treatment. The mixture was stirred at room temperature for 60 min. The product was filtered and washed with deionized water and then added to hydrochloric acid solution of palladium chloride for activation treatment. The mixture was stirred at room temperature for 60 min and then filtered and washed with deionized water. After repeated cycles of sensitization and activation, the product was vacuum dried at 60 °C. The obtained product was basalt with trace Pd particles attached.

[0046] (2) Preparation of basalt with magnetic nanoparticles attached: The basalt with trace amounts of Pd particles obtained in step (1) was added to the reaction solution containing nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O), sodium citrate dihydrate (Na3C6H5O7·2H2O), sodium succinate (C4H4Na2O4) and dimethylamine borane (DMAB). The reaction was carried out at a certain temperature for a certain time. The product was filtered and washed with deionized water and dried under vacuum at 60°C to obtain basalt with magnetic nanoparticles attached.

[0047] (3) Preparation of basalt uniformly coated with magnetic metal layer, bicomponent alloy or multicomponent FeCoNi alloy layer: The basalt with magnetic nanoparticles obtained in step (2) is added to the reaction solution, which contains nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), ferrous sulfate heptahydrate (FeSO4·7H2O), sodium citrate dihydrate (Na3C6H5O7·2H2O), potassium sodium tartrate (NaKC4H4O6), sodium hydroxide (NaOH) and hydrazine hydrate (N2H4·H2O, 80%). The reaction is carried out under oil bath conditions for a certain time. The product is washed with deionized water and dried under vacuum at 60°C to obtain basalt uniformly coated with magnetic metal or alloy layer.

[0048] In the preferred embodiment, the concentration of hydrochloric acid used in step (1) is 0.1–1 mol / L, more preferably 1 mol / L. The concentration of stannous chloride used in step (1) is 0.05–0.5 mol / L, more preferably 0.2 mol / L. The concentration of palladium chloride used in step (1) is 0.1–2 g / L, more preferably 1 g / L. After immersion in the hydrochloric acid solution of stannous chloride in step (1), the basalt is filtered and washed with deionized water, and then immersed in the hydrochloric acid solution of palladium chloride. This constitutes one cycle. After filtration and washing, the basalt is then successively immersed in the hydrochloric acid solution of stannous chloride and the hydrochloric acid solution of palladium chloride. This cycle is repeated 5–7 times. After the process of successively immersing the basalt in the hydrochloric acid solution of stannous chloride and the hydrochloric acid solution of palladium chloride in step (1) is repeated multiple times, the basalt is filtered and washed with deionized water, and then dried in a vacuum. The vacuum drying time in step (1) is 3–12 hours, preferably 12 hours. The ratio of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O), sodium citrate dihydrate (Na3C6H5O7·2H2O), sodium succinate (C4H4Na2O4), dimethylamine borane (DMAB), and water in the reaction solution in step (2) is 0–1.051 g: 0–1.124 g: 0–0.784 g: 0–1.47 g: 0–0.810 g: 0.294–0.885 g: 20–100 ml.

[0049] In a preferred embodiment, the type of nanoparticles obtained on the basalt surface can be controlled by adjusting the types of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), and ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O) added in step (2). For example, the basalt obtained in step (1) can be immersed in a reaction solution of nickel sulfate hexahydrate (NiSO4·6H2O), sodium succinate (C4H4Na2O4), and dimethylamine borane (DMAB) to obtain a basalt surface with Ni(B). Similarly, the basalt surface obtained in a reaction solution of cobalt sulfate heptahydrate (CoSO4·7H2O), sodium succinate (C4H4Na2O4), and dimethylamine borane (DMAB) has a Co(B) nanoparticle surface (e.g., ...). Figure 4 (As shown).

[0050] In a preferred embodiment, step (2) involves controlling the types and proportions of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), and ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O) added to the reaction solution. This allows the formation of nanoparticles of different alloys on the basalt surface. For example, immersing the basalt obtained in step (1) into a reaction solution of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), sodium citrate dihydrate (Na3C6H5O7·2H2O), and dimethylamine borane (DMAB) yields CoNi(B) alloy nanoparticles on the basalt surface. Figure 6 and Figure 11 As shown), by adjusting the ratio of nickel sulfate hexahydrate (NiSO4·6H2O) and cobalt sulfate heptahydrate (CoSO4·7H2O), different types of CoNi(B) alloy particles can be obtained; basalt obtained in step (1) is immersed in a reaction solution of nickel sulfate hexahydrate (NiSO4·6H2O), ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O), sodium succinate (C4H4Na2O4), sodium citrate dihydrate (Na3C6H5O7·2H2O), and dimethylamine borane (DMAB) to obtain NiFe(B) nanoparticles (such as...) on the surface of basalt. Figure 15 as well as Figure 16 As shown in the figure, by adjusting the addition ratio of nickel sulfate hexahydrate (NiSO4·6H2O) and ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O) in the solution, different types of NiFe(B) nanoparticles can be obtained.

[0051] In a preferred embodiment, the number of nanoparticles on the basalt surface can be controlled by adjusting the amount of metal salt added in step (2). Taking CoNi(B) nanoparticles as an example, in Example 3, the basalt from step (1) was added to the reaction solution, which contained 281 mg of nickel sulfate hexahydrate (NiSO4·6H2O) and 281 mg of cobalt sulfate heptahydrate (CoSO4·7H2O), resulting in the following... Figure 6 The basalt shown has a surface containing a small amount of CoNi(B) nanoparticles. In Example 4, when the reaction solution contained 0.789 g of nickel sulfate hexahydrate (NiSO4·6H2O) and 0.562 g of cobalt sulfate heptahydrate (CoSO4·7H2O), a large number of CoNi(B) nanoparticles were obtained, forming a nanolayer coating on the basalt surface. Figure 11 As shown, the number of magnetic nanoparticles on the basalt surface can be controlled by changing the reaction time under certain temperature and reaction solution conditions.

[0052] In a preferred embodiment, the quantity and morphology of the nanoparticles obtained on the basalt surface can be controlled by adjusting the reaction time in step (2). For example, in Example 5, the NiFe(B) nanoparticles obtained after basalt was immersed in a solution and reacted for 1 hour have interstitial dense arrangement on the basalt surface (e.g., ...). Figure 15 As shown), after immersing basalt in a solution and reacting for 2 hours, NiFe(B) nanolayer particles coat the basalt, as... Figure 16 As shown.

[0053] In this preferred embodiment, the greater the number of basalt surface alloy nanoparticles obtained in step (2), the better the catalytic effect, and the easier it is to promote the uniform composite of the reduced magnetic metal or alloy with the basalt in step (3) (compare Example 3 and Example 4). If the number of basalt surface alloy particles is too small, the catalytic effect is poor, and the composite of the reduced metal particles with the basalt in step (3) may not be guaranteed. However, if the number of basalt surface magnetic nanoparticles is too large, forming a thicker metal layer, the content of B in the final sample will increase.

[0054] In the preferred embodiment, the reaction temperature for the magnetic nanoparticles to attach to basalt in step (2) is 10–30°C, preferably 15°C. The reaction time for the magnetic nanoparticles to attach to basalt in step (2) is controlled to be 30–120 min. After filtering and washing the product with deionized water until neutral in step (2), the product is vacuum dried for 3–12 hours, preferably 12 hours. The magnetic nanoparticles obtained in step (2) contain boron and are amorphous.

[0055] In step (3), the proportions of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), ferrous sulfate heptahydrate (FeSO4·7H2O), sodium citrate dihydrate (Na3C6H5O7·2H2O), potassium sodium tartrate (NaKC4H4O6), sodium hydroxide (NaOH), hydrazine hydrate (N2H4·H2O, 80%), and water (H2O) in the reaction solution are 0–2.376 g: 0–2.81 g: 0–1.390 g: 0–4.705 g: 0–3.153 g: 0.45–1.6 g: 1–6 ml: 100–200 ml.

[0056] In particular, as a preferred option, in step (3), the types and proportions of nickel sulfate hexahydrate (NiSO4·6H2O), cobalt sulfate heptahydrate (CoSO4·7H2O), and ferrous sulfate heptahydrate (FeSO4·7H2O) in the reaction solution can be adjusted to regulate the type of metal or alloy layer composited with basalt. For example, in Example 2, the surface of basalt is coated with Co, and in Example 4, a composite of FeCoNi alloy layer and basalt is obtained.

[0057] In the preferred embodiment, in step (3), the oil bath heating and stirring time is 10–120 min, and the thickness of the metal or alloy layer on the basalt surface can be adjusted by adjusting the heating and stirring time. In step (3), the oil bath heating temperature is 50–80℃. The oil bath heating and stirring time is 10–120 min. After filtering and washing the product with deionized water until neutral in step (3), the product is vacuum dried for 3–12 hours, preferably 12 hours. The two-dimensional basalt micron-sheet composite material uniformly coated with magnetic metal, bicomponent magnetic alloy or multicomponent FeCoNi alloy is prepared according to the above method. The magnetic metal layer, bicomponent magnetic alloy or FeCoNi alloy layer obtained in step (3) does not contain other impurities and has high crystallinity.

[0058] Working principle of the invention:

[0059] By optimizing the electroless plating process, in step (1), basalt is successively immersed in hydrochloric acid solution of stannous chloride and hydrochloric acid solution of palladium chloride, and the sites and quantities of Pd on the basalt surface are controlled by repeated cycles. In step (2), Pd particles on the basalt surface catalyze the composite of magnetic metal nanoparticles onto the basalt surface. In step (3), the magnetic metal nanoparticles on the basalt surface further catalyze the composite of magnetic metal, bicomponent magnetic alloy or multicomponent FeCoNi alloy with hydrazine as a reducing agent and basalt, and finally obtain a basalt composite with a uniform and tight coating of metal or alloy layer.

[0060] Compared to current chemical plating synthesis processes, this invention has the following advantages: It is not limited to a specific metal or alloy, but allows for the uniform deposition of monocomponent magnetic metals, bicomponent or ternary magnetic alloys onto the surface of a ceramic basalt matrix, resulting in various magnetic metal-basalt composites for use as microwave absorbing materials. This invention first attaches trace amounts of palladium (Pd) particles to basalt, followed by the attachment of magnetic metal nanoparticles, further forming a magnetic alloy coated with monocomponent, bicomponent, or ternary magnetic metals. While this method directly coats the basalt surface with magnetic particles, and although dimethylamine borane (DMAB) introduces impurity B, it is understood that the significant reduction in magnetic loss capability is only achieved by introducing impurity B into the final metal layer used for coating. Firstly, the magnetic particles formed in this step of the present invention have a certain degree of magnetism, which will not lead to a reduction in the overall magnetic loss performance. Secondly, this step does not form the final metal layer used for coating, but is used to attach magnetic particles. The metal layer formed in step S30 of the present invention does not contain impurity B, which will not lead to a significant weakening of the magnetic loss capability. Furthermore, the direct coupling between the magnetic particles formed in step S30 is more conducive to improving the magnetic loss. On the other hand, in step (3) of forming the coating layer, the reducing agent hydrazine hydrate can still be used. The resulting magnetic metal, bicomponent magnetic alloy or multicomponent FeCoNi alloy is uniform and does not contain other impurities such as B, and will not form borides, etc., which would reduce the magnetic loss performance. However, the coating layer is formed on the basis of the magnetic metal nanoparticles in step (2). The metal layer is no longer difficult to combine with the substrate. The metal or alloy layer can be uniformly and densely coated on the surface of the ceramic substrate, which can play a role in not hindering electron migration and helping to improve the conductivity loss. The large heterogeneous interface formed between the metal layer and the ceramic substrate helps to improve the dielectric loss capability. The direct coupling between the magnetic particles of the metal layer helps to improve the magnetic loss performance.

[0061] In Example 1, the magnetic Co particles obtained by immersing basalt in a composite solution of Co with hydrazine as a reducing agent mostly agglomerated and grew on their own, with only a small portion growing on the surface of the basalt (e.g., Figure 3 (As shown). In this invention, activated and sensitized basalt is reduced and grown with dimethylamine borane (DMAB) to form magnetic nanoparticles on its surface. The basalt with the magnetic nanoparticles can catalyze the reduction of magnetic metals by hydrazine, and magnetic alloy layers can grow uniformly on the basalt surface (e.g., ...). Figure 5 , Figure 12 and Figure 13 As shown in the figures, a uniform coating of a magnetic metal or alloy layer free of non-metallic impurities is achieved on the surface of basalt. In Examples 2-5 below, the magnetic metal nanoparticles are preferably Co nanoparticles, and the metal layer is a Co metal layer. Alternatively, the magnetic metal nanoparticles are preferably magnetic CoNi nanoparticles, and the alloy layer is a multi-component FeCoNi alloy layer. In these examples, the relevant reagents in the solutions used to form the corresponding nanoparticles and coating layers were selected, and the proportions of each reagent were determined. This further illustrates the preparation of the composite material of the specific nanoparticles and coating layers prepared by the present invention. It is understood that the accompanying drawings used in this invention are image acquisitions of the nanoparticles and coating layers specifically formed in each embodiment, demonstrating the certainty of the preparation of the corresponding composite materials in the embodiments and their corresponding effects.

[0062] Example 1: The method for preparing composite materials includes:

[0063] (1) Pd particles adhering to the surface of basalt: A certain amount of basalt (such as...) Figure 2 The basalt was immersed in a 0.2 mol / L hydrochloric acid solution containing stannous chloride, with 1 mol / L hydrochloric acid solution as the solvent. After stirring at room temperature for 1 h and washing with deionized water, the basalt was immersed in a 1 g / L hydrochloric acid solution containing palladium chloride, with 1 mol / L hydrochloric acid solution as the solvent. The mixture was stirred at room temperature for 1 h and then washed with deionized water. This process was repeated 7 times. The basalt was then vacuum dried at 60 °C for 12 h.

[0064] (2) Basalt was immersed in a complex solution of Co with hydrazine as a reducing agent.

[0065] Weigh 2.4 g of cobalt sulfate heptahydrate (CoSO4·7H2O) and dissolve it in 80 ml of distilled water. Then add 2.4 g of potassium sodium tartrate (NaKC4H4O6) and dissolve it. Add 1.6 g of sodium hydroxide (NaOH) to 20 ml of distilled water and dissolve it completely, then add it dropwise to the above solution. Then slowly add 4 ml of hydrazine hydrate (N2H4·H2O, 80%) to the solution. Set the oil bath heating temperature to 55℃ and stir. Add the above activated and sensitized basalt to the reaction solution. After reacting for 2 hours, terminate the reaction. Wash three times with distilled water and vacuum dry at 60℃ for 12 hours. The product obtained is as follows. Figure 3 As shown, Co particles agglomerate on their own and do not combine with basalt. Only a small number of Co particles are dispersed and aggregated on the surface of basalt and are not evenly distributed.

[0066] Example 2: The method for preparing composite materials includes:

[0067] (1) Pd particles adhering to the surface of basalt: A certain amount of basalt was immersed in a hydrochloric acid solution with a concentration of 0.2 mol / L stannous chloride and a 1 mol / L hydrochloric acid solution as the solvent; stirred at room temperature for 1 h, washed with deionized water, and then immersed in a hydrochloric acid solution with a concentration of 1 g / L palladium chloride and a 1 mol / L hydrochloric acid solution as the solvent, stirred at room temperature for 1 h, filtered and washed with deionized water, and this process was repeated 7 times, and then vacuum dried at 60℃ for 12 h.

[0068] (2) Co(B) nanoparticles composited on the surface of basalt microsheets: 0.667 g of cobalt sulfate heptahydrate (CoSO4·7H2O) was dissolved in 50 ml of H2O and fully dissolved by ultrasonic vibration. Then, 0.625 g of sodium succinate (C4H4Na2O4) was added and dissolved by ultrasonic vibration. Then, 0.36 g of dimethylamine borane (DMAB) was weighed and added to the above solution as a reducing agent. The solution was stirred thoroughly with a glass cup to dissolve the DMAB. Finally, the basalt from step (1) was added and magnetically stirred at 15 °C. The reaction was terminated after 1 h. The solution was washed 3 times with distilled water and vacuum dried at 60 °C for 12 h. After cooling, the product was obtained as shown in the figure. Figure 4 The image shows basalt uniformly coated with Co(B) nanolayers. The magnetic metal nanoparticles include B and are amorphous.

[0069] (3) Co-coated surface of basalt microsheets: 2.4 g of cobalt sulfate heptahydrate (CoSO4·7H2O) was dissolved in 80 ml of distilled water and ultrasonically vibrated until fully dissolved; then 2.4 g of potassium sodium tartrate (NaKC4H4O6) was added and ultrasonically dissolved; then 1.6 g of sodium hydroxide (NaOH) was dissolved in 20 ml of H2O and slowly added to the above solution to adjust the pH; then 4 ml of hydrazine hydrate (N2H4·H2O, 80%) was added as a reducing agent. The oil bath heating temperature was set to 55℃ and stirred. The basalt with the above surface coated with Co(B) nanoparticles was added to the reaction solution, and the reaction was terminated after 2 hours. The basalt was washed 3 times with distilled water and vacuum dried at 60℃ for 12 hours to obtain the following product. Figure 5 The basalt shown is covered with a Co layer.

[0070] Example 3: The method for preparing composite materials includes:

[0071] (1) Pd particles adhering to the surface of basalt: A certain amount of basalt was immersed in a hydrochloric acid solution with a concentration of 0.2 mol / L stannous chloride and a 1 mol / L hydrochloric acid solution as the solvent; stirred at room temperature for 1 h, washed with deionized water, and then immersed in a hydrochloric acid solution with a concentration of 1 g / L palladium chloride and a 1 mol / L hydrochloric acid solution as the solvent, stirred at room temperature for 1 h, filtered and washed with deionized water, and this process was repeated 7 times, and then vacuum dried at 60℃ for 12 h.

[0072] (2) CoNi(B) nanoparticles composited on the surface of basalt microsheets: 0.281 g of nickel sulfate hexahydrate (NiSO4·6H2O) and 0.281 g of cobalt sulfate heptahydrate (CoSO4·7H2O) were weighed and dissolved in 40 ml of H2O. After ultrasonic vibration, the solution was fully dissolved. Then, 0.588 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) was added and ultrasonically dissolved. Next, 0.558 g of dimethylamine borane (DMAB) was weighed and added to the above solution as a reducing agent. The solution was stirred thoroughly to dissolve the DMAB. Finally, Pd-coated basalt was added, and the mixture was magnetically stirred at 15 °C. The reaction was terminated after 2 h. The mixture was washed three times with distilled water and vacuum dried at 60 °C for 12 h. After cooling, the surface of the basalt contained a small amount of CoNi(B) nanoparticles, such as... Figure 6 As shown.

[0073] (3) FeCoNi alloy layer composite on basalt microsheet surface: 1.3124 g of nickel sulfate hexahydrate (NiSO4·6H2O), 0.8433 g of cobalt sulfate heptahydrate (CoSO4·7H2O), and 0.8343 g of ferrous sulfate heptahydrate (FeSO4·7H2O) were weighed and dissolved in 80 ml of distilled water, and then dissolved by ultrasonic vibration; then 2.941 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) was added and dissolved by ultrasonication; then 0.45 g of sodium hydroxide (NaOH) was dissolved in 20 ml of H2O and slowly added to the above solution to adjust the pH; then 1.2 ml of hydrazine hydrate (N2H4·H2O, 80%) was added as a reducing agent. The oil bath heating temperature was set to 80℃ and stirred. The basalt with CoNi(B) nanoparticles on its surface was added to the reaction solution. The reaction was terminated after 2 hours, washed three times with distilled water, and vacuum dried at 60°C for 12 hours. After cooling, the crystallinity and morphology of the FeCoNi alloy layer coating on the basalt surface could be determined according to... Figure 7 , Figure 8 , Figure 9 , Figure 10 As shown. Figure 7 The FeCoNi alloy obtained by reduction with hydrazine hydrate shown has high crystallinity. Figure 8 The surface of the basalt is coated with an FeCoNi alloy layer, but the coating rate is low, and complete coating is not achieved. In some cases, the basalt surface will not be coated with an FeCoNi alloy layer if CoNi(B) nanoparticles are not attached or the number of attached CoNi(B) nanoparticles is small. Figure 9 No FeCoNi alloy grew on the surface of the middle section of the basalt. Figure 9 EDS energy dispersive spectroscopy analysis of the complex revealed that the mass fractions of Si and O were much higher than the contents of Fe, Co, and Ni. Figure 10 As shown in the image, Si and O are constituent elements of basalt. Since the basalt in this sample was not completely encapsulated, EDS analysis was performed... Figure 9 The mass fractions of Si and O elements in basalt are higher than those in other magnetic metals. Therefore, if the number of magnetic nanoparticles on the basalt surface is too small, it is not conducive to the complete coating of the basalt by the FeCoNi alloy layer.

[0074] Example 4: The method for preparing composite materials includes:

[0075] (1) Pd particles adhering to the surface of basalt: A certain amount of basalt was immersed in a hydrochloric acid solution with a concentration of 0.2 mol / L stannous chloride and a 1 mol / L hydrochloric acid solution as the solvent; stirred at room temperature for 1 h, washed with deionized water, and then immersed in a hydrochloric acid solution with a concentration of 1 g / L palladium chloride and a 1 mol / L hydrochloric acid solution as the solvent, stirred at room temperature for 1 h, filtered and washed with deionized water, and this process was repeated 7 times, and then vacuum dried at 60℃ for 12 h.

[0076] (2) CoNi(B) nanoparticles composited on the surface of basalt microsheets: 0.789 g of nickel sulfate hexahydrate (NiSO4·6H2O) and 0.562 g of cobalt sulfate heptahydrate (CoSO4·7H2O) were weighed and dissolved in 50 ml of H2O. After ultrasonic vibration, the solution was fully dissolved. Then, 1.47 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) was added and ultrasonically dissolved. Next, 0.885 g of dimethylamine borane (DMAB) was weighed and added to the above solution as a reducing agent. The solution was stirred thoroughly to dissolve the DMAB. Finally, Pd-coated basalt was added, and the mixture was magnetically stirred at 15 °C. The reaction was terminated after 1 h. The mixture was washed three times with distilled water and vacuum dried at 60 °C for 12 h. After cooling, the surface of the basalt contained CoNi(B) nanoparticles. Figure 11 The CoN(B) nanoparticles shown are interconnected to form a CoNi(B) nanolayer that coats the surface of basalt.

[0077] (3) FeCoNi alloy layer composite on basalt microsheet surface: 1.3124 g of nickel sulfate hexahydrate (NiSO4·6H2O), 0.8433 g of cobalt sulfate heptahydrate (CoSO4·7H2O), and 0.8343 g of ferrous sulfate heptahydrate (FeSO4·7H2O) were weighed and dissolved in 80 ml of distilled water, and then dissolved by ultrasonic vibration; then 2.941 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) was added and dissolved by ultrasonication; then 0.45 g of sodium hydroxide (NaOH) was dissolved in 20 ml of H2O and slowly added to the above solution to adjust the pH; then 1.2 ml of hydrazine hydrate (N2H4·H2O, 80%) was added as a reducing agent. The oil bath heating temperature was set to 80℃ and stirred. The basalt with CoNi(B) nanoparticles coated on its surface was added to the reaction solution. The reaction was terminated after 2 hours, and the sample was washed three times with distilled water. It was then vacuum dried at 60°C for 12 hours. After cooling, the basalt surface was coated with an FeCoNi alloy layer. The resulting sample is shown below. Figure 12 , Figure 13As shown, the basalt surface is uniformly coated with an FeCoNi alloy layer, which has a significant effect on... Figure 13 EDS energy dispersive spectroscopy analysis of the sample showed that the main elements were Fe, Co, and Ni, with very low contents of Si and Al. Figure 14 As shown in the figure, this is because the FeCoNi alloy layer is uniformly distributed on the surface of the basalt. When scanning, only Fe, Co, and Ni elements are counted, while the elements contained in the completely covered basalt are not counted.

[0078] Comparing Examples 3 and 4, it is evident that insufficient CoNi(B) magnetic nanoparticles on the basalt surface hinders the uniform coating of the FeCoNi alloy layer by hydrazine reduction. Conversely, sufficient CoNi(B) magnetic nanoparticles on the basalt surface promote uniform coating of the FeCoNi alloy layer.

[0079] Example 5: The method for preparing composite materials includes:

[0080] (1) Pd particles adhering to the surface of basalt: A certain amount of basalt was immersed in a hydrochloric acid solution with a concentration of 0.2 mol / L stannous chloride and a 1 mol / L hydrochloric acid solution as the solvent; stirred at room temperature for 1 h, washed with deionized water, and then immersed in a hydrochloric acid solution with a concentration of 1 g / L palladium chloride and a 1 mol / L hydrochloric acid solution as the solvent, stirred at room temperature for 1 h, filtered and washed with deionized water, and this process was repeated 7 times, and then vacuum dried at 60℃ for 12 h.

[0081] (2) Surface composite of FeNi(B) nanoparticles on basalt microsheets: 0.789 g of nickel sulfate hexahydrate (NiSO4·6H2O) and 0.784 g of ferrous ammonium sulfate hexahydrate (Fe(NH4)2·(SO4)2·6H2O) were weighed and dissolved in 40 ml of H2O. After complete dissolution by ultrasonic vibration, 0.294 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) and 0.648 g of sodium succinate (C Dissolve the 4H4Na2O4 solution by ultrasonication. Then, weigh 0.885 g of dimethylamine borane (DMAB) as a reducing agent and add it to the solution. Stir thoroughly in a glass beaker until the DMAB dissolves. Finally, add Pd-coated basalt and stir magnetically at room temperature. Terminate the reaction after 1 hour. Wash three times with distilled water and vacuum dry at 60°C for 12 hours. After cooling, the basalt surface contains NiFe(B) nanoparticles. Figure 15The NiFe(B) nanoparticles shown are densely packed with interstices on the basalt surface. After reacting under the same conditions for 2 hours, as... Figure 16 As shown, NiFe(B) nanoparticles form a nano-coating on the surface of basalt. The number of magnetic nanoparticles on the basalt surface can be controlled by changing the reaction time.

[0082] (3) Basalt surface composite FeCoNi alloy layer: 1.3124 g of nickel sulfate hexahydrate (NiSO4·6H2O), 0.562 g of cobalt sulfate heptahydrate (CoSO4·7H2O), and 0.5562 g of ferrous sulfate heptahydrate (FeSO4·7H2O) were weighed and dissolved in 80 ml of distilled water, and then ultrasonically vibrated to dissolve completely; then 2.941 g of sodium citrate dihydrate (Na3C6H5O7·2H2O) was added and ultrasonically dissolved; then 0.45 g of sodium hydroxide (NaOH) was dissolved in 20 ml of H2O and slowly added to the above solution to adjust the pH; then 1.2 ml of hydrazine hydrate (N2H4·H2O, 80%) was added as a reducing agent. The oil bath heating temperature was set to 80℃ and stirred. The basalt with FeNi(B) nanoparticles on its surface was added to the reaction solution. The reaction was terminated after 2 hours. The basalt was washed three times with distilled water and dried under vacuum at 60°C for 12 hours. After cooling, the surface of the basalt was coated with an FeCoNi alloy layer.

[0083] The present invention relates to a method for preparing a two-dimensional basalt microsheet composite material coated with a magnetic metal layer, a bicomponent alloy, and a multicomponent FeCoNi alloy layer, and its application. The preparation method includes the following steps: (1) obtaining basalt with trace amounts of Pd particles on its surface through multiple cycles of sensitization and activation at room temperature. (2) adding the basalt with trace amounts of Pd obtained in step (1) to a magnetic nanoparticle reaction solution, where Pd particles catalyze the growth of magnetic nanoparticles on the basalt surface at room temperature. (3) adding the basalt with magnetic nanoparticles obtained in step (2) to a synthesis solution of a magnetic metal layer, a bicomponent alloy, and a multicomponent FeCoNi alloy, where, at a certain temperature, magnetic nanoparticles catalyze the uniform coating of the magnetic metal or alloy layer onto the basalt surface. The resulting composite material exhibits excellent magnetic loss, electrical conductance loss, and dielectric loss capabilities, making it easier to achieve strong microwave absorption performance. Although the description of the present invention is based on specific embodiments, those skilled in the art should understand that the present invention may also encompass other embodiments within the scope of the present invention as stated herein.

[0084] Example 6: Includes the same first step as Examples 2-5, except that the amounts of each component are different in the second and third steps.

[0085]

[0086] The volume of water used in the second step above was 50 ml, and the reaction temperature was 15℃.

[0087] The reaction temperature in the third step above is 80℃.

[0088] Example 7: Includes the same first step as Examples 2-5, except that the amounts of each component are different in the second and third steps.

[0089]

[0090] The reaction temperature for the second step above is 15℃.

[0091] The reaction temperature in the third step above is 55℃.

[0092] Although the invention has been described through specific embodiments, those skilled in the art will understand that the invention may also encompass other embodiments within the scope of the invention as described herein.

Claims

1. A method for preparing a magnetic metal-coated two-dimensional basalt micron-sheet composite material, characterized in that, include: S10. After sensitizing and activating basalt, trace amounts of palladium (Pd) particles are attached. S20. The basalt with trace amounts of palladium (Pd) particles obtained in step S10 is reduced and grown with dimethylamine borane (DMAB) to grow magnetic metal nanoparticles on the surface of the basalt. S30. The magnetic metal obtained in step S20, which is attached to basalt with magnetic metal nanoparticles, is uniformly grown on the surface of basalt to form a magnetic metal layer. The magnetic metal nanoparticles in step S20 include Co(B) nanoparticles. The magnetic metal layer in step S30 includes a Co metal layer.

2. The preparation method according to claim 1, characterized in that, Step S10 specifically includes repeatedly sensitizing and activating basalt. After repeated sensitization and activation, the resulting product is vacuum dried for 3-12 hours at a temperature of 55-65°C. The dried product is basalt with trace amounts of palladium (Pd) particles attached. The sensitization process involves immersing the basalt in a 0.05-0.5 mol / L stannous chloride hydrochloric acid solution with a concentration of 0.1-1 mol / L and stirring at room temperature for 60 minutes. The activation process involves filtering and washing the sensitized product with deionized water and then adding it to a 0.1-2 g / L palladium chloride hydrochloric acid solution with a concentration of 0.1-1 mol / L and stirring at room temperature for 60 minutes.

3. The preparation method according to claim 1 or 2, characterized in that, The magnetic metal nanoparticles in step S20 include Co(B) nanoparticles. Step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution contains cobalt sulfate heptahydrate (CoSO4·7H2O): sodium succinate (C4H4Na2O4): dimethylamine borane (DMAB): water (H2O) in a ratio of 0.281~0.843g: 0.486~0.81g: 0.177~0.471g: 30~60ml. The reaction temperature is 10~30℃, and the reaction time is 30~120min. After the reaction, the product is filtered and washed with deionized water, and then vacuum dried at 55~65℃ to obtain basalt with attached magnetic metal nanoparticles.

4. The preparation method according to claim 3, characterized in that, The magnetic metal layer in step S30 includes a Co metal layer. Step S30 includes adding basalt with attached magnetic metal nanoparticles to a reaction solution. The reaction solution contains cobalt sulfate heptahydrate (CoSO4·7H2O): sodium potassium tartrate (NaKC4H4O6): sodium hydroxide (NaOH): hydrazine hydrate (N2H4·H2O): water (H2O) in the following proportions: 1.686~2.81g: 1.892~3.153g: 0.45g~1.6g: 1~6ml: 100~200ml. The reaction is carried out in an oil bath at a temperature of 50~60℃ for 30~120min. The product obtained after the reaction is washed with deionized water and dried under vacuum at 55~65℃ to obtain basalt coated with a magnetic metal layer.

5. A method for preparing an alloy-coated two-dimensional basalt micron-sheet composite material, characterized in that, include: S10. After sensitizing and activating basalt, trace amounts of palladium (Pd) particles are attached. S20. The basalt with trace amounts of palladium (Pd) particles obtained in step S10 is reduced and grown with dimethylamine borane (DMAB) to grow magnetic metal nanoparticles on the surface of the basalt. S30. The basalt catalytic hydrazine reduction magnetic metal alloy with attached magnetic metal nanoparticles obtained in step S20 is uniformly grown on the surface of basalt to form an alloy layer. The magnetic metal nanoparticles in step S20 include magnetic CoNi(B) nanoparticles. The alloy layer in step S30 comprises a multi-component FeCoNi alloy.

6. The preparation method according to claim 5, characterized in that, Step S10 specifically includes repeatedly sensitizing and activating basalt. After repeated sensitization and activation, the resulting product is vacuum dried for 3-12 hours at a temperature of 55-65°C. The dried product is basalt with trace amounts of palladium (Pd) particles attached. The sensitization process involves immersing the basalt in a 0.05-0.5 mol / L stannous chloride hydrochloric acid solution with a concentration of 0.1-1 mol / L and stirring at room temperature for 60 minutes. The activation process involves filtering and washing the sensitized product with deionized water and then adding it to a 0.1-2 g / L palladium chloride hydrochloric acid solution with a concentration of 0.1-1 mol / L and stirring at room temperature for 60 minutes.

7. The preparation method according to claim 5 or 6, characterized in that, The magnetic metal nanoparticles in step S20 include magnetic CoNi(B) nanoparticles. Step S20 includes adding basalt with trace amounts of palladium (Pd) particles attached to a reaction solution. The reaction solution contains nickel sulfate hexahydrate (NiSO4·6H2O): cobalt sulfate heptahydrate (CoSO4·7H2O): sodium citrate dihydrate (Na3C6H5O7·2H2O): dimethylamine borane (DMAB): water (H2O) in a ratio of 0.263~1.051g: 0.281~1.124g: 0.588~1.47g: 0.294~0.885g: 30~60ml. The reaction temperature is 10~30℃, and the reaction time is 30~120min. After the reaction, the product is filtered and washed with deionized water, and then vacuum dried at 55~65℃ to obtain basalt with attached magnetic metal nanoparticles.

8. The preparation method according to claim 7, characterized in that, The alloy layer in step S30 comprises a multi-component FeCoNi alloy. Step S30 includes adding basalt with attached magnetic metal nanoparticles to a reaction solution. The reaction solution contains nickel sulfate hexahydrate (NiSO4·6H2O): cobalt sulfate heptahydrate (CoSO4·7H2O): ferrous sulfate heptahydrate (FeSO4·7H2O): sodium citrate dihydrate (Na3C6H5O7·2H2O): sodium hydroxide (NaOH): hydrazine hydrate (N2H2O). The reaction mixture of H2O and water (H2O) was 0.784~1.573g: 0.562~1.407g: 0.556~1.390g: 2.941~4.705g: 0.45~1.6g: 1~6ml: 100~200ml. The reaction was carried out in an oil bath at a temperature of 70~90℃ for 30~120min. The product was washed with deionized water and dried under vacuum at 55~65℃ to obtain basalt with an alloy coating.

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