Honeycomb composite microwave absorbing materials and their applications

Abstract

This invention relates to a honeycomb structure composite absorbing material and its application. The honeycomb structure composite absorbing material includes a honeycomb core layer and skins disposed on the upper and lower surfaces of the honeycomb core layer. The honeycomb core layer is prepared from resin and a composite magnetic material. The composite magnetic material comprises a composite material composed of porous graphene ellipsoids and zinc sulfide nanomaterials, and an organic insulating material coating the surface of the composite material. In the composite material, multiple porous graphene ellipsoids are arranged in an orderly manner to form a graphene cluster, and the zinc sulfide nanomaterials are fused into the graphene cluster. Because the honeycomb structure composite absorbing material of this invention has excellent absorption performance and is thin and light, external structural components of electronic devices made from it can not only make electronic devices thinner and lighter but also effectively improve the electromagnetic shielding performance of electronic devices.

Description

Technical Field

[0001] This invention relates to the field of electromagnetic absorbing materials technology, and in particular to honeycomb structure composite absorbing materials and their applications. Background Technology

[0002] Structural absorbing materials are widely used in the packaging design of external structural components such as the casings of electronic devices, serving both heat dissipation and electromagnetic wave absorption purposes. However, most structural absorbing materials are currently made of metals and plastics, which generally result in thicker materials, heavier weights, and limited electromagnetic shielding effectiveness, leading to electromagnetic wave leakage and thus limited practical application value. Summary of the Invention

[0003] Therefore, it is necessary to provide a honeycomb structure composite absorbing material and its application to address the above-mentioned technical problems. The honeycomb structure composite absorbing material has excellent wave absorption performance and is lightweight. When used to manufacture external structural components of electronic devices, it can not only make electronic devices thinner and lighter, but also effectively improve the electromagnetic shielding performance of electronic devices.

[0004] This invention provides a honeycomb structure composite absorbing material, comprising a honeycomb core layer and a skin disposed on the upper and lower surfaces of the honeycomb core layer;

[0005] The raw materials for preparing the honeycomb core layer include resin and composite magnetic materials. The composite magnetic materials include a composite material composed of porous graphene ellipsoids and zinc sulfide nanomaterials, and an organic insulating material coated on the surface of the composite material. In the composite material, multiple porous graphene ellipsoids are arranged in an orderly manner to form a graphene group, and the zinc sulfide nanomaterials are fused into the graphene group.

[0006] In one embodiment, the composite magnetic material has a mass fraction of 50%-60% in the honeycomb core layer.

[0007] In one embodiment, the thickness of the honeycomb core layer is 3mm-8mm.

[0008] In one embodiment, the honeycomb core layer is composed of multiple hexagonal unit cells, the side length of which is 3mm-5mm and the wall thickness is 0.3mm-0.7mm.

[0009] In one embodiment, the skin is selected from metal skin.

[0010] In one embodiment, the porous graphene ellipsoids in the graphene group are arranged in a three-dimensional array.

[0011] In one embodiment, the porous graphene ellipsoid has an equatorial radius of 100nm-120nm and a polar radius of 200nm-250nm.

[0012] In one embodiment, the pore size of the porous graphene ellipsoid is 14nm-25nm, and the ratio of the particle size of the zinc sulfide nanomaterial to the pore size of the porous carbon rod is 1:8-1:12.

[0013] In one embodiment, the mass ratio of the zinc sulfide nanomaterial to the graphene group in the composite magnetic material is 1:3-1:5.

[0014] The present invention also provides a method for using the aforementioned honeycomb structure composite absorbing material to prepare external structural components for electronic devices.

[0015] This invention, through the selection of materials and the control of structure in the composite magnetic material, achieves an insertion loss of approximately 25 dB in the 20 MHz-1200 MHz frequency band, exhibiting excellent wave absorption performance. Furthermore, the low density of graphene and zinc sulfide results in a low-density and lightweight composite magnetic material composed of graphene and zinc sulfide nanomaterials.

[0016] Furthermore, the honeycomb core layer made from the composite magnetic material and resin of this invention is not only lightweight but also possesses excellent wave absorption performance. Therefore, the honeycomb structure composite wave absorbing material constructed using this material exhibits excellent wave absorption performance and is thin and light. When used to manufacture external structural components for electronic devices, it not only enables the electronic devices to be made thinner and lighter but also effectively improves the electromagnetic shielding performance of the electronic devices. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the structure of a honeycomb composite absorbing material according to an embodiment of the present invention;

[0019] Figure 2 A schematic diagram of the honeycomb core layer of a honeycomb structure composite microwave absorbing material;

[0020] Figure 3 This is a high-magnification scanning electron microscope image of the graphene group obtained in Example 1;

[0021] Figure 4This is a high-magnification scanning electron microscope image of the composite magnetic material prepared in Example 1;

[0022] Figure 5 Electromagnetic compatibility radiated interference diagram for blank samples;

[0023] Figure 6 The electromagnetic compatibility radiation disturbance diagram of the sample is shown.

[0024] In the diagram: 10, honeycomb core layer; 20, skin; 101, hexagonal unit cell. Detailed Implementation

[0025] To facilitate understanding of the present invention, it will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. Rather, these embodiments or examples are provided to make the disclosure of the present invention more thorough and complete.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments or examples only and is not intended to limit the invention. The optional scope of the term "and / or" as used herein includes any one of two or more of the related listed items, as well as any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all related listed items.

[0027] like Figure 1 and Figure 2 As shown, the honeycomb structure composite absorbing material provided by the present invention includes a honeycomb core layer 10 and a skin 20 disposed on the upper and lower surfaces of the honeycomb core layer 10.

[0028] Specifically, the raw materials for preparing the honeycomb core layer 10 include resin and composite magnetic materials. The composite magnetic materials include a composite material composed of porous graphene ellipsoids and zinc sulfide nanomaterials, and an organic insulating material coated on the surface of the composite material. In the composite material, multiple porous graphene ellipsoids are arranged in an orderly manner to form a graphene group, and the zinc sulfide nanomaterials are fused into the graphene group.

[0029] Specifically, the zinc sulfide nanomaterials are integrated into the graphene group in the following ways: zinc sulfide nanomaterials are attached to the surface of at least a portion of the porous graphene ellipsoids, and zinc sulfide nanomaterials are filled in at least a portion of the gaps in the graphene group; furthermore, when the particle size of the zinc sulfide nanomaterials is smaller than the pore size of the porous graphene ellipsoids, the integration of the zinc sulfide nanomaterials into the graphene group also includes the presence of zinc sulfide nanomaterials within the channels of at least a portion of the porous graphene ellipsoids. Of course, the specific integration method will not have a substantial impact on the wave absorption performance.

[0030] Different structural types and materials exhibit varying electromagnetic wave conversion capabilities. In this invention, graphene and zinc sulfide are combined in terms of materials. Structurally, graphene particles are bonded together with binders such as phenolic resin to form porous graphene ellipsoids, which are then arranged in an orderly manner to form graphene clusters. Zinc sulfide nanomaterials are integrated into these graphene clusters in various ways. This allows for faster and more efficient conversion of electromagnetic waves into heat energy. Furthermore, graphene's excellent thermal conductivity enables rapid heat transfer, resulting in an insertion loss of approximately 25 dB for the composite magnetic material in the 20 MHz-1200 MHz frequency band, demonstrating excellent wave absorption performance.

[0031] Meanwhile, the composite magnetic material of this invention uses a graphene cluster composed of multiple porous graphene ellipsoids arranged in an orderly manner as the matrix, and integrates zinc sulfide nanomaterials. It exhibits a dense structure, good toughness, and is not prone to breakage or failure under load. Furthermore, the low density of graphene and zinc sulfide results in a low-density and lightweight composite magnetic material. In addition, the composite material is coated with an organic insulating material, which not only imparts insulation to the composite magnetic material but also enhances the stability of the composite material's bonding. Optionally, during the coating process, the organic insulating material can partially coat the surface of the composite material or completely coat the composite material; preferably, the organic insulating material completely coats the composite material. The organic insulating material is preferably a block polymer, such as ethylene oxide and propylene oxide block copolymer ether.

[0032] Furthermore, the honeycomb core layer made from the composite magnetic material and resin of this invention is not only lightweight but also possesses excellent wave absorption performance. Therefore, the honeycomb structure composite wave absorbing material constructed using this material exhibits excellent wave absorption performance and is also thin and lightweight.

[0033] To further optimize the wave absorption performance of honeycomb structure composite wave absorbing materials, composite magnetic materials can be further optimized.

[0034] For example, in composite magnetic materials, when multiple porous graphene ellipsoids are arranged in an orderly manner to form a graphene group, the porous graphene ellipsoids are arranged in a three-dimensional array; and / or, the equatorial radius of the porous graphene ellipsoids is 100nm-120nm, and the polar radius is 200nm-250nm; and / or, the pore size of the porous graphene ellipsoids is 14nm-25nm, and the ratio of the particle size of the zinc sulfide nanomaterial to the pore size of the porous graphene ellipsoids is 1:8-1:12.

[0035] Furthermore, the mass ratio of porous graphene ellipsoids to zinc sulfide nanomaterials in the composite magnetic material can be further optimized, as can the mass fraction of the composite magnetic material in the honeycomb core layer 10. In one embodiment, the mass ratio of the zinc sulfide nanomaterials to the graphene group in the composite magnetic material is 1:3-1:5; in another embodiment, the mass fraction of the composite magnetic material in the honeycomb core layer 10 is 50%-60%.

[0036] In the honeycomb core layer 10, the choice of resin material will not affect its wave absorption effect. The present invention does not limit the choice of resin. Preferably, it is selected from epoxy resin, phenolic resin, etc.

[0037] Furthermore, the structure of the honeycomb core layer 10 can be further optimized. In one embodiment, the honeycomb core layer 10 is composed of a plurality of hexagonal unit cells 101. The side length a of the hexagonal unit cell 101 is 3mm-5mm, the wall thickness b is 0.3mm-0.7mm, and the thickness h of the honeycomb core layer is 3mm-8mm. That is, the depth of the hexagonal unit cell 101 is 3mm-8mm.

[0038] The present invention does not impose any special restrictions on the material and thickness of the skin 20. Preferably, the skin 20 is selected from metal skin, and further selected from aluminum skin and iron skin, etc. The thickness of the skin 20 is preferably 0.4mm-1mm.

[0039] This invention does not limit the preparation method of composite magnetic materials; any preparation method can be used to obtain them, as long as the structure and materials meet the above-mentioned conditions of this invention, the desired effect can be achieved.

[0040] In one embodiment, the preparation method of the composite magnetic material includes the following steps: preparing graphene groups using a colloidal crystal template method, then mixing the graphene groups with zinc sulfide nanomaterials, adding organic insulating materials, heating to a viscous state, and then cooling to obtain the composite magnetic material.

[0041] The specific steps for preparing graphene groups using the colloidal crystal template method include: preparing a first formulation by mixing graphene with water, then mixing the first formulation with a binder to form a second formulation, then adding the second formulation to a colloidal crystal template and heating it under an inert atmosphere, and then cooling it under a reducing atmosphere to obtain graphene groups.

[0042] The graphene to water mass ratio is 1:2-1:4, the graphene to binder mass ratio is 10:1-10:3, the binder is preferably a resin-based binder, such as phenolic resin, the graphene to colloidal crystal mass ratio is 6:1-12:1, the colloidal crystal template is selected from polymethyl methacrylate colloidal crystal template, the heating temperature is preferably 180℃-220℃, the heating time is preferably 20h-28h, the inert atmosphere is selected from nitrogen, argon, etc., and the reducing atmosphere is selected from carbon monoxide, hydrogen, etc.

[0043] To further improve the stability of graphene, a reducing catalyst, such as SnCl2 or FeCl2, can be added to the first formulation. The mass ratio of graphene to the reducing catalyst is 1:1 to 2:1. Then, the mixture is heated in an inert gas and cooled in a reducing atmosphere to obtain a more stable first formulation. The preferred heating temperature is 220℃ to 280℃, and the preferred heating time is 4h to 8h.

[0044] Similarly, the present invention does not limit the preparation method of the honeycomb structure composite absorbing material. Preferably, the composite magnetic material is mixed with resin to form a composition, and then the composition is injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer 10 is obtained. Finally, a skin 20 is provided on the upper and lower surfaces of the honeycomb core layer 10 to obtain the honeycomb structure composite absorbing material.

[0045] The present invention also provides a method for using the aforementioned honeycomb structure composite absorbing material to manufacture external structural components of electronic devices, such as housings.

[0046] Because the honeycomb structure composite absorbing material of the present invention has excellent wave absorption performance and is thin and light, the external structural components of electronic devices made from it can not only make the electronic devices thinner and lighter, but also effectively improve the electromagnetic shielding performance of the electronic devices.

[0047] The following specific embodiments will further illustrate the honeycomb structure composite absorbing material and its applications.

[0048] Example 1

[0049] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0050] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of graphene to polymethyl methacrylate colloidal crystals of 8:1. The mixture was then placed in an argon atmosphere and heated at 200°C for 24 hours, followed by cooling in a carbon monoxide atmosphere to obtain the desired product. Figure 3 The graphene group shown is composed of porous graphene ellipsoids arranged in a three-dimensional array. The equatorial radius of the porous graphene ellipsoids is 100 nm, the polar radius is 210 nm, and the pore size is 18 nm.

[0051] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, then ethylene oxide and propylene oxide block copolymer ether were added, and the mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the desired result was obtained. Figure 4 The composite magnetic material shown.

[0052] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0053] Example 2

[0054] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0055] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0056] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 5:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0057] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0058] Example 3

[0059] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0060] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0061] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 3:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0062] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0063] Example 4

[0064] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0065] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 180°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 200 nm, and the pore size being 14 nm.

[0066] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.7 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0067] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0068] Example 5

[0069] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0070] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 220°C for 22 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with an equatorial radius of 110 nm, a polar radius of 210 nm, and a pore size of 17 nm.

[0071] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.7 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0072] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0073] Example 6

[0074] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0075] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 220°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 120 nm, the polar radius being 220 nm, and the pore size being 22 nm.

[0076] Graphene groups and zinc sulfide nanomaterials with a particle size of 2 nm were added to water, wherein the mass ratio of graphene groups to zinc sulfide nanomaterials was 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0077] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 5 mm. Each hexagonal unit cell has a side length of 4 mm and a wall thickness of 0.5 mm. The aluminum skin has a thickness of 0.7 mm.

[0078] Example 7

[0079] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0080] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0081] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0082] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 50% by mass, and the core layer is composed of multiple hexagonal unit cells. The core layer has a thickness of 5 mm, the hexagonal unit cells have a side length of 4 mm and a wall thickness of 0.5 mm, and the aluminum skin has a thickness of 0.7 mm.

[0083] Example 8

[0084] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0085] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0086] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0087] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 60% by mass, and the core layer is composed of multiple hexagonal unit cells. The core layer has a thickness of 5 mm, the hexagonal unit cells have a side length of 4 mm and a wall thickness of 0.5 mm, and the aluminum skin has a thickness of 0.7 mm.

[0088] Example 9

[0089] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0090] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0091] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0092] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass, and the honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 3 mm. Each hexagonal unit cell has a side length of 3 mm and a wall thickness of 0.3 mm. The aluminum skin has a thickness of 0.7 mm.

[0093] Example 10

[0094] Graphene powder was added to water at a mass ratio of 1:3 and mixed. Then, SnCl2 was added at a mass ratio of 1:1 to the graphene powder. The mixture was placed in an argon atmosphere and heated at 250°C for 6 hours, followed by cooling in a CO atmosphere to obtain the first formulation. The first formulation was then mixed with phenolic resin to obtain the second formulation, wherein the mass ratio of graphene powder to phenolic resin was 10:2.

[0095] The second formulation was added to polymethyl methacrylate colloidal crystals at a mass ratio of 8:1. The mixture was then heated at 200°C for 24 hours in an argon atmosphere and cooled in a carbon monoxide environment to obtain a graphene cluster. This graphene cluster consisted of porous graphene ellipsoids arranged in a three-dimensional array, with the equatorial radius of the porous graphene ellipsoids being 100 nm, the polar radius being 210 nm, and the pore size being 18 nm.

[0096] Graphene groups and zinc sulfide nanomaterials with a particle size of 1.8 nm were added to water, with a mass ratio of graphene groups to zinc sulfide nanomaterials of 4:1. The mixture was stirred and mixed, and then ethylene oxide and propylene oxide block copolymer ether were added. The mixture was placed in an argon atmosphere and heated to 150°C until it reached a viscous state. After cooling, the composite magnetic material was obtained.

[0097] A composite magnetic material is mixed with phenolic resin to form a composition, which is then injected into a honeycomb mold using equipment such as a hydraulic press. After curing, a honeycomb core layer is obtained. Finally, aluminum skins are applied to the upper and lower surfaces of the honeycomb core layer to obtain a honeycomb structure composite microwave absorbing material. The composite magnetic material in the honeycomb core layer comprises 55% by mass. The honeycomb core layer, composed of multiple hexagonal unit cells, has a thickness of 8 mm. Each hexagonal unit cell has a side length of 5 mm and a wall thickness of 0.7 mm. The aluminum skin has a thickness of 0.7 mm.

[0098] Comparative Example 1

[0099] Comparative Example 1 was carried out in accordance with Example 1, except that the second formulation was added to polymethyl methacrylate colloidal crystals and heated at 150°C for 24 hours to obtain a three-dimensional arrangement of spherical graphene groups.

[0100] Comparative Example 2

[0101] Comparative Example 2 was carried out in accordance with Example 1, except that the second formulation was added to polymethyl methacrylate colloidal crystals and heated at 190°C for 18 hours to obtain a three-dimensional arrangement of rod-shaped graphene groups.

[0102] Comparative Example 3

[0103] Comparative Example 3 was carried out in accordance with Example 1, except that carbon nanotubes were used instead of graphene to obtain a group of carbon nanotubes arranged in three dimensions of porous carbon nanotube ellipsoids.

[0104] The microwave absorption performance of the honeycomb structure composite microwave absorbing materials obtained in Examples 1-10 and Comparative Examples 1-3 was tested. The test methods are shown below, and the test results are shown in Table 1.

[0105] Absorption performance: Refer to GB / T32596 to test absorption bandwidth and insertion loss.

[0106] Table 1

[0107] Example 1 0.03-1 24-33 Example 2 0.03-1 23-32 Example 3 0.03-1 24-31 Example 4 0.04-1 24-29 Example 5 0.05-1 23-29 Example 6 0.08-1 23-28 Example 7 0.03-1 24-31 Example 8 0.03-1 25-34 Example 9 0.03-1 23-29 Example 10 0.03-1 25-32 Comparative Example 1 7-14 14-20 Comparative Example 2 7-14 12-18 Comparative Example 3 7-14 14-19

[0108] Application Experiment:

[0109] The honeycomb structure composite absorbing material obtained in Example 1 was used to make the housing of a security camera, and a sample was obtained.

[0110] Blank sample: Standard security camera, with an aluminum casing.

[0111] The test sample and blank sample were tested in an electromagnetic compatibility semi-anechoic chamber, and the results are as follows: Figure 5 He Ru Figure 6 As shown, from Figure 5 and Figure 6 It is known that the shell made of the honeycomb structure composite absorbing material of the present invention has excellent shielding effect and can better prevent electromagnetic waves from radiating outward.

[0112] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0113] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A honeycomb structure composite microwave absorbing material, characterized in that, It includes a honeycomb core layer and a skin disposed on the upper and lower surfaces of the honeycomb core layer; The honeycomb core layer is prepared using resin and composite magnetic materials. The composite magnetic materials include a composite material composed of porous graphene ellipsoids and zinc sulfide nanomaterials, and an organic insulating material coating the surface of the composite material. In the composite material, multiple porous graphene ellipsoids are arranged in an orderly manner to form a graphene cluster. The zinc sulfide nanomaterials are fused into the graphene cluster. The mass ratio of the zinc sulfide nanomaterials to the graphene cluster is 1:3 to 1:

5. The equatorial radius of the porous graphene ellipsoids is 100nm-120nm, the polar radius is 200nm-250nm, and the pore size of the porous graphene ellipsoids is 14nm-25nm.

2. The honeycomb structure composite absorbing material according to claim 1, characterized in that, The composite magnetic material has a mass fraction of 50%-60% in the honeycomb core layer.

3. The honeycomb structure composite absorbing material according to claim 1, characterized in that, The thickness of the honeycomb core layer is 3mm-8mm.

4. The honeycomb structure composite absorbing material according to claim 3, characterized in that, The honeycomb core layer is composed of multiple hexagonal unit cells, each with a side length of 3mm-5mm and a wall thickness of 0.3mm-0.7mm.

5. The honeycomb structure composite absorbing material according to claim 1, characterized in that, The skin is selected from metal skin.

6. The honeycomb structure composite absorbing material according to any one of claims 1-5, characterized in that, The thickness of the skin is 0.4mm-1mm.

7. The honeycomb structure composite absorbing material according to any one of claims 1-5, characterized in that, In the graphene group, the porous graphene ellipsoids are arranged in a three-dimensional array.

8. The honeycomb structure composite absorbing material according to any one of claims 1-5, characterized in that, The ratio of the particle size of the zinc sulfide nanomaterial to the pore size of the porous graphene ellipsoid is 1:8 to 1:

12.

9. The honeycomb structure composite absorbing material according to any one of claims 1-5, characterized in that, The resin is selected from epoxy resin or phenolic resin.

10. A honeycomb structure composite absorbing material as described in any one of claims 1-9 is used to prepare an external structural component for electronic devices.

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