CN107381555B - A kind of three-dimensional grapheme of structure-controllable and its preparation method of composite material - Google Patents

Abstract

The invention belongs to graphene composite material preparation fields, and disclose a kind of three-dimensional grapheme and its composite material and preparation method thereof of structure-controllable.This method includes the following steps：(a) design construction CAD model, and the three-dimensional resinous structure of corresponding structure is obtained by increasing material manufacturing；(b) it uses chemical plating method in copper coating or nickel metal layer the three-dimensional resinous structure obtained in step (a), and removes resin material and obtain the three-dimensional structure template of copper or nickel；(c) graphene is generated on three-dimensional structure metal form using chemical vapour deposition technique, the three-dimensional grapheme of required structure-controllable is thus made.By being further processed to obtain graphene composite material to obtained graphene.Through the invention, it can be achieved that the regulation and control of three-dimensional grapheme structure, and obtain effectively, the high quality of accurate control, multifunction three-dimensional graphene composite material product, this method is easy to operate, short preparation period, adapts to wide.

Description

A preparation method of three-dimensional graphene and its composite materials with controllable structure

technical field

The invention belongs to the field of preparation of graphene composite materials, and more specifically relates to a preparation method of three-dimensional graphene with controllable structure and a composite material thereof.

Background technique

Graphene is a two-dimensional (2D) crystal material composed of a single layer of carbon atoms. It has very important application prospects in scientific fields such as storage. Composite materials prepared from graphene have also attracted much attention because of their improvements in the mechanical, thermal and electrical properties of the original materials.

However, there is a strong interaction force between 2D single-layer graphene sheets, and it is easy to aggregate. The graphene materials we usually use are mostly in the form of powder, which leads to its excellent specific surface area and thermal and electrical conductivity. limit. The preparation of existing graphene composite materials usually adopts graphene powder as an additive, and due to the uncontrollability of graphene distribution, the amount of graphene added to the composite material is relatively large (such as the amount of graphene added in conductive plastics is 4 to 10%) and The performance optimization of composite materials is limited (the mechanical properties of composite materials show a trend of first increasing and then decreasing with the increase of graphene addition). To solve this problem, the researchers connected multiple sheets of graphene together to form a three-dimensional honeycomb skeleton structure, that is, three-dimensional (3D) graphene. In addition to the inherent physical and chemical properties of graphene, 3D graphene has abundant pores, ultra-light density, large specific surface area, low thermal conductivity, high electrical conductivity, good mechanical compressibility and structural stability. Compared with single-layer graphene, it has better performance and broader application prospects in the fields of hydrogen storage, catalysis, sensing technology, supercapacitors and flexible/stretchable conductive composite materials.

For this reason, some solutions have been proposed in the prior art. For example, CN102674321A discloses a graphene film deposited on the surface of a three-dimensional foamed nickel template by chemical vapor deposition, and obtains porous foamed graphene after dissolving the porous metal substrate. However, the method uses metal foam as a template, wherein Both the pore characteristics and the orientation of graphene sheets cannot be effectively controlled; CN105776186A discloses a method for preparing a three-dimensional graphene porous material with controllable growth and structure by using SLM forming metal templates. The method is prepared by SLM additive manufacturing technology Metal template growth graphene, the metal template surface quality prepared by SLM is relatively poor, so the prepared graphene quality is relatively poor, is difficult to be applied to the preparation of composite material; CN106349658A, CN105749865A and CN106349658A announced the preparation method of three-dimensional graphene composite material Both use powdered three-dimensional graphene as the composite agent, and the dispersion of graphene has been improved to a certain extent, but agglomeration still occurs, and the orientation of graphene sheets cannot be adjusted.

Contents of the invention

In view of the above defects or improvement needs of the prior art, the present invention provides a method for preparing three-dimensional graphene and its composite materials with controllable structure, through the design and manufacture of three-dimensional templates, the regulation and control of the quality of the electroless metal layer and the graphene The growth and other links of the graphene are studied and designed, thus solving the technical problem of uncontrollable external shape and internal structure of three-dimensional graphene and its composite materials.

In order to achieve the above object, according to one aspect of the present invention, a method for preparing three-dimensional graphene with controllable structure is provided, wherein the method comprises the following steps:

(a) Constructing a CAD model for the three-dimensional structure required for the preparation of three-dimensional graphene, and obtaining a three-dimensional resin structure of the corresponding structure through additive manufacturing of the CAD model;

(b) the three-dimensional resin structure obtained in the step (a) is plated with a copper or nickel metal layer on the surface by an electroless plating method, thereby obtaining a resin structure with a metal coating on the surface, and removing the metal coating by chemical corrosion or heat treatment Resin material in the resin structure to obtain a three-dimensional structure template plated with copper or nickel;

(c) using a chemical vapor deposition method to generate graphene on the three-dimensional structure metal template obtained in step (b), thereby obtaining the desired three-dimensional graphene.

Further preferably, in step (a), the step of additive manufacturing includes photocuring, fusion deposition and laser selective sintering.

Further preferably, in the step (b), the copper plating solution adopted during the copper plating by the electroless plating method is one or a combination of copper sulfate, copper chloride, basic copper carbonate, copper tartrate or copper acetate; The nickel plating solution used in electroless nickel plating is one or a combination of nickel sulfate or nickel acetate; and the thickness of the metal plating layer ranges from 1 μm to 50 μm.

Further preferably, in step (b), the method for removing the resin material adopts chemical corrosion or heat treatment, wherein the chemical corrosion uses acetone, ethanol or carbon tetrachloride as the etchant, and the temperature of the heat treatment is 300° C. to 900°C.

Further preferably, in step (c), the carbon source used in the chemical vapor deposition is one or a combination of methane, ethylene, acetylene or styrene.

According to another aspect of the present invention, a method for preparing a three-dimensional graphene composite metal material is provided, characterized in that the preparation method comprises the following steps: for the three-dimensional graphene prepared by any one of claims 1-5 , using casting or hot isostatic pressing to fill the metal into the voids of its internal structure, thereby preparing a three-dimensional graphene composite metal material.

According to another aspect of the present invention, a kind of preparation method of three-dimensional graphene composite resin is provided, it is characterized in that, this preparation method comprises the following steps:

(c1) For the three-dimensional graphene obtained by any one of claims 1-5, spin-coat a layer of resin support layer on its surface, and then immerse in the corrosion solution until the metal template of the three-dimensional graphene is completely dissolved to obtain a band Three-dimensional graphene with a support layer, wherein the resin support layer material adopts polymethyl methacrylate (PMMA) or polydimethylsiloxane (PDMS); the corrosion solution adopts hydrochloric acid, sulfuric acid, nitric acid, chlorine One or a combination of iron oxide or ammonium persulfate, the temperature range of the corrosion process is 30°C to 90°C;

(c2) Filling the resin material into the voids of the three-dimensional graphene with the support layer by means of injection molding and solvent evaporation, thereby preparing a three-dimensional graphene composite resin material.

Further preferably, in step (c2), the resin material is PMMA, PDMS, polyamide (PA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC ), acrylonitrile-styrene-butadiene copolymer (ABS), polystyrene (PS), epoxy resin (EP), phenolic resin (PF), polyether ether ketone (PEEK) or polyvinyl alcohol (PVA ) in one or a combination.

According to another aspect of the present invention, a kind of preparation method of three-dimensional graphene composite ceramics is provided, it is characterized in that, this preparation method comprises the following steps:

(d1) for the three-dimensional graphene obtained by any one of claims 1-5, spin-coat a layer of resin support layer on its surface, then immerse in the corrosion solution until the metal template of the three-dimensional graphene is completely dissolved, by This obtains the three-dimensional graphene that has support layer, wherein, described resin support layer material adopts polymethyl methacrylate (PMMA) or polydimethylsiloxane (PDMS); Described corrosion solution adopts hydrochloric acid, sulfuric acid, One or a combination of nitric acid, ferric chloride or ammonium persulfate, the temperature range of the corrosion process is 30°C to 90°C;

(d2) Filling the ceramic material into the three-dimensional graphene voids with the support layer by filling ceramic slurry and colloidal molding, and then removing the carbon dioxide in the preliminary ceramic composite material by organic solvent corrosion or heat treatment. The resin support layer is filled with ceramic slurry and colloidal molding method to refill the ceramic material, and finally the refilled product is subjected to hot isostatic pressing or normal pressure sintering to obtain a three-dimensional graphene composite ceramic material.

Further preferably, in step (d2), the ceramic slurry material is selected from one or a combination of Al ₂ O ₃ , ZrO ₂ , TiO ₂ , SiO ₂ or SiC.

Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:

1. The present invention uses additive manufacturing combined with electroless metal plating layer as a template, and uses chemical vapor deposition to grow three-dimensional graphene on the metal template, and can design and prepare three-dimensional graphene composite materials with specific shapes and structures according to requirements, which can effectively overcome The defects of uneven distribution of graphene and uncontrollable orientation of graphene sheets in graphene composite materials existing in the prior art lay the foundation for improving the performance of three-dimensional graphene composite materials;

2. Using additive manufacturing combined with electroless plating to prepare metal templates for chemical vapor deposition of three-dimensional graphene, since the surface quality of electroless metal plating is better than that of additive manufacturing directly formed metal templates, the technology of the present invention is conducive to the growth of high-quality three-dimensional graphene Graphene is conducive to the preparation and performance improvement of three-dimensional graphene composite materials;

3. This method has the characteristics of simple operation, short preparation period and wide application range, and is especially suitable for designing according to needs. The preparation of internal graphene composite structures can obtain effective and precisely controlled high-quality, multifunctional three-dimensional graphene composite material products.

Description of drawings

Fig. 1 is a flow chart of the preparation method of three-dimensional graphene and its composite material with controllable structure constructed according to a preferred embodiment of the present invention.

Detailed ways

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.

A method for preparing a structure-controllable three-dimensional graphene composite material provided by the present invention combines additive manufacturing, chemical plating and CVD technology to prepare a three-dimensional graphene material that meets the design requirements and structure controllable, and then adds the corresponding composite material components As a supporting filling material, at the same time dissolving corrosive liquid or heat treatment to decompose to remove unnecessary components in the composite material, and finally prepare three-dimensional graphene composite metal, resin, and ceramic materials with controllable structure.

Specifically include the following steps:

(1) Construct the CAD model of the required three-dimensional porous structure, and design its external shape and internal structure respectively;

The CAD model described in step (1) presents an ordered periodic porous structure or an interconnected three-dimensional structure arranged according to design requirements, and its unit size is between 0.1-10mm, and the porosity is between 30-99%. Tune.

(2) Based on the CAD model constructed in step (1), a three-dimensional resin structure of corresponding shape is obtained by photocuring, fused deposition or laser selective sintering additive manufacturing technology;

The additive manufacturing technology described in step (2) includes light curing, fusion deposition, and laser selective sintering technologies; the three-dimensional structure prepared by forming is a resin material.

(3) Copper or nickel metal layer is plated on the surface of the three-dimensional resin structure prepared in step (2) by electroless copper plating or electroless nickel plating process; wherein the copper plating or nickel plating process adopted includes resin structure cleaning, roughening, After neutralization, sensitization and activation, a copper or nickel plating solution is used to plate a copper or nickel metal layer on the surface of the treated resin structure, and the thickness of the plated metal layer is between 1 and 50 μm. Then, the resin structure coated with the metal layer is removed by chemical corrosion or heat treatment to obtain a copper or nickel three-dimensional structure template;

The copper plating liquid adopted in the step (3) is copper salt with copper sulfate, cupric chloride, basic copper carbonate, copper tartrate, copper acetate; The nickel plating liquid that adopts is nickel salt with nickel sulfate, nickel acetate; The thickness of the metal layer is controlled between 1 and 50 μm.

The chemical etching method used in step (3) is to corrode the resin template with acetone, ethanol, and carbon tetrachloride; the heat treatment method is to decompose and remove the resin structure at 300-900° C.

(4) grow graphene on the prepared metal template of step (3) by chemical vapor deposition: in this process, metal template is put into CVD tube furnace, feeds argon as shielding gas; Then in Under the condition of feeding argon, heat the sample to the reaction temperature; after reaching the reaction temperature, feed argon and hydrogen to keep warm; then feed methane and hydrogen, and keep the pressure in the tube furnace, and start the chemical vapor deposition reaction; after the reaction The sample is cooled to room temperature under the condition of feeding argon and hydrogen, thereby preparing three-dimensional graphene grown on the metal template;

The carbon sources used in the chemical vapor deposition process in step (4) are methane, ethylene, acetylene, and styrene; the number of graphene layers grown on the surface of the three-dimensional metal template prepared in step (3) is 1-20 layers.

(5) Prepare a certain concentration of corrosive liquid, spin-coat a layer of resin support layer on the surface of the product obtained in step (4), then immerse in the prepared corrosive liquid, and reflow at a temperature of 30-90°C until the The above metal templates are completely dissolved: the copper metal template prepared by copper plating uses FeCl ₃ or (NH ₄ ) ₂ S ₂ O ₈ solution as the etching solution; the nickel metal template prepared by nickel plating uses HCl solution as the etching solution. A composite three-dimensional graphene material with a support layer is obtained;

The resin support layer described in step (5) is PMMA, PDMS; Corrosive solution is selected from one or its mixture of following substances: hydrochloric acid, sulfuric acid, nitric acid, ferric chloride and ammonium persulfate; Corrosion process control temperature is at 30 ℃～ 90°C.

(6) the preparation of three-dimensional graphene composite metal material, the metal structure that the surface that step (4) makes has graphene is long as composite additive material, adopts the method for casting, hot isostatic pressing to make metal fill template space, make Obtain three-dimensional graphene composite metal material;

The filling metal in step (6) is copper or nickel; the proportion of three-dimensional graphene in the composite material is 0.01-10wt%.

(7) The three-dimensional graphene with the resin support layer is used for injection molding and solvent evaporation to make the resin material fill the template gap to obtain a three-dimensional graphene composite resin material; the three-dimensional graphene with the resin support layer is filled with ceramic slurry Material, colloidal molding method, so that the ceramic material fills the gap, and then use organic solvent corrosion or heat treatment to remove the resin support layer, fill the gap with ceramic slurry, colloidal molding method, and then hot isostatic pressing or normal pressure Sintering produces a three-dimensional graphene composite ceramic material.

Prepare the three-dimensional graphene composite resin material filling resin described in step (7) and be the one in PMMA, PDMS, PA, PE, PP, PVC, PC, ABS, PS, EP, PF, PEEK, PVA; Prepare three-dimensional graphite The filling material of the graphene composite ceramic material is Al ₂ O ₃ , ZrO ₂ , TiO ₂ , SiO ₂ , SiC; the proportion of three-dimensional graphene in the composite material is 0.01-10 wt%.

In summary, the general idea of the present invention mainly includes three aspects. One is to establish a CAD model according to the material design requirements, and to prepare a metal template conforming to the CAD model through additive manufacturing and chemical plating technology; The first is to use CVD technology to grow three-dimensional graphene with controllable structure; the third is to add the corresponding composite material components as support filling materials, and at the same time configure corrosive solution to dissolve or heat treatment to decompose to remove unnecessary components in the composite material, and finally produce Three-dimensional graphene composite metal, resin, and ceramic materials with controllable structure must meet the design requirements.

The solutions of the present invention will be further described below in conjunction with specific examples.

Example 1

(1) Use CAD software to establish a three-dimensional porous unit body with a unit size of 0.1mm. The unit body array is designed as a periodic porous structure with a porosity of 30% and an orderly arrangement. The external size of the model is 50mm×50mm ×10mm.

(2) The resin structure of the constructed CAD model was prepared by light-curing additive manufacturing technology.

(3) After cleaning, roughening, neutralizing, sensitizing, and activating the prepared resin structure, adopt an electroless copper plating process to plate a copper metal layer on the surface of the resin structure. The electroless copper plating solution uses copper sulfate as copper salt, and formaldehyde As a reducing agent, the thickness of the plated metal copper layer is 1 μm. Soak the prepared resin structure coated with the metal layer in acetone, take it out after the resin structure is completely dissolved, and then wash and dry it.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of argon flow rate of 300 sccm, the sample was heated to 900° C. in 50 minutes; Insulate at 900°C for 35 minutes under the conditions of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, methane gas flow rate of 10sccm, and tube furnace pressure of 50Pa, the metal template is kept at 900°C for 15 minutes; 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thereby preparing three-dimensional graphene grown on a metal template, and the number of graphene layers is 1 layer.

(5) Putting the copper structure with graphene growing on the surface into a mold, pouring molten copper to fill the gaps under protective atmosphere conditions, cooling and demoulding, and obtaining a three-dimensional graphene composite copper material. The test results show that the three-dimensional graphene is uniformly distributed in the composite copper matrix according to the design requirements.

Example 2

(1) Using CAD software, a three-dimensional porous unit body with a unit size of 10mm is correspondingly established. The unit body array is designed as a periodic porous structure with a porosity of 99% and an orderly arrangement. The external size of the model is 100mm×100mm× 100mm.

(2) The resin structure of the constructed CAD model was prepared by fused deposition additive manufacturing technology.

(3) After cleaning, coarsening, neutralizing, sensitizing and activating the prepared resin structure, adopt the electroless nickel plating process to plate a copper metal layer on the surface of the resin structure. The electroless nickel plating solution adopts nickel sulfate as nickel salt, sub Sodium phosphate is used as a reducing agent, and the thickness of the metal nickel layer plated is 50 μm. The prepared resin structure coated with the metal layer was heat-treated at 900° C. for 3 hours under a nitrogen protective atmosphere to decompose and remove the resin structure.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of an argon flow of 300 sccm, the sample was heated to 1050° C. in 50 minutes; Insulate at 1050°C for 35 minutes under the conditions of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, acetylene gas flow rate of 50sccm, and tube furnace pressure of 200Pa, the metal template was kept at 1100°C for 15 minutes; 1. Cooling to room temperature under the condition of hydrogen flow rate of 50 sccm, thus producing three-dimensional graphene grown on the metal template, the number of graphene layers is 20 layers.

(5) Configure 3 wt% PMMA ethanol solution, spin-coat on the prepared metal template with graphene on the surface, and keep the PMMA solidified at 150° C. for 30 minutes. Prepare a 3 mol/L FeCl ₃ aqueous solution, immerse the prepared product in it, and reflux at a temperature of 30° C. until the metal template is completely dissolved.

(6) Inject the melted PMMA into the voids of the material prepared in step (5) by injection molding, and cool to obtain the three-dimensional graphene composite PMMA material. The test results show that the three-dimensional graphene is uniformly distributed in the composite PMMA matrix according to the design requirements.

Example 3

(1) Using CAD software, correspondingly establish a sheet structure model with a spacing of 1 mm, and the external size of the model with a sheet thickness of 1 mm is 50 mm × 50 mm × 50 mm.

(2) The resin structure of the constructed CAD model was prepared by laser selective sintering additive manufacturing technology.

(3) After cleaning, roughening, neutralizing, sensitizing and activating the prepared resin structure, adopt an electroless copper plating process to plate a copper metal layer on the surface of the resin structure, and the electroless copper plating solution adopts copper chloride as copper salt, Formaldehyde is used as a reducing agent, and the thickness of the plated metal copper layer is 3 μm. Soak the prepared resin structure coated with the metal layer in acetone, take it out after the resin structure is completely dissolved, and then wash and dry it.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of an argon flow of 300 sccm, the sample was heated to 1000° C. in 50 minutes; 50sccm, hydrogen flow rate of 50sccm at 1000°C for 35 minutes; under the conditions of hydrogen flow rate of 30sccm, methane gas flow rate of 20sccm, and tube furnace pressure of 130Pa, the metal template was kept at 1000°C for 15 minutes; then argon flow rate of 60sccm 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thus producing three-dimensional graphene grown on a metal template, and the number of graphene layers is 3 layers.

(5) Configure 3wt% PMMA ethanol solution, spin-coat on the prepared metal template with graphene on the surface, and keep the PMMA solidified at 100° C. for 30 minutes. Prepare a 3 mol/L FeCl ₃ aqueous solution, immerse the prepared product in it, and reflux at a temperature of 50° C. until the metal template is completely dissolved.

(6) Inject the Al ₂ O ₃ slurry into the gap of the material prepared in step (5) by colloidal molding method, heat and solidify, and then heat-treat at 600°C for 3 hours to decompose and remove the PMMA support layer, and the Al ₂ O 3 ₃ The slurry is injected into PMMA to remove the generated voids, heated and solidified and sintered at high temperature to obtain a three-dimensional graphene composite Al ₂ O ₃ ceramic material. The test results show that the three-dimensional graphene is uniformly distributed in the composite Al ₂ O ₃ matrix according to the design requirements.

Example 4

(1) Using CAD software, a three-dimensional porous unit body with a unit size of 3mm is correspondingly established. The unit body array is designed as a periodic porous structure with a porosity of 85% and an orderly arrangement. The external size of the model is 50mm×50mm× 50mm.

(2) The resin structure of the constructed CAD model was prepared by light-curing additive manufacturing technology.

(3) After cleaning, coarsening, neutralizing, sensitizing, and activating the prepared resin structure, an electroless nickel plating process is used to plate a copper metal layer on the surface of the resin structure. The electroless copper plating solution adopts copper sulfate as copper salt, and formaldehyde As a reducing agent, the thickness of the plated metal copper layer is 5 μm. The prepared resin structure coated with the metal layer was heat-treated at 300° C. for 5 hours under a nitrogen protective atmosphere to decompose and remove the resin structure.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of an argon flow of 300 sccm, the sample was heated to 1050° C. in 50 minutes; Insulate at 1050°C for 35 minutes under the conditions of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, acetylene gas flow rate of 50sccm, and tube furnace pressure of 200Pa, the metal template was kept at 1100°C for 15 minutes; 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thereby preparing three-dimensional graphene grown on a metal template, and the number of graphene layers is 1 layer.

(5) Configure the PDMS curing liquid, mix the polymerized monomer and the curing agent at a mass ratio of 10:1, spin-coat on the prepared metal template with graphene on the surface, and keep the temperature at 80°C for 30 minutes to polymerize PDMS solidify. Prepare a 3 mol/L (NH ₄ ) ₂ S ₂ O ₈ solution, immerse the prepared product in it, and reflux at a temperature of 30° C. until the metal template is completely dissolved.

(6) Prepare the PDMS solidified solution, mix the polymerized monomer and the solidified agent at a mass ratio of 10:1, inject the PDMS solidified solution into the gap of the material prepared in step (5), and cool to obtain the three-dimensional graphene composite PDMS material. The test results show that the three-dimensional graphene is uniformly distributed in the composite PDMS matrix according to the design requirements.

Example 5

(1) Use CAD software to establish a three-dimensional porous unit body with a unit size of 0.2 mm. The unit body array is designed as a periodic porous structure with a porosity of 50% and an orderly arrangement. The external size of the model is 10 mm×10 mm ×10mm.

(2) The resin structure of the constructed CAD model was prepared by light-curing additive manufacturing technology.

(3) After cleaning, roughening, neutralizing, sensitizing and activating the prepared resin structure, the electroless nickel plating process is used to plate a nickel metal layer on the surface of the resin structure. The electroless nickel plating solution adopts nickel acetate as nickel salt, sub Sodium phosphate is used as the reducing agent, and the thickness of the metal nickel layer is 10 μm. The prepared resin structure coated with the metal layer is soaked in carbon tetrachloride, taken out after the resin structure is completely dissolved, then washed and dried.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of an argon flow of 300 sccm, the sample was heated to 1000° C. in 50 minutes; Insulate at 1000°C for 30 minutes under the condition of 50sccm, hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, methane gas flow rate of 10sccm, and tube furnace pressure of 50Pa, the metal template is kept at 900°C for 15 minutes; 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thus preparing a three-dimensional graphene grown on a metal template, and the number of graphene layers is 5 layers.

(5) Put the nickel structure with graphene growing on the surface into the mold, fill it with nickel metal powder under protective atmosphere conditions, use hot isostatic pressing technology to densify the material, cool and demould, and obtain the three-dimensional graphene composite nickel material . The test results show that the three-dimensional graphene is uniformly distributed in the composite nickel matrix according to the design requirements.

Example 6

(1) Use CAD software to establish a three-dimensional porous unit body with a unit size of 0.1mm, in which the unit body array is designed as a periodic porous structure with a porosity of 90% and an orderly arrangement, and the external size of the model is 100mm×100mm ×100mm.

(2) The resin structure of the constructed CAD model was prepared by fused deposition additive manufacturing technology.

(3) After cleaning, coarsening, neutralizing, sensitizing and activating the prepared resin structure, adopt the electroless nickel plating process to plate a copper metal layer on the surface of the resin structure. The electroless nickel plating solution adopts nickel sulfate as nickel salt, sub Sodium phosphate is used as the reducing agent, and the thickness of the metal nickel layer is 25 μm. The prepared resin structure coated with the metal layer was heat-treated at 800° C. for 4 hours under a nitrogen protective atmosphere to decompose and remove the resin structure.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a shielding gas; under the condition of an argon flow of 300 sccm, the sample was heated to 950° C. in 50 minutes; Insulate at 950°C for 35 minutes under the condition of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, acetylene gas flow rate of 50sccm, and tube furnace pressure of 200Pa, the metal template is kept at 1100°C for 15 minutes; then the argon flow rate is 60sccm 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thereby preparing three-dimensional graphene grown on a metal template, and the number of graphene layers is 10 layers.

(5) A 3wt% PMMA anisole solution was prepared, spin-coated on the prepared metal template with graphene on the surface, and kept at 100° C. for 40 minutes to solidify the PMMA. Prepare a 3 mol/L FeCl ₃ aqueous solution, immerse the prepared product in it, and reflux at a temperature of 50° C. until the metal template is completely dissolved.

(6) ZrO ₂ slurry is injected into the gap of the material prepared in step (5), heated and solidified, then heat treated at 900°C for 2 hours, the PMMA support layer is decomposed and removed, and ZrO ₂ slurry is injected into PMMA to remove the generated voids, heat solidified and sintered by hot isostatic pressing to obtain a three-dimensional graphene composite _ZrO2 ceramic material. The test results show that the three-dimensional graphene is uniformly distributed in the composite ZrO ₂ matrix according to the design requirements.

Example 7

(1) Using CAD software, correspondingly establish a sheet structure model with a spacing of 3mm, and a sheet thickness of 0.5mm. The external dimensions of the model are 30mm×30mm×30mm.

(2) The resin structure of the constructed CAD model was prepared by laser selective sintering additive manufacturing technology.

(3) After cleaning, roughening, neutralizing, sensitizing and activating the prepared resin structure, adopt an electroless copper plating process to plate a copper metal layer on the surface of the resin structure, and the electroless copper plating solution adopts copper chloride as copper salt, Formaldehyde is used as a reducing agent, and the thickness of the plated metal copper layer is 2 μm. Soak the prepared resin structure coated with the metal layer in ethanol, take it out after the resin structure is completely dissolved, then wash and dry.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a protective gas; under the condition of an argon flow of 300 sccm, the sample was heated to 1050° C. in 50 minutes; Insulate at 1050°C for 35 minutes under the conditions of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, acetylene gas flow rate of 50sccm, and tube furnace pressure of 200Pa, the metal template was kept at 1100°C for 15 minutes; 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thereby preparing three-dimensional graphene grown on a metal template, and the number of graphene layers is 1 layer.

(5) A 3 wt % PMMA anisole solution was prepared, spin-coated on the prepared metal template with graphene on the surface, and kept at 100° C. for 30 minutes to solidify the PMMA. Prepare a 3 mol/L FeCl ₃ aqueous solution, immerse the prepared product in it, and reflux at a temperature of 50° C. until the metal template is completely dissolved.

(6) The PMMA solution is injected into the voids of the material prepared in step (5) by solvent evaporation, and the solvent is evaporated and solidified to obtain a three-dimensional graphene composite PMMA material. The test results show that the three-dimensional graphene is uniformly distributed in the composite PMMA matrix according to the design requirements.

Example 8

(1) Using CAD software, a three-dimensional porous unit body with a unit size of 1mm is correspondingly established. The unit body array is designed as a periodic porous structure with a porosity of 35% and an orderly arrangement. The external size of the model is 150mm×150mm× 50mm.

(2) The resin structure of the constructed CAD model was prepared by light-curing additive manufacturing technology.

(3) After cleaning, coarsening, neutralizing, sensitizing and activating the prepared resin structure, adopt the electroless nickel plating process to plate a copper metal layer on the surface of the resin structure. The electroless nickel plating solution adopts nickel sulfate as nickel salt, sub Sodium phosphate is used as a reducing agent, and the thickness of the metal nickel layer is 20 μm. The prepared resin structure coated with the metal layer was heat-treated at 600° C. for 5 hours under a nitrogen protective atmosphere to decompose and remove the resin structure.

(4) Put the metal template prepared in step (3) into a CVD tube furnace, and feed argon as a shielding gas; under the condition of an argon flow of 300 sccm, the sample was heated to 950° C. in 50 minutes; Insulate at 950°C for 35 minutes under the conditions of 50sccm and hydrogen flow rate of 50sccm; under the conditions of hydrogen flow rate of 30sccm, acetylene gas flow rate of 50sccm, and tube furnace pressure of 50Pa, the metal template was kept at 1100°C for 15 minutes; 1. Cooling to room temperature under the condition of a hydrogen flow rate of 50 sccm, thus preparing a three-dimensional graphene grown on a metal template, and the number of graphene layers is 5 layers.

(5) Configure the PDMS curing liquid, mix the polymerized monomer and curing agent at a mass ratio of 10:1, spin-coat on the prepared metal template with graphene on the surface, and keep the temperature at 60°C for 60 minutes to polymerize PDMS solidify. Prepare a 3 mol/L sulfuric acid solution, immerse the prepared product in it, and reflux at a temperature of 90° C. until the metal template is completely dissolved.

(6) Configure the PDMS solidified solution, mix the polymerized monomer and the solidified agent at a mass ratio of 10:1, inject the PDMS solidified solution into the gap of the material prepared in step (5), and cool to obtain a three-dimensional graphene composite PDMS material. The test results show that the three-dimensional graphene is uniformly distributed in the composite PDMS matrix according to the design requirements.

It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.

Claims (6)

1. a preparation method of three-dimensional graphene composite resin, is characterized in that, the preparation method comprises the following steps: (a) Prepare three-dimensional graphene, spin-coat a layer of resin support layer on its surface, then immerse in the corrosion solution until the metal template of the three-dimensional graphene dissolves completely, obtain three-dimensional graphene with support layer, wherein, the resin The material of the support layer is polymethyl methacrylate or polydimethylsiloxane; the corrosion solution is one or a combination of hydrochloric acid, sulfuric acid, nitric acid, ferric chloride or ammonium persulfate, and the temperature range of the corrosion process is 30 ℃～90℃; (b) Filling the resin material into the voids of the three-dimensional graphene with the support layer by means of injection molding and solvent evaporation, thereby preparing a three-dimensional graphene composite resin material. 2. the preparation method of a kind of three-dimensional graphene composite resin as claimed in claim 1 is characterized in that, in step (b), described resin material is PMMA, PDMS, polyamide, polyethylene, polypropylene, polypropylene One or a combination of vinyl chloride, polycarbonate, acrylonitrile-styrene-butadiene copolymer, polystyrene, epoxy resin, phenolic resin, polyetheretherketone or polyvinyl alcohol. 3. the preparation method of a kind of three-dimensional graphene composite resin as claimed in claim 1, is characterized in that, in step (a), described preparation three-dimensional graphene preferably adopts following method: (a1) Constructing a CAD model for the three-dimensional structure required for the three-dimensional graphene to be prepared, and obtaining a three-dimensional resin structure of the corresponding structure through additive manufacturing of the CAD model; (a2) The three-dimensional resin structure obtained in the step (a1) is plated with a copper or nickel metal layer on the surface by an electroless plating method, thereby obtaining a resin structure with a metal coating on the surface, and removing the metal coating resin by chemical corrosion or heat treatment Resin material in the structure to obtain a three-dimensional structure template plated with copper or nickel; (a3) Generating graphene on the metal template with the three-dimensional structure obtained in step (a2) by chemical vapor deposition, thereby obtaining the desired three-dimensional graphene. 4. a preparation method of three-dimensional graphene composite ceramics, characterized in that, the preparation method may further comprise the steps: (a) preparing three-dimensional graphene, spin-coating a resin support layer on its surface, then immersing in the corrosion solution until the metal template of the three-dimensional graphene is completely dissolved, thus obtaining three-dimensional graphene with a support layer, wherein, The material of the resin support layer is polymethyl methacrylate or polydimethylsiloxane; the corrosion solution is one or a combination of hydrochloric acid, sulfuric acid, nitric acid, ferric chloride or ammonium persulfate, and the corrosion process temperature is The range is 30℃～90℃; (b) filling ceramic slurry and colloidal molding, filling the ceramic material into the voids of the three-dimensional graphene with a support layer, and then removing the resin support layer by organic solvent corrosion or heat treatment, and The ceramic material is refilled by filling ceramic slurry and colloidal molding, and finally hot isostatic pressing or normal pressure sintering is carried out on the refilled product, thereby preparing a three-dimensional graphene composite ceramic material. 5. the preparation method of a kind of three-dimensional graphene composite ceramics as claimed in claim 4, is characterized in that, in step (a), described preparation three-dimensional graphene preferably adopts following method: (a1) Constructing a CAD model for the three-dimensional structure required for the three-dimensional graphene to be prepared, and obtaining a three-dimensional resin structure of the corresponding structure through additive manufacturing of the CAD model; (a2) The three-dimensional resin structure obtained in the step (a1) is plated with a copper or nickel metal layer on the surface by an electroless plating method, thereby obtaining a resin structure with a metal coating on the surface, and removing the metal coating resin by chemical corrosion or heat treatment Resin material in the structure to obtain a three-dimensional structure template plated with copper or nickel; (a3) Generating graphene on the metal template with the three-dimensional structure obtained in step (a2) by chemical vapor deposition, thereby obtaining the required three-dimensional graphene. 6. The preparation method of a kind of three-dimensional graphene composite ceramics as claimed in claim 4 or 5, is characterized in that, in step (d2), described ceramic slurry material selects Al ₂ O ₃ , ZrO ₂ , TiO ₂ , SiO ₂ or SiC in one or a combination.