A graphene / basalt fiber multi-scale material, its preparation method and application

Abstract

The present invention discloses a graphene / basalt fiber multi-scale material, its preparation method and application, which include the following steps: (1) React graphene oxide with an amino silane coupling agent in the presence of a solvent to obtain amino-functionalized graphene oxide; successively perform degumming and roughening treatments on basalt fibers to obtain pretreated basalt fibers; (2) Disperse the amino-functionalized graphene oxide obtained in step (1) in an organic solvent to obtain a dispersion, immerse the pretreated basalt fibers in the dispersion, filter and wash them, and then perform drying treatment under hydrogen conditions to obtain the graphene / basalt fiber multi-scale material. For the graphene / basalt fiber multi-scale material prepared by the present invention, graphene is uniformly and firmly modified on the fiber surface, and the surface-modified graphene has a low oxygen content, and it can be used as a reinforcing material in copper-based composites, which can effectively improve the bonding strength between basalt fibers and the copper matrix.

Description

Technical Field

[0001] The present invention relates to the technical field of new material preparation, and particularly relates to a graphene / basalt fiber multi-scale material, a preparation method thereof and an application thereof. Background Art

[0002] Basalt fiber is a newly emerging fiber that has developed rapidly in recent years. It has a wide range of sources, rich resources, excellent performance, and low manufacturing cost. It is an ideal substitute for high-performance fibers represented by carbon fiber and can be widely used in various civilian and military fields. At present, high-strength fibers have been very widely used in the field of composite materials. As one of the "four major fibers", basalt fiber has developed very rapidly in the field of metal matrix composites due to its low cost and high performance.

[0003] Basalt fiber reinforced copper matrix composites have been widely studied and valued because they combine the characteristics of high strength and high modulus of basalt fiber and the excellent electrical and thermal conductivity of copper. However, due to the poor wettability between basalt fiber and copper matrix, the interfacial bonding force between the two is poor, which often limits the performance of basalt fiber reinforcement. At present, the research on improving the bonding strength between basalt fiber and copper matrix mainly focuses on two aspects: alloying of copper matrix and surface modification of basalt fiber. Although the alloying method can effectively improve the mechanical properties of pure copper, the plasticity and electrical and thermal conductivity of the material will also be significantly reduced; the traditional surface modification method of basalt fiber is mainly the metal layer on the surface of basalt fiber. However, during high-temperature sintering, the metal layer is more likely to combine with the copper matrix and peel off from the surface of carbon fiber. In addition, Patent CN107254066A discloses a method for preparing a graphene-grafted basalt fiber multi-scale reinforcement. By using the surface grafting method, basalt fiber is first coated with dopamine, and then amino-functionalized graphene is grafted onto the dopamine-modified basalt fiber surface to obtain a graphene-grafted basalt fiber multi-scale reinforcement. Although the above method improves the wettability and roughness of basalt fiber and improves the interfacial compatibility between it and the matrix in the composite material to a certain extent, the distribution of graphene oxide on the surface of the modified fiber is uneven and the adhesion effect is not good. Therefore, the improvement effect on the strength of the composite material is limited. In order to further improve the dispersion and adhesion effect of graphene on the surface of basalt fiber to meet the application performance requirements of basalt fiber after surface treatment, a new surface modification treatment process for basalt fiber is urgently needed to improve its interfacial strength with copper matrix. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a graphene / basalt fiber multi-scale material, its preparation method and application. The present invention uses a silane coupling agent containing an amino functional group to modify graphene oxide, improves the dispersion stability of graphene oxide in the dispersion liquid, and reacts with the polar groups on the surface of basalt fiber through the amide bond formed by the reaction of the amino group with the carboxyl group on the surface of graphene oxide, grafts graphene oxide uniformly and firmly onto the surface of basalt fiber, and then dries under hydrogen conditions to obtain basalt fiber modified with graphene with low oxygen content. The prepared graphene / basalt fiber multi-scale material can be used as a reinforcing material in copper-based composites. On the one hand, the surface graphene can strengthen the mechanical meshing effect between the fiber and the copper matrix, and at the same time, Cu-O-C is formed after high-temperature sintering at the interface, and the interface bonding is firm, further improving the mechanical strength of the copper-based composite material.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] The first aspect of the present invention provides a preparation method of a graphene / basalt fiber multi-scale material, which is characterized by including the following steps:

[0007] (1) React graphene oxide with an amino silane coupling agent in the presence of a solvent to obtain amino-functionalized graphene oxide; perform degumming and roughening treatments on basalt fiber in sequence to obtain pretreated basalt fiber;

[0008] (2) Disperse the amino-functionalized graphene oxide obtained in step (1) in an organic solvent to obtain a dispersion liquid, immerse the pretreated basalt fiber in the dispersion liquid, filter and wash, and then dry under hydrogen conditions to obtain the graphene / basalt fiber multi-scale material.

[0009] Further, in step (1), the mass-volume ratio of the graphene oxide to the amino silane coupling agent is 10 mg: 1-2 mL; the amino silane coupling agent is NH2(CH2)3Si(OC2H5)3.

[0010] Further, in step (1), the solvent is a mixed solvent of ethanol and water mixed at a volume ratio of 1:1.

[0011] In this invention, graphene oxide is modified with a silane coupling agent having an amino functional group. The amino group of the silane coupling agent reacts with the carboxyl group on the surface of graphene to form an amide bond, enabling the successful grafting of the silane coupling agent onto the surface of graphene oxide. The polar functional groups ionize in water to form an electrostatic repulsion effect, and the hydrophilic functional groups form hydrogen bonds with water molecules, improving the dispersion stability of graphene and thus reducing the agglomeration phenomenon of graphene oxide, which is beneficial to the uniform adsorption of graphene oxide on the surface of basalt fibers. In addition, polar groups will be formed on the surface of the basalt fibers after roughening treatment, which will react with the amide bonds of the surface-modified graphene oxide, so that graphene oxide is uniformly and firmly modified on the surface of basalt fibers.

[0012] Further, in step (1), the temperature of the reaction is 60 - 90 °C, and the reaction time is 20 - 24 h.

[0013] Further, in step (1), graphene oxide and an amino silane coupling agent are reacted in the presence of a solvent. After the reaction is complete, the fibers are taken out and dried in vacuo at 50 - 100 °C to obtain amino-functionalized graphene oxide.

[0014] Further, in step (1), the specific operations of degumming and roughening treatment are as follows: The basalt fibers are immersed in an acetone solution for 4 - 8 h, and the degummed basalt fibers are obtained after filtration and drying. Then, they are ultrasonicated in a 60 - 70 wt% concentrated nitric acid and / or concentrated sulfuric acid solution for 2 - 4 h, and the pretreated basalt fibers are obtained after filtration and drying.

[0015] The colloid on the surface of basalt fibers will affect the composite of the fibers with other materials, and the fibers need to be degummed before use; while using strong acid to roughen the degummed basalt fibers can, on the one hand, enhance the roughness of the fiber surface, create grooves on the smooth surface of the fiber, and at the same time add polar groups on the surface, enabling graphene oxide to firmly bind to the fiber through valence bonds.

[0016] Further, the degumming treatment can also be carried out by high-temperature calcination, but the high-temperature calcination method will damage the structure of the fibers to a certain extent.

[0017] Further, the above roughening treatment is more preferably concentrated nitric acid.

[0018] Further, in step (2), the amino-functionalized graphene oxide is dispersed in an organic solvent and ultrasonicated at 20 - 40 KHz for 1 - 2 h to obtain a dispersion; the organic solvent is tetrahydrofuran.

[0019] Further, in step (2), the temperature of impregnation is 20 - 40 °C, and the impregnation time is 20 - 24 h.

[0020] Further, in step (2), the temperature of the drying treatment is 100-200°C, and the time of the drying treatment is 4-6 h. The oxygen content on the surface of graphene oxide is too high, about 20-30%. If basalt fibers modified with graphene oxide are directly used to reinforce metals, the high oxygen content will reduce the performance of the metals. Therefore, in the present invention, reduction drying treatment is carried out under hydrogen conditions, which can effectively reduce the oxygen content on the surface of the modified fibers to below 10%.

[0021] The second aspect of the present invention provides a graphene / basalt fiber multi-scale material prepared by the preparation method described in the first aspect.

[0022] The third aspect of the present invention provides an application of the graphene / basalt fiber multi-scale material described in the second aspect in the preparation of copper-based composites.

[0023] The beneficial effects of the present invention are as follows:

[0024] 1. The present invention provides a graphene / basalt fiber multi-scale material. First, graphene oxide is modified with a silane coupling agent containing an amino functional group to improve the dispersion stability of graphene oxide in the dispersion liquid, and the amide bond formed by the reaction of the amino group with the carboxyl group on the surface of graphene oxide reacts with the polar groups on the surface of basalt fibers, grafting graphene oxide uniformly and firmly onto the surface of basalt fibers. Then, drying is carried out under hydrogen conditions to obtain basalt fibers modified with graphene with a low oxygen content. The graphene / basalt fiber multi-scale material prepared by the present invention has graphene uniformly and firmly modified on the fiber surface, and the oxygen content of the surface-modified graphene is low. It can be used as a reinforcing material in copper-based composites and can effectively improve the bonding strength between basalt fibers and copper matrix.

[0025] 2. Using the graphene / basalt fiber multi-scale material described in the present invention as a reinforcing material to prepare copper-based composites, the graphene firmly bonded to the fiber surface increases the surface roughness of basalt carbon fibers on the one hand, thereby increasing the contact area between them and the copper matrix and strengthening the interfacial mechanical meshing effect between the two. At the same time, the formation of a chemical bond Cu-O-C at the interface between graphene oxide and the copper matrix during high-temperature sintering makes the interface bonding relatively firm and improves the mechanical strength of the copper-based composites. Therefore, the copper-based composites prepared with the above-mentioned graphene / basalt fiber multi-scale material as a reinforcing material have the characteristics of high strength and high hardness. Description of the Drawings

[0026] Figure 1 is the SEM morphology diagram of the raw material basalt fiber;

[0027] Figure 2 is the SEM morphology diagram of the basalt fiber after degumming and roughening;

[0028] Figure 3 SEM morphology diagram of the graphene / basalt fiber multi-scale material prepared in Example 1;

[0029] Figure 4 SEM morphology diagram of the graphene / basalt fiber multi-scale material prepared in Comparative Example 1;

[0030] Figure 5 SEM morphology diagram of the graphene / basalt fiber multi-scale material prepared in Comparative Example 2;

[0031] Figure 6 SEM morphology diagram of the graphene / basalt fiber multi-scale material prepared in Comparative Example 3. Detailed implementation manners

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this invention belongs. The terms used in the description of this invention herein are for the purpose of describing specific embodiments only and are not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0033] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and be able to implement it, but the examples given are not intended to limit the present invention.

[0034] Example 1

[0035] This example relates to the preparation of a graphene / basalt fiber multi-scale material, including the following steps:

[0036] (1) Charge graphene oxide, ethanol, and deionized water into a reagent tube in a ratio of 10 mg: 10 mL: 10 mL, ultrasonically process for 3 h at room temperature, then drop 1 mL of silane coupling agent KH-550 into the reagent tube, and react at 70 °C for 24 h to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it warm in a vacuum drying oven at 60 °C for 12 h to obtain amino-functionalized graphene oxide. Perform degumming and roughening treatments on basalt fibers: Immerse 50 mg of basalt fibers in an acetone solution for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and ultrasonically oscillate for 3 h, filter and dry to obtain pretreated basalt fibers.

[0037] (2) Load 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and sonicate for 2 h at a sonication frequency of 25 Hz to obtain Solution II; place the pretreated basalt fibers into Solution II and let it stand for 24 h to obtain Solution III; repeatedly filter and wash Solution III, and then keep it in a hydrogen-filled tube furnace at 150 °C for 6 h to obtain the graphene / basalt fiber multi-scale material.

[0038] The original morphology of the basalt fibers is as Figure 1 shown, with a smooth and flat surface. The morphology of the pretreated basalt fibers is as Figure 2 shown, with a large number of grooves on the surface, greatly increasing the surface roughness. The morphology of the graphene / basalt fiber multi-scale material prepared in this example is as Figure 3 shown, with sheet-like graphene oxide uniformly modified on the surface of the basalt fibers.

[0039] Example 2

[0040] This example relates to the preparation of a graphene / basalt fiber multi-scale material, including the following steps:

[0041] (1) Load graphene oxide, ethanol, and deionized water into a reagent tube in a ratio of 10 mg: 10 mL: 10 mL, sonicate at room temperature for 2 h, then add 2 mL of silane coupling agent KH-550 dropwise to the reagent tube, and react at 70 °C for 24 h to obtain Solution I. Repeatedly filter and wash Solution I, and then keep it in a vacuum drying oven at 50 °C for 12 h to obtain amino-functionalized graphene oxide. Perform degumming and roughening treatments on the basalt fibers: place 50 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; place the degummed basalt fibers into a 65 wt% nitric acid solution and ultrasonically vibrate for 2 h, filter and dry to obtain the pretreated basalt fibers.

[0042] (2) Load 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and sonicate for 2 h at a sonication frequency of 30 Hz to obtain Solution II; place the pretreated basalt fibers into Solution II and let it stand for 24 h to obtain Solution III; repeatedly filter and wash Solution III, and then keep it in a hydrogen-filled tube furnace at 100 °C for 6 h to obtain the graphene / basalt fiber multi-scale material.

[0043] Example 3

[0044] This example relates to the preparation of a graphene / basalt fiber multi-scale material, including the following steps:

[0045] (1) Load graphene oxide, ethanol, and deionized water into a reagent tube at a ratio of 10 mg: 10 mL: 10 mL, and ultrasonically treat it for 3 h at room temperature. Subsequently, add 2 mL of silane coupling agent KH-550 to the reagent tube and react it at 70 °C for 24 h to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it in a vacuum drying oven at 50 °C for 15 h to obtain amino-functionalized graphene oxide. Carry out degumming and roughening treatment on basalt fibers: Put 50 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and ultrasonically vibrate for 2 h, filter and dry to obtain pretreated basalt fibers.

[0046] (2) Load 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and ultrasonically treat it for 1 h with an ultrasonic frequency of 30 Hz to obtain Solution II; put the pretreated basalt fibers into Solution II and let it stand for 20 h to obtain Solution III; filter and wash Solution III repeatedly, and then keep it in a hydrogen-filled tube furnace at 200 °C for 4 h to obtain a graphene / basalt fiber multi-scale material.

[0047] Example 4

[0048] This example relates to the preparation of a graphene / basalt fiber multi-scale material, including the following steps:

[0049] (1) Load graphene oxide, ethanol, and deionized water into a reagent tube at a ratio of 10 mg: 10 mL: 10 mL, and ultrasonically treat it for 2 h at room temperature. Subsequently, add 2 mL of silane coupling agent KH-550 to the reagent tube and react it at 90 °C for 20 h to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it in a vacuum drying oven at 50 °C for 12 h to obtain amino-functionalized graphene oxide. Carry out degumming and roughening treatment on basalt fibers: Put 50 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and ultrasonically vibrate for 2 h, filter and dry to obtain pretreated basalt fibers.

[0050] (2) Load 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and ultrasonically treat it for 2 h with an ultrasonic frequency of 30 Hz to obtain Solution II; put the pretreated basalt fibers into Solution II and let it stand for 20 h to obtain Solution III; filter and wash Solution III repeatedly, and then keep it in a hydrogen-filled tube furnace at 100 °C for 4 h to obtain a graphene / basalt fiber multi-scale material.

[0051] Comparative Example 1

[0052] This comparative example relates to the preparation of a graphene / basalt fiber multi-scale material, which is different from Example 1 in that: in step (1), no silane coupling agent KH-550 is added for treatment, and it specifically includes the following steps:

[0053] (1) Load graphene oxide, ethanol, and deionized water into a reagent tube at a ratio of 10 mg: 10 mL: 10 mL, and perform ultrasonic treatment for 3 h at room temperature to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it warm in a vacuum drying oven at 60 °C for 12 h to obtain dispersed graphene oxide. Perform degumming and coarsening treatment on basalt fibers: Put 50 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and perform ultrasonic oscillation for 3 h, filter and dry to obtain pretreated basalt fibers.

[0054] (2) Load 10 mg of dispersed graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and perform ultrasonic treatment for 2 h at an ultrasonic frequency of 25 Hz to obtain Solution II; put the pretreated basalt fibers into Solution II and let it stand for 24 h to obtain Solution III; filter and wash Solution III repeatedly, and then keep it warm in a tube furnace filled with hydrogen at 150 °C for 6 h to obtain a graphene / basalt fiber multi-scale material.

[0055] The morphology of the graphene / basalt fiber multi-scale material prepared in this comparative example is as Figure 4 shown, and almost no graphene oxide is adsorbed on the surface of the basalt fibers.

[0056] Comparative Example 2

[0057] This comparative example relates to the preparation of a graphene / basalt fiber multi-scale material, which specifically includes the following steps:

[0058] (1) Load graphene oxide, ethanol, and deionized water into a reagent tube at a ratio of 10 mg: 10 mL: 10 mL, perform ultrasonic treatment for 3 h at room temperature, then drop 1 mL of silane coupling agent KH-550 into the reagent tube, and react at 70 °C for 24 h to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it warm in a vacuum drying oven at 60 °C for 12 h to obtain amino-functionalized graphene oxide. Perform degumming and coarsening treatment on basalt fibers: Put 200 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and perform ultrasonic oscillation for 2 h, filter and dry to obtain pretreated basalt fibers.

[0059] (2) Put 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and ultrasonically treat for 2 h at an ultrasonic frequency of 25 Hz to obtain Solution II; put the pretreated basalt fiber into Solution II and let it stand for 24 h to obtain Solution III; repeatedly filter and wash Solution III, and then keep it warm in a hydrogen-filled tube furnace at 100 °C for 6 h to obtain the graphene / basalt fiber multi-scale material.

[0060] The morphology of the graphene / basalt fiber multi-scale material prepared in this comparative example is as Figure 5 shown. Since the content of basalt fiber is relatively large, the amount of graphene oxide adsorbed on the surface of the basalt fiber treated by the above method is small.

[0061] Comparative Example 3

[0062] This comparative example relates to the preparation of a graphene / basalt fiber multi-scale material, which is different from Example 1 in that: in step (1), ethylenediamine is added instead of the silane coupling agent KH-550 to perform amino-functionalization treatment on graphene oxide, and dopamine is used to modify the basalt fiber, which specifically includes the following steps:

[0063] (1) Put graphene oxide, ethanol and deionized water into a reagent tube according to the ratio of 10 mg: 10 mL: 10 mL, ultrasonically treat at room temperature for 3 h, drop 2 mL of ethylenediamine into the reagent tube, and react at 70 °C for 24 h to obtain Solution I. Repeatedly filter and wash Solution I, and then keep it warm in a vacuum drying oven at 60 °C for 12 h to obtain amino-functionalized graphene oxide. Debond and roughen the basalt fiber: put 50 mg of basalt fiber into an acetone solution and soak for 4 h, filter and dry; put the debonded basalt fiber into a 65 wt% nitric acid solution and ultrasonically vibrate for 3 h, filter and dry to obtain the pretreated basalt fiber; prepare 10 mL of Tris-HCL buffer solution (concentration 10 mmol / L, pH = 8.5), add the pretreated basalt fiber and ultrasonically disperse for 10 min, then add 0.2 g of dopamine hydrochloride, stir at room temperature for 24 h, wash and dry to obtain the dopamine-modified basalt fiber.

[0064] (2) Put 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and ultrasonically treat for 2 h at an ultrasonic frequency of 25 Hz to obtain Solution II; put the dopamine-modified basalt fiber into Solution II and let it stand for 24 h to obtain Solution III; repeatedly filter and wash Solution III, and then keep it warm in a hydrogen-filled tube furnace at 150 °C for 6 h to obtain the graphene / basalt fiber multi-scale material.

[0065] The morphology of the graphene / basalt fiber multi-scale material prepared in this comparative example is asFigure 6 As shown, graphene oxide is unevenly distributed on the surface of basalt fibers and serious agglomeration occurs.

[0066] Comparative Example 4

[0067] This comparative example relates to the preparation of a graphene / basalt fiber multi-scale material. The difference from Example 1 is that in step (2), it is directly dried in an air atmosphere, which specifically includes the following steps:

[0068] (1) Load 10 mg of graphene oxide, 10 mL of ethanol, and 10 mL of deionized water into a reagent tube, ultrasonically treat for 3 h at room temperature, then drop 1 mL of silane coupling agent KH-550 into the reagent tube, and react at 70 °C for 24 h to obtain Solution I. Filter and wash Solution I repeatedly, and then keep it warm in a vacuum drying oven at 60 °C for 12 h to obtain amino-functionalized graphene oxide. Perform degumming and roughening treatments on basalt fibers: Put 50 mg of basalt fibers into an acetone solution and soak for 4 h, filter and dry; put the degummed basalt fibers into a 65 wt% nitric acid solution and ultrasonically vibrate for 3 h, filter and dry to obtain pretreated basalt fibers.

[0069] (2) Load 10 mg of amino-functionalized graphene oxide and 50 mL of tetrahydrofuran solution into a reagent tube and ultrasonically treat for 2 h with an ultrasonic frequency of 25 Hz to obtain Solution II; put the pretreated basalt fibers into Solution II and let it stand for 24 h to obtain Solution III; filter and wash Solution III repeatedly, and then keep it warm in a tubular furnace with an air atmosphere at 150 °C for 6 h to obtain a graphene oxide / basalt fiber multi-scale material.

[0070] Performance Test

[0071] Respectively, take the graphene (graphene oxide) / basalt fiber multi-scale materials prepared in the above examples and comparative examples as reinforcing materials and add them to the copper matrix in the same content to prepare basalt fiber-reinforced copper matrix composites, and perform performance characterization on the prepared composites. The characterization results are shown in Table 1 below:

[0072] Table 1 Performance Characterization Data

[0073]

[0074] As shown in Table 1, the tensile strength, hardness, etc. of the copper-based composite material prepared by using the graphene / basalt fiber multi-scale material prepared in Examples 1 to 4 as a reinforcing material are significantly improved. Compared with Example 1, Comparative Example 1 does not add a silane coupling agent to treat graphene oxide, and only a very small amount of graphene oxide is adsorbed on the fiber surface. The strength and hardness of the copper-based composite material obtained by its enhanced treatment are much lower than those of Example 1; Comparative Example 2 has less graphene oxide on the fiber surface, and compared with Comparative Example 1, the hardness and strength of the prepared copper-based composite material are improved, but the improvement is limited. According to the prior art, dopamine is used as a bridge to combine graphene oxide with basalt fiber. Due to the uneven distribution of graphene oxide on the fiber surface and the presence of serious agglomeration, the tensile strength of the copper-based composite material prepared by its enhancement is lower than that of Comparative Example 2.

[0075] In addition, compared with other embodiments and comparative examples, comparative example 4 was not subjected to reduction drying treatment under a hydrogen atmosphere, and the oxygen content of the prepared graphene oxide / basalt fiber multi-scale material was much higher than that of other embodiments and comparative examples. The copper-based composite material prepared by reinforcing the graphene oxide / basalt fiber multi-scale material with a high oxygen content had a lower hardness and tensile strength than comparative example 1. It can be seen that too high an oxygen content will significantly reduce the mechanical properties of the composite material.

[0076] The above-described embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or changes made by those skilled in the art based on the present invention are within the protection scope of the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. A preparation method of a graphene / basalt fiber multi-scale material, characterized in that, It includes the following steps: (1) React graphene oxide with an amino-silane coupling agent in the presence of a solvent to obtain amino-functionalized graphene oxide; successively degum and roughen basalt fibers to obtain pretreated basalt fibers; the amino-silane coupling agent is NH2(CH2)3Si(OC2H5)3; (2) Disperse the amino-functionalized graphene oxide obtained in step (1) in an organic solvent to obtain a dispersion, immerse the pretreated basalt fibers in the dispersion, filter, wash, and then dry under hydrogen conditions to obtain the graphene / basalt fiber multi-scale material.

2. The preparation method according to claim 1, wherein, In step (1), the mass-volume ratio of graphene oxide to the amino-silane coupling agent is 10 mg: 1-2 mL.

3. The preparation method according to claim 1, characterized in that, In step (1), the solvent is a mixed solvent of ethanol and water with a volume ratio of 1:

1.

4. The preparation method according to claim 1, wherein, In step (1), the reaction temperature is 60-90 °C and the reaction time is 20-24 h.

5. The preparation method according to claim 1, characterized in that, In step (1), the specific operations of degumming and roughening are as follows: Immerse the basalt fibers in an acetone solution for 4-8 h, filter and dry to obtain degummed basalt fibers, and then place them in a 60-70 wt% concentrated nitric acid and / or concentrated sulfuric acid solution and ultrasonicate for 2-4 h, filter and dry to obtain pretreated basalt fibers.

6. The preparation method according to claim 1, characterized in that, In step (2), disperse the amino-functionalized graphene oxide in an organic solvent and ultrasonicate at 20-40 KHz for 1-2 h to obtain a dispersion; the organic solvent is tetrahydrofuran.

7. The preparation method according to claim 1, characterized in that, In step (2), the impregnation temperature is 20-40 °C and the impregnation time is 20-24 h.

8. The preparation method according to claim 1, wherein In step (2), the drying temperature is 100-200 °C and the drying time is 4-6 h.

9. A graphene / basalt fiber multi-scale material prepared by the preparation method according to any one of claims 1-8.

10. An application of the graphene / basalt fiber multi-scale material according to claim 9 in the preparation of a copper-based composite material.

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