阅读说明：本技术 一种碳纤维编织布生长氧化铜纳米线复合材料及其制备方法 (Copper oxide nanowire composite material grown on carbon fiber woven cloth and preparation method thereof ) 是由 贾晓华 肖青峰 杨进 宋浩杰 李永 王思哲 于 2020-12-02 设计创作，主要内容包括：本发明公开了一种碳纤维编织布生长氧化铜纳米线复合材料及其制备方法,制备方法包括以下步骤：步骤1：配制电镀液；步骤2：配制过硫酸铵-氢氧化钠混合溶液；步骤3：碳纤维编织布预处理；步骤4：对预处理过的碳纤维编织布进行电镀处理；步骤5：将镀铜的碳纤维编织布在过硫酸铵-氢氧化钠混合溶液中浸泡；步骤6：将表面生长氢氧化铜纳米线的碳纤维编织布进行加热分解处理,即得到复合材料。制备方法重复性强,制备工艺简单方便,制备周期短；制备的复合材料形貌均匀尺度可控,利用形貌可控的线状氧化铜修饰碳纤维,氧化铜与碳纤维之间结合力强,进而有效的改善碳纤维与聚合物基的界面结合,进而提高复合材料的摩擦及力学性能。(The invention discloses a copper oxide nanowire composite material grown on carbon fiber woven cloth and a preparation method thereof, wherein the preparation method comprises the following steps: step 1: preparing electroplating solution; step 2: preparing ammonium persulfate-sodium hydroxide mixed solution; and step 3: pretreating carbon fiber woven cloth; and 4, step 4: electroplating the pretreated carbon fiber woven cloth; and 5: soaking the copper-plated carbon fiber woven cloth in an ammonium persulfate-sodium hydroxide mixed solution; step 6: and (3) heating and decomposing the carbon fiber woven cloth with the copper hydroxide nanowires growing on the surface to obtain the composite material. The preparation method has strong repeatability, simple and convenient preparation process and short preparation period; the prepared composite material is uniform in appearance and controllable in size, the carbon fiber is modified by the linear copper oxide with controllable appearance, and the bonding force between the copper oxide and the carbon fiber is strong, so that the interface bonding between the carbon fiber and a polymer base is effectively improved, and the friction and mechanical properties of the composite material are improved.)

1. A preparation method of a copper oxide nanowire composite material grown on carbon fiber woven cloth is characterized by comprising the following steps:

step 1: preparing an electroplating solution: adding 5-10 g of blue vitriol, 1-4 g of sodium tartrate dihydrate, 20-36 g of sodium citrate dihydrate and 2-5 g of potassium nitrate into 0.5-1L of deionized water, and stirring and dispersing;

step 2: preparing an ammonium persulfate-sodium hydroxide mixed solution: adding ammonium persulfate and sodium hydroxide into 10-20 mL of deionized water according to the mass ratio of 3 (9-10), and stirring and dispersing;

and step 3: pretreating carbon fiber woven cloth: cutting the carbon fiber woven cloth, then carrying out ultrasonic cleaning and drying;

and 4, step 4: cutting the carbon fiber woven cloth pretreated in the step 3 into 10-15 cm²Soaking the fabric into the electroplating solution obtained in the step (1) for electroplating treatment, taking out the fabric after the electroplating is finished, and cleaning and drying the fabric to obtain copper-plated carbon fiber woven fabric;

and 5: soaking the copper-plated carbon fiber woven cloth in the step 4 in the ammonium persulfate-sodium hydroxide mixed solution in the step 2, taking out after soaking, cleaning and drying to obtain the carbon fiber woven cloth with copper hydroxide nanowires growing on the surface;

step 6: and (5) heating and decomposing the carbon fiber woven cloth with the copper hydroxide nanowires growing on the surface in the step (5) to decompose the copper hydroxide nanowires into copper oxide nanowires, thus obtaining the composite material.

2. The preparation method of the carbon fiber woven cloth grown copper oxide nanowire composite material as claimed in claim 1, wherein the stirring in step 1 and step 2 is performed by a magnetic stirrer at room temperature for 20min to 60min, and the dispersion is performed by ultrasonic dispersion.

3. The preparation method of the carbon fiber woven cloth growth copper oxide nanowire composite material according to claim 1, wherein the mass ratio of ammonium persulfate to sodium hydroxide in the step 2 is 1: 3.

4. the method for preparing the copper oxide nanowire composite material grown on the carbon fiber woven cloth according to claim 1, wherein the ultrasonic cleaning in the step 3 is performed by ultrasonic cleaning in a mixed solution of absolute ethyl alcohol and acetone, and the composite material is cleaned by deionized water and dried for later use after the ultrasonic cleaning.

5. The method for preparing the copper oxide nanowire composite material grown on the carbon fiber woven cloth according to claim 1, wherein the electroplating solution in the step 4 is placed in a Hull cell, the pretreated carbon fiber woven cloth is connected with a negative electrode of an electroplating power supply, and a positive electrode of the electroplating power supply is connected with a phosphor copper anode.

6. The preparation method of the carbon fiber woven cloth growth copper oxide nanowire composite material as claimed in claim 5, wherein the current of the electroplating treatment in the step 4 is 1-15A, and the electroplating time is 5-30 min.

7. The preparation method of the carbon fiber woven cloth grown copper oxide nanowire composite material as claimed in claim 1, wherein the soaking time in the step 5 is 5-30 min.

8. The preparation method of the copper oxide nanowire composite material grown on the carbon fiber woven cloth, according to claim 1, is characterized in that the temperature of the heating decomposition treatment in the step 6 is 150-200 ℃, and the time is 20-90 min.

9. The preparation method of the carbon fiber woven cloth growth copper oxide nanowire composite material, according to claim 1, is characterized in that the cleaning in the step 4 and the step 5 is performed by absolute ethyl alcohol and deionized water, the drying in the step 3, the step 4 and the step 5 is performed by an air blast drying oven, the drying temperature is 60-70 ℃, and the drying time is 60-120 min.

10. The composite material is characterized by being prepared by the preparation method for growing the copper oxide nanowire composite material on the carbon fiber woven cloth according to any one of claims 1 to 9.

Technical Field

The invention belongs to the field of nano composite material preparation, and particularly relates to a copper oxide nanowire composite material grown on carbon fiber woven cloth and a preparation method thereof.

Background

Carbon fiber, as a high-performance fiber, has excellent properties such as high specific strength, high modulus, small coefficient of thermal expansion, low coefficient of friction, and the like, and is one of the most widely used reinforcing materials in recent years. However, the surface of the carbon fiber is nonpolar and consists of a highly crystalline graphitized basal plane, and the surface lacks functional groups, so that the interface bonding between polymers of the carbon fiber is poor, and the surface modification of the carbon fiber is required to achieve the ideal reinforcing effect. Copper and copper oxide composites have been widely accepted in the friction art as anti-wear additives, where copper and copper oxide form a transfer film between the friction pairs, absorbing shear forces exerted on the substrate and thereby reducing wear. Composite nanostructured materials often have the properties of individual component materials, not only to complement performance, but also to derive new synergistic functions. Therefore, the copper oxide nanowire modified carbon fiber is expected to be widely applied to the fields of friction and mechanical properties of the carbon fiber reinforced polymer matrix composite.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a copper oxide nanowire composite material grown on carbon fiber woven cloth and a preparation method thereof, wherein the preparation method has strong repeatability, simple and convenient preparation process and short preparation period; the prepared composite material is uniform in appearance and controllable in size, the carbon fiber is modified by the linear copper oxide with controllable appearance, and the bonding force between the copper oxide and the carbon fiber is strong, so that the interface bonding between the carbon fiber and a polymer base is effectively improved, and the friction and mechanical properties of the composite material are improved.

In order to realize the purpose, the invention provides a preparation method of a copper oxide nanowire composite material grown on carbon fiber woven cloth, which comprises the following steps:

step 1: preparing an electroplating solution: adding 5-10 g of blue vitriol, 1-4 g of sodium tartrate dihydrate, 20-36 g of sodium citrate dihydrate and 2-5 g of potassium nitrate into 0.5-1L of deionized water, and stirring and dispersing;

step 2: preparing an ammonium persulfate-sodium hydroxide mixed solution: adding ammonium persulfate and sodium hydroxide into 10-20 mL of deionized water according to the mass ratio of 3 (9-10), and stirring and dispersing;

and step 3: pretreating carbon fiber woven cloth: cutting the carbon fiber woven cloth, then carrying out ultrasonic cleaning and drying;

and 4, step 4: cutting the carbon fiber woven cloth pretreated in the step 3 into 10-15 cm²Soaking the fabric into the electroplating solution obtained in the step (1) for electroplating treatment, taking out the fabric after the electroplating is finished, and cleaning and drying the fabric to obtain copper-plated carbon fiber woven fabric;

and 5: soaking the copper-plated carbon fiber woven cloth in the step 4 in the ammonium persulfate-sodium hydroxide mixed solution in the step 2, taking out after soaking, cleaning and drying to obtain the carbon fiber woven cloth with copper hydroxide nanowires growing on the surface;

step 6: and (5) heating and decomposing the carbon fiber woven cloth with the copper hydroxide nanowires growing on the surface in the step (5) to decompose the copper hydroxide nanowires into copper oxide nanowires, thus obtaining the composite material.

Preferably, the stirring in step 1 and step 2 is performed for 20min to 60min by using a magnetic stirrer at room temperature, and the dispersion is performed by using ultrasonic dispersion.

Preferably, the mass ratio of ammonium persulfate to sodium hydroxide in the step 2 is 1: 3.

preferably, the ultrasonic cleaning in the step 3 is performed by ultrasonic cleaning in a mixed solution of absolute ethyl alcohol and acetone, and the ultrasonic cleaning is performed, then the cleaning is performed by deionized water, and the drying is performed for standby.

Preferably, the electroplating solution in the step 4 is placed in a Hull cell, the pretreated carbon fiber woven cloth is connected with the negative electrode of an electroplating power supply, and the positive electrode of the electroplating power supply is connected with a phosphor copper anode.

Preferably, the current of the electroplating treatment in the step 4 is 1-15A, and the electroplating time is 5-30 min.

Preferably, the soaking time in the step 5 is 5-30 min.

Preferably, the temperature of the thermal decomposition treatment in the step 6 is 150-200 ℃ and the time is 20-90 min.

Preferably, the cleaning in the step 4 and the step 5 is performed by using absolute ethyl alcohol and deionized water, and the drying in the step 3, the step 4 and the step 5 is performed by using a forced air drying oven, wherein the drying temperature is 60-70 ℃, and the drying time is 60-120 min.

The invention also provides a composite material prepared by the preparation method for growing the copper oxide nanowire composite material on the carbon fiber woven cloth.

Compared with the prior art, the preparation method has mild process conditions, and compared with the traditional carbon fiber surface modification technology, the preparation method comprises the following steps: plasma etching, acid washing oxidation and the like, the modification mode of the invention does not damage the structure of the carbon fiber, and the intrinsic performance of the carbon fiber can be preserved to the maximum extent; the growth size of the copper oxide in the two-dimensional direction is controllable, the copper oxide nanowires grow on the surface of the carbon fiber uniformly and compactly, the specific surface area of the carbon fiber can be greatly improved, and the high-strength copper oxide nanowire has a high reinforcing effect on the interface bonding strength between the carbon fiber and a polymer. The preparation method disclosed by the invention is simple in process, low in cost, easy to realize large-scale production in an enlarged mode, and wide in practical application value and industrial production prospect. The prepared composite material is uniform in appearance and controllable in size, the carbon fiber is modified by the linear copper oxide with controllable appearance, and the bonding force between the copper oxide and the carbon fiber is strong, so that the interface bonding between the carbon fiber and a polymer base is effectively improved.

Drawings

FIG. 1 is an SEM image of a composite material prepared according to example 1 of the present invention;

FIG. 2 is an SEM image of a composite material prepared according to example 2 of the present invention;

FIG. 3 is an EDS spectrum of Cu element of the composite material prepared in example 2 of the present invention;

fig. 4 is an XRD spectrum of the composite materials prepared in examples 1 and 2 of the present invention.

Detailed Description

The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The invention provides a preparation method of a copper oxide nanowire composite material grown on carbon fiber woven cloth, which comprises the following steps:

1. preparing an electroplating solution: preparing a uniform aqueous solution from copper sulfate pentahydrate, sodium tartrate dihydrate, sodium citrate dihydrate and potassium nitrate according to a certain proportion, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution; the amount of the blue vitriod is 5g to 10g, the amount of the sodium tartrate dihydrate is 1g to 4g, the amount of the sodium citrate dihydrate is 20g to 36g, the amount of the potassium nitrate is 2g to 5g, and the amount of the deionized water is 0.5L to 1L; stirring for 20-60 min at room temperature by using a magnetic stirrer, and dispersing by using ultrasonic dispersion;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding ammonium persulfate and sodium hydroxide into deionized water according to a certain proportion, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid; adding ammonium sulfate and sodium hydroxide into 10-20 mL of deionized water according to the mass ratio of 3 (9-10), and stirring and dispersing; namely, if the mass of the ammonium sulfate is 3g, the mass of the sodium hydroxide is 9-10 g; preferably, the mass ratio of ammonium persulfate to sodium hydroxide is 1: 3, namely if the mass of the ammonium sulfate is 3g, the mass of the sodium hydroxide is 9 g; stirring for 20-60 min at room temperature by using a magnetic stirrer, and dispersing by using ultrasonic dispersion;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into a certain size, putting the commercial carbon fiber woven cloth into mixed solution of ethanol and acetone, and ultrasonically cleaning the commercial carbon fiber woven cloth to remove industrial sizing agent on the surface of the carbon fiber woven cloth; cutting the pretreated carbon fiber woven cloth into 10-15 cm²(ii) a Preferably, ultrasonic cleaning is carried out for 2h in a mixed solution of absolute ethyl alcohol and acetone, the mixture is washed clean by deionized water and dried for later use after ultrasonic cleaning, and drying is carried out by adopting a forced air drying oven, wherein the drying temperature is 60-70 ℃, and the drying time is 60min～120min；

4. Placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth pretreated in the step 3 in the solution, connecting the carbon fiber woven cloth to the negative electrode of an electroplating power supply, connecting the positive electrode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating process, and taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning and drying; preferably, the surface of the carbon fiber cloth is cleaned by absolute ethyl alcohol and deionized water, and the surface is dried by adopting a blast drying oven at a low temperature of 60-70 ℃ for 60-120 min; preferably, the current of the electroplating treatment is 1-15A, and the electroplating time is 5-30 min;

5. soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2), taking out the carbon fiber woven cloth after soaking is finished, and cleaning and drying the carbon fiber woven cloth to obtain the carbon fiber cloth with copper hydroxide nanowires growing on the surface; preferably, the soaking time is 5-30 min; washing the surface of the carbon fiber cloth by deionized water and ethanol, and drying at a low temperature of 60-70 ℃ for 60-120 min by adopting a blast drying oven;

6. heating the carbon fiber woven cloth with the copper hydroxide nanowires growing on the surface in a high-temperature environment to decompose copper hydroxide and oxidize the copper hydroxide into copper oxide nanowires, wherein the heating decomposition treatment temperature is preferably 150-200 ℃ and the time is 20-90 min;

the preparation method has the advantages of strong repeatability, simple and convenient preparation process and short preparation period; the prepared composite material is uniform in appearance and controllable in size, the carbon fiber is modified by the linear copper oxide with controllable appearance, and the bonding force between the copper oxide and the carbon fiber is strong, so that the interface bonding between the carbon fiber and a polymer base is effectively improved, and the friction and mechanical properties of the composite material are improved.

The present invention will be described with reference to specific examples.

Example 1:

1. preparing an electroplating solution: dissolving 5g of copper sulfate pentahydrate, 4g of sodium tartrate dihydrate, 36g of sodium citrate dihydrate and 5g of potassium nitrate in 1L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 10g of sodium hydroxide into 20mL of deionized water, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 15cm²Fixing the size, putting the carbon fiber woven cloth into a mixed solution of ethanol and acetone for ultrasonic cleaning for 2 hours to remove the industrial sizing agent on the surface of the carbon fiber woven cloth, then washing the carbon fiber woven cloth by using deionized water, and drying the carbon fiber woven cloth by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 2A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 10 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 150-200 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Example 2:

1. preparing an electroplating solution: dissolving 5g of copper sulfate pentahydrate, 4g of sodium tartrate dihydrate, 36g of sodium citrate dihydrate and 5g of potassium nitrate in 1L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 10g of sodium hydroxide into 20mL of deionized water, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 15cm²Fixing the size, putting the carbon fiber woven cloth into a mixed solution of ethanol and acetone for ultrasonic cleaning for 2 hours to remove the industrial sizing agent on the surface of the carbon fiber woven cloth, then washing the carbon fiber woven cloth by using deionized water, and drying the carbon fiber woven cloth by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 2A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 5 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 150-200 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Example 2 the same procedure as in example 1 was followed except that the soaking time in the ammonium persulfate and sodium hydroxide solution was 5 minutes.

Scanning the composite materials prepared in the embodiments 1 and 2 by an SEM electron microscope, wherein in the figure 1, the length of the copper oxide nanowire in the SEM image soaked for 10min in the mixed solution of ammonium persulfate and sodium hydroxide is longer, and in the figure 2, the length of the copper nanowire in the SEM image soaked for 5min in the mixed solution of ammonium sulfate and sodium hydroxide is shorter, so that the growth scale of the copper oxide nanowire in the two-dimensional direction can be controlled by controlling the soaking time in the mixed solution of ammonium persulfate and sodium hydroxide, and the copper oxide nanowire is distributed on the surface of the carbon fiber more densely without agglomeration, which is beneficial to the stress concentration phenomenon between the carbon fiber cloth and the matrix.

EDS (electron-dispersive spectroscopy) analysis is carried out on the composite material prepared in example 2, and referring to the EDS analysis of Cu in FIG. 3, the existence of Cu element further proves the existence of the deposited copper oxide nanowires and the copper oxide nanowires are uniformly and densely wrapped on the surface of the carbon fiber.

XRD analysis was performed on the composite materials prepared in examples 1 and 2, and referring to fig. 4, only one peak appeared in the XRD curve of the carbon fiber, which is a characteristic peak of carbon at a position of 26 °. The characteristic reflection peaks at 43.5 °, 50.6 ° and 74.2 ° correspond to the (111), (200) and (220) planes of the Cu particles, respectively. Diffraction peaks at 35.9 °, 39.2 °, 49.2 °, 58.26 °, 61.5 °, 66.3 °, 68.6 ° and 75.4 °, which together with the (110), (002), (202), (113), (311), (220) and (004) planes of copper oxide, demonstrate the crystalline structure of copper oxide on the surface of carbon fibers.

Example 3:

1. preparing an electroplating solution: dissolving 5g of copper sulfate pentahydrate, 1g of sodium tartrate dihydrate, 20g of sodium citrate dihydrate and 2g of potassium nitrate in 0.5L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 9g of sodium hydroxide into 10mL of deionized water, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 10cm²Fixing the size, putting the carbon fiber woven cloth into a mixed solution of ethanol and acetone for ultrasonic cleaning for 2 hours to remove the industrial sizing agent on the surface of the carbon fiber woven cloth, then washing the carbon fiber woven cloth by using deionized water, and drying the carbon fiber woven cloth by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 1A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 15 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 150 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Example 4:

1. preparing an electroplating solution: dissolving 10g of copper sulfate pentahydrate, 3g of sodium tartrate dihydrate, 25g of sodium citrate dihydrate and 4g of potassium nitrate in 0.8L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 10g of sodium hydroxide into 15mL of deionized water, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 12cm²Fixing the size, putting the carbon fiber woven cloth into a mixed solution of ethanol and acetone for ultrasonic cleaning for 2 hours to remove the industrial sizing agent on the surface of the carbon fiber woven cloth, then washing the carbon fiber woven cloth by using deionized water, and drying the carbon fiber woven cloth by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 10A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 20 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 200 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Example 5:

1. preparing an electroplating solution: dissolving 7g of copper sulfate pentahydrate, 2g of sodium tartrate dihydrate, 30g of sodium citrate dihydrate and 3g of potassium nitrate in 0.7L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 10g of sodium hydroxide into 18mL of deionized water, and fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 14cm²Fixing size, ultrasonic cleaning in mixed solution of ethanol and acetone for 2 hr to remove industrial sizing agent on the surface of woven carbon fiber cloth, and deionized waterWashing and drying by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 15A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 30 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 180 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Example 6:

1. preparing an electroplating solution: dissolving 8g of copper sulfate pentahydrate, 1g of sodium tartrate dihydrate, 28g of sodium citrate dihydrate and 4g of potassium nitrate in 0.9L of deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a blue mixed solution;

2. preparing an ammonium persulfate-sodium hydroxide mixed solution: adding 3g of ammonium persulfate and 10g of sodium hydroxide into 16mL of deionized water, fully stirring, and uniformly performing ultrasonic treatment to obtain colorless transparent liquid;

3. pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 15cm²Fixing the size, putting the carbon fiber woven cloth into a mixed solution of ethanol and acetone for ultrasonic cleaning for 2 hours to remove the industrial sizing agent on the surface of the carbon fiber woven cloth, then washing the carbon fiber woven cloth by using deionized water, and drying the carbon fiber woven cloth by using a blast drying oven for later use;

4. placing the mixed solution obtained in the step 1 in a Hull cell, then immersing the carbon fiber woven cloth treated in the step 3 in the solution to be connected with the cathode of an electroplating power supply, connecting the anode of the electroplating power supply with a phosphor-copper anode, carrying out an electroplating copper process under the current of 8A, taking out the copper-plated carbon fiber woven cloth after the electroplating is finished, cleaning the surface of the carbon fiber woven cloth by using absolute ethyl alcohol, and drying at low temperature;

5. and (3) soaking the copper-plated carbon fiber cloth obtained in the step (4) in the solution obtained in the step (2) for 15 minutes to obtain carbon fiber cloth with copper hydroxide nanowires growing on the surface, taking out the carbon fiber woven cloth after the soaking is finished, cleaning the surface of the carbon fiber cloth by deionized water and absolute ethyl alcohol, and then heating the carbon fiber cloth at a high temperature of 160 ℃ to obtain copper oxide nanowires, thus obtaining the composite material.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.