CN101311306A - Method for plating copper on surface of carbon nanotube - Google Patents

Abstract

The invention discloses a preparation method for plating copper on the surface of a carbon nano-tube, which is characterized by adopting Cu2+ as the source of the elementary substance copper and adopting Zn or HCHO as a reducing agent. When adopting Zn as the reducing agent, the main reagents are: CuSO4.5H2O, Zn powder, glycerol, glycol, potassium sodium tartrate, FeSO4.7H2O and HNO3. When adopting the HCHO as the reducing agent, the main reagents are: CuSO4.5H2O, HCHO, EDTANa2, FeCl3.7H2O, triethanolamine, a, a-bipyridine, NaOH and HNO3. The technological process of the plating copper on the surface of the carbon nano-tube is as follows: carbon nano-tube oxidation, water scrubbing, plating, water scrubbing and drying. The preparation method of the plating copper on the surface of the carbon nano-tube of the invention not only changes the traditional way of palladium catalysis but also has the advantages of low price and convenient operation, which simplifies process and is simple.

Description

A kind of preparation method of copper plating on the surface of carbon nanotubes

technical field

The invention relates to the technology of electroless copper plating on the surface of nanometer materials, and in particular provides a method for preparing copper plating on the surface of nanometer carbon tubes.

Background technique

Carbon nanotubes are the most characteristic new class of one-dimensional nano functional materials discovered in the early 1990s. Their unique structures can be used to prepare nanocomposites filled with metal or metal oxides. In order to give full play to the unique functions of carbon nanotubes, relevant scholars have turned their attention to modification and surface modification, forming new hotspots and cutting-edge research topics; coating carbon nanotubes with different materials can obtain one-dimensional carbon nanotubes with special properties. nanocomposites. The technology of copper plating on ordinary materials is relatively mature, but for nanomaterials, the technology of electroless copper plating is more complicated and difficult to operate.

In the prior art, there have been applications of carbon nanotubes coated with different metals, but their common characteristics are that the process route is long, the operation is complicated, and the precious metal palladium is used as the catalyst, so the cost is high and the industrialization is limited.

Contents of the invention

The purpose of the present invention is to provide a method that can plate copper on carbon nanometer tubes without palladium catalysis.

The invention provides a method for preparing copper plating on the surface of carbon nanotubes, which is characterized in that: Cu2+ is used as the source of elemental copper, and the reducing agent is Zn or HCHO;

In the preparation method of copper plating on the surface of carbon nanotubes of the present invention, the process flow of copper plating on the surface of carbon nanotubes is as follows: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

When Zn is used as the reducing agent, the main reagents are CuSO4 5H2O, Zn powder, glycerol, ethylene glycol, potassium sodium tartrate, FeSO4 7H2O, HNO3; the concentration of Cu2SO4 5H2O is required to be 6.0-7.0g/ l. The concentration of glycerol is required to be 125-140ml/l, the concentration of ethylene glycol is required to be 85-95ml/l, the concentration of potassium sodium tartrate is required to be 8.0-9.0g/l, and the concentration of FeSO4·7H2O is required to be 3.0 ~4.0g/l, the concentration of zinc powder is required to be 1.80~1.90g/l; the process conditions are: the reaction time is 50~70 minutes, the reaction temperature is 0~25°C, the complexing agent is glycerin, ethylene glycol, Potassium sodium tartrate is used in combination, and the additive Fe2+ (FeSO4) is added to the plating solution;

In the preparation method of copper plating on the surface of carbon nanotubes of the present invention, the oxidation method of carbon nanotubes in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared into a certain amount according to the ratio of 3:2 (volume ratio) solution, adding carbon nanotubes, heating and stirring for 25-35 minutes, and controlling the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

In the preparation method of copper plating on the surface of carbon nanotubes of the present invention, when Zn is used as a reducing agent, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: copper sulfate, potassium sodium tartrate, ethylene glycol, propane Triol, FeSO4 7H2O, carbon nanotube and reducing agent zinc powder press 0.19～0.21 (unit: gram): 0.2～0.3 (unit: gram): 2.5～2.9 (unit: milliliter): 2～6 (unit: milliliter) ): 0.1～0.15 (unit: gram): 0.1～0.2 (unit: gram) ratio; dissolve copper sulfate and potassium sodium tartrate in the above proportion with an appropriate amount of deionized water, and after combining the two, add the above proportion ethylene glycol, glycerol, and water to dissolve FeSO4·7H2O in the above ratio, add the carbon nanotubes and reducing agent zinc powder that have been oxidized with nitric acid in the above ratio, and stir at 0-25°C for 50-70 minutes. Suction filtration, washing and drying after the end;

When Zn is used as the reducing agent, the electroless copper plating process is a process in which formaldehyde as the reducing agent reduces the main salt Cu2+ to precipitate elemental copper and effectively coats the carbon nanotubes. From the reaction results, the total reaction is two and a half The reactions consist of redox reactions, each reaction and corresponding electrode potential are as follows:

Oxidation reaction:

Zn→Zn2++2e

Reduction reaction:

Cu2++2e→Cu

Its overall reaction is:

Cu2++Zn→Cu↓+Zn2+

If a good copper cladding layer is obtained on carbon nanotubes, the key is to determine the process conditions. Through a large number of exploratory experiments, after determining the experimental method, the single factor optimization scheme was adopted to study the influence of zinc powder concentration in the bath, bath temperature, plating time, complexing agent selection and initiator on the coating effect. Affected by better process conditions.

When Zn is used as the reducing agent, under the premise of ensuring that the concentration of Cu2+ is appropriate and complexed by an appropriate amount of complexing agent, if the elemental copper is continuously and effectively coated on the carbon nanotubes, it is necessary to ensure that there is a sufficient amount of reducing agent in the system. Zinc powder, but because the reducing agent is a solid, if there is too much excess, there is difficulty in separation. From the experimental principle, this is a simple replacement reaction. Although there is a complexing agent involved, as long as the reaction time is sufficient, the zinc powder can be completely consumed Therefore, the amount of zinc powder should be as close to the concentration of Cu2+ as possible; in addition, if you want to control the reaction speed, the zinc powder should not be too fine, and it is better to be thicker. Through a series of experiments, the optimal amount of zinc powder in the plating solution is 1.85g /L.

When Zn is used as the reducing agent, the temperature of the plating solution has a direct impact on the quality of copper plating of carbon nanotubes. The increase of the plating temperature can enhance the reaction kinetics of ions in the plating solution, thereby increasing the reaction speed. However, for carbon nanotubes In other words, too fast deposition speed often brings unfavorable factors, because of its graphitized structure, extremely thin tube diameter, large curvature, and too fast reaction speed, it is difficult for the precipitated copper to deposit on the outer surface of the tube well, and agglomeration is easy to occur , so the plating temperature should be properly controlled to achieve the purpose of controlling the deposition rate to a certain extent. Through experiments at different temperature ranges between 0 and 25°C, the plating effect is good. In order to simplify operation and save energy, room temperature is sufficient.

When Zn is used as the reducing agent, under certain other conditions, the quality of the coating will vary with different plating times. If you want to obtain a continuous, dense, and uniform coating, you must ensure sufficient reaction time. The series of time conditions According to the exploration of the experiment, the good plating time is 1 hour.

When Zn is used as the reducing agent, in order to control the reaction speed as much as possible and obtain a better coating, it is necessary to add a suitable and appropriate amount of complexing agent. If the complexing agent is excessive or the proportion is not suitable, the plating effect will not be good. According to the plating effect of different combinations of complexing agents, glycerin, ethylene glycol, and potassium sodium tartrate have the best compounding effect, and their complexing ability is moderate, which controls the copper deposition speed and makes the coating surface continuous, uniform and smooth. Very beautiful and beautiful.

When Zn is used as the reducing agent, an appropriate amount of additive Fe2+ (FeSO4) is added to the plating solution. Its addition does not need to use traditional palladium as a catalyst to activate the carbon nanotubes, and can directly electroless copper plating on the oxidized carbon tubes. .

When HCHO is used as the reducing agent, the main reagents are CuSO4 5H2O, HCHO, EDTANa2, FeCl3 7H2O, triethanolamine, α, α-bipyridyl, NaOH, HNO3; the concentration of HCHO is required to be 35ml/L; the process conditions The requirements are: the plating temperature is 60°C, the pH value is 12.5, the complexing agent is used in combination with EDTA and TEA, the plating time is 1.5 hours, and an appropriate amount of Fe3+ (FeCl3) is added to the plating solution.

When adopting HCHO as a reducing agent, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: copper sulfate, EDTA disodium salt, triethanolamine, sodium hydroxide, α, α-bipyridine, FeCl3 by 0.4 ～0.5 (unit: gram): 0.1～0.2 (unit: gram): 1.0～1.4 (unit: milliliter): 0.1～0.5 (unit: gram): 0.4～0.8 (unit: mg): 0.023～0.024 (unit: gram) ratio; use deionized water to dissolve copper sulfate, EDTA disodium salt, triethanolamine, sodium hydroxide, α, α-bipyridyl, FeCl respectively in the above ratio, and mix the above-mentioned prepared solutions in order Together, adjust the pH to 12.5 with the above ratio of sodium hydroxide solution, then add formaldehyde and the above ratio of carbon nanotubes, stir and heat for plating, the temperature is controlled at 60 ° C, and the reaction time is 1.5 hours. During the reaction, timely add NaOH solution to maintain the required pH range. After the reaction, filter with suction, wash with deionized water, and finally dry in a quick drying oven.

When HCHO is used as the reducing agent, the electroless copper plating process is a process in which formaldehyde as the reducing agent reduces the main salt Cu2+ to precipitate elemental copper and effectively coats the carbon nanotubes. From the reaction results, the overall reaction is composed of two Redox reactions consisting of half-reactions, each reaction and corresponding electrode potential are as follows:

Oxidation reaction:

Formaldehyde must be in an alkaline medium with a pH>11 to have a reducing effect.

Reduction reaction:

Its overall reaction is:

Cu2++2HCHO+4OH-→Cu↓+2HCOO-+H2↑+2H2O

Under the strong alkaline conditions in the actual system, the reducing ability of formaldehyde also depends on the pH value of the solution. To ensure that Cu2+ ions do not form Cu(OH)2 precipitates, enough Cu2+ complexing agents must be added.

It can be seen from the principle and process that when HCHO is used as the reducing agent, there are many factors that affect the plating effect, but under the premise of sufficient Cu2+, the main factors are the amount of HCHO, the temperature of the plating solution, the time of the plating solution, the pH value, the network Mixture selection, initiator selection and dosage, stabilizer selection, etc., we used a single factor optimization program to investigate these factors respectively.

When HCHO is used as the reducing agent, under the premise of ensuring that the concentration of Cu2+ is appropriate and complexed by an appropriate amount of complexing agent, if the elemental copper is continuously and effectively coated on the carbon nanotubes, it is necessary to ensure that there is a sufficient amount of reducing agent in the system. Formaldehyde, on the one hand, is because formaldehyde mainly exists in the form of methylene glycol CH2(OH)2 and its anion CH2OHO- in alkaline solution, and the latter is the main active component of the reaction, thus causing the actual formaldehyde The amount used is higher than the theoretical amount; on the other hand, in the reaction process, formaldehyde is lost due to heating and volatilization, and the experimental results show that if the reducing amount is insufficient, not only the reaction speed will decrease, but also the copper cannot be fully analyzed, thereby affecting the carbon tube. overlay effect. The optimal formaldehyde concentration in the plating solution is obtained through series of experiments to be 35ml/L.

When HCHO is used as the reducing agent, the temperature of the plating solution has a direct impact on the quality of carbon nanotube copper plating, and the increase of the plating temperature can enhance the reaction kinetics of ions in the plating solution, thereby increasing the reaction speed. However, for carbon nanotubes In other words, too fast deposition speed often brings disadvantages, because carbon nanotubes are extremely thin in diameter and large in curvature, and copper agglomeration is easy to occur if the reaction speed is too fast, so the plating temperature should be properly controlled to achieve a certain degree of control over the deposition speed the goal of. From the experimental results, the better plating temperature is 60°C.

When HCHO is used as the reducing agent, the electroless copper plating of carbon nanotubes is very sensitive to the pH value. Formaldehyde has a reducing effect when the pH is greater than 11. When the pH is greater than 13, the oxidation reaction and disproportionation reaction activity increase simultaneously, but the disproportionation reaction is dominant. , thereby hindering the reduction of Cu2+. In the experiment, the plating effect was examined when the pH was 11.5, 12, 12.5, and 13, and the effect was the best when the pH was 12.5, so the optimum pH was 12.5.

When HCHO is used as the reducing agent, the reduction of formaldehyde to Cu2+ occurs under alkaline conditions. In order to prevent the side reaction of Cu(OH)2 precipitation, a suitable and appropriate amount of complexing agent must be added to achieve control of the reaction. For the purpose of speed, if the complexing agent is excessive, the effective collision probability between Cu2+ and formaldehyde will be reduced, so that copper cannot be fully and continuously precipitated. Experimental results show that the combined use of EDTA and TEA has a better effect.

When HCHO is used as the reducing agent, under certain other conditions, the quality of the coating will vary with different plating times. There is discontinuous copper deposition on the surface of carbon tubes in 0.5 hours, and copper precipitation is more continuous but dense in 1 hour. The performance is poor, and a dense and continuous coating is formed in 1.5 hours, so the better time is 1.5 hours.

When HCHO is used as the reducing agent, Fe3+ (FeCl3) is added in an appropriate amount in the plating solution, and its addition does not need to use traditional palladium chloride to activate the carbon nanotubes, and can directly electroless copper-plate on the oxidized carbon nanotubes; The stabilizer has the functions of stabilizing the plating solution, preventing decomposition, and controlling the speed of copper deposition. It is preferably a, a-bipyridine, and methanol is also acceptable if the conditions are suitable.

The advantages of the present invention: the present invention provides a palladium-free preparation method for copper plating on the surface of carbon nanotubes, which is cheap, easy to operate, and simplifies the process.

Description of drawings

Figure 1 shows the appearance of carbon nanotubes after copper plating and reduction.

Detailed ways

Example 1

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is Zn; its main reagents are CuSO4 5H2O, Zn powder, glycerol, ethylene glycol, potassium sodium tartrate, FeSO4 7H2O, HNO3; the concentration requirement of Cu2SO4·5H2O is 6.5g/l, the concentration requirement of glycerol is 133ml/l, the concentration requirement of ethylene glycol is 90ml/l, the concentration requirement of potassium sodium tartrate is 8.5g/l l, the concentration of FeSO4 7H2O is required to be 3.5g/l, the concentration of zinc powder is required to be 1.85g/l; the process conditions are as follows: the reaction time is 1 hour, the reaction temperature is 0-25°C, and the complexing agent is glycerol , ethylene glycol, and potassium sodium tartrate are used in combination, and the additive Fe2+ (FeSO4) is added to the plating solution;

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 30 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.198g copper sulfate and 0.25g potassium sodium tartrate with an appropriate amount of deionized water, and mix the two After merging, add 2.7ml of ethylene glycol, 4ml of glycerin and dissolve 0.105g of FeSO4 7H2O with an appropriate amount of water, add water until the total amount of V is 30ml, add 0.15g of carbon nanotubes after nitric acid oxidation treatment and reducing agent zinc powder , stirred for one hour at a temperature of 0-25° C., suction filtered, washed, and dried after the reaction was completed.

Example 2

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is Zn; its main reagents are CuSO4 5H2O, Zn powder, glycerol, ethylene glycol, potassium sodium tartrate, FeSO4 7H2O, HNO3; the concentration requirement of Cu2SO4·5H2O is 6.0g/l, the concentration requirement of glycerol is 125ml/l, the concentration requirement of ethylene glycol is 85ml/l, the concentration requirement of potassium sodium tartrate is 8.0g/l l, the concentration of FeSO4 7H2O is required to be 3.0g/l, and the concentration of zinc powder is required to be 1.80g/l; the process conditions are as follows: the reaction time is 50 minutes, the reaction temperature is 0-25°C, and the complexing agent is glycerin, Ethylene glycol and potassium sodium tartrate are used in combination, and the additive Fe2+ (FeSO4) is added to the plating solution;

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 25 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.198g copper sulfate and 0.25g potassium sodium tartrate with an appropriate amount of deionized water, and mix the two After merging, add 2.7ml of ethylene glycol, 4ml of glycerin and dissolve 0.105g of FeSO4 7H2O with an appropriate amount of water, add water until the total amount of V is 30ml, add 0.15g of carbon nanotubes after nitric acid oxidation treatment and reducing agent zinc powder , stirred at a temperature of 0-25°C for 50 minutes, suction filtered, washed and dried after the reaction.

Example 3

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is Zn; its main reagents are CuSO4 5H2O, Zn powder, glycerol, ethylene glycol, potassium sodium tartrate, FeSO4 ·7H2O, HNO3; the concentration requirement of Cu2SO4·5H2O is 7.0g/l, the concentration requirement of glycerol is 140ml/l, the concentration requirement of ethylene glycol is 95ml/l, the concentration requirement of potassium sodium tartrate is 9.0g/l l, the concentration of FeSO4 7H2O is required to be 4.0g/l, and the concentration of zinc powder is required to be 1.90g/l; the process conditions are as follows: the reaction time is 70 minutes, the reaction temperature is 0-25°C, and the complexing agent is glycerin, Ethylene glycol and potassium sodium tartrate are used in combination, and the additive Fe2+ (FeSO4) is added to the plating solution;

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 35 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.198g copper sulfate and 0.25g potassium sodium tartrate with an appropriate amount of deionized water, and mix the two After merging, add 2.7ml of ethylene glycol, 4ml of glycerin and dissolve 0.105g of FeSO4 7H2O with an appropriate amount of water, add water until the total amount of V is 30ml, add 0.15g of carbon nanotubes after nitric acid oxidation treatment and reducing agent zinc powder , stirred at a temperature of 0-25°C for 70 minutes, suction filtered, washed and dried after the reaction.

Example 4

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is HCHO; the main reagents are CuSO4 5H2O, HCHO, EDTANa2, FeCl3 7H2O, triethanolamine, α, α-linked Pyridine, NaOH, HNO3; the concentration of HCHO is required to be 35ml/L; the process conditions are: the plating temperature is 60°C, the pH value is 12.5, the complexing agent is used in combination with EDTA and TEA, and the plating time is 1.5 hours , An appropriate amount of Fe3+ (FeCl3) is added to the plating solution.

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 30 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.45g copper sulfate, 0.115g EDTA disodium salt, 1.2ml Triethanolamine, 0.3g sodium hydroxide, 0.6mg α, α-bipyridine and 0.0236g FeCl3, the above prepared solutions are mixed together in sequence, add water until the total amount of V is 30ml, and adjust the pH to 12.5, then add formaldehyde and carbon nanotubes, stir and heat for plating, control the temperature at 60°C, and the reaction time is 1.5 hours. During the reaction, add NaOH solution in time to maintain the required pH range. After the reaction is completed, filter with suction , washed with deionized water, and finally dried in a quick drying oven.

Example 5

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is HCHO; the main reagents are CuSO4 5H2O, HCHO, EDTANa2, FeCl3 7H2O, triethanolamine, α, α-linked Pyridine, NaOH, HNO3; the concentration of HCHO is required to be 30ml/L; the process conditions are: the plating temperature is 50°C, the pH value is 11.5, the complexing agent is used in combination with EDTA and TEA, and the plating time is 80 minutes. An appropriate amount of Fe3+ (FeCl3) is added to the plating solution.

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 25 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.45g copper sulfate, 0.115g EDTA disodium salt, 1.2ml Triethanolamine, 0.3g sodium hydroxide, 0.6mg a, a-bipyridine and 0.0236g FeCl3, mix the above prepared solutions together in sequence, add water until the total amount of V is 30ml, adjust the pH with sodium hydroxide solution To 11.5, add formaldehyde and carbon nanotubes, stir and heat for plating, control the temperature at 60°C, and the reaction time is 80 minutes. During the reaction, add NaOH solution in time to maintain the required pH range. Filtered, washed with deionized water, and finally dried in a quick drying oven.

Example 6

The preparation method of copper plating on the surface of carbon nanotubes in this embodiment adopts Cu2+ as the source of elemental copper, and the reducing agent is HCHO; the main reagents are CuSO4 5H2O, HCHO, EDTANa2, FeCl3 7H2O, triethanolamine, α, α-linked Pyridine, NaOH, HNO3; the concentration of HCHO is required to be 40ml/L; the process conditions are: the plating temperature is 70°C, the pH value is 13.0, the complexing agent is used in combination with EDTA and TEA, and the plating time is 100 minutes. An appropriate amount of Fe3+ (FeCl3) is added to the plating solution.

The preparation method of the copper plating on the surface of the carbon nanotubes, the process flow of the copper plating on the surface of the carbon nanotubes is: carbon nanotube oxidation-→water washing-→plating-→water washing-→drying.

The preparation method of copper plating on the surface of carbon nanotubes, the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is as follows: concentrated nitric acid and deionized water are prepared in a ratio of 3:2 (volume ratio) to a certain amount solution, add carbon nanotubes, heat and stir for 35 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried.

The preparation method of copper plating on the surface of carbon nanotubes, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: dissolve 0.45g copper sulfate, 0.115g EDTA disodium salt, 1.2ml Triethanolamine, 0.3g sodium hydroxide, 0.6mg a, a-bipyridine and 0.0236g FeCl3, mix the above prepared solutions together in sequence, add water until the total amount of V is 30ml, adjust the pH with sodium hydroxide solution to 13.0, then add formaldehyde and carbon nanotubes, stir and heat for plating, the temperature is controlled at 60°C, and the reaction time is 100 minutes. During the reaction, add NaOH solution in time to maintain the required pH range. Filtered, washed with deionized water, and finally dried in a quick drying oven.

Claims (4)

1. A preparation method for copper plating on the surface of carbon nanotubes, characterized in that: Cu2+ is used as the source of elemental copper, and the reducing agent is Zn or HCHO; When Zn is used as the reducing agent, the main reagents are CuSO4 5H2O, Zn powder, glycerol, ethylene glycol, potassium sodium tartrate, FeSO4 7H2O, HNO3; the concentration of Cu2SO4 5H2O is required to be 6.0-7.0g/ l. The concentration of glycerol is required to be 125-140ml/l, the concentration of ethylene glycol is required to be 85-95ml/l, the concentration of potassium sodium tartrate is required to be 8.0-9.0g/l, and the concentration of FeSO4·7H2O is required to be 3.0 ~4.0g/l, the concentration of zinc powder is required to be 1.80~1.90g/l; the process conditions are: the reaction time is 50~70 minutes, the reaction temperature is 0~25°C, the complexing agent is glycerin, ethylene glycol, Potassium sodium tartrate is used in combination, and the additive Fe2+ (FeSO4) is added to the plating solution; When HCHO is used as the reducing agent, the main reagents are CuSO4 5H2O, HCHO, EDTANa2, FeCl3 7H2O, triethanolamine, α, α-bipyridyl, NaOH, HNO3; the concentration of HCHO is required to be 30-40ml/L; The process conditions are as follows: the plating temperature is 50-70°C, the pH range is 11.5-13.0, the complexing agent is used in combination with EDTA and TEA, the plating time is 80-100 minutes, and Fe3+ (FeCl3) is added to the plating solution. 2. According to claim 1, it is characterized in that: the process flow of copper plating on the surface of carbon nanotubes is: oxidation of carbon nanotubes—→water washing—→plating—→water washing—→drying. 3. According to claim 1 or 2, it is characterized in that: the carbon nanotube oxidation method in the process flow of copper plating on the surface of carbon nanotubes is: preparing concentrated nitric acid and deionized water in a ratio of 3:2 (volume ratio) Form a certain amount of solution, add carbon nanotubes, heat and stir for 25-35 minutes, and control the temperature at 60-65°C. Then it was filtered by suction, washed with deionized water until neutral, filtered by suction and dried. 4. According to claim 1 or 2, it is characterized in that: when Zn is used as a reducing agent, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: copper sulfate, potassium sodium tartrate, ethylene glycol , glycerol, FeSO4 7H2O, carbon nanotubes and reducing agent zinc powder according to 0.19～0.21 (unit: gram): 0.2～0.3 (unit: gram): 2.5～2.9 (unit: milliliter): 2～6 (unit : milliliter): 0.1～0.15 (unit: gram): 0.1～0.2 (unit: gram) ratio; dissolve copper sulfate and potassium sodium tartrate in the above ratio with deionized water, after combining the two, add the above ratio ethylene glycol, glycerol, and water to dissolve FeSO4·7H2O in the above ratio, add the carbon nanotubes and reducing agent zinc powder that have been oxidized with nitric acid in the above ratio, and stir at 0-25°C for 50-70 minutes. Suction filtration, washing and drying after the end; When adopting HCHO as a reducing agent, the plating method in the process flow of copper plating on the surface of carbon nanotubes is: copper sulfate, EDTA disodium salt, triethanolamine, sodium hydroxide, α, α-bipyridine, FeCl3 by 0.4 ～0.5 (unit: gram): 0.1～0.2 (unit: gram): 1.0～1.4 (unit: milliliter): 0.1～0.5 (unit: gram): 0.4～0.8 (unit: mg): 0.023～0.024 (unit: gram) ratio; use deionized water to dissolve copper sulfate, EDTA disodium salt, triethanolamine, sodium hydroxide, α, α-bipyridyl, FeCl respectively in the above ratio, and mix the above-mentioned prepared solutions in order Together, use the above ratio of sodium hydroxide solution to adjust the pH to 11.5-13.0, then add formaldehyde and the above ratio of carbon nanotubes, stir and heat for plating, the temperature is controlled at 50-70 ° C, and the reaction time is 80-100 minutes. During the reaction, NaOH solution was added in time to maintain the required pH range. After the reaction was completed, it was filtered with suction, washed with deionized water, and finally dried in a quick drying oven.

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