CN101311306A - Method for plating copper on surface of carbon nanotube - Google Patents
Method for plating copper on surface of carbon nanotube Download PDFInfo
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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
Technical field
The present invention relates to nano-material surface electroless copper technology, a kind of method for plating copper on surface of carbon nanotube is provided especially.
Background technology
CNT (carbon nano-tube) is the new class 1-dimention nano functional materials of just found foot sign of earlier 1990s, and its unique texture can prepare the nano composite material that metal or metal oxide are filled.In order to give full play to the CNT (carbon nano-tube) unique function,, the new focus and the research topic in forward position have been formed about the scholar throws into sight in modification and the finishing; With different substances coating nano carbon pipe, the one-dimensional nano-composite material that available can be special.Copper facing on common material, technology are ripe, but for nano material, the technology of electroless copper is comparatively complicated, and operation is difficult to.
In the prior art, existing CNT (carbon nano-tube) coats the application of different metal, but its common feature is, operational path is long, complicated operation, and all adopting the noble metal palladium is catalyzer, thus with high costs, industrialization is restricted.
Summary of the invention
The object of the present invention is to provide a kind of method, can be without palladium catalysis, copper facing on CNT (carbon nano-tube).
The invention provides a kind of method for plating copper on surface of carbon nanotube, it is characterized in that: adopting with Cu2+ is the elemental copper source, and reductive agent is Zn or HCHO;
In the method for plating copper on surface of carbon nanotube of the present invention, the technical process of CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
When adopting Zn to be reductive agent, its main agents is CuSO45H2O, Zn powder, glycerol, ethylene glycol, Seignette salt, FeSO47H2O, HNO3; Wherein the concentration requirement of Cu2SO45H2O is 6.0～7.0g/l, the concentration requirement of glycerol is 125～140ml/l, the concentration requirement of ethylene glycol is 85～95ml/l, the concentration requirement of Seignette salt is 8.0～9.0g/l, the concentration requirement of FeSO47H2O is 3.0～4.0g/l, and the concentration requirement of zinc powder is 1.80～1.90g/l; Processing condition require: the reaction times is 50～70 minutes, and temperature of reaction is 0～25 ℃, and complexing agent adds additive Fe2+ (FeSO4) with glycerine, ethylene glycol, the compound use of Seignette salt in the plating bath;
In the method for plating copper on surface of carbon nanotube of the present invention, CNT (carbon nano-tube) method for oxidation in the technical process of CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 25～35 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
In the method for plating copper on surface of carbon nanotube of the present invention, when adopting Zn to be reductive agent, the solution and coating method in the technical process of CNT (carbon nano-tube) copper coating is: with copper sulfate, Seignette salt, ethylene glycol, glycerol, FeSO47H2O, CNT (carbon nano-tube) and reductive agent zinc powder by 0.19～0.21 (unit: gram): 0.2～0.3 (unit: gram): 2.5～2.9 (units: milliliter): 2～6 (units: milliliter): 0.1～0.15 (unit: gram): the ratio proportioning of 0.1～0.2 (unit: restrain); Dissolve as above copper sulfate, the Seignette salt of ratio with proper amount of deionized water, after the two merging, add the ethylene glycol, glycerol of as above ratio and with the as above FeSO47H2O of ratio of water dissolution, add as above the CNT (carbon nano-tube) and the reductive agent zinc powder through the nitric acid oxidation processing of ratio, stirred 50～70 minutes under 0～25 ℃ of temperature, reaction finishes back suction filtration, washing, oven dry;
When adopting Zn to be reductive agent, the electroless copper process is as the formaldehyde of reductive agent elemental copper to be separated out in main salt Cu2+ reduction to be coated on process on the CNT (carbon nano-tube) effectively, from reaction result, total reaction is the redox reaction that two half-reactions are formed, and the electropotential of each reaction and correspondence is as follows:
Oxidizing reaction:
Zn→Zn2++2e
Reduction reaction:
Cu2++2e→Cu
Its total reaction is:
Cu2++Zn→Cu↓+Zn2+
If obtain good copper-clad coating on CNT (carbon nano-tube), key is determining of processing condition.By a large amount of exploitative experiments, after determining experimental technique, adopt single factor optimizing scheme, studied that zinc powder concentration, bath temperature, plating time, complexing agent in the plating bath are selected and initiator etc. to the influence of its covered effect, obtain preferable processing condition.
When adopting Zn to be reductive agent, guarantee Cu2+ concentration suitable and by the prerequisite of an amount of complexing agent complexing under, if be coated on the CNT (carbon nano-tube) with making the elemental copper continuous effective, the reductive agent zinc powder that has capacity in must guarantee system, but because reductive agent is a solid, as excessive too many, there is separation difficulty, from experimental principle as can be known, this is a simple replacement(metathesis)reaction, although there is complexing agent to participate in, as long as the reaction times is enough, zinc powder can consume only fully, so the amount of zinc powder is bordering on quite with Cu2+ concentration as far as possible; In addition, if think controls reaction speed, zinc powder is too thinless, and is suitably thick a bit for well, obtains by serial experiment that preferable zinc powder amount is 1.85g/L in the plating bath.
When adopting Zn to be reductive agent, bath temperature has a direct impact CNT (carbon nano-tube) copper facing quality, plating temperature improves, can strengthen the reacting dynamics characteristic of plating bath intermediate ion, thereby raising speed of response, yet for CNT (carbon nano-tube), sedimentation velocity is too fast to tend to bring unfavorable factor, and because of its carbonization structure, and caliber is superfine, curvature is big, speed of response is too fast, and the copper of separating out is difficult to the outside surface of deposited tube preferably, is prone to agglomeration, therefore suitably must control plating temperature, go up the purpose of control sedimentation velocity to acquire a certain degree.By differing temps section experiment between 0～25 ℃, the plating effect is all good, and for simplifying the operation, save energy gets final product with room temperature.
When adopting Zn to be reductive agent, under the certain situation of other condition, different plating times, quality of coating is also different, if expect continuous, fine and close, uniform coating layer, must guarantee the enough reaction times, by the exploration of serial time conditions experiment, drawing the plating time of forging a good relationship is 1 hour.
When adopting Zn to be reductive agent, be controls reaction speed as far as possible, obtain better coating, also must add suitable and an amount of complexing agent, if complexing agent is excessive or proportioning is improper, then the plating effect is bad, through the complexing agent plating effect with various combination is seen, best with glycerine, ethylene glycol, the compound result of use of Seignette salt, its complex ability is moderate, controlled heavy copper speed, make the coating appearance continuously, evenly, very attractive in appearance, beautiful.
When adopting Zn to be reductive agent, add additive Fe2+ (FeSO4) in the plating bath in right amount, its adding does not need to come the activation treatment CNT (carbon nano-tube) with traditional palladium as catalyzer, directly electroless copper on the carbon pipe after the oxidation.
When adopting HCHO to be reductive agent, its main agents is CuSO45H2O, HCHO, EDTANa2, FeCl37H2O, trolamine, a, a-dipyridyl, NaOH, HNO3; Wherein the concentration requirement of HCHO is 35ml/L; Processing condition require: plating temperature is 60 ℃, and pH value is 12.5, and complexing agent is with EDTA and the compound use of TEA, and plating time is 1.5 hours, adds Fe3+ (FeCl3) in the plating bath in right amount.
When adopting HCHO to be reductive agent, solution and coating method in the technical process of CNT (carbon nano-tube) copper coating is: copper sulfate, EDTA two are received salt, trolamine, sodium hydroxide, a, and a-dipyridyl, FeCl3 are in 0.4～0.5 (unit: gram): 0.1～0.2 (unit: gram): 1.0～1.4 (units: milliliter): 0.1～0.5 (unit: gram): 0.4～0.8 (unit: milligram): 0.023～0.024 (unit: ratio proportioning gram); Dissolve as above copper sulfate, the EDTA two of ratio respectively with deionized water and receive salt, trolamine, sodium hydroxide, a, a-dipyridyl, FeCl3, the above-mentioned solution for preparing is admixed together sequentially, sodium hydroxide solution with as above ratio is regulated PH to 12.5, add the formaldehyde and the as above CNT (carbon nano-tube) of ratio again, the stirring heating plating, temperature control is at 60 ℃, and the reaction times is 1.5 hours, between the reaction period, add NaOH solution in good time, to keep required pH scope, after question response finishes, suction filtration, use deionized water wash, place the flash baking case dry at last.
When adopting HCHO to be reductive agent, the electroless copper process is as the formaldehyde of reductive agent elemental copper to be separated out in main salt Cu2+ reduction to be coated on process on the CNT (carbon nano-tube) effectively, from reaction result, the redox reaction that total reaction is made up of two half-reactions, the electropotential of each reaction and correspondence is as follows:
Oxidizing reaction:
Formaldehyde must just have reductive action in the alkaline medium of pH＞11,
Reduction reaction:
Its total reaction is:
Cu2++2HCHO+4OH-→Cu↓+2HCOO-+H2↑+2H2O
Under the strong alkaline condition in practical systems, the reducing power of formaldehyde also depends on the pH value of solution.Guarantee that the Cu2+ ion does not form Cu (OH) 2 precipitations, also must add the complexing agent of enough Cu2+.
By principle and technological process as can be known, when adopting HCHO to be reductive agent, the factor that influences the plating effect is more, but under the prerequisite of capacity Cu2+, mainly contain HCHO consumption, bath temperature, plating bath time, pH value, complexing agent selection, initiator selection and consumption, selection of stabilizers etc., we adopt single factor optimizing scheme, respectively these factors are investigated.
When adopting HCHO to be reductive agent, guarantee Cu2+ concentration suitable and by the prerequisite of an amount of complexing agent complexing under, if be coated on the CNT (carbon nano-tube) with making the elemental copper continuous effective, the reductive agent formaldehyde that has capacity in must guarantee system, be because formaldehyde mainly is the form existence with methylene glycol CH2 (OH) 2 and negatively charged ion CH2OHO-thereof in basic solution on the one hand, and wherein the latter is only the main active ingredient of reaction, thereby causes actual formaldehyde consumption to be higher than theoretical consumption; On the other hand, in reaction process, formaldehyde is lost because of heated volatile, and experimental result shows that if the reductive agent quantity not sufficient, not only speed of response descends, and copper can not fully separate out, thereby influences the covered effect of carbon pipe.Obtain by serial experiment that preferable concentration of formaldehyde is 35ml/L in the plating bath.
When adopting HCHO to be reductive agent, bath temperature has a direct impact CNT (carbon nano-tube) copper facing quality, and plating temperature improves, and can strengthen the reacting dynamics characteristic of plating bath intermediate ion, thereby raising speed of response, yet for CNT (carbon nano-tube), sedimentation velocity is too fast to tend to bring unfavorable factor, because the CNT (carbon nano-tube) diameter is superfine, curvature is big, speed of response is prone to the copper agglomeration too soon, therefore suitably must control plating temperature, goes up the purpose of control sedimentation velocity to acquire a certain degree.From experiment effect, plating temperature is 60 ℃ preferably.
When adopting HCHO to be reductive agent, the CNT (carbon nano-tube) electroless copper is very responsive to pH value, and formaldehyde o'clock has reductive action in PH＞11, and in PH＞13 o'clock, oxidizing reaction and disproportionation reaction activity improve simultaneously, but disproportionation reaction preponderates, thereby has hindered the reduction of Cu2+.Examined or check PH in the experiment respectively and be 11.5,12,12.5,13 o'clock plating effect, pH value is best 12.5 o'clock effects, so best pH value is 12.5.
When adopting HCHO to be reductive agent, reduction takes place under alkaline condition formaldehyde to Cu2+, for preventing side reaction Cu (OH) 2 sedimentary generations, must add suitable and an amount of complexing agent, to reach the purpose of controls reaction speed, if complexing agent is excessive, can cause Cu2+ and formaldehyde effective collision probability to reduce, copper can not be separated out fully continuously.Experimental result shows better with EDTA and the compound result of use of TEA.
When adopting HCHO to be reductive agent, under the certain situation of other condition, different plating times, quality of coating is also different, 0.5 it is more continuous that the existing discontinuous copper deposition of hour carbon tube-surface, 1 hour copper are separated out, but compactness is poor, 1.5 hour formed densification and successive coating, so the time is 1.5 hours preferably.
When adopting HCHO to be reductive agent, add Fe3+ (FeCl3) in the plating bath in right amount, its adding need be with traditional Palladous chloride activation treatment CNT (carbon nano-tube), directly electroless copper on the CNT (carbon nano-tube) after the oxidation; Stablizer has stable plating bath, prevent to decompose and can control and sink the copper velocity function, and with a, the a-dipyridyl can also as the suitable methyl alcohol of condition for well.
Advantage of the present invention: the invention provides the catalytic method for plating copper on surface of carbon nanotube of a kind of no palladium, low price, easy to operate has been simplified technology.
Description of drawings
Fig. 1 is CNT (carbon nano-tube) copper facing and reduction back outward appearance.
Embodiment
Embodiment 1
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is Zn; Its main agents is CuSO45H2O, Zn powder, glycerol, ethylene glycol, Seignette salt, FeSO47H2O, HNO3; Wherein the concentration requirement of Cu2SO45H2O is 6.5g/l, the concentration requirement of glycerol is 133ml/l, and the concentration requirement of ethylene glycol is 90ml/l, and the concentration requirement of Seignette salt is 8.5g/l, the concentration requirement of FeSO47H2O is 3.5g/l, and the concentration requirement of zinc powder is 1.85g/l; Processing condition require: the reaction times is 1 hour, and temperature of reaction is 0～25 ℃, and complexing agent adds additive Fe2+ (FeSO4) with glycerine, ethylene glycol, the compound use of Seignette salt in the plating bath;
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 30 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: with proper amount of deionized water dissolving 0.198g copper sulfate, 0.25g Seignette salt, after the two merging, add 2.7ml ethylene glycol, 4ml glycerol and with the FeSO47H2O of suitable quantity of water dissolving 0.105g, adding water to the V total amount is 30ml, add 0.15g carbon nanotube and reductive agent zinc powder after nitric acid oxidation is handled, stirred one hour under 0～25 ℃ of temperature, reaction finishes back suction filtration, washing, oven dry.
Embodiment 2
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is Zn; Its main agents is CuSO45H2O, Zn powder, glycerol, ethylene glycol, Seignette salt, FeSO47H2O, HNO3; Wherein the concentration requirement of Cu2SO45H2O is 6.0g/l, the concentration requirement of glycerol is 125ml/l, and the concentration requirement of ethylene glycol is 85ml/l, and the concentration requirement of Seignette salt is 8.0g/l, the concentration requirement of FeSO47H2O is 3.0g/l, and the concentration requirement of zinc powder is 1.80g/l; Processing condition require: the reaction times is 50 minutes, and temperature of reaction is 0～25 ℃, and complexing agent adds additive Fe2+ (FeSO4) with glycerine, ethylene glycol, the compound use of Seignette salt in the plating bath;
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 25 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: with proper amount of deionized water dissolving 0.198g copper sulfate, 0.25g Seignette salt, after the two merging, add 2.7ml ethylene glycol, 4ml glycerol and with the FeSO47H2O of suitable quantity of water dissolving 0.105g, adding water to the V total amount is 30ml, add 0.15g carbon nanotube and reductive agent zinc powder after nitric acid oxidation is handled, stirred 50 minutes under 0～25 ℃ of temperature, reaction finishes back suction filtration, washing, oven dry.
Embodiment 3
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is Zn; Its main agents is CuSO45H2O, Zn powder, glycerol, ethylene glycol, Seignette salt, FeSO47H2O, HNO3; Wherein the concentration requirement of Cu2SO45H2O is 7.0g/l, the concentration requirement of glycerol is 140ml/l, and the concentration requirement of ethylene glycol is 95ml/l, and the concentration requirement of Seignette salt is 9.0g/l, the concentration requirement of FeSO47H2O is 4.0g/l, and the concentration requirement of zinc powder is 1.90g/l; Processing condition require: the reaction times is 70 minutes, and temperature of reaction is 0～25 ℃, and complexing agent adds additive Fe2+ (FeSO4) with glycerine, ethylene glycol, the compound use of Seignette salt in the plating bath;
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 35 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: with proper amount of deionized water dissolving 0.198g copper sulfate, 0.25g Seignette salt, after the two merging, add 2.7ml ethylene glycol, 4ml glycerol and with the FeSO47H2O of suitable quantity of water dissolving 0.105g, adding water to the V total amount is 30ml, add 0.15g carbon nanotube and reductive agent zinc powder after nitric acid oxidation is handled, stirred 70 minutes under 0～25 ℃ of temperature, reaction finishes back suction filtration, washing, oven dry.
Embodiment 4
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is HCHO; Its main agents is CuSO45H2O, HCHO, EDTANa2, FeCl37H2O, trolamine, a, a-dipyridyl, NaOH, HNO3; Wherein the concentration requirement of HCHO is 35ml/L; Processing condition require: plating temperature is 60 ℃, and pH value is 12.5, and complexing agent is with EDTA and the compound use of TEA, and plating time is 1.5 hours, adds Fe3+ (FeCl3) in the plating bath in right amount.
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 30 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: dissolve 0.45g copper sulfate respectively with proper amount of deionized water, 0.115gEDTA two receive salt, 1.2ml trolamine, 0.3g sodium hydroxide, 0.6mg a, a-dipyridyl and 0.0236g FeCl3, the above-mentioned solution for preparing is admixed together sequentially, adding water to the V total amount is that 30ml regulates PH to 12.5 with sodium hydroxide solution, add formaldehyde and CNT (carbon nano-tube) again, the stirring heating plating, temperature control is at 60 ℃, reaction times is 1.5 hours, between the reaction period, add NaOH solution, to keep required pH scope in good time, after question response finishes, suction filtration is used deionized water wash, places the flash baking case dry at last.
Embodiment 5
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is HCHO; Its main agents is CuSO45H2O, HCHO, EDTANa2, FeCl37H2O, trolamine, a, a-dipyridyl, NaOH, HNO3; Wherein the concentration requirement of HCHO is 30ml/L; Processing condition require: plating temperature is 50 ℃, and pH value is 11.5, and complexing agent is with EDTA and the compound use of TEA, and plating time is 80 minutes, adds Fe3+ (FeCl3) in the plating bath in right amount.
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 25 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: dissolve 0.45g copper sulfate respectively with proper amount of deionized water, 0.115gEDTA two receive salt, 1.2ml trolamine, 0.3g sodium hydroxide, 0.6mg a, a-dipyridyl and 0.0236g FeCl3, the above-mentioned solution for preparing is admixed together sequentially, adding water to the V total amount is 30ml, regulate PH to 11.5 with sodium hydroxide solution, add formaldehyde and CNT (carbon nano-tube) again, the stirring heating plating, temperature control is at 60 ℃, and the reaction times is 80 minutes, between the reaction period, add NaOH solution in good time, to keep required pH scope, after question response finishes, suction filtration, use deionized water wash, place the flash baking case dry at last.
Embodiment 6
The present embodiment method for plating copper on surface of carbon nanotube, adopting with Cu2+ is the elemental copper source, reductive agent is HCHO; Its main agents is CuSO45H2O, HCHO, EDTANa2, FeCl37H2O, trolamine, a, a-dipyridyl, NaOH, HNO3; Wherein the concentration requirement of HCHO is 40ml/L; Processing condition require: plating temperature is 70 ℃, and pH value is 13.0, and complexing agent is with EDTA and the compound use of TEA, and plating time is 100 minutes, adds Fe3+ (FeCl3) in the plating bath in right amount.
Described method for plating copper on surface of carbon nanotube, the technical process of its CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
Described method for plating copper on surface of carbon nanotube, CNT (carbon nano-tube) method for oxidation in the technical process of its CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 35 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
Described method for plating copper on surface of carbon nanotube, solution and coating method in the technical process of its CNT (carbon nano-tube) copper coating is: dissolve 0.45g copper sulfate respectively with proper amount of deionized water, 0.115gEDTA two receive salt, 1.2ml trolamine, 0.3g sodium hydroxide, 0.6mg a, a-dipyridyl and 0.0236g FeCl3, the above-mentioned solution for preparing is admixed together sequentially, adding water to the V total amount is 30ml, regulate PH to 13.0 with sodium hydroxide solution, add formaldehyde and CNT (carbon nano-tube) again, the stirring heating plating, temperature control is at 60 ℃, and the reaction times is 100 minutes, between the reaction period, add NaOH solution in good time, to keep required pH scope, after question response finishes, suction filtration, use deionized water wash, place the flash baking case dry at last.
Claims (4)
1, a kind of method for plating copper on surface of carbon nanotube is characterized in that: adopting with Cu2+ is the elemental copper source, and reductive agent is Zn or HCHO;
When adopting Zn to be reductive agent, its main agents is CuSO45H2O, Zn powder, glycerol, ethylene glycol, Seignette salt, FeSO47H2O, HNO3; Wherein the concentration requirement of Cu2SO45H2O is 6.0～7.0g/l, the concentration requirement of glycerol is 125～140ml/l, the concentration requirement of ethylene glycol is 85～95ml/l, the concentration requirement of Seignette salt is 8.0～9.0g/l, the concentration requirement of FeSO47H2O is 3.0～4.0g/l, and the concentration requirement of zinc powder is 1.80～1.90g/l; Processing condition require: the reaction times is 50～70 minutes, and temperature of reaction is 0～25 ℃, and complexing agent adds additive Fe2+ (FeSO4) with glycerine, ethylene glycol, the compound use of Seignette salt in the plating bath;
When adopting HCHO to be reductive agent, its main agents is CuSO45H2O, HCHO, EDTANa2, FeCl37H2O, trolamine, a, a-dipyridyl, NaOH, HNO3; Wherein the concentration requirement of HCHO is 30～40ml/L; Processing condition require: plating temperature is 50～70 ℃, and the pH value scope is 11.5～13.0, and complexing agent is with EDTA and the compound use of TEA, and plating time is 80～100 minutes, adds Fe3+ (FeCl3) in the plating bath.
2, described according to claim 1, it is characterized in that: the technical process of CNT (carbon nano-tube) copper coating is: the CNT (carbon nano-tube) oxidation-→ washing-→ plating-→ washing-→ drying.
3, described according to claim 1 or 2, it is characterized in that: the CNT (carbon nano-tube) method for oxidation in the technical process of CNT (carbon nano-tube) copper coating is: concentrated nitric acid and deionized water are mixed with certain quantity solution in 3: 2 (volume ratio) ratios, added the CNT (carbon nano-tube) heated and stirred 25～35 minutes, 60～65 ℃ of controlled temperature.Suction filtration is washed till neutrality with deionized water more then, suction filtration, oven dry.
4, described according to claim 1 or 2, it is characterized in that: when adopting Zn to be reductive agent, the solution and coating method in the technical process of CNT (carbon nano-tube) copper coating is: with copper sulfate, Seignette salt, ethylene glycol, glycerol, FeSO47H2O, CNT (carbon nano-tube) and reductive agent zinc powder by 0.19～0.21 (unit: gram): 0.2～0.3 (unit: gram): 2.5～2.9 (units: milliliter): 2～6 (units: milliliter): 0.1～0.15 (unit: gram): the ratio proportioning of 0.1～0.2 (unit: restrain); With deionized water dissolving as above copper sulfate, the Seignette salt of ratio, after the two merging, add the ethylene glycol, glycerol of as above ratio and with the as above FeSO47H2O of ratio of water dissolution, add as above the CNT (carbon nano-tube) and the reductive agent zinc powder through the nitric acid oxidation processing of ratio, stirred 50～70 minutes under 0～25 ℃ of temperature, reaction finishes back suction filtration, washing, oven dry;
When adopting HCHO to be reductive agent, solution and coating method in the technical process of CNT (carbon nano-tube) copper coating is: copper sulfate, EDTA two are received salt, trolamine, sodium hydroxide, a, and a-dipyridyl, FeCl3 are in 0.4～0.5 (unit: gram): 0.1～0.2 (unit: gram): 1.0～1.4 (units: milliliter): 0.1～0.5 (unit: gram): 0.4～0.8 (unit: milligram): 0.023～0.024 (unit: ratio proportioning gram); Dissolve the as above copper sulfate of ratio respectively with deionized water, EDTA two receives salt, trolamine, sodium hydroxide, a, the a-dipyridyl, FeCl3, the above-mentioned solution for preparing is admixed together sequentially, sodium hydroxide solution with as above ratio is regulated PH to 11.5～13.0, add the formaldehyde and the as above CNT (carbon nano-tube) of ratio again, the stirring heating plating, temperature control is at 50～70 ℃, and the reaction times is 80～100 minutes, between the reaction period, add NaOH solution in good time, to keep required pH scope, after question response finishes, suction filtration, use deionized water wash, place the flash baking case dry at last.
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