CN103469182B - Palladium-free chemical copper-plating method on graphite nanosheet surface - Google Patents
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Abstract
The invention discloses a palladium-free chemical copper-plating method on a graphite nanosheet surface. The palladium-free chemical copper-plating method is characterized in that a graphite nanosheet which is coated with a complete and compact metal copper housing on the surface is finally obtained through dispersing, coarsening, surface hydroxylation, activating, copper plating and passivating in sequence. The graphite nanosheet has a plurality of hydroxyls after surface hydroxylation treatment, and is activated, so that active ions and the graphite nanosheet are combined by chemical bonds, and binding force between a coating and the graphite nanosheet is strong; moreover, a problem that stannous chloride and palladium chloride which are dear and not environment-friendly are used in conventional graphite surface treatment is overcome. Besides, a complexing agent used by copper plating liquid provided by the invention is a composite complexing agent of sodium ethylene diamine tetracetate and citrate, wherein addition of the citrate is 100-400 times the sodium ethylene diamine tetracetate, hardness of the coating is regulated by regulating a proportion of the citrate and the sodium ethylene diamine tetracetate, thereby avoiding only using dear sodium ethylene diamine tetracetate as the complexing agent. The palladium-free chemical copper-plating method disclosed by the invention has environment-friendly effect, is economical and practical, and has good application prospect.
Description
Technical field
The present invention relates to a kind of graphite nanosheets surface chemical plating Copper treatment and copper facing graphite nanosheets preparation method, belong to electroless copper technical field, the copper facing graphite nanosheets of preparation can be used as the conductive filler material in composite conductive polymer.
Background technology
Along with the development of science and technology, conductive polymers is due to the electrical property of its uniqueness, magnetic property and become the focus of research.Now widely used conductive polymers is filled-type, and Typical fillers has metal-powder, carbon black, carbon nanotube, graphite (comprising Graphene) etc.In numerous conductive filler material, graphite nanosheets because radius-thickness ratio is larger, in polymeric matrix, more easily can form conductive network, cheap price, abundant reserves and be widely used in electro-conductive material.Take graphite oxide as raw material, can prepare expanded graphite, under hyperacoustic effect, the laminated structure generation stripping of expanded graphite can obtain graphite nanosheets.But, the electric conductivity of graphite nanosheets limits the raising of conductive polymers conductivity, because copper-base graphite matrix material not only has the superior lubricity of graphite, and possess the good electroconductibility of copper-based material, thermal conductivity and mechanical property, and electroless copper raw material is cheap and be easy to get, thus prepare in graphite nanosheets Electroless copper the selection that copper-plated graphite becomes desirable.
In recent years, graphite nanosheets surface chemistry is silver-plated, document and the patent of nickel plating have been reported [Zhang Yi, neat heat China, Duan Guochen, Deng. the preparation of nickel plating graphite nanosheets and sign [J] thereof. matrix material journal, 29(1): 35-42 patented invention CN101054483A employing electroless plating is silver-plated on graphite nanosheets].Although the document of graphite surface electroless copper also have report [Liu Zhengang, Liu Yihan, Luo Hongjie, etc. the technique of Electroless Copper Plating on Graphite Particles Surfce and effect [J] thereof. material protection, 2009,42(5): 20-23; Du Chunkuan. the research [J] of Study on Electroless Copper of Graphite Surface technique. education of science man, 2008,5:362-363.] but its graphite used is general graphite, and the graphite granule obtained is mainly used in bearing, li-ion electrode materials etc.And adopt SnCl
2sensitization and PdCl
2activation carries out surface treatment to graphite, and not only the price of palladium is high, even and if by dispergation process, remaining SnCl
2also not easily eliminate, its existence can suppress the growth of metal plating.
Summary of the invention
The object of the invention is to overcome and used palladium catalyst in graphite electroless copper expensive in the past, remaining SnCl
2also not easily eliminate, complexing agent tartrate conventional in plating solution makes that copper facing sedimentation rate is low, bath stability is low and ductility of electrodeposited film is poor, and single employing ethylenediamine tetraacetic acid (EDTA) is as deficiencies such as complexing agent are expensive, adopts one without palladium without SnCl
2copper-plating technique activates graphite nanosheets surface, and adopts a kind of new electroless copper formula to carry out copper facing on graphite nanosheets surface, and the volume obtaining copper accounts for the copper facing graphite nanosheets of the 60-80% of cumulative volume.
Technical scheme
Graphite nanosheets surface, without a method for palladium electroless copper, is characterized in that technological process is as follows: the dispersion → alligatoring → surface hydroxylation → activation → copper coating → passivation of graphite nanosheets.
Graphite nanosheets surface, without a method for palladium electroless copper, is characterized in that comprising the following steps:
Step 1, dispersion treatment: by graphite nanosheets ultrasonic disperse 10-30 minute in dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Step 2, roughening treatment: graphite nanosheets alkali lye step 1 obtained ultrasonic 15-50 minute at 30-50 DEG C, then filter, and is neutral by deionized water wash to filtrate;
Step 3, surface hydroxylation process: graphite nanosheets step 2 processed puts into hydrogen peroxide basic solution, be heated to 40-100 DEG C, and Keep agitation in addition, treatment time is 30-100 minute, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
Step 4, activation treatment: graphite nanosheets step 3 processed puts into activation solution, at room temperature with magnetic agitation process 10-80 minute, then filter, and washes three times, alcohol wash twice, obtains the graphite nanosheets activated after 50-80 DEG C of vacuum-drying;
Step 5, preparation plating solution: by the concentration that the concentration of copper sulfate is 10-40g/L, the concentration of lemon hydrochlorate is 10-50g/L, ethylenediamine tetraacetic acid (EDTA) is received be 0.1-1g/L, the concentration of di-mercaptobenzothiazolby is 20mg/L, copper sulfate, lemon hydrochlorate, ethylenediamine tetraacetic acid (EDTA) are received, di-mercaptobenzothiazolby joins in deionized water, mix, and regulate pH to 11-13 with ammoniacal liquor, obtain chemical plating fluid;
Step 6, the graphite nanosheets after activation treatment is put into plating solution stirring reaction 20-60 minute at 25-50 DEG C, then add reduced liquid, complete graphite nanosheets Electroless copper;
Step 7, Passivation Treatment: at room temperature, be immersed in passivation 1-5 minute in passivating solution, then filter by copper coating graphite nanosheets, 60-100 DEG C of vacuum-drying, obtain the copper facing graphite nanosheets of surface-brightening.
Hydrogen peroxide basic solution described in step 3 by hydrogen peroxide solution and ammoniacal liquor formulated, be the hydrogen peroxide of 20-60g/L and concentration containing concentration be the ammoniacal liquor of 30-150g/L.
Hydrogen peroxide basic solution described in step 3 by hydrogen peroxide solution and ammoniacal liquor formulated, be the hydrogen peroxide of 30-50g/L and concentration containing concentration be the ammoniacal liquor of 60-120g/L.
Described ammonia concn is 1-5 times of hydrogen peroxide concentration.
Described activation solution is containing methyl alcohol, 1-10g/L silane coupling agent, 10-40g/L potassium hydroxide, 1-10g/L active ion, 0.5-5mg/L hydrazine hydrate, by silane coupling agent, Silver Nitrate, potassium hydroxide, hydrazine hydrate joins in methyl alcohol, and at 30-70 DEG C of stirring reaction 1-4 hour, normal temperature is cooled to room temperature.
Described silane coupling agent is a kind of containing amino silicoorganic compound, and active ion is Ag
+or Ni
2+.
Described lemon hydrochlorate add-on is 100-400 times of sodium ethylene diamine tetracetate.
Described reduced liquid is one or more compounds such as hypophosphite, formaldehyde, oxoethanoic acid, sodium borohydride, ammonia borine or sugar, and the ratio of plating solution and reduced liquid volume is 0.8-1.3.
Described passivating solution is BTA and Na
2moO
4, ZnSO
4or Na
2siO
3the aqueous solution of one or more composite compounds.
The present invention relates to the method for a kind of graphite nanosheets surface without palladium electroless copper by graphite nanosheets successively dispersion, alligatoring, surface hydroxylation, activation, copper facing, passivation successively, finally obtain the graphite nanosheets of complete, the fine and close metallic copper shell of Surface coating one deck.Graphite nanosheets is with great amount of hydroxy group after surface hydroxylation process, again through overactivation, active ion and graphite nanosheets is made to pass through chemical bonds, coating and graphite nanosheets bonding force are strong, and overcome Graphite processing costliness and tin protochloride, the Palladous chloride of non-environmental protection in the past.In addition, copper plating bath provided by the invention complexing agent used is sodium ethylene diamine tetracetate and lemon hydrochlorate compound complex agent, and lemon hydrochlorate add-on is 100-400 times of sodium ethylene diamine tetracetate, adjust coating hardness by the ratio between adjustment lemon hydrochlorate and sodium ethylene diamine tetracetate, avoid the pure sodium ethylene diamine tetracetate of costliness that uses as complexing agent.The inventive method environmental protection, economic, practical, there is good application more prospect.
In the copper facing graphite nanosheets that the present invention adopts aforesaid method to obtain, the volume of copper accounts for the 40-60% of cumulative volume, there is the advantages such as high electroconductibility, thermal conductivity, low cost, low-resistivity, and the conductive filler material be used as in composite conductive polymer, make composite conductive polymer have good mechanical property.The inventive method technique is simple, equipment requirements is low, economic environmental protection, be easy to mass-producing, the layers of copper of uniformly continous on obtained graphite nanosheets plated surface.
Accompanying drawing explanation
Fig. 1: the schema of the inventive method
Fig. 2: graphite nanosheets scanning electron microscope (SEM) photo
Fig. 3: example 1 product S EM photo
Fig. 4: example 2 product S EM photo
Fig. 5: example 3 product S EM photo
Fig. 6: example 4 product S EM photo
Fig. 7: example 5 product S EM photo
Fig. 8: example 6 product S EM photo
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1:
The first step: dispersion treatment: take 0.1g graphite nanosheets ultrasonic disperse 15 minutes in 50ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 100ml, at 35 DEG C ultrasonic 30 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 50ml concentration is 40g/L and concentration is the ammonia soln of 60g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.15gAgNO
3, 1gKOH, 1mg hydrazine hydrate puts into the methanol solution that 50ml concentration is 3g/L KH550,50 DEG C of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 30 minutes, then filter, wash three times, alcohol wash twice, at 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 1g copper sulfate, 2g triammonium citrate, 0.05g ethylenediamine tetraacetic acid (EDTA) are received, 1mg di-mercaptobenzothiazolby is put into 50ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparing 50ml concentration with the formaldehyde that massfraction is 37% is the formaldehyde solution of 0.8mol/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 30 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 100ml massfraction be 0.2% BTA and massfraction be the Na of 0.6%
2moO
4in passivating solution, ultrasonic passivation 2 minutes, then filters, vacuum-drying at 80 DEG C, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 3.
Embodiment 2:
The first step: dispersion treatment: take 0.1g graphite nanosheets ultrasonic disperse 15 minutes in 50ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 100ml, at 35 DEG C ultrasonic 30 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 50ml concentration is 40g/L and concentration is the ammonia soln of 80g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.15gAgNO
3, 1gKOH, 1mg hydrazine hydrate puts into the methanol solution that 50ml concentration is 3g/L KH550,60 DEG C of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 30 minutes, then filter, wash three times, alcohol wash twice, at 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 1g copper sulfate, 2g triammonium citrate, 0.1g ethylenediamine tetraacetic acid (EDTA) are received, 1mg di-mercaptobenzothiazolby is put into 50ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparation 50ml concentration is the glyoxylic acid solution of 10g/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 30 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 100ml massfraction be 0.1% BTA, massfraction be the Na of 0.3%
2moO
4, massfraction is 0.05%ZnSO
4, massfraction is 0.01%Na
2siO
3passivating solution in ultrasonic passivation 2 minutes, then filter, vacuum-drying at 80 DEG C, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 4.
Embodiment 3:
The first step: dispersion treatment: take 0.2g graphite nanosheets ultrasonic disperse 20 minutes in 100ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 200ml, at 35 DEG C ultrasonic 35 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 100ml concentration is 40g/L and concentration is the ammonia soln of 60g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.3gAgNO
3, 2gKOH, 2mg hydrazine hydrate puts into the methanol solution that 100ml concentration is 3g/L KH550,50 DEG C of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 35 minutes, then filter, wash three times, alcohol wash twice, at 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 2g copper sulfate, 2g triammonium citrate, 0.1g ethylenediamine tetraacetic acid (EDTA) are received, 2mg di-mercaptobenzothiazolby is put into 100ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparing 100ml concentration with the formaldehyde that massfraction is 37% is the formaldehyde solution of 0.8mol/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 30 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 200ml massfraction be 0.2% BTA and massfraction be the Na of 0.6%
2moO
4in passivating solution, ultrasonic passivation 2 minutes, then filters, vacuum-drying at 80 DEG C, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 5.
Embodiment 4:
The first step: dispersion treatment: take 0.2g graphite nanosheets ultrasonic disperse 15 minutes in 100ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 200ml, at 35 DEG C ultrasonic 35 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 100ml concentration is 40g/L and concentration is the ammonia soln of 80g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.3gAgNO
3, 2gKOH, 2mg hydrazine hydrate puts into the methanol solution that 100ml concentration is 3g/L KH550,60 DEG C of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 35 minutes, then filter, wash three times, alcohol wash twice, at 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 2g copper sulfate, 4g triammonium citrate, 0.2g ethylenediamine tetraacetic acid (EDTA) are received, 2mg di-mercaptobenzothiazolby is put into 100ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparation 100ml concentration is the glyoxylic acid solution of 10g/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 30 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 200ml massfraction be 0.1% BTA, massfraction be the Na of 0.3%
2moO
4, massfraction is 0.05%ZnSO
4, massfraction is 0.01%Na
2siO
3passivating solution in ultrasonic passivation 2 minutes, then filter, vacuum-drying at 80 DEG C, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 6.
Embodiment 5:
The first step: dispersion treatment: take 0.3g graphite nanosheets ultrasonic disperse 20 minutes in 150ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 300ml, at 35 DEG C ultrasonic 35 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 150ml concentration is 40g/L and concentration is the ammonia soln of 60g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.45gAgNO
3, 3gKOH, 3mg hydrazine hydrate puts into the methanol solution that 150ml concentration is 3g/L KH550,50 DEG C of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 35 minutes, then filter, wash three times, alcohol wash twice, at 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 3g copper sulfate, 6g triammonium citrate, 0.15g ethylenediamine tetraacetic acid (EDTA) are received, 3mg di-mercaptobenzothiazolby is put into 150ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparing 150ml concentration with the formaldehyde that massfraction is 37% is the formaldehyde solution of 0.8mol/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 30 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 300ml massfraction be 0.2% BTA and massfraction be the Na of 0.6%
2moO
4in passivating solution, ultrasonic passivation 2 minutes, then filters, vacuum-drying at 80 DEG C, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 7.
Embodiment 6:
The first step: dispersion treatment: take 0.3g graphite nanosheets ultrasonic disperse 20 minutes in 150ml dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets the first step obtained puts into the 20g/LNaOH solution of 300ml, at 35 DEG C ultrasonic 30 minutes, then filters, and is neutral by deionized water wash to filtrate;
3rd step: surface hydroxylation process: the graphite nanosheets after second step roughening treatment is put into the hydrogen peroxide that 150ml concentration is 40g/L and concentration is the ammonia soln of 80g/L, Keep agitation in addition, temperature of reaction is 85 DEG C, reaction times is 50 minutes, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
4th step: activation treatment: take 0.45gAgNO
3, 3gKOH, 3mg hydrazine hydrate puts into the methanol solution that 150ml concentration is 3g/L KH550,60 DEG C of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd and put into activation solution, at room temperature with magnetic agitation process 30 minutes, then filter, wash three times, alcohol wash twice,
At 60 DEG C of vacuum-drying 2h, obtain the graphite nanosheets activated;
5th step: preparation plating solution and activation solution:
Plating solution: take 3g copper sulfate, 6g triammonium citrate, 0.3g ethylenediamine tetraacetic acid (EDTA) are received, 3mg di-mercaptobenzothiazolby is put into 150ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: preparation 150ml concentration is the glyoxylic acid solution of 10g/L;
6th step: the graphite nanosheets after the 4th step activation treatment is put into plating solution stirring reaction 40 minutes at 35 DEG C, more slowly add reduced liquid, react 35 minutes, complete graphite nanosheets Electroless copper;
7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step obtains is immersed in 300ml massfraction be 0.1% BTA, massfraction be the Na of 0.3%
2moO
4, massfraction is 0.05%ZnSO
4, massfraction is 0.01%Na
2siO
3passivating solution in ultrasonic passivation 2 minutes, then filter, vacuum-drying at 80 DEG C, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the metallic copper shell that graphite nanosheets Surface coating one deck is complete, fine and close, as shown in Figure 8.
Claims (9)
1. graphite nanosheets surface is without a method for palladium electroless copper, it is characterized in that comprising the following steps:
Step 1, dispersion treatment: by graphite nanosheets ultrasonic disperse 10-30 minute in dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Step 2, roughening treatment: graphite nanosheets alkali lye step 1 obtained ultrasonic 15-50 minute at 30-50 DEG C, then filter, and is neutral by deionized water wash to filtrate;
Step 3, surface hydroxylation process: graphite nanosheets step 2 processed puts into hydrogen peroxide basic solution, be heated to 40-100 DEG C, and Keep agitation in addition, treatment time is 30-100 minute, then filter, be neutral by deionized water wash to filtrate, obtain the graphite nanosheets of surface containing great amount of hydroxy group;
Step 4, activation treatment: graphite nanosheets step 3 processed puts into activation solution, at room temperature with magnetic agitation process 10-80 minute, then filter, and washes three times, alcohol wash twice, obtains the graphite nanosheets activated after 50-80 DEG C of vacuum-drying;
Step 5, preparation plating solution: by the concentration that the concentration of copper sulfate is 10-40g/L, the concentration of Citrate trianion is 10-50g/L, ethylenediamine tetraacetic acid (EDTA) is received be 0.1-1g/L, the concentration of di-mercaptobenzothiazolby is 20mg/L, copper sulfate, Citrate trianion, ethylenediamine tetraacetic acid (EDTA) are received, di-mercaptobenzothiazolby joins in deionized water, mix, and regulate pH to 11-13 with ammoniacal liquor, obtain chemical plating fluid;
Step 6, the graphite nanosheets after activation treatment is put into plating solution stirring reaction 20-60 minute at 25-50 DEG C, then add reduced liquid, complete graphite nanosheets Electroless copper;
Step 7, Passivation Treatment: at room temperature, be immersed in passivation 1-5 minute in passivating solution, then filter by copper coating graphite nanosheets, 60-100 DEG C of vacuum-drying, obtain the copper facing graphite nanosheets of surface-brightening.
2. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: the hydrogen peroxide basic solution described in step 3 by hydrogen peroxide solution and ammoniacal liquor formulated, be the hydrogen peroxide of 20-60g/L and concentration containing concentration be the ammoniacal liquor of 30-150g/L.
3. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: the hydrogen peroxide basic solution described in step 3 by hydrogen peroxide solution and ammoniacal liquor formulated, be the hydrogen peroxide of 30-50g/L and concentration containing concentration be the ammoniacal liquor of 60-120g/L.
4. the graphite nanosheets surface according to Claims 2 or 3, without the method for palladium electroless copper, is characterized in that: described ammonia concn is 1-5 times of hydrogen peroxide concentration.
5. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: described activation solution is containing methyl alcohol, 1-10g/L silane coupling agent, 10-40g/L potassium hydroxide, 1-10g/L active ion, 0.5-5mg/L hydrazine hydrate, silane coupling agent, Silver Nitrate, potassium hydroxide, hydrazine hydrate are joined in methyl alcohol, at 30-70 DEG C of stirring reaction 1-4 hour, normal temperature is cooled to room temperature.
6. graphite nanosheets surface according to claim 5 is without the method for palladium electroless copper, it is characterized in that: described silane coupling agent is a kind of containing amino silicoorganic compound, and active ion is Ag
+.
7. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: described lemon hydrochlorate add-on is 100-400 times of sodium ethylene diamine tetracetate.
8. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: described reduced liquid is hypophosphite, formaldehyde, oxoethanoic acid, sodium borohydride, ammonia borine or one or more compounds of sugar, and the ratio of plating solution and reduced liquid volume is 0.8-1.3.
9. graphite nanosheets surface according to claim 1 is without the method for palladium electroless copper, it is characterized in that: described passivating solution is BTA and Na
2moO
4, ZnSO
4or Na
2siO
3the aqueous solution of one or more composite compounds.
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| CN103691937B (en) * | 2013-12-31 | 2016-03-09 | 武汉理工大学 | A kind of method preparing nickel bag graphite compound particle |
| CN103878366B (en) * | 2014-04-16 | 2016-07-06 | 湖南大学 | Copper clad chromium composite powder and its preparation method and application |
| CN104477892B (en) * | 2014-12-12 | 2016-08-24 | 盐城市新能源化学储能与动力电源研究中心 | Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method |
| CN105274504B (en) * | 2015-11-27 | 2018-04-20 | 中国科学院电工研究所 | One kind is in expanded graphite process for copper coating on surface |
| CN106350789B (en) * | 2016-09-18 | 2019-07-02 | 电子科技大学 | A kind of preparation method of electromagnetic shielding film metal layer |
| CN107163624A (en) * | 2017-04-21 | 2017-09-15 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of silver-plated nano graphite microchip conductive filler |
| CN109384428B (en) * | 2017-08-08 | 2021-07-16 | 北京青年路混凝土有限公司 | Non-ignition concrete and preparation method thereof |
| CN110699952B (en) * | 2019-09-29 | 2022-01-21 | 济南大学 | Method for preparing electromagnetic shielding cloth |
| CN112908707B (en) * | 2021-02-04 | 2022-10-11 | 广州金立电子有限公司 | High-temperature-resistant capacitor and preparation method thereof |
| CN113999432B (en) * | 2021-11-18 | 2023-05-26 | 彗晶新材料科技(杭州)有限公司 | Fe 3 O 4 Preparation method of @ MWCNTs nanocomposite and electronic equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547692A (en) * | 1968-10-17 | 1970-12-15 | Engelhard Min & Chem | Metal coating carbon substrates |
| CN101230456A (en) * | 2007-11-01 | 2008-07-30 | 株洲文辉新材电碳厂 | Copper-plating graphite composite material and preparation method thereof |
| CN101302080A (en) * | 2007-05-10 | 2008-11-12 | 西北工业大学 | Pretreatment method of chemical plating conductive magneto-conductive glass fibre |
| CN101508596A (en) * | 2008-06-11 | 2009-08-19 | 晟茂（青岛）能源替代产品研发有限公司 | Metal coating plumbago composite material and method of producing the same |
| CN102086517A (en) * | 2009-12-08 | 2011-06-08 | 沈阳临德陶瓷研发有限公司 | Chemical nickel-plating method for carbon fiber |
| CN102206816A (en) * | 2011-05-04 | 2011-10-05 | 天津大学 | Method for chemically and orderly plating copper and plating tin on graphite flake and application of plated graphite flake |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101250A (en) * | 1984-10-24 | 1986-05-20 | Idemitsu Kosan Co Ltd | Preparation of metal supported particle |
| DE50100123D1 (en) * | 2001-05-14 | 2003-04-24 | Franz Oberflaechentechnik Gmbh | Metal coating of graphite |
-
2013
- 2013-08-30 CN CN201310391050.2A patent/CN103469182B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547692A (en) * | 1968-10-17 | 1970-12-15 | Engelhard Min & Chem | Metal coating carbon substrates |
| CN101302080A (en) * | 2007-05-10 | 2008-11-12 | 西北工业大学 | Pretreatment method of chemical plating conductive magneto-conductive glass fibre |
| CN101230456A (en) * | 2007-11-01 | 2008-07-30 | 株洲文辉新材电碳厂 | Copper-plating graphite composite material and preparation method thereof |
| CN101508596A (en) * | 2008-06-11 | 2009-08-19 | 晟茂（青岛）能源替代产品研发有限公司 | Metal coating plumbago composite material and method of producing the same |
| CN102086517A (en) * | 2009-12-08 | 2011-06-08 | 沈阳临德陶瓷研发有限公司 | Chemical nickel-plating method for carbon fiber |
| CN102206816A (en) * | 2011-05-04 | 2011-10-05 | 天津大学 | Method for chemically and orderly plating copper and plating tin on graphite flake and application of plated graphite flake |
Non-Patent Citations (1)
| Title |
|---|
| 镀铜石墨粉的制备研究;李艳 等;《表面技术》;20060228;第35卷(第1期);第60-62页 * |
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