CN103469182A - Palladium-free chemical copper-plating method on graphite nanosheet surface - Google Patents
Palladium-free chemical copper-plating method on graphite nanosheet surface Download PDFInfo
- Publication number
- CN103469182A CN103469182A CN2013103910502A CN201310391050A CN103469182A CN 103469182 A CN103469182 A CN 103469182A CN 2013103910502 A CN2013103910502 A CN 2013103910502A CN 201310391050 A CN201310391050 A CN 201310391050A CN 103469182 A CN103469182 A CN 103469182A
- Authority
- CN
- China
- Prior art keywords
- graphite nanosheets
- graphite
- copper
- solution
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 Electroless copper and process and copper facing graphite nanosheets preparation method, belong to the 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 scientific and technological development, conductive polymers is because its unique electrical property, magnetic property become the focus of research.Now widely used conductive polymers is filled-type, and common filler has metal-powder, carbon black, carbon nanotube, graphite (comprising Graphene) etc.In numerous conductive filler materials, graphite nanosheets because radius-thickness ratio is larger, can in polymeric matrix, more easily form conductive network, cheap price, abundant reserves be widely used in electro-conductive material.Take graphite oxide as raw material, can prepare expanded graphite, under hyperacoustic effect, the laminated structure of expanded graphite is peeled off and can be obtained graphite nanosheets.Yet, the electric conductivity of graphite nanosheets has limited the raising of conductive polymers conductivity, because the copper-base graphite matrix material not only has the superior lubricity of graphite, and possesses the electroconductibility that copper-based material is good, thermal conductivity and mechanical property, and the electroless copper raw material is cheap and be easy to get, thereby prepares copper-plated graphite in the graphite nanosheets Electroless copper and become desirable selection.
In recent years, the 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 thereof [J]. the 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 thereof [J]. material protection, 2009,42(5): 20-23; Du Chunkuan. the research of Study on Electroless Copper of Graphite Surface technique [J]. education of science man, 2008,5:362-363.] but its graphite used is general graphite, and resulting graphite granule is mainly used in bearing, li-ion electrode materials etc.And adopt SnCl
2sensitization and PdCl
2activation is carried out surface treatment to graphite, and not only the price of palladium is high, even and process remaining SnCl by dispergation
2also be difficult for eliminating, its existence can suppress the growth of metal plating.
Summary of the invention
The object of the invention is to overcome and used expensive, the remaining SnCl of palladium catalyst in the graphite electroless copper in the past
2also be difficult for eliminating, in plating solution, complexing agent tartrate commonly used makes that the 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 costlinesses, adopt a kind of without palladium without SnCl
2copper-plating technique is activated the graphite nanosheets surface, and adopts a kind of new electroless copper formula to carry out copper facing on the graphite nanosheets surface, and the volume that obtains copper accounts for the copper facing graphite nanosheets of the 60-80% of cumulative volume.
Technical scheme
A kind of graphite nanosheets surface, without the method for palladium electroless copper, is characterized in that technological process is as follows: the dispersion → alligatoring of graphite nanosheets → surface hydroxylation → activation → copper coating → passivation.
A kind of graphite nanosheets surface, without the method for palladium electroless copper, is characterized in that comprising the following steps:
Step 1, dispersion treatment: by graphite nanosheets ultrasonic dispersion 10-30 minute in dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Step 2, roughening treatment: alkali lye ultrasonic 15-50 minute under 30-50 ℃ for the graphite nanosheets that step 1 is obtained, then filter, by deionized water wash to filtrate, be neutral;
Step 3, surface hydroxylation are processed: the graphite nanosheets that step 2 is processed is put into the hydrogen peroxide basic solution, be heated to 40-100 ℃, and continued to stir, 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: the graphite nanosheets that step 3 is processed is put into activation solution, at room temperature by magnetic agitation, processes 10-80 minute, then filters, and washes three times, and alcohol wash twice obtains the graphite nanosheets activated after 50-80 ℃ of vacuum-drying;
Step 5, preparation plating solution: the concentration that is 10-40g/L, lemon hydrochlorate by the concentration of copper sulfate is that the concentration that concentration that 10-50g/L, ethylenediamine tetraacetic acid (EDTA) are received is 0.1-1g/L, di-mercaptobenzothiazolby is 20mg/L, by copper sulfate, lemon hydrochlorate, ethylenediamine tetraacetic acid (EDTA) receive, 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 to plating solution at 25-50 ℃ of lower stirring reaction 20-60 minute, then add reduced liquid, complete the graphite nanosheets Electroless copper;
Step 7, Passivation Treatment: at room temperature, the copper coating graphite nanosheets is immersed in to passivation 1-5 minute in passivating solution, then filters, 60-100 ℃ of vacuum-drying, obtain the copper facing graphite nanosheets of surface-brightening.
Hydrogen peroxide basic solution described in step 3 is formulated by hydrogen peroxide solution and ammoniacal liquor, the ammoniacal liquor that the hydrogen peroxide that is 20-60g/L containing concentration and concentration are 30-150g/L.
Hydrogen peroxide basic solution described in step 3 is formulated by hydrogen peroxide solution and ammoniacal liquor, the ammoniacal liquor that the hydrogen peroxide that is 30-50g/L containing concentration and concentration are 60-120g/L.
The 1-5 that described ammonia concn is hydrogen peroxide concentration doubly.
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 ℃ of stirring reaction 1-4 hour, normal temperature is cooled to room temperature.
Described silane coupling agent is a kind of amino silicoorganic compound that contain, and active ion is Ag
+or Ni
2+.
The 100-400 that described lemon hydrochlorate add-on is sodium ethylene diamine tetracetate doubly.
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 a kind of graphite nanosheets surface without the method for palladium electroless copper by successively dispersion successively of graphite nanosheets, alligatoring, surface hydroxylation, activation, copper facing, passivation, finally obtain the graphite nanosheets that surface has coated intact, fine and close metallic copper shell.Graphite nanosheets is with great amount of hydroxy group after surface hydroxylation is processed, again through overactivation, make active ion and graphite nanosheets pass through chemical bonds, coating and graphite nanosheets bonding force are strong, and have overcome tin protochloride, the Palladous chloride of expensive and non-environmental protection for Graphite processing 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 the 100-400 that lemon hydrochlorate add-on is sodium ethylene diamine tetracetate doubly, adjust coating hardness by the ratio of adjusting between lemon hydrochlorate and sodium ethylene diamine tetracetate, avoided the expensive sodium ethylene diamine tetracetate of pure use as complexing agent.The inventive method environmental protection, economic, practical, have more prospect of good application.
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 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, even continuous copper layer on prepared graphite nanosheets plated surface.
The 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 photos
Fig. 5: example 3 product S EM photos
Fig. 6: example 4 product S EM photos
Fig. 7: example 5 product S EM photos
Fig. 8: example 6 product S EM photos
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1:
The first step: dispersion treatment: take the ultrasonic dispersion 15 minutes in the 50ml dehydrated alcohol of 0.1g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 100ml, and under 35 ℃ ultrasonic 30 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 50ml concentration is 40g/L and concentration are 60g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.15gAgNO
3, 1gKOH, 1mg hydrazine hydrate put into the methanol solution that 50ml concentration is 3g/L KH550,50 ℃ of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 30 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice, at 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 1g copper sulfate, 2g triammonium citrate, 0.05g ethylenediamine tetraacetic acid (EDTA) are received, the 1mg di-mercaptobenzothiazolby is put into the 50ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the formaldehyde solution that the formaldehyde that is 37% with massfraction preparation 50ml concentration is 0.8mol/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 30 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the Na that BTA that the 100ml massfraction is 0.2% and massfraction are 0.6%
2moO
4in passivating solution, ultrasonic passivation is 2 minutes, then filters, and 80 ℃ of lower vacuum-dryings, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 3.
Embodiment 2:
The first step: dispersion treatment: take the ultrasonic dispersion 15 minutes in the 50ml dehydrated alcohol of 0.1g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 100ml, and under 35 ℃ ultrasonic 30 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 50ml concentration is 40g/L and concentration are 80g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.15gAgNO
3, 1gKOH, 1mg hydrazine hydrate put into the methanol solution that 50ml concentration is 3g/L KH550,60 ℃ of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 30 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice, at 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 1g copper sulfate, 2g triammonium citrate, 0.1g ethylenediamine tetraacetic acid (EDTA) are received, the 1mg di-mercaptobenzothiazolby is put into the 50ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the glyoxylic acid solution that preparation 50ml concentration is 10g/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 30 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the BTA that the 100ml massfraction is 0.1%, the Na that massfraction is 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, 80 ℃ of lower vacuum-dryings, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 4.
Embodiment 3:
The first step: dispersion treatment: take the ultrasonic dispersion 20 minutes in the 100ml dehydrated alcohol of 0.2g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 200ml, and under 35 ℃ ultrasonic 35 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 100ml concentration is 40g/L and concentration are 60g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.3gAgNO
3, 2gKOH, 2mg hydrazine hydrate put into the methanol solution that 100ml concentration is 3g/L KH550,50 ℃ of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 35 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice, at 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 2g copper sulfate, 2g triammonium citrate, 0.1g ethylenediamine tetraacetic acid (EDTA) are received, the 2mg di-mercaptobenzothiazolby is put into the 100ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the formaldehyde solution that the formaldehyde that is 37% with massfraction preparation 100ml concentration is 0.8mol/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 30 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the Na that BTA that the 200ml massfraction is 0.2% and massfraction are 0.6%
2moO
4in passivating solution, ultrasonic passivation is 2 minutes, then filters, and 80 ℃ of lower vacuum-dryings, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 5.
Embodiment 4:
The first step: dispersion treatment: take the ultrasonic dispersion 15 minutes in the 100ml dehydrated alcohol of 0.2g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 200ml, and under 35 ℃ ultrasonic 35 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 100ml concentration is 40g/L and concentration are 80g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.3gAgNO
3, 2gKOH, 2mg hydrazine hydrate put into the methanol solution that 100ml concentration is 3g/L KH550,60 ℃ of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 35 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice, at 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 2g copper sulfate, 4g triammonium citrate, 0.2g ethylenediamine tetraacetic acid (EDTA) are received, the 2mg di-mercaptobenzothiazolby is put into the 100ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the glyoxylic acid solution that preparation 100ml concentration is 10g/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 30 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the BTA that the 200ml massfraction is 0.1%, the Na that massfraction is 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, 80 ℃ of lower vacuum-dryings, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 6.
Embodiment 5:
The first step: dispersion treatment: take the ultrasonic dispersion 20 minutes in the 150ml dehydrated alcohol of 0.3g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 300ml, and under 35 ℃ ultrasonic 35 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 150ml concentration is 40g/L and concentration are 60g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.45gAgNO
3, 3gKOH, 3mg hydrazine hydrate put into the methanol solution that 150ml concentration is 3g/L KH550,50 ℃ of stirring reactions 4 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 35 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice, at 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 3g copper sulfate, 6g triammonium citrate, 0.15g ethylenediamine tetraacetic acid (EDTA) are received, the 3mg di-mercaptobenzothiazolby is put into the 150ml deionized water and mixed, and regulate pH to 12 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the formaldehyde solution that the formaldehyde that is 37% with massfraction preparation 150ml concentration is 0.8mol/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 30 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the Na that BTA that the 300ml massfraction is 0.2% and massfraction are 0.6%
2moO
4in passivating solution, ultrasonic passivation is 2 minutes, then filters, and 80 ℃ of lower vacuum-dryings, obtains the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 7.
Embodiment 6:
The first step: dispersion treatment: take the ultrasonic dispersion 20 minutes in the 150ml dehydrated alcohol of 0.3g graphite nanosheets, then filter, obtain the graphite nanosheets disperseed;
Second step: roughening treatment: the graphite nanosheets that the first step is obtained is put into the 20g/LNaOH solution of 300ml, and under 35 ℃ ultrasonic 30 minutes, then filter, by deionized water wash to filtrate, be neutral;
The 3rd step: surface hydroxylation is processed: the graphite nanosheets after the second step roughening treatment is put into to the ammonia soln that hydrogen peroxide that 150ml concentration is 40g/L and concentration are 80g/L, continued to stir, temperature of reaction is 85 ℃, 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;
The 4th step: activation treatment: take 0.45gAgNO
3, 3gKOH, 3mg hydrazine hydrate put into the methanol solution that 150ml concentration is 3g/L KH550,60 ℃ of stirring reactions 3 hours, normal temperature was cooled to room temperature and obtains activation solution.Obtain graphite nanosheets by the 3rd one and put into activation solution, at room temperature process 30 minutes by magnetic agitation, then filter, wash three times, alcohol wash twice,
At 60 ℃ of vacuum-drying 2h, obtain the graphite nanosheets of activation;
The 5th step: preparation plating solution and activation solution:
Plating solution: take that 3g copper sulfate, 6g triammonium citrate, 0.3g ethylenediamine tetraacetic acid (EDTA) are received, the 3mg di-mercaptobenzothiazolby is put into the 150ml deionized water and mixed, and regulate pH to 12.5 with ammoniacal liquor, obtain chemical plating fluid;
Reduced liquid: the glyoxylic acid solution that preparation 150ml concentration is 10g/L;
The 6th step: the graphite nanosheets after the 4th step activation treatment is put into to plating solution 35 ℃ of lower stirring reactions 40 minutes, more slowly add reduced liquid, react 35 minutes, complete the graphite nanosheets Electroless copper;
The 7th step: Passivation Treatment: at room temperature, the copper coating graphite nanosheets that the 6th step is obtained is immersed in the BTA that the 300ml massfraction is 0.1%, the Na that massfraction is 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, 80 ℃ of lower vacuum-dryings, obtain the copper facing graphite nanosheets of surface-brightening.
Through sem observation, the graphite nanosheets surface has coated intact, fine and close metallic copper shell, as shown in Figure 8.
Claims (9)
1. a graphite nanosheets surface, without the method for palladium electroless copper, is characterized in that comprising the following steps:
Step 1, dispersion treatment: by graphite nanosheets ultrasonic dispersion 10-30 minute in dehydrated alcohol, then filter, obtain the graphite nanosheets disperseed;
Step 2, roughening treatment: alkali lye ultrasonic 15-50 minute under 30-50 ℃ for the graphite nanosheets that step 1 is obtained, then filter, by deionized water wash to filtrate, be neutral;
Step 3, surface hydroxylation are processed: the graphite nanosheets that step 2 is processed is put into the hydrogen peroxide basic solution, be heated to 40-100 ℃, and continued to stir, 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: the graphite nanosheets that step 3 is processed is put into activation solution, at room temperature by magnetic agitation, processes 10-80 minute, then filters, and washes three times, and alcohol wash twice obtains the graphite nanosheets activated after 50-80 ℃ of vacuum-drying;
Step 5, preparation plating solution: the concentration that is 10-40g/L, lemon hydrochlorate by the concentration of copper sulfate is that the concentration that concentration that 10-50g/L, ethylenediamine tetraacetic acid (EDTA) are received is 0.1-1g/L, di-mercaptobenzothiazolby is 20mg/L, by copper sulfate, lemon hydrochlorate, ethylenediamine tetraacetic acid (EDTA) receive, 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 to plating solution at 25-50 ℃ of lower stirring reaction 20-60 minute, then add reduced liquid, complete the graphite nanosheets Electroless copper;
Step 7, Passivation Treatment: at room temperature, the copper coating graphite nanosheets is immersed in to passivation 1-5 minute in passivating solution, then filters, 60-100 ℃ of vacuum-drying, obtain the copper facing graphite nanosheets of surface-brightening.
2. graphite nanosheets according to claim 1 surface is without the method for palladium electroless copper, it is characterized in that: the hydrogen peroxide basic solution described in step 3 is formulated by hydrogen peroxide solution and ammoniacal liquor, the ammoniacal liquor that the hydrogen peroxide that is 20-60g/L containing concentration and concentration are 30-150g/L.
3. graphite nanosheets according to claim 1 surface is without the method for palladium electroless copper, it is characterized in that: the hydrogen peroxide basic solution described in step 3 is formulated by hydrogen peroxide solution and ammoniacal liquor, the ammoniacal liquor that the hydrogen peroxide that is 30-50g/L containing concentration and concentration are 60-120g/L.
According to claim 1 or 2 or 3 described graphite nanosheets surfaces without the method for palladium electroless copper, it is characterized in that: the 1-5 that described ammonia concn is hydrogen peroxide concentration is doubly.
5. graphite nanosheets according to claim 1 surface 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, by silane coupling agent, Silver Nitrate, potassium hydroxide, hydrazine hydrate joins in methyl alcohol, at 30-70 ℃ of stirring reaction 1-4 hour, normal temperature is cooled to room temperature.
6. graphite nanosheets according to claim 5 surface, without the method for palladium electroless copper, is characterized in that: described silane coupling agent is a kind of amino silicoorganic compound that contain, and active ion is Ag
+or Ni
2+.
7. graphite nanosheets according to claim 1 surface, without the method for palladium electroless copper, is characterized in that: the 100-400 that described lemon hydrochlorate add-on is sodium ethylene diamine tetracetate doubly.
8. graphite nanosheets according to claim 1 surface is without the method for palladium electroless copper, it is characterized in that: 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.
9. graphite nanosheets according to claim 1 surface, without the method for palladium electroless copper, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310391050.2A CN103469182B (en) | 2013-08-30 | 2013-08-30 | Palladium-free chemical copper-plating method on graphite nanosheet surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310391050.2A CN103469182B (en) | 2013-08-30 | 2013-08-30 | Palladium-free chemical copper-plating method on graphite nanosheet surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103469182A true CN103469182A (en) | 2013-12-25 |
| CN103469182B CN103469182B (en) | 2015-05-13 |
Family
ID=49794218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310391050.2A Active CN103469182B (en) | 2013-08-30 | 2013-08-30 | Palladium-free chemical copper-plating method on graphite nanosheet surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103469182B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691937A (en) * | 2013-12-31 | 2014-04-02 | 武汉理工大学 | Nickel-coated graphite composite particle preparation method |
| CN103878366A (en) * | 2014-04-16 | 2014-06-25 | 湖南大学 | Copper-coated chromium composite powder and preparation method and application thereof |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| CN105274504A (en) * | 2015-11-27 | 2016-01-27 | 中国科学院电工研究所 | Method for chemically plating copper on surface of expanded graphite |
| CN106350789A (en) * | 2016-09-18 | 2017-01-25 | 电子科技大学 | Preparation method of metal layer for electromagnetic shielding film |
| 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 |
| CN109384428A (en) * | 2017-08-08 | 2019-02-26 | 北京青年路混凝土有限公司 | Misfire concrete and preparation method thereof |
| CN110699952A (en) * | 2019-09-29 | 2020-01-17 | 济南大学 | Method for preparing electromagnetic shielding cloth |
| CN112908707A (en) * | 2021-02-04 | 2021-06-04 | 广州金立电子有限公司 | High-temperature-resistant capacitor and preparation method thereof |
| CN113999432A (en) * | 2021-11-18 | 2022-02-01 | 彗晶新材料科技(杭州)有限公司 | Fe3O4Preparation method of @ MWCNTs nano composite material and electronic equipment |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547692A (en) * | 1968-10-17 | 1970-12-15 | Engelhard Min & Chem | Metal coating carbon substrates |
| JPS61101250A (en) * | 1984-10-24 | 1986-05-20 | Idemitsu Kosan Co Ltd | Preparation of metal supported particle |
| US20040094424A1 (en) * | 2001-05-14 | 2004-05-20 | Franz Oberflachentechnik Gmbh & Co Kg | Graphite metal coating |
| 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 |
-
2013
- 2013-08-30 CN CN201310391050.2A patent/CN103469182B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547692A (en) * | 1968-10-17 | 1970-12-15 | Engelhard Min & Chem | Metal coating carbon substrates |
| JPS61101250A (en) * | 1984-10-24 | 1986-05-20 | Idemitsu Kosan Co Ltd | Preparation of metal supported particle |
| US20040094424A1 (en) * | 2001-05-14 | 2004-05-20 | Franz Oberflachentechnik Gmbh & Co Kg | Graphite metal coating |
| 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 |
|---|
| 李艳 等: "镀铜石墨粉的制备研究", 《表面技术》, vol. 35, no. 1, 28 February 2006 (2006-02-28), pages 60 - 62 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691937B (en) * | 2013-12-31 | 2016-03-09 | 武汉理工大学 | A kind of method preparing nickel bag graphite compound particle |
| CN103691937A (en) * | 2013-12-31 | 2014-04-02 | 武汉理工大学 | Nickel-coated graphite composite particle preparation method |
| CN103878366A (en) * | 2014-04-16 | 2014-06-25 | 湖南大学 | Copper-coated chromium composite powder and preparation method and application thereof |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| 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 |
| CN105274504A (en) * | 2015-11-27 | 2016-01-27 | 中国科学院电工研究所 | Method for chemically plating copper on surface of expanded graphite |
| 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 |
| CN106350789A (en) * | 2016-09-18 | 2017-01-25 | 电子科技大学 | Preparation method of metal layer for electromagnetic shielding film |
| 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 |
| CN109384428A (en) * | 2017-08-08 | 2019-02-26 | 北京青年路混凝土有限公司 | Misfire concrete and preparation method thereof |
| CN110699952A (en) * | 2019-09-29 | 2020-01-17 | 济南大学 | Method for preparing electromagnetic shielding cloth |
| CN110699952B (en) * | 2019-09-29 | 2022-01-21 | 济南大学 | Method for preparing electromagnetic shielding cloth |
| CN112908707A (en) * | 2021-02-04 | 2021-06-04 | 广州金立电子有限公司 | High-temperature-resistant capacitor and preparation method thereof |
| CN113999432A (en) * | 2021-11-18 | 2022-02-01 | 彗晶新材料科技(杭州)有限公司 | Fe3O4Preparation method of @ MWCNTs nano composite material and electronic equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103469182B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103469182B (en) | Palladium-free chemical copper-plating method on graphite nanosheet surface | |
| CN108103485B (en) | Preparation method for coating metal copper or nickel on surface of graphene | |
| CN102950283B (en) | Preparation method for superfine silver plating copper powder used for electronic paste | |
| CN102732863B (en) | Method for preparing magnetic-field-assisted graphite carbon material chemical plating magnetic metal | |
| CN103464742B (en) | The compound coating raw powder's production technology of the coated tungsten of a kind of copper clad silver | |
| CN102133636B (en) | Method for preparing anti-migration flaky silver coated copper powder | |
| CN109957144B (en) | Preparation method of conductive filler with silver-plated surface | |
| CN109423636B (en) | Preparation method of secondary silver-plated high-conductivity filler | |
| CN102747345A (en) | Method for chemically plating nickel on surface of copper circuit of PCB (printed circuit board) by dipping and activating nickel | |
| CN109423637A (en) | A kind of preparation method of high conductive material | |
| CN108118528B (en) | Flexible conductive textile | |
| CN102683050B (en) | Preparation method of nano Ag-SnO2 electric contact composite | |
| CN107498064A (en) | A kind of preparation method of high temperature electric slurry ultra-fine copper galactic nucleus shell composite powder | |
| CN110102758B (en) | Cu-X/C composite material and preparation method thereof | |
| CN105965010A (en) | Preparation method for silver-plating copper powder | |
| CN102906306A (en) | Method for direct metallization of non-conductive substrates | |
| CN105063580A (en) | Preparation method of nickel-coated graphite powder for electroconductive rubber of electromagnetic shielding material | |
| CN103103590A (en) | Direct-electroplating conductive liquid and preparation method thereof | |
| CN107447208B (en) | Method for preparing Pd-Ni-Fe-P alloy film by chemical plating-displacement | |
| CN103691965A (en) | Preparation method for copper/silver heterojunction nano-particles | |
| CN104439271A (en) | Method for preparing multilayer metal complex having excellent surface properties | |
| CN101962763A (en) | Chemical plating peptizing liquid and method for performing non-metal surface treatment | |
| CN103611933B (en) | A kind of sonochemistry efficiently prepares the method for nickel coated copper composite powder | |
| CN113059155A (en) | Preparation method of nickel-coated graphite composite powder material for conductive silica gel | |
| CN102534585B (en) | Preparation method of Al-Ag alloy powder plated with silver chemically |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |