CN108546938A - A kind of preparation method of nickel coated carbon nano tube compound material - Google Patents
A kind of preparation method of nickel coated carbon nano tube compound material Download PDFInfo
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- CN108546938A CN108546938A CN201810396627.1A CN201810396627A CN108546938A CN 108546938 A CN108546938 A CN 108546938A CN 201810396627 A CN201810396627 A CN 201810396627A CN 108546938 A CN108546938 A CN 108546938A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1855—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by mechanical pretreatment, e.g. grinding, sanding
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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Abstract
The present invention relates to a kind of preparation methods of nickel coated carbon nano tube compound material, including：（1）Carbon nanotube grinding, concentrated nitric acid immersion, hydrofluoric acid clean impurity elimination；（2）Sensitizing solution is added to be sensitized, ultrasound, stirring 4 20 minutes, filtering, the sensitizing solution is by SnCl2It is prepared with HCl；（3）Add activating solution to activate, is filtered after the completion of ultrasound, the lower activation activation in 7 30 minutes of stirring, the activating solution is by Pb (NO3)2And HNO3It prepares；（4）Add nickel liquid, reducing agent, adjusts pH to 8.5 9.5, be warming up to 65 75 DEG C; it is stirred to react 14 hours, filtration washing to neutrality, lower 380 DEG C of nitrogen protection is heat-treated 4 hours; up to nickel coated carbon nanotube, the nickel liquid, reducing agent and pH adjusting agent are by inventor's autogamy；Nickel coated carbon nano tube compound material coating uniformity produced by the present invention, continuity are good, and binding force is strong, and metal grain size is controllable, are suitble to promote and apply.
Description
Technical field
The invention belongs to carbon nano tube compound material technical field, specifically a kind of nickel coated carbon nano tube compound material
Preparation method.
Background technology
Since carbon nanotube is found since 1991, with the excellent properties of its unique mechanics, magnetics, electricity etc.,
It is used widely in catalyst carrier, nano-device, electrode material and hydrogen storage material etc., since carbon nanotube is numerous
Field is worth with potential huge applications, and especially it is with high axial strength（About 100 times of steel）, prodigious length
Diameter ratio（Generally 100-1000）, larger specific surface area, high-temperature stability, high abrasion resistance and good thermal conductivity, can
With for preparing the good advanced composite material (ACM) of high intensity, stability.R＆D direction common at present concentrates on metal/carbon nanotube
In the research of composite material, especially nickel coated carbon nano tube compound material is the hot spot of Recent study.
Currently, the preparation method of nickel coated carbon nano tube compound material mainly have surface chemical plating, surface electrochemistry plating and
Vapour deposition process.Surface chemical plating is that metal ion in solution reduction is deposited on plating piece matrix surface using reducing agent to be formed
Coating；Surface electrochemistry plating is that plating piece is connected with the cathode of DC power supply, and the metal material and DC power supply of plating are just
Extremely it is connected, when energized, process of the metal to be plated in cathode surface of solids deposited metal layer or alloy；Vapor deposition is to pass through
Either physically or chemically, make metal deposit in carbon nano tube surface.Surface chemical plating is compared with other two methods, because it has
Equipment is simple, without using extraneous power supply, can become research nickel packet directly the plating on conductor or non-conductive material the advantages that
Cover the prefered method of carbon nanomaterial preparation process.
Nickel coated carbon nano tube compound material is prepared currently with surface chemistry electroplating method, although achieving certain progress,
But existing method is still all also in the stage of fumbling at present, there are manufacturing costs higher, coating uniformity and thickness are difficult to
The problems such as control.Therefore, a kind of feasibility height is researched and developed, manufacturing cost is low, and reaching enables metallic nickel uniformly continuous to be coated on
Carbon nano tube surface and thickness of coating is controllable, the preparation method of the nickel coated carbon nano tube compound material of the smooth densification of clad at
For urgent problem to be solved in industry.
Invention content
The purpose of the present invention prepares nickel coated carbon nanotube composite aiming at existing at present using surface chemical plating
The problems such as process of material is also immature, and there are manufacturing costs higher, coating uniformity and thickness are difficult to control, provides one kind
The preparation method of nickel coated carbon nano tube compound material.
A kind of preparation method of nickel coated carbon nano tube compound material of the present invention, is made of following step successively：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 0.5-2 hours, be transferred in glass container, add
Enter the concentrated nitric acid solution that mass fraction is 69% and submerge carbon nanotube, is stirred at room temperature 12-24 hours, distilled water rushes after filtering
It is washed till neutrality, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 30-40% is added, at room temperature
Stirring 6-12 hours, distilled water flushing is dried to neutrality at 65-75 DEG C after filtering；
（2）In step（1）The sensitizing solution that 40-100 times of carbon nanotube mass is added in carbon nanotube that treated carries out at sensitization
It manages, first opens ultrasonic oscillator 2-10 minutes in activation process, be then turned on magnetic stirring apparatus 2-10 minutes；Mistake after the completion of sensitization
Filter；SnCl in the sensitizing solution2Mass concentration be 20-40g/L, the mass concentration of HCl is 50-200g/L；
（3）60-120 times of activating solution of carbon nanotube mass is added in carbon nanotube after sensitized treatment to be activated, activated
Ultrasonic oscillator is first opened in journey 2-10 minutes, be then turned on magnetic stirring apparatus 5-20 minutes；It is filtered after the completion of activation；The work
Change Pb (NO in liquid3)2Mass concentration be 0.2-0.8g/L, HNO3Mass concentration be 70-280g/L；
（4）The nickel liquid of 150-400 times of carbon nanotube mass is added in carbon nanotube after activation process, then into nickel liquid
The reducing agent that 100-260 times of carbon nanotube mass is added is heated to 65- with pH adjusting agent tune pH to 8.5-9.5 under stirring
It 75 DEG C, is reacted 1-4 hours under magnetic agitation, neutrality is washed with distilled water to after filtering, then be placed in quartz boat in nitrogen protection
Under 4 hours are heat-treated at 380 DEG C to get nickel coated carbon nanotube, the clad uniformly continuous of the nickel coated carbon nanotube,
Smooth densification, metallic nickel grain diameter are 50-150nm；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 10- containing nickel salt in nickel liquid
50g/L, 10-40g/L containing complexing agent, ammonium salt-containing 10-50g/L, the reducing agent are the connection for using mass concentration as 10-50g/L
Ammonia, the pH adjusting agent are that the ammonium hydroxide for being 5-6% by urea and mass fraction is 1 in mass ratio:1 ratio is formulated；It is described
Nickel salt is using arbitrary two kinds in nickel chloride, nickel sulfate or nickel acetate；The ammonium salt is by ammonium chloride and two kinds of originals of ammonium sulfate
Material is formulated；The complexing agent is to use ammonium pyrophosphate or sodium potassium tartrate tetrahydrate.
The ultrasound intensity when ultrasound is 0.35W/m2, supersonic frequency 30KHZ；Magneton rule when the magnetic agitation
Lattice are 20mm, rotating speed 200-500rpm/min.
For the present invention in preparation process, the pretreatment of carbon nanotube is to use agate mill to carry out carbon nanotube first
Grinding makes its dispersion, and concentrated nitric acid is then added in carbon nanotube impregnates carbon nanotube 12-24 hours, makes carbon nano tube surface oxygen
Change and generate carbonyl, hydroxy functional group, improves its surface-active, after filtration and washing is clean, add mass fraction 30-40%'s
Hydrofluoric acid solution, for removing the remaining catalyst of carbon nanotube（It needs to use catalyst in carbon nanotube preparation process, and
Catalyst cannot completely remove, but remaining catalyst influences whether carbon nano tube surface chemical nickel plating efficiency and effect, because
It is first removed it in this present invention）, improve carbon nanotube and metal and its compatibility of compound, improve metallic nickel and carbon nanometer
The binding force of pipe surface；
The sensitization of carbon nanotube is sensitized using homemade sensitizing solution, in the present invention sensitizing solution be using stannous chloride and
Hydrochloric acid solution is formulated, and is hydrolyzed using stannous ion, forms one layer of colloid in carbon nano tube surface, which is easy
Oxidation, large area reflecting point is provided for next step activation process；
The activation of carbon nanotube is activated using homemade activating solution, and activating solution is that palladium nitrate and nitric acid are prepared in the present invention
It forms, nitric acid can control the hydrolysis rate of palladium nitrate in activating solution, and generation is evenly distributed, grain size is small, active strong palladium particle
It uniformly is attached to carbon nano tube surface, uniform catalytic center is provided for next step chemical nickel plating；
Carbon nanotube chemical nickel plating, be use homemade nickel liquid, reducing agent and pH adjusting agent, wherein nickel liquid using nickel salt,
Complexing agent and ammonium salt are formulated, and reducing agent uses hydrazine, pH adjusting agent to be formulated using urea and ammonium hydroxide（Alkali can be controlled
Stablize, gradually decompose, plays the role of stable regulation pH）, the present invention has the characteristics that strong reducing property and weakly alkaline using hydrazine
Nickel salt is restored, using the stability of pH adjusting agent, controls the thickness and uniformity of coating, mixing nickel salt reduction is adjusted and generates nickel list
Matter crystal grain is fine and closely woven and particle size is controllable, and porosity is low, finally forms one layer of uniform, continuous nickel plating in carbon nano tube surface
Layer, and the smooth densification of coating.
Compared with prior art, the present invention having the following advantages that：
（1）By being ground to carbon nanotube, concentrated nitric acid, hydrofluoric acid treatment, make carbon nano tube surface formed high density activation
Point is conducive to subsequently sensitization and activation process；
（2）By carrying out sensitization and activation process to carbon nanotube, good catalytic surface is formed in carbon nano tube surface, favorably
It is deposited in catalytic center in metallic nickel, forms continuous, uniform, compact nickel coating；
（3）By homemade nickel liquid, coordinate hydrazine reducing agent, urea+ammonium hydroxide pH adjusting agent can be with equal control chemical nickel plating
Coating deposition thickness and uniformity, and nickel simple substance size of microcrystal size is controllable, and porosity is low, coating uniformity, continuity,
Binding force is preferable；
（4）Used raw material is marketable material, and concise in technology, is produced convenient for organizational purchasing, and cost is relatively low.
Present invention process is reasonable, significant effect, and nickel coated carbon nano tube surface coating uniformity obtained, continuity are good,
Binding force of cladding material is strong, and metal grain size is controllable, and raw material used is marketable material, is produced convenient for buying and tissue,
It is suitble to promote and apply.
Description of the drawings
Fig. 1 is the SEM photograph of nickel coated carbon nano tube compound material prepared by the embodiment of the present invention 1；
Fig. 2 is the TEM photos of nickel coated carbon nano tube compound material prepared by the embodiment of the present invention 1.
Specific implementation mode
Embodiment 1
A kind of preparation method of nickel coated carbon nano tube compound material, is made of following step successively：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 1 hour, be transferred in glass container, matter is added
It measures the concentrated nitric acid solution that score is 69% and submerges carbon nanotube, be stirred at room temperature 24 hours, distilled water flushing is into after filtering
Property, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 40% is added, it is small to be stirred at room temperature 6
When, distilled water flushing is dried to neutrality at 70 DEG C after filtering；
（2）In step（1）The sensitizing solution that 70 times of carbon nanotube mass is added in carbon nanotube that treated carries out sensitized treatment, quick
Ultrasonic oscillator is first opened during changing 5 minutes, be then turned on magnetic stirring apparatus 4 minutes；It is filtered after the completion of sensitization；The sensitization
SnCl in liquid2Mass concentration be 30g/L, the mass concentration of HCl is 120g/L；
（3）90 times of activating solutions of carbon nanotube mass are added in carbon nanotube after sensitized treatment to be activated, in activation process
It first opens ultrasonic oscillator 6 minutes, is then turned on magnetic stirring apparatus 10 minutes；It is filtered after the completion of activation；Pb in the activating solution
(NO3)2Mass concentration be 0.4g/L, HNO3Mass concentration be 140g/L；
（4）The nickel liquid of 300 times of carbon nanotube mass is added in carbon nanotube after activation process, then is added into nickel liquid
The reducing agent that 200 times of carbon nanotube mass is heated to 70 DEG C, under magnetic agitation with pH adjusting agent tune pH to 9.0 under stirring
Reaction 3 hours, is washed with distilled water to neutrality, then be placed in quartz boat and be heat-treated 4 at 380 DEG C under nitrogen protection after filtering
Hour is 50-70nm to get nickel coated carbon nanotube, nickel coated carbon nano tube compound material obtained, metallic nickel grain diameter,
It forms continuous, uniform nickel coating in carbon nano tube surface, and porosity is small, and clad is smooth fine and close and is combined with carbon nanotube
Closely；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 10g/L containing nickel salt in nickel liquid,
10g/L containing complexing agent, ammonium salt-containing 10g/L, the reducing agent are the hydrazine for using mass concentration as 10g/L, the pH adjusting agent
Be the ammonium hydroxide for being 5-6% by urea and mass fraction it is 1 in mass ratio:1 ratio is formulated；The nickel salt is by nickel acetate
It is 1 in mass ratio with nickel sulfate:1 prepares；It is 4 in mass ratio that the ammonium salt, which is by ammonium chloride and ammonium sulfate,:6 prepare；The network
Mixture is prepared using sodium potassium tartrate tetrahydrate.
The ultrasound intensity when ultrasound is 0.35W/m2, supersonic frequency 30KHZ；Magneton rule when the magnetic agitation
Lattice are 20mm, rotating speed 300rpm/min.
It is the SEM photograph of nickel coated carbon nano tube compound material made from the present embodiment referring to Fig. 1, Fig. 2, Fig. 1, from Fig. 1
As can be seen that the smooth densification of nickel coated layer in carbon nanotube made from the present embodiment；Fig. 2 is nickel coated made from the present embodiment
The TEM photos of carbon nano tube compound material, figure it is seen that metallic nickel can continuously and uniformly be coated on carbon nanotube
Surface, porosity is low, the smooth densification of clad.
Embodiment 2
A kind of preparation method of nickel coated carbon nano tube compound material of the present invention, is made of following step successively：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 1.5 hours, be transferred in glass container, be added
The concentrated nitric acid solution that mass fraction is 69% submerges carbon nanotube, is stirred at room temperature 20 hours, distilled water flushing is into after filtering
Property, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 30% is added, it is small to be stirred at room temperature 12
When, distilled water flushing is dried to neutrality at 65 DEG C after filtering；
（2）In step（1）The sensitizing solution that 100 times of carbon nanotube mass is added in carbon nanotube that treated carries out sensitized treatment,
Ultrasonic oscillator is first opened in activation process 8 minutes, be then turned on magnetic stirring apparatus 8 minutes；It is filtered after the completion of sensitization；It is described quick
Change SnCl in liquid2Mass concentration be 40g/L, the mass concentration of HCl is 200g/L；
（3）120 times of activating solutions of carbon nanotube mass are added in carbon nanotube after sensitized treatment to be activated, in activation process
It first opens ultrasonic oscillator 10 minutes, is then turned on magnetic stirring apparatus 20 minutes；It is filtered after the completion of activation；In the activating solution
Pb(NO3)2Mass concentration be 0.8g/L, HNO3Mass concentration be 280g/L；
（4）The nickel liquid of 400 times of carbon nanotube mass is added in carbon nanotube after activation process, then is added into nickel liquid
The reducing agent that 260 times of carbon nanotube mass is heated to 65 DEG C, under magnetic agitation with pH adjusting agent tune pH to 9.5 under stirring
Reaction 4 hours, is washed with distilled water to neutrality, then be placed in quartz boat and be heat-treated 4 at 380 DEG C under nitrogen protection after filtering
Hour is 70- to get nickel coated carbon nanotube, nickel coated carbon nano tube compound material obtained, metallic nickel grain diameter
110nm forms continuous, uniform nickel coating in carbon nano tube surface, and porosity is small, clad it is smooth fine and close and with carbon nanometer
Pipe is tightly combined；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 40g/L containing nickel salt in nickel liquid,
30g/L containing complexing agent, ammonium salt-containing 50g/L, the reducing agent are the hydrazine for using mass concentration as 50g/L, the pH adjusting agent
Be the ammonium hydroxide for being 5-6% by urea and mass fraction it is 1 in mass ratio:1 ratio is formulated；The nickel salt by nickel chloride and
Nickel sulfate is 6 in mass ratio:4 ratio is prepared；It is 7 in mass ratio that the ammonium salt, which is by ammonium chloride and ammonium sulfate,:3 ratio is matched
System；The complexing agent is prepared using ammonium pyrophosphate.
The ultrasound intensity when ultrasound is 0.35W/m2, supersonic frequency 30KHZ；Magneton rule when the magnetic agitation
Lattice are 20mm, rotating speed 400rpm/min.
Embodiment 3
A kind of preparation method of nickel coated carbon nano tube compound material of the present invention, is made of following step successively：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 0.5 hour, be transferred in glass container, be added
The concentrated nitric acid solution that mass fraction is 69% submerges carbon nanotube, is stirred at room temperature 12 hours, distilled water flushing is into after filtering
Property, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 35% is added, it is small to be stirred at room temperature 10
When, distilled water flushing is dried to neutrality at 75 DEG C after filtering；
（2）In step（1）The sensitizing solution that 40 times of carbon nanotube mass is added in carbon nanotube that treated carries out sensitized treatment, quick
Ultrasonic oscillator is first opened during changing 10 minutes, be then turned on magnetic stirring apparatus 10 minutes；It is filtered after the completion of sensitization；It is described quick
Change SnCl in liquid2Mass concentration be 35g/L, the mass concentration of HCl is 100g/L；
（3）60 times of activating solutions of carbon nanotube mass are added in carbon nanotube after sensitized treatment to be activated, in activation process
It first opens ultrasonic oscillator 10 minutes, is then turned on magnetic stirring apparatus 20 minutes；It is filtered after the completion of activation；In the activating solution
Pb(NO3)2Mass concentration be 0.6g/L, HNO3Mass concentration be 70g/L；
（4）The nickel liquid of 150 times of carbon nanotube mass is added in carbon nanotube after activation process, then is added into nickel liquid
The reducing agent that 150 times of carbon nanotube mass is heated to 75 DEG C, under magnetic agitation with pH adjusting agent tune pH to 8.5 under stirring
Reaction 2 hours, is washed with distilled water to neutrality, then be placed in quartz boat and be heat-treated 4 at 380 DEG C under nitrogen protection after filtering
Hour is 120- to get nickel coated carbon nanotube, nickel coated carbon nano tube compound material obtained, metallic nickel grain diameter
180nm forms continuous, uniform nickel coating in carbon nano tube surface, and porosity is small, clad it is smooth fine and close and with carbon nanometer
Pipe is tightly combined；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 45g/L containing nickel salt in nickel liquid,
35g/L containing complexing agent, ammonium salt-containing 45g/L, the reducing agent are the hydrazine for using mass concentration as 45g/L, the pH adjusting agent
Be the ammonium hydroxide for being 5-6% by urea and mass fraction it is 1 in mass ratio:1 ratio is formulated；The nickel salt is by nickel chloride
It is 6 in mass ratio with nickel acetate:4 ratio is prepared；It is 8 in mass ratio that the ammonium salt, which is by ammonium chloride and ammonium sulfate,:2 ratio
It prepares；The complexing agent is prepared using sodium potassium tartrate tetrahydrate.
The ultrasound intensity when ultrasound is 0.35W/m2, supersonic frequency 30KHZ；Magneton rule when the magnetic agitation
Lattice are 20mm, rotating speed 500rpm/min.
Embodiment 4
A kind of preparation method of nickel coated carbon nano tube compound material of the present invention, is made of following step successively：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 1.5 hours, be transferred in glass container, be added
The concentrated nitric acid solution that mass fraction is 69% submerges carbon nanotube, is stirred at room temperature 15 hours, distilled water flushing is into after filtering
Property, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 35% is added, it is small to be stirred at room temperature 8
When, distilled water flushing is dried to neutrality at 70 DEG C after filtering；
（2）In step（1）The sensitizing solution that 80 times of carbon nanotube mass is added in carbon nanotube that treated carries out sensitized treatment, quick
Ultrasonic oscillator is first opened during changing 2 minutes, be then turned on magnetic stirring apparatus 2 minutes；It is filtered after the completion of sensitization；The sensitization
SnCl in liquid2Mass concentration be 20g/L, the mass concentration of HCl is 50g/L；
（3）100 times of activating solutions of carbon nanotube mass are added in carbon nanotube after sensitized treatment to be activated, in activation process
It first opens ultrasonic oscillator 2 minutes, is then turned on magnetic stirring apparatus 5 minutes；It is filtered after the completion of activation；Pb in the activating solution
(NO3)2Mass concentration be 0.2g/L, HNO3Mass concentration be 200g/L；
（4）The nickel liquid of 150-400 times of carbon nanotube mass is added in carbon nanotube after activation process, then into nickel liquid
The reducing agent that 100 times of carbon nanotube mass is added is heated to 70 DEG C, magnetic force stirs with pH adjusting agent tune pH to 8.5 under stirring
Lower reaction 1 hour is mixed, neutrality is washed with distilled water to after filtering, then is placed in quartz boat hot at 380 DEG C under nitrogen protection
Processing 4 hours is to get nickel coated carbon nanotube, nickel coated carbon nano tube compound material obtained, and metallic nickel grain diameter is
100-150nm forms continuous, uniform nickel coating in carbon nano tube surface, and porosity is small, the smooth fine and close and and carbon of clad
Nanotube is tightly combined；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 10- containing nickel salt in nickel liquid
50g/L, 10-40g/L containing complexing agent, ammonium salt-containing 10-50g/L, the reducing agent are the connection for using mass concentration as 10-50g/L
Ammonia, the pH adjusting agent are that the ammonium hydroxide for being 5-6% by urea and mass fraction is 1 in mass ratio:1 ratio is formulated；It is described
Nickel salt is using arbitrary two kinds in nickel chloride, nickel sulfate or nickel acetate；The ammonium salt is by ammonium chloride and two kinds of originals of ammonium sulfate
Material is formulated；The complexing agent is to use ammonium pyrophosphate or sodium potassium tartrate tetrahydrate.
The ultrasound intensity when ultrasound is 0.35W/m2, supersonic frequency 30KHZ；Magneton rule when the magnetic agitation
Lattice are 20mm, rotating speed 200rpm/min.
Claims (2)
1. a kind of preparation method of nickel coated carbon nano tube compound material, it is characterised in that be made of successively following step：
（1）It weighs appropriate carbon nanotube and is placed in agate mortar formula mill and grind 0.5-2 hours, be transferred in glass container, add
Enter the concentrated nitric acid solution that mass fraction is 69% and submerge carbon nanotube, is stirred at room temperature 12-24 hours, distilled water rushes after filtering
It is washed till neutrality, then carbon nanotube is transferred in plastic containers, the hydrofluoric acid solution that mass fraction is 30-40% is added, at room temperature
Stirring 6-12 hours, distilled water flushing is dried to neutrality at 65-75 DEG C after filtering；
（2）In step（1）The sensitizing solution that 40-100 times of carbon nanotube mass is added in carbon nanotube that treated carries out at sensitization
It manages, first opens ultrasonic oscillator 2-10 minutes in activation process, be then turned on magnetic stirring apparatus 2-10 minutes；Mistake after the completion of sensitization
Filter；SnCl in the sensitizing solution2Mass concentration be 20-40g/L, the mass concentration of HCl is 50-200g/L；
（3）60-120 times of activating solution of carbon nanotube mass is added in carbon nanotube after sensitized treatment to be activated, activated
Ultrasonic oscillator is first opened in journey 2-10 minutes, be then turned on magnetic stirring apparatus 5-20 minutes；It is filtered after the completion of activation；The work
Change Pb (NO in liquid3)2Mass concentration be 0.2-0.8g/L, HNO3Mass concentration be 70-280g/L；
（4）The nickel liquid of 150-400 times of carbon nanotube mass is added in carbon nanotube after activation process, then into nickel liquid
The reducing agent that 100-260 times of carbon nanotube mass is added is heated to 65- with pH adjusting agent tune pH to 8.5-9.5 under stirring
It 75 DEG C, is reacted 1-4 hours under magnetic agitation, neutrality is washed with distilled water to after filtering, then be placed in quartz boat in nitrogen protection
Under 4 hours are heat-treated at 380 DEG C to get nickel coated carbon nanotube, the clad uniformly continuous of the nickel coated carbon nanotube,
Smooth densification, metallic nickel grain diameter are 50-150nm；
Above-mentioned steps（4）Described in nickel liquid be to be formulated by nickel salt, complexing agent and ammonium salt, 10- containing nickel salt in nickel liquid
50g/L, 10-40g/L containing complexing agent, ammonium salt-containing 10-50g/L, the reducing agent are the connection for using mass concentration as 10-50g/L
Ammonia, the pH adjusting agent are that the ammonium hydroxide for being 5-6% by urea and mass fraction is 1 in mass ratio:1 ratio is formulated；It is described
Nickel salt is using arbitrary two kinds in nickel chloride, nickel sulfate or nickel acetate；The ammonium salt is by ammonium chloride and two kinds of originals of ammonium sulfate
Material is formulated；The complexing agent is to use ammonium pyrophosphate or sodium potassium tartrate tetrahydrate.
2. a kind of preparation method of nickel coated carbon nano tube compound material according to claim 1, it is characterised in that：It is described
Ultrasound intensity when ultrasonic is 0.35W/m2, supersonic frequency 30KHZ；Magneton specification when the magnetic agitation is 20mm, is turned
Speed is 200-500rpm/min.
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