CN108546938B - Preparation method of nickel-coated carbon nanotube composite material - Google Patents

Preparation method of nickel-coated carbon nanotube composite material Download PDF

Info

Publication number
CN108546938B
CN108546938B CN201810396627.1A CN201810396627A CN108546938B CN 108546938 B CN108546938 B CN 108546938B CN 201810396627 A CN201810396627 A CN 201810396627A CN 108546938 B CN108546938 B CN 108546938B
Authority
CN
China
Prior art keywords
nickel
nano tube
carbon nano
solution
mass
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.)
Active
Application number
CN201810396627.1A
Other languages
Chinese (zh)
Other versions
CN108546938A (en
Inventor
左小华
邓祥义
邵秀荣
左正
蔺绍江
王小波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Bolin Environmental Protection Technology Co.,Ltd.
Original Assignee
Hubei Polytechnic University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hubei Polytechnic University filed Critical Hubei Polytechnic University
Priority to CN201810396627.1A priority Critical patent/CN108546938B/en
Publication of CN108546938A publication Critical patent/CN108546938A/en
Application granted granted Critical
Publication of CN108546938B publication Critical patent/CN108546938B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • 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
    • 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

Abstract

The invention relates to a preparation method of a nickel-coated carbon nanotube composite material, which comprises the following steps: (1) grinding carbon nano tubes, soaking in concentrated nitric acid, and cleaning with hydrofluoric acid to remove impurities; (2) adding sensitizing solution to sensitize, ultrasonically stirring for 4-20 min, and filtering, wherein the sensitizing solution is prepared from SnCl2And preparing HCl; (3) activating with activating solution prepared from Pb (NO), ultrasonic activating under stirring for 7-30 min, and filtering3)2And HNO3Preparing; (4) adding a nickelating solution and a reducing agent, adjusting the pH value to 8.5-9.5, heating to 65-75 ℃, stirring for reaction for 1-4 hours, filtering and washing to be neutral, and carrying out heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nanotube, wherein the nickelating solution, the reducing agent and the pH regulator are prepared by an inventor; the nickel-coated carbon nanotube composite material prepared by the invention has good coating uniformity and continuity, strong binding force and controllable metal crystal grain size, and is suitable for popularization and application.

Description

Preparation method of nickel-coated carbon nanotube composite material
Technical Field
The invention belongs to the technical field of carbon nanotube composite materials, and particularly relates to a preparation method of a nickel-coated carbon nanotube composite material.
Background
Since 1991, carbon nanotubes have been discovered, due to their unique excellent properties in mechanics, magnetics, electricity, etc., and are widely used in catalyst carriers, nano devices, electrode materials, hydrogen storage materials, etc., since carbon nanotubes have a potentially great application value in many fields, especially have very high axial strength (about 100 times of steel), very large aspect ratio (generally 100 + 1000), large specific surface area, high temperature stability, high wear resistance, and good thermal conductivity, they can be used to prepare novel composite materials with high strength and good stability. The current common research and development direction focuses on the research of metal/carbon nanotube composite materials, and particularly, nickel-coated carbon nanotube composite materials are hot spots of research in recent years.
At present, the preparation methods of the nickel-coated carbon nanotube composite material mainly comprise surface chemical plating, surface electrochemical plating and vapor deposition. The surface chemical plating is that metal ions in a solution are reduced and deposited on the surface of a substrate of a plated piece by utilizing a reducing agent to form a plating layer; the surface electrochemical plating is a process of connecting a plated piece with the negative pole of a direct current power supply, connecting a plated metal material with the positive pole of the direct current power supply, and depositing a metal layer or an alloy on the surface of a cathode solid by the metal to be plated when the direct current power supply is electrified; vapor deposition is the deposition of metal on the surface of carbon nanotubes by physical or chemical means. Compared with other two methods, the surface chemical plating method has the advantages of simple equipment, no need of using an external power supply, direct plating on a conductor or non-conductor material and the like, and becomes a preferred method for researching the preparation process of the nickel-coated carbon nano material.
Although certain progress is made in the preparation of the nickel-coated carbon nanotube composite material by using a surface chemical plating method at present, the existing methods are still in a research stage, and the problems of high preparation cost, difficulty in controlling the uniformity and thickness of a plating layer and the like exist. Therefore, the development of a method for preparing a nickel-coated carbon nanotube composite material, which has high feasibility and low preparation cost, can uniformly and continuously coat the surface of the carbon nanotube with metal nickel, has a controllable coating thickness and a smooth and compact coating layer, is a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel-coated carbon nano tube composite material, aiming at the problems that the existing process method for preparing the nickel-coated carbon nano tube composite material by utilizing surface chemical plating is not mature, the preparation cost is high, the uniformity and the thickness of a plating layer are difficult to control and the like.
The invention relates to a preparation method of a nickel-coated carbon nanotube composite material, which sequentially comprises the following steps of:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 0.5-2 hours, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 12-24 hours at room temperature, filtering, washing with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 30-40%, stirring for 6-12 hours at room temperature, filtering, washing with the distilled water to be neutral, and drying at 65-75 ℃;
(2) adding a sensitizing solution with the mass 40-100 times that of the carbon nano tube into the carbon nano tube treated in the step (1) for sensitizing treatment, wherein in the sensitizing process, an ultrasonic oscillator is started for 2-10 minutes, and then a magnetic stirrer is started for 2-10 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of the (B) is 20-40 g/L, and the mass concentration of the (B) is 50-200 g/L;
(3) adding an activating solution with the mass of 60-120 times that of the carbon nano tube into the sensitized carbon nano tube for activation, starting an ultrasonic oscillator for 2-10 minutes and then starting a magnetic stirrer for 5-20 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2The mass concentration of (A) is 0.2-0.8 g/L3The mass concentration of the (B) is 70-280 g/L;
(4) adding a nickelating solution with the mass of 150-400 times that of the carbon nano tube into the activated carbon nano tube, adding a reducing agent with the mass of 100-260 times that of the carbon nano tube into the nickelating solution, adjusting the pH to 8.5-9.5 by using a pH regulator, heating to 65-75 ℃ under stirring, reacting for 1-4 hours under magnetic stirring, filtering, washing to be neutral by using distilled water, and then placing in a quartz boat for heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nano tube, wherein the coating layer of the nickel-coated carbon nano tube is uniform, continuous, smooth and compact, and the particle size of metal nickel particles is 50-150 nm;
the nickelizing liquid in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, wherein the nickelizing liquid contains 10-50 g/L of nickel salt, 10-40 g/L of complexing agent and 10-50 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 10-50 g/L, the pH regulator is prepared from urea and 5-6% ammonia water in mass ratio of 1:1, the nickel salt is prepared from any two of nickel chloride, nickel sulfate or nickel acetate, the ammonium salt is prepared from two raw materials of ammonium chloride and ammonium sulfate, and the complexing agent is ammonium pyrophosphate or potassium sodium tartrate.
The ultrasonic intensity in the ultrasonic is 0.35W/m2The ultrasonic frequency is 30 KHZ; the magnetic particle specification during magnetic stirring is 20mm, and the rotating speed is 200-.
In the preparation process, the pretreatment of the carbon nano tube comprises the steps of firstly grinding the carbon nano tube by using an agate grinder to disperse the carbon nano tube, then adding concentrated nitric acid into the carbon nano tube to soak the carbon nano tube for 12-24 hours, oxidizing the surface of the carbon nano tube to generate carbonyl and hydroxyl functional groups, improving the surface activity of the carbon nano tube, filtering and washing the carbon nano tube, and then adding a hydrofluoric acid solution with the mass fraction of 30-40% for removing the residual catalyst of the carbon nano tube (the catalyst is required to be used in the preparation process of the carbon nano tube, and cannot be completely removed, but the residual catalyst can influence the chemical nickel plating efficiency and effect on the surface of the carbon nano tube, so that the residual catalyst is removed firstly in the invention), the compatibility of the carbon nano tube with metal and compounds thereof is improved, and the bonding force;
the sensitization of the carbon nano tube is carried out by adopting a self-made sensitization liquid, the sensitization liquid is prepared by adopting stannous chloride and hydrochloric acid solution, stannous ions are utilized for hydrolysis, a layer of colloid is formed on the surface of the carbon nano tube, and the colloid cation is easy to oxidize and provides a large-area reaction point for the next activation treatment;
activating the carbon nano tube by using a self-made activating solution, wherein the activating solution is prepared from palladium nitrate and nitric acid, the nitric acid in the activating solution can control the hydrolysis speed of the palladium nitrate, and palladium particles which are uniformly distributed, small in particle size and strong in activity are uniformly attached to the surface of the carbon nano tube so as to provide a uniform catalytic center for the next step of chemical nickel plating;
the invention relates to a carbon nano tube chemical nickel plating, which adopts self-made nickel plating solution, a reducing agent and a pH regulator, wherein the nickel plating solution is prepared by adopting nickel salt, a complexing agent and ammonium salt, the reducing agent adopts hydrazine, and the pH regulator is prepared by adopting urea and ammonia water (which can control the alkali stability and gradually decompose and play a role in stably regulating the pH).
Compared with the prior art, the invention has the following advantages:
(1) the carbon nano tube is ground, treated by concentrated nitric acid and hydrofluoric acid, so that high-density activation points are formed on the surface of the carbon nano tube, and subsequent sensitization and activation treatment are facilitated;
(2) through sensitizing and activating the carbon nano tube, a good catalytic surface is formed on the surface of the carbon nano tube, which is beneficial to the deposition of metallic nickel at a catalytic center to form a continuous, uniform and tightly combined nickel coating;
(3) the deposition thickness and uniformity of a plating layer of chemical nickel plating can be uniformly controlled by self-made nickel solution, hydrazine reducing agent, urea and ammonia water pH regulator, the grain size of the nickel simple substance grains is controllable, the porosity is low, and the uniformity, continuity and bonding force of the plating layer are good;
(4) the adopted raw materials are all commercially available raw materials, the process is simple, the organization, the purchase and the production are convenient, and the cost is low.
The method has reasonable process and obvious effect, the prepared nickel-coated carbon nano tube has good uniformity and continuity of the surface coating, strong binding force of the coating and controllable metal grain size, and the used raw materials are all commercially available raw materials, so the method is convenient for purchase and tissue production and is suitable for popularization and application.
Drawings
FIG. 1 is an SEM photograph of a nickel-coated carbon nanotube composite material prepared in example 1 of the present invention;
fig. 2 is a TEM photograph of the nickel-coated carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
Example 1
A preparation method of a nickel-coated carbon nanotube composite material sequentially comprises the following steps:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 1 hour, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 24 hours at room temperature, filtering, washing the carbon nanotubes with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 40%, stirring for 6 hours at room temperature, filtering, washing the carbon nanotubes with the distilled water to be neutral, and drying at 70 ℃;
(2) adding a sensitizing solution with the mass of 70 times that of the carbon nano tube into the carbon nano tube treated in the step (1) for sensitizing treatment, wherein in the sensitizing process, an ultrasonic oscillator is started for 5 minutes, and then a magnetic stirrer is started for 4 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of (2) is 30 g/L, and the mass concentration of (3) is 120 g/L;
(3) adding an activation solution which is 90 times of the mass of the carbon nano tube into the sensitized carbon nano tube for activation, starting an ultrasonic oscillator for 6 minutes and then starting a magnetic stirrer for 10 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2Has a mass concentration of 0.4 g/L3The mass concentration of (2) is 140 g/L;
(4) adding a nickelating solution 300 times the mass of the carbon nano tube into the activated carbon nano tube, adding a reducing agent 200 times the mass of the carbon nano tube into the nickelating solution, adjusting the pH to 9.0 by using a pH regulator, heating to 70 ℃ under stirring, reacting for 3 hours under magnetic stirring, filtering, washing to be neutral by using distilled water, placing in a quartz boat, and carrying out heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nano tube, wherein the prepared nickel-coated carbon nano tube composite material has the metal nickel particle size of 50-70nm, forms a continuous and uniform nickel coating on the surface of the carbon nano tube, has small porosity, is smooth and compact in coating and is tightly combined with the carbon nano tube;
the nickel solution in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, wherein the nickel solution contains 10 g/L of nickel salt, 10 g/L of complexing agent and 10 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 10 g/L, the pH regulator is prepared from urea and 5-6% ammonia water according to the mass ratio of 1:1, the nickel salt is prepared from nickel acetate and nickel sulfate according to the mass ratio of 1:1, the ammonium salt is prepared from ammonium chloride and ammonium sulfate according to the mass ratio of 4:6, and the complexing agent is prepared from sodium potassium tartrate.
The ultrasonic intensity in the ultrasonic process is 0.35W/m2The ultrasonic frequency is 30 KHZ; the specification of the magnetons during magnetic stirring is 20mm, and the rotating speed is 300 rpm/min.
Referring to fig. 1 and 2, fig. 1 is an SEM photograph of the nickel-coated carbon nanotube composite material prepared in this example, and it can be seen from fig. 1 that the nickel-coated layer on the carbon nanotube prepared in this example is smooth and dense; fig. 2 is a TEM photograph of the nickel-coated carbon nanotube composite material prepared in this example, and as can be seen from fig. 2, metal nickel can be continuously and uniformly coated on the surface of the carbon nanotube, the porosity is low, and the coating layer is smooth and dense.
Example 2
The invention relates to a preparation method of a nickel-coated carbon nanotube composite material, which sequentially comprises the following steps of:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 1.5 hours, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 20 hours at room temperature, filtering, washing with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 30%, stirring for 12 hours at room temperature, filtering, washing with distilled water to be neutral, and drying at 65 ℃;
(2) adding a sensitizing solution with the mass 100 times that of the carbon nano tube into the carbon nano tube treated in the step (1) for sensitizing treatment, wherein in the sensitizing process, an ultrasonic oscillator is started for 8 minutes first, and then a magnetic stirrer is started for 8 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of (2) is 40 g/L, and the mass concentration of (3) is 200 g/L;
(3) adding an activation solution with the mass of 120 times that of the carbon nano tube into the sensitized carbon nano tube for activation, starting an ultrasonic oscillator for 10 minutes and then starting a magnetic stirrer for 20 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2Has a mass concentration of 0.8 g/L3Has a mass concentration of 280 g/L；
(4) Adding a nickeling liquid with the mass of 400 times that of the carbon nano tube into the carbon nano tube after activation treatment, adding a reducing agent with the mass of 260 times that of the carbon nano tube into the nickeling liquid, adjusting the pH to 9.5 by using a pH regulator, heating to 65 ℃ under stirring, reacting for 4 hours under magnetic stirring, filtering, washing to be neutral by using distilled water, placing in a quartz boat, and carrying out heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nano tube, wherein the prepared nickel-coated carbon nano tube composite material has the metal nickel particle size of 70-110nm, forms a continuous and uniform nickel coating on the surface of the carbon nano tube, has small porosity, is smooth and compact in coating and is tightly combined with the carbon nano tube;
the nickel solution in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, the nickel solution contains 40 g/L of nickel salt, 30 g/L of complexing agent and 50 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 50 g/L, the pH regulator is prepared from urea and 5-6% ammonia water according to the mass ratio of 1:1, the nickel salt is prepared from nickel chloride and nickel sulfate according to the mass ratio of 6:4, the ammonium salt is prepared from ammonium chloride and ammonium sulfate according to the mass ratio of 7:3, and the complexing agent is prepared from ammonium pyrophosphate.
The ultrasonic intensity in the ultrasonic process is 0.35W/m2The ultrasonic frequency is 30 KHZ; the specification of the magnetons during magnetic stirring is 20mm, and the rotating speed is 400 rpm/min.
Example 3
The invention relates to a preparation method of a nickel-coated carbon nanotube composite material, which sequentially comprises the following steps of:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 0.5 hour, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 12 hours at room temperature, filtering, washing with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 35%, stirring for 10 hours at room temperature, filtering, washing with distilled water to be neutral, and drying at 75 ℃;
(2) carbon nano treated in step (1)Adding a sensitizing solution with the mass 40 times that of the carbon nano tube into the rice tube for sensitizing treatment, starting the ultrasonic oscillator for 10 minutes in the sensitizing process, and then starting the magnetic stirrer for 10 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of (2) is 35 g/L, and the mass concentration of (3) is 100 g/L;
(3) adding an activating solution with the mass of 60 times that of the carbon nano tube into the sensitized carbon nano tube for activation, starting the ultrasonic oscillator for 10 minutes and then starting the magnetic stirrer for 20 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2Has a mass concentration of 0.6 g/L3The mass concentration of (A) is 70 g/L;
(4) adding a nickelating solution with the mass of 150 times that of the carbon nano tube into the carbon nano tube after activation treatment, adding a reducing agent with the mass of 150 times that of the carbon nano tube into the nickelating solution, adjusting the pH to 8.5 by using a pH regulator, heating to 75 ℃ under stirring, reacting for 2 hours under magnetic stirring, filtering, washing to be neutral by using distilled water, placing in a quartz boat, and carrying out heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nano tube, wherein the prepared nickel-coated carbon nano tube composite material has the metal nickel particle size of 120-180nm, forms a continuous and uniform nickel coating on the surface of the carbon nano tube, has small porosity, is smooth and compact in coating and is tightly combined with the carbon nano tube;
the nickelizing liquid in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, the nickelizing liquid contains 45 g/L of nickel salt, 35 g/L of complexing agent and 45 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 45 g/L, the pH regulator is prepared from urea and 5-6% ammonia water according to the mass ratio of 1:1, the nickel salt is prepared from nickel chloride and nickel acetate according to the mass ratio of 6:4, the ammonium salt is prepared from ammonium chloride and ammonium sulfate according to the mass ratio of 8:2, and the complexing agent is prepared from sodium potassium tartrate.
The ultrasonic intensity in the ultrasonic process is 0.35W/m2The ultrasonic frequency is 30 KHZ; the specification of the magnetons during magnetic stirring is 20mm, and the rotating speed is 500 rpm/min.
Example 4
The invention relates to a preparation method of a nickel-coated carbon nanotube composite material, which sequentially comprises the following steps of:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 1.5 hours, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 15 hours at room temperature, filtering, washing with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 35%, stirring for 8 hours at room temperature, filtering, washing with distilled water to be neutral, and drying at 70 ℃;
(2) adding a sensitizing solution with the mass of 80 times that of the carbon nano tube into the carbon nano tube treated in the step (1) for sensitizing treatment, wherein in the sensitizing process, an ultrasonic oscillator is started for 2 minutes first, and then a magnetic stirrer is started for 2 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of (A) is 20 g/L, and the mass concentration is 50 g/L;
(3) adding an activating solution with the mass of 100 times that of the carbon nano tube into the sensitized carbon nano tube for activation, starting an ultrasonic oscillator for 2 minutes and then starting a magnetic stirrer for 5 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2Has a mass concentration of 0.2 g/L3The mass concentration of (A) is 200 g/L;
(4) adding a nickelating solution with the mass of 400 times that of the carbon nano tube into the activated carbon nano tube, adding a reducing agent with the mass of 100 times that of the carbon nano tube into the nickelating solution, adjusting the pH to 8.5 by using a pH regulator, heating to 70 ℃ under stirring, reacting for 1 hour under magnetic stirring, filtering, washing to be neutral by using distilled water, placing in a quartz boat, and carrying out heat treatment for 4 hours at 380 ℃ under the protection of nitrogen, so as to obtain the nickel-coated carbon nano tube, wherein the particle size of the metal nickel particle is 150nm, a continuous and uniform nickel coating is formed on the surface of the carbon nano tube, the porosity is small, and the coating is smooth and compact and is tightly combined with the carbon nano tube;
the nickelizing liquid in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, wherein the nickelizing liquid contains 10-50 g/L of nickel salt, 10-40 g/L of complexing agent and 10-50 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 10-50 g/L, the pH regulator is prepared from urea and 5-6% ammonia water in mass ratio of 1:1, the nickel salt is prepared from any two of nickel chloride, nickel sulfate or nickel acetate, the ammonium salt is prepared from two raw materials of ammonium chloride and ammonium sulfate, and the complexing agent is ammonium pyrophosphate or potassium sodium tartrate.
The ultrasonic intensity in the ultrasonic process is 0.35W/m2The ultrasonic frequency is 30 KHZ; the specification of the magnetons during magnetic stirring is 20mm, and the rotating speed is 200 rpm/min.

Claims (2)

1. A preparation method of a nickel-coated carbon nanotube composite material is characterized by sequentially comprising the following steps of:
(1) weighing a proper amount of carbon nanotubes, placing the carbon nanotubes in an agate mortar grinder, grinding for 0.5-2 hours, transferring the carbon nanotubes into a glass container, adding a concentrated nitric acid solution with the mass fraction of 69% to immerse the carbon nanotubes, stirring for 12-24 hours at room temperature, filtering, washing with distilled water to be neutral, transferring the carbon nanotubes into a plastic container, adding a hydrofluoric acid solution with the mass fraction of 30-40%, stirring for 6-12 hours at room temperature, filtering, washing with the distilled water to be neutral, and drying at 65-75 ℃;
(2) adding a sensitizing solution with the mass 40-100 times that of the carbon nano tube into the carbon nano tube treated in the step (1) for sensitizing treatment, wherein in the sensitizing process, an ultrasonic oscillator is started for 2-10 minutes, and then a magnetic stirrer is started for 2-10 minutes; filtering after sensitization is finished; SnCl in the sensitizing solution2The mass concentration of the (B) is 20-40 g/L, and the mass concentration of the (B) is 50-200 g/L;
(3) adding an activating solution with the mass of 60-120 times that of the carbon nano tube into the sensitized carbon nano tube for activation, starting an ultrasonic oscillator for 2-10 minutes and then starting a magnetic stirrer for 5-20 minutes in the activation process; filtering after the activation is finished; pb (NO) in the activating solution3)2The mass concentration of (A) is 0.2-0.8 g/L3The mass concentration of the (B) is 70-280 g/L;
(4) adding a nickelating solution with the mass of 150-400 times that of the carbon nano tube into the activated carbon nano tube, adding a reducing agent with the mass of 100-260 times that of the carbon nano tube into the nickelating solution, adjusting the pH to 8.5-9.5 by using a pH regulator, heating to 65-75 ℃ under stirring, reacting for 1-4 hours under magnetic stirring, filtering, washing to be neutral by using distilled water, and then placing in a quartz boat for heat treatment for 4 hours at 380 ℃ under the protection of nitrogen to obtain the nickel-coated carbon nano tube, wherein the coating layer of the nickel-coated carbon nano tube is uniform, continuous, smooth and compact, and the particle size of metal nickel particles is 50-150 nm;
the nickelizing liquid in the step (4) is prepared from nickel salt, a complexing agent and ammonium salt, wherein the nickelizing liquid contains 10-50 g/L of nickel salt, 10-40 g/L of complexing agent and 10-50 g/L of ammonium salt, the reducing agent adopts hydrazine with the mass concentration of 10-50 g/L, the pH regulator is prepared from urea and 5-6% ammonia water in mass ratio of 1:1, the nickel salt is prepared from any two of nickel chloride, nickel sulfate or nickel acetate, the ammonium salt is prepared from two raw materials of ammonium chloride and ammonium sulfate, and the complexing agent is ammonium pyrophosphate or potassium sodium tartrate.
2. The method of claim 1, wherein the method comprises the following steps: the ultrasonic intensity in the ultrasonic process is 0.35W/m2The ultrasonic frequency is 30 KHZ; the magnetic particle specification during magnetic stirring is 20mm, and the rotating speed is 200-.
CN201810396627.1A 2018-04-28 2018-04-28 Preparation method of nickel-coated carbon nanotube composite material Active CN108546938B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810396627.1A CN108546938B (en) 2018-04-28 2018-04-28 Preparation method of nickel-coated carbon nanotube composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810396627.1A CN108546938B (en) 2018-04-28 2018-04-28 Preparation method of nickel-coated carbon nanotube composite material

Publications (2)

Publication Number Publication Date
CN108546938A CN108546938A (en) 2018-09-18
CN108546938B true CN108546938B (en) 2020-07-14

Family

ID=63513072

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810396627.1A Active CN108546938B (en) 2018-04-28 2018-04-28 Preparation method of nickel-coated carbon nanotube composite material

Country Status (1)

Country Link
CN (1) CN108546938B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074251A (en) * 2018-10-19 2020-04-28 洛阳尖端技术研究院 Wave-absorbing material and preparation method thereof
CN113512188B (en) * 2021-08-06 2022-07-12 宁夏清研高分子新材料有限公司 Low-loss LCP material and preparation method thereof
CN115180660B (en) * 2022-07-07 2023-11-17 湖北理工学院 Synthesis method of flower-shaped hierarchical nano-structure bimetallic sulfide electrode material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1329554C (en) * 2004-01-13 2007-08-01 长沙力元新材料股份有限公司 Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof
CN100564595C (en) * 2007-05-23 2009-12-02 湖北工业大学 The method of multiple-wall carbon nanotube chemical nickel plating on surface zinc
CN101429652B (en) * 2008-07-29 2011-06-08 张建玲 Method for plating nickel on iron powder surface
CN101818337A (en) * 2009-11-16 2010-09-01 兰州理工大学 Coating method of high-density Ni layer of carbon nano tube
CN101701334B (en) * 2009-11-16 2011-09-07 哈尔滨工业大学 Method for plating nickel layer on surface of multiwall carbon nanotube
CN102787308A (en) * 2012-08-09 2012-11-21 汕头大学 Method for carrying out nickel plating coating on MWNT (multi-walled carbon nanotube)
KR20160137178A (en) * 2015-05-22 2016-11-30 성균관대학교산학협력단 METHOD FOR ELECTRICAL CONTACT MATERIALS INCLUDING AG PLATED CNTs
CN106702356B (en) * 2017-01-12 2019-01-18 卜庆革 Electric-conducting polyimide fiber and its product and preparation method

Also Published As

Publication number Publication date
CN108546938A (en) 2018-09-18

Similar Documents

Publication Publication Date Title
CN108546938B (en) Preparation method of nickel-coated carbon nanotube composite material
US8067062B2 (en) Carbon nano tube electrode formed by directly growing carbon nano tube on surface of carbon paper and supporting platinum-based nano catalyst on carbon nano tube using CVD method and manufacturing method thereof
CN100487162C (en) Self assembly chemical silver plating method on non metal material surface
CN102732863B (en) Method for preparing magnetic-field-assisted graphite carbon material chemical plating magnetic metal
CN105947971A (en) Preparation method of ferromagnetic nanowire array
CN108636137B (en) Film composite material loaded with indium zinc sulfide and polyvinylidene fluoride and preparation method thereof
CN109894610B (en) Metal-coated spherical cast tungsten carbide powder and preparation method thereof
CN103436845A (en) Method for coating TiC layer on surface of diamond particles
CN112853409A (en) Silver-containing plating solution and preparation method of foam metal material
CN101157130A (en) A method of preparing nickel silicon carbide complex powder by heavy pressure hydrogen reduction
JP5764294B2 (en) Silver-coated nickel powder and method for producing the same
JP2003034879A (en) Ni-PLATED PARTICLE AND MANUFACTURING METHOD THEREFOR
JPH1161424A (en) Electroless silver-plated powder and its production
JP4063655B2 (en) Conductive electroless plating powder and manufacturing method thereof
CN101758230A (en) Method for chemical plating of metal on particle surface
WO2016023405A1 (en) Method for coating metal nanoparticles on surface of oxide ceramic powder
JP3905014B2 (en) Conductive electroless plating powder and manufacturing method thereof
JP3871653B2 (en) Method for producing conductive fine particles
CN108097949B (en) A kind of production method of tin plating nickel powder
CN116354338A (en) Method for short-time rapid high-temperature thermal shock treatment of MOF surface growth CNTs
JP2006052101A (en) Method of forming metal coating film on ceramic base material surface and metallized ceramic base material
CN107868948A (en) A kind of method of the chemical plating cobalt coated tungsten carbide based on cobalt salt activation
CN103028736A (en) Silver-coated cobalt powder and preparation method thereof
CN112719264A (en) Preparation method of polystyrene/silver composite microspheres
JP2004131800A (en) Conductive electroless plating powder and method for manufacturing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201109

Address after: No. 100-20, Shicheng village, Xinfeng Town, Dantu District, Zhenjiang City, Jiangsu Province, 212000

Patentee after: Jiangsu Bolin Environmental Protection Technology Co.,Ltd.

Address before: 435000 No. 16 Guilin North Road, Hubei, Huangshi

Patentee before: HUBEI POLYTECHNIC University