CN111139461B - Method for chemically plating nickel on surface of graphene - Google Patents
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- CN111139461B CN111139461B CN202010058662.XA CN202010058662A CN111139461B CN 111139461 B CN111139461 B CN 111139461B CN 202010058662 A CN202010058662 A CN 202010058662A CN 111139461 B CN111139461 B CN 111139461B
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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
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- 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
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- 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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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
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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
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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Abstract
The invention relates to a method for chemically plating nickel on the surface of graphene, belonging to the technical field of composite material preparation. According to the method, firstly, surface oil removal and slight corrosion treatment are carried out on graphene so as to improve the deposition efficiency of nickel atoms on the surface of the graphene; then adding other metals with lower potential than the nickel electrode into the chemical plating solution as reaction media, wherein the metals are oxidized and corroded in the plating solution to release electrons, the electrons are transmitted to the graphene through the combined action of mechanical stirring and ultrasound, the nickel atoms in the chemical plating solution are reduced on the surface of the graphene to form an activation center of autocatalytic deposition, then under the coordination action of a reducing agent, a nickel plating layer on the surface gradually grows on the basis of the nickel autocatalytic activation center, and finally a uniform and compact plating layer is formed. The method has the advantages of simple process, low cost, uniform and compact prepared nickel plating layer, high coverage rate and high repeatability, and can be used for mass production under the condition of ensuring high-quality plating layer.
Description
Technical Field
The invention relates to a method for chemically plating nickel on the surface of graphene, belonging to the technical field of composite material preparation.
Background
Graphene is a novel carbon nanomaterial, and is formed by passing sp through carbon atoms2The hybrid orbitals are tightly combined into a honeycomb crystal structure, and the stable structure ensures that the hybrid orbitals have excellent thermal and electrical properties, extremely high Young modulus (1TPa) and breaking strength (125 GPa). Graphene has important application prospects in the aspects of composite materials, micro-nano processing, biomedicine, energy storage batteries and the like, and is considered to be a revolutionary material. However, since graphene is a two-dimensional material and has high surface energy, it is very easy to cause serious agglomeration under the action of van der waals force, which is also the current practical application of graphiteThe main difficulties of (1). Therefore, the method has important significance for carrying out surface modification on the graphene, relieving the agglomeration degree and further improving the dispersion capability of the graphene.
Chemical nickel plating is an important method for modifying the surface of graphene. The nickel has good mechanical strength and ductility, can resist high temperature, has high chemical stability, can not be oxidized in the air, and can play a good protection role in the nano structure of the graphene. However, since graphene atoms are bonded by covalent bonds and the chemical bond of the nickel plating layer is a metal bond, it is difficult to perform uniform and dense plating on the graphene surface by a chemical reduction method. The existing commonly used chemical nickel plating method needs to add graphene into SnCl2And PdCl2In hydrochloric acid solution, chemical reduction plating can be performed after Pd catalytic centers are formed on the surface of graphene through sensitization and activation. Because the noble metal palladium salt is introduced in the process, the preparation cost is high, and the preparation process needs to be cleaned and transferred for many times, so the application is not very convenient. Therefore, the process and method for preparing electroless nickel-plated graphene still need to be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for chemically plating nickel on the surface of graphene, which is mainly based on the relation between electrode potential and metal electron gaining and losing capacity and the autocatalysis phenomenon of nickel, realizes the uniform and compact growth of a nickel plating layer on the surface of graphene, and avoids the use of SnCl2And PdCl2The method has the advantages of simple process, low cost and high repeatability, and can be used for mass production under the condition of ensuring high-quality plating.
The purpose of the invention is realized by the following technical scheme.
A method for chemically plating nickel on the surface of graphene comprises the following steps:
removing oil stains on the surface of graphene, then placing the graphene into an HF solution with the mass fraction of 10% -30% for ultrasonic treatment for 20-40 min, and cleaning and drying the graphene to obtain acid-treated graphene;
soaking a non-powder metal medium with electrode potential lower than nickel in an inorganic acid solution, starting timing when continuous bubbles are generated on the surface of the metal medium, continuing to react for not less than 3min, and then cleaning and drying to obtain an acid-treated metal medium;
uniformly dispersing the acid-treated graphene in chemical plating solution, immersing the acid-treated metal medium in the chemical plating solution, adding a reducing agent when the temperature of the chemical plating solution reaches 50-80 ℃, then reacting for not less than 90min under the combined action of ultrasonic and mechanical stirring, removing the unreacted metal medium, collecting solid powder, cleaning and drying the collected solid powder, and obtaining the nickel-plated graphene.
Wherein the chemical plating solution is a solution with pH of 10-13 prepared from soluble nickel salt, citrate, a pH regulator and deionized water, and Ni2+The concentration of the citrate in the chemical plating solution is 0.04 mol/L-0.07 mol/L, the concentration of the citrate in the chemical plating solution is 0.02 mol/L-0.05 mol/L, and the pH regulator is NaOH, KOH, ammonia water and the like; the reducing agent is hydrazine hydrate, sodium hypophosphite or sodium borohydride; in the process of reaction in the chemical plating solution, the ultrasonic power is 80W-120W, and the stirring speed is 150 r/min-200 r/min.
Further, adding the graphene into an acetone solution with the temperature of 30-50 ℃ for ultrasonic treatment to remove oil stains on the surface of the graphene.
Further, the ultrasonic power of the ultrasonic treatment of the graphene in the HF solution is preferably 80W-120W.
Further, the concentration of graphene in the HF solution is preferably 0.5g/L to 1.0 g/L.
Further, the inorganic acid solution is preferably a hydrochloric acid solution, a sulfuric acid solution, or a nitric acid solution.
Further, the material of the metal medium is preferably iron or aluminum, and the shape of the metal medium can be sheet, block, strip or granule.
Further, the concentration of the acid-treated graphene in the electroless plating solution is preferably 0.03g/L to 0.06 g/L.
Further, the chemical plating solution is a solution with the pH value of 10-13, which is prepared from nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and water, wherein the concentration of the nickel sulfate hexahydrate in the chemical plating solution is 10-18 g/L, and the concentration of the sodium citrate in the chemical plating solution is 5-15 g/L.
Furthermore, the mass fraction of hydrazine hydrate in the chemical plating solution is 3-7%, the concentration of sodium hypophosphite in the chemical plating solution is 15-25 g/L, and the molar ratio of sodium borohydride to nickel ions in the chemical plating solution is 1: (10-1000).
Has the advantages that:
(1) according to the invention, the graphene is subjected to surface oil removal and slight corrosion treatment, so that the deposition efficiency of nickel atoms on the surface of the graphene is improved;
(2) adding other metals with lower potential than that of the nickel electrode into the chemical plating solution as reaction media, wherein the metals are oxidized and corroded in the plating solution to release electrons and are conducted to the graphene through the combined action of mechanical stirring and ultrasound, the nickel atoms in the chemical plating solution are reduced on the surface of the graphene to form an activation center of autocatalytic deposition, then under the coordination action of a reducing agent, a nickel plating layer on the surface grows gradually on the basis of the nickel autocatalytic activation center, and finally a uniform and compact plating layer is formed, so that SnCl can be used for removing the nickel from the chemical plating solution2And PdCl2The plating of nickel on the surface of the graphene is realized under the condition of (1);
(3) the method disclosed by the invention is simple in process and low in cost, and the prepared nickel plating layer is uniform and compact, high in coverage rate and high in repeatability, so that the spontaneous agglomeration degree of graphene is obviously reduced, and the dispersion capability of the graphene is improved.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of acid-treated graphene in example 1.
Fig. 2 is a low-power scanning electron microscope image of the nickel-plated graphene prepared in example 1.
Fig. 3 is a high-power scanning electron microscope image of the nickel-plated graphene prepared in example 1.
Fig. 4 is a graph of energy spectrum analysis of the nickel-plated graphene prepared in example 1.
Fig. 5 is a graph comparing the X-ray diffraction patterns of nickel-plated graphene and nickel-non-plated graphene prepared in example 1.
Fig. 6 is a comparative raman spectrum of nickel-plated graphene and nickel-non-plated graphene prepared in example 1.
Fig. 7 is a high-power scanning electron microscope image of the nickel-plated graphene prepared in example 2.
Fig. 8 is a high-power scanning electron microscope photograph of the nickel-plated graphene prepared in example 3.
Fig. 9 is a high-power scanning electron microscope photograph of the nickel-plated graphene prepared in example 4.
Fig. 10 is a high-power scanning electron microscope photograph of the nickel-plated graphene prepared in example 5.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public perspective unless otherwise specified.
In the following examples:
dilute hydrochloric acid: 15% by mass of hydrochloric acid aqueous solution;
dilute sulfuric acid: 30% by mass of sulfuric acid aqueous solution;
graphene: the purity is 99.7%, the number of layers is 6-11, Suzhou carbofeng graphene Co., Ltd;
hydrazine hydrate: the analysis is pure, and the mass fraction is 80%;
scanning electron microscope: Quanta-200F, U.S. FEI;
x-ray diffractometer: d8 advance, Bruker, germany;
a Raman spectrometer: inVia-Reflex, Renishaw, uk.
Example 1
The specific steps of chemically plating nickel on the surface of the graphene are as follows:
first step, graphene pretreatment
(1.1) adding graphene into an acetone solution at 30 ℃ for ultrasonic treatment for 40min, centrifuging to separate solid from liquid, and washing the collected solid with deionized water to obtain graphene with a clean surface;
(1.2) adding graphene with a clean surface into an HF solution with a mass fraction of 10%, wherein the concentration of the graphene in the HF solution is 0.5g/L, then carrying out ultrasonic treatment for 20min under 120W of ultrasonic power, separating solid from liquid through centrifugation, washing the collected solid with deionized water and ethanol until the pH value of the filtrate is 7, and then drying in a vacuum drying oven at 40 ℃ to obtain acid-treated graphene;
second, electroless plating
(2.1) soaking the iron foil in dilute hydrochloric acid or dilute sulfuric acid, starting timing when continuous bubbles are generated on the surface of the iron foil, continuing to react for 5min, taking out, cleaning and drying to obtain the acid-treated iron foil;
(2.2) preparing chemical plating solution with nickel sulfate hexahydrate concentration of 10g/L, sodium citrate concentration of 5g/L and pH of 10 by nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and deionized water; adding acid-treated graphene into chemical plating solution according to the concentration of 0.03g/L, performing ultrasonic dispersion uniformly, immersing an acid-treated iron foil into the chemical plating solution, hydrolyzing hydrazine hydrate according to the proportion of 1:10 when the temperature of the chemical plating solution reaches 50 ℃, slowly dropping the hydrolyzed hydrazine hydrate into the chemical plating solution until the mass fraction of the hydrazine hydrate in the chemical plating solution is 5%, setting the ultrasonic power to be 120W and the stirring speed to be 200r/min, then reacting for 120min under the combined action of ultrasonic and mechanical stirring, removing the unreacted iron foil, collecting solid powder by using a magnet, cleaning the collected solid powder by using deionized water and ethanol, and then drying in a vacuum drying box at 40 ℃ to obtain the nickel-plated graphene.
As can be seen from fig. 1, the graphene structure after HF solution treatment still remains lamellar, and no significant structural damage occurs, but at this time, the degree of aggregation of graphene is high, and the graphene structure appears as stacked clusters. As can be seen from fig. 2, after the chemical nickel plating is performed on the graphene, the aggregation degree of the graphene is obviously reduced under the protection of the nickel plating layer, the nickel-plated graphene is in a single-sheet shape, and the complete plating rate of the surface of the graphene is very high. As can be seen from fig. 3, the nickel plating layer on the surface of the graphene is uniform and dense. According to fig. 5, the characteristic diffraction peak of graphene in the XRD diffraction spectrum of nickel-plated graphene still exists, which indicates that the graphene structure is well preserved, and only nickel is derived except the characteristic peak of grapheneThe peak emission, combined with fig. 4, indicates that the nickel plating layer has a pure composition and a low degree of oxidation. According to FIG. 6, I in Raman spectra before and after chemical nickel plating of grapheneD/IGThe change is not large, which indicates that the damage degree of the chemical nickel plating process to the special structure of the graphene is very low.
Example 2
The specific steps of chemically plating nickel on the surface of the graphene are as follows:
first step, graphene pretreatment
(1.1) adding graphene into an acetone solution at 40 ℃ for ultrasonic treatment for 30min, centrifuging to separate solid from liquid, and washing the collected solid with deionized water to obtain graphene with a clean surface;
(1.2) adding graphene with a clean surface into an HF solution with the mass fraction of 30%, wherein the concentration of the graphene in the HF solution is 1g/L, then carrying out ultrasonic treatment for 40min under 100W of ultrasonic power, separating solid from liquid through centrifugation, washing the collected solid with deionized water and ethanol until the pH value of filtrate is 7, and then putting the filtrate into a vacuum drying box with the temperature of 40 ℃ for drying to obtain acid-treated graphene;
second, electroless plating
(2.1) soaking the iron foil in dilute hydrochloric acid or dilute sulfuric acid, starting timing when continuous bubbles are generated on the surface of the iron foil, continuing to react for 3min, taking out, cleaning and drying to obtain the acid-treated iron foil;
(2.2) preparing chemical plating solution with nickel sulfate hexahydrate concentration of 13g/L, sodium citrate concentration of 10g/L and pH of 11 by nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and deionized water; adding acid-treated graphene into chemical plating solution according to the concentration of 0.05g/L, performing ultrasonic dispersion uniformly, immersing an acid-treated iron foil into the chemical plating solution, hydrolyzing hydrazine hydrate according to the proportion of 1:10 when the temperature of the chemical plating solution reaches 60 ℃, slowly dropping the hydrolyzed hydrazine hydrate into the chemical plating solution to ensure that the mass fraction of the hydrazine hydrate in the chemical plating solution is 5%, setting the ultrasonic power to be 100W and the stirring rate to be 180r/min, then reacting for 150min under the combined action of ultrasonic and mechanical stirring, removing the unreacted iron foil, collecting solid powder by using a magnet, cleaning the collected solid powder by using deionized water and ethanol, and then drying in a vacuum drying box at 40 ℃ to obtain the nickel-plated graphene.
As can be seen from fig. 7, the nickel plating layer on the surface of the graphene is uniform and dense. XRD, energy spectrum and Raman characterization show that the nickel coating is pure in component and low in oxidation degree, and the damage degree of the chemical nickel plating process to the graphene characteristic structure is low.
Example 3
The specific steps of chemically plating nickel on the surface of the graphene are as follows:
first step, graphene pretreatment
(1.1) adding graphene into an acetone solution at 50 ℃ for ultrasonic treatment for 20min, centrifuging to separate solid from liquid, and washing the collected solid with deionized water to obtain graphene with a clean surface;
(1.2) adding graphene with a clean surface into an HF solution with the mass fraction of 20%, wherein the concentration of the graphene in the HF solution is 0.8g/L, then carrying out ultrasonic treatment for 30min under the ultrasonic power of 80W, separating solid from liquid through centrifugation, washing the collected solid with deionized water and ethanol until the pH value of the filtrate is 7, and then drying in a vacuum drying oven at 40 ℃ to obtain acid-treated graphene;
second, electroless plating
(2.1) soaking the iron foil in dilute hydrochloric acid or dilute sulfuric acid, starting timing when continuous bubbles are generated on the surface of the iron foil, continuing to react for 4min, taking out, cleaning and drying to obtain the acid-treated iron foil;
(2.2) preparing chemical plating solution with nickel sulfate hexahydrate concentration of 18g/L, sodium citrate concentration of 15g/L and pH of 13 by using nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and deionized water; adding acid-treated graphene into chemical plating solution according to the concentration of 0.06g/L, performing ultrasonic dispersion uniformly, immersing an acid-treated iron foil into the chemical plating solution, hydrolyzing hydrazine hydrate according to the proportion of 1:10 when the temperature of the chemical plating solution reaches 80 ℃, slowly dropping the hydrolyzed hydrazine hydrate into the chemical plating solution until the mass fraction of the hydrazine hydrate in the chemical plating solution is 5%, setting the ultrasonic power at 80W and the stirring rate at 150r/min, then reacting for 100min under the combined action of ultrasonic and mechanical stirring, removing the unreacted iron foil, collecting solid powder by using a magnet, cleaning the collected solid powder by using deionized water and ethanol, and then drying in a vacuum drying oven at 40 ℃ to obtain the nickel-plated graphene.
As can be seen from fig. 8, the nickel plating layer on the surface of the graphene is uniform and dense. XRD, energy spectrum and Raman characterization show that the nickel coating is pure in component and low in oxidation degree, and the damage degree of the chemical nickel plating process to the graphene characteristic structure is low.
Example 4
The specific steps of chemically plating nickel on the surface of the graphene are as follows:
first step, graphene pretreatment
(1.1) adding graphene into an acetone solution at 40 ℃ for ultrasonic treatment for 30min, centrifuging to separate solid from liquid, and washing the collected solid with deionized water to obtain graphene with a clean surface;
(1.2) adding graphene with a clean surface into an HF solution with the mass fraction of 20%, wherein the concentration of the graphene in the HF solution is 0.6g/L, then carrying out ultrasonic treatment for 40min under 100W of ultrasonic power, separating solid from liquid through centrifugation, washing the collected solid with deionized water and ethanol until the pH value of the filtrate is 7, and then drying in a vacuum drying oven at 40 ℃ to obtain acid-treated graphene;
second, electroless plating
(2.1) soaking the iron foil in dilute hydrochloric acid or dilute sulfuric acid, starting timing when continuous bubbles are generated on the surface of the iron foil, continuing to react for 3min, taking out, cleaning and drying to obtain the acid-treated iron foil;
(2.2) preparing chemical plating solution with nickel sulfate hexahydrate concentration of 13g/L, sodium citrate concentration of 10g/L and pH of 11 by nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and deionized water; adding acid-treated graphene into chemical plating solution according to the concentration of 0.04g/L, performing ultrasonic dispersion uniformly, immersing acid-treated iron foil into the chemical plating solution, slowly dropping sodium hypophosphite solution into the chemical plating solution when the temperature of the chemical plating solution reaches 70 ℃, enabling the concentration of sodium hypophosphite in the chemical plating solution to be 20g/L, setting the ultrasonic power to be 100W and the stirring speed to be 200r/min, then reacting for 90min under the combined action of ultrasonic and mechanical stirring, removing unreacted iron foil, collecting solid powder by using a magnet, cleaning the collected solid powder by using deionized water and ethanol, and then drying in a vacuum drying oven at 40 ℃ to obtain the nickel-plated graphene.
As can be seen from fig. 9, the nickel plating layer on the graphene surface is uniform and dense. XRD, energy spectrum and Raman characterization show that the nickel coating is pure in component and low in oxidation degree, and the damage degree of the chemical nickel plating process to the graphene characteristic structure is low.
Example 5
The specific steps of chemically plating nickel on the surface of the graphene are as follows:
first step, graphene pretreatment
(1.1) adding graphene into an acetone solution at 40 ℃ for ultrasonic treatment for 30min, centrifuging to separate solid from liquid, and washing the collected solid with deionized water to obtain graphene with a clean surface;
(1.2) adding graphene with a clean surface into an HF solution with the mass fraction of 30%, wherein the concentration of the graphene in the HF solution is 0.7g/L, then carrying out ultrasonic treatment for 30min under 100W of ultrasonic power, separating solid from liquid through centrifugation, washing the collected solid with deionized water and ethanol until the pH value of the filtrate is 7, and then drying in a vacuum drying oven at 40 ℃ to obtain acid-treated graphene;
second, electroless plating
(2.1) soaking the aluminum sheet in dilute hydrochloric acid or dilute sulfuric acid, timing when continuous bubbles are generated on the surface of the aluminum sheet, continuously reacting for 5min, taking out, cleaning and drying to obtain an acid-treated aluminum sheet;
(2.2) preparing chemical plating solution with nickel sulfate hexahydrate concentration of 13g/L, sodium citrate concentration of 10g/L and pH of 12 by nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and deionized water; adding acid-treated graphene into chemical plating solution according to the concentration of 0.05g/L, performing ultrasonic dispersion uniformly, immersing an acid-treated aluminum sheet into the chemical plating solution, hydrolyzing hydrazine hydrate according to the proportion of 1:10 when the temperature of the chemical plating solution reaches 70 ℃, slowly dropping the hydrolyzed hydrazine hydrate into the chemical plating solution to ensure that the mass fraction of the hydrazine hydrate in the chemical plating solution is 5%, setting the ultrasonic power to be 100W and the stirring rate to be 180r/min, then reacting for 130min under the combined action of ultrasonic and mechanical stirring, removing unreacted aluminum sheet, collecting solid powder by using a magnet, cleaning the collected solid powder by using deionized water and ethanol, and then placing the cleaned solid powder into a vacuum drying box at 40 ℃ for drying to obtain the nickel-plated graphene.
As can be seen from fig. 10, the nickel plating layer on the surface of the graphene is uniform and dense. XRD, energy spectrum and Raman characterization show that the nickel coating is pure in component and low in oxidation degree, and the damage degree of the chemical nickel plating process to the graphene characteristic structure is low.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for chemically plating nickel on the surface of graphene is characterized by comprising the following steps: the steps of the method are as follows,
removing oil stains on the surface of graphene, then placing the graphene into an HF solution with the mass fraction of 10% -30% for ultrasonic treatment for 20-40 min, and cleaning and drying the graphene to obtain acid-treated graphene;
soaking a non-powder metal medium with electrode potential lower than nickel in an inorganic acid solution, starting timing when continuous bubbles are generated on the surface of the metal medium, continuing to react for not less than 3min, and then cleaning and drying to obtain an acid-treated metal medium;
uniformly dispersing the acid-treated graphene in chemical plating solution, immersing the acid-treated metal medium in the chemical plating solution, adding a reducing agent when the temperature of the chemical plating solution reaches 50-80 ℃, then reacting for not less than 90min under the combined action of ultrasonic and mechanical stirring, removing the unreacted metal medium, collecting solid powder, cleaning and drying the solid powder to obtain nickel-plated graphene;
wherein the metal medium is made of iron or aluminum;
the chemical plating solution is a solution with the pH value of 10-13, which is prepared from soluble nickel salt, citrate, a pH regulator and deionized water, and Ni2+The concentration of the citrate in the chemical plating solution is 0.04 mol/L-0.07 mol/L, the concentration of the citrate in the chemical plating solution is 0.02 mol/L-0.05 mol/L, and the pH regulator is NaOH, KOH or ammonia water; the reducing agent is hydrazine hydrate, sodium hypophosphite or sodium borohydride; in the process of reaction in the chemical plating solution, the ultrasonic power is 80W-120W, and the stirring speed is 150 r/min-200 r/min.
2. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: and adding the graphene into an acetone solution at the temperature of 30-50 ℃ for ultrasonic treatment to remove oil stains on the surface of the graphene.
3. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the ultrasonic power of the ultrasonic treatment of the graphene in the HF solution is 80-120W.
4. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the concentration of the graphene in the HF solution is 0.5 g/L-1.0 g/L.
5. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the inorganic acid solution is hydrochloric acid solution, sulfuric acid solution or nitric acid solution.
6. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the metal medium is in the shape of a sheet, a block, a strip or a particle.
7. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the concentration of the acid-treated graphene in the chemical plating solution is 0.03-0.06 g/L.
8. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: the chemical plating solution is a solution with the pH value of 10-13, which is prepared from nickel sulfate hexahydrate, sodium citrate, sodium hydroxide and water, wherein the concentration of the nickel sulfate hexahydrate in the chemical plating solution is 10-18 g/L, and the concentration of the sodium citrate in the chemical plating solution is 5-15 g/L.
9. The method for chemically plating nickel on the surface of the graphene according to claim 1, wherein the method comprises the following steps: when the reducing agent is hydrazine hydrate, the mass fraction of the hydrazine hydrate in the chemical plating solution is 3 to 7 percent; when the reducing agent is sodium hypophosphite, the concentration of the sodium hypophosphite in the chemical plating solution is 15 g/L-25 g/L; when the reducing agent is sodium borohydride, the molar ratio of the sodium borohydride to the nickel ions in the chemical plating solution is 1: (10-1000).
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| CN111781152B (en) * | 2020-07-10 | 2021-05-11 | 德州学院 | Graphene-sensitized optical fiber lactic acid sensor and preparation method thereof |
| CN114703468A (en) * | 2022-03-21 | 2022-07-05 | 晶澳（扬州）太阳能科技有限公司 | Method for plating nickel layer on silicon substrate and preparation method of solar cell nickel electrode |
| CN114952073A (en) * | 2022-05-09 | 2022-08-30 | 广西大学 | Preparation method of nickel-plated graphene reinforced tin-based soldering paste |
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