CN110453206B - Metal-sandwiched layer flake graphite and preparation method and application thereof - Google Patents
Metal-sandwiched layer flake graphite and preparation method and application thereof Download PDFInfo
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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
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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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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- 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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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
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The invention discloses a preparation method of metal layer sandwiched crystalline flake graphite, which comprises the following steps: carrying out sensitization and activation treatment on the layered flake graphite in sequence, so that metal Pd is adsorbed on the surface and the interlayer of the flake graphite, and a nucleation site is formed on the metal Pd; and plating metal layers on the surfaces and the layers of the layered flake graphite by a chemical plating method to obtain the metal-sandwiched flake graphite. The invention also discloses the metal layer-sandwiched flake graphite prepared by the method and application thereof. When the metal layer-sandwiched flake graphite prepared by the method is used for a copper-based composite material, the bonding strength of the flake graphite and a copper matrix can be improved.
Description
Technical Field
The invention relates to the technical field of new material preparation, in particular to metal layer-sandwiched crystalline flake graphite, and a preparation method and application thereof.
Background
The graphite is an allotrope of carbon, has grey black color and greasy feeling, has a hexagonal layered flaky crystal structure, has strong bonding force between atoms in a single layer and low pi bond bonding force between layers, and is easy to break to generate relative slippage; light weight (density of 2.2-2.3 g/cm)3) The melting point is up to 3527 ℃, the heat resistance temperature in air is 454 ℃, and no chemical reaction occurs between the rubber and metal. At normal temperature, after the pi bonds between the graphite layers are broken, a cleavage plane is formed, the cleavage plane has certain adsorption capacity to gas in the air, the cleavage plane is the support of the lubricating performance of the graphite, and the lubricating performance of the cleavage plane is still kept good at the temperature of 638 ℃.
Graphite has the advantages of excellent lubricity, high thermal conductivity, damping capacity, high temperature stability and the like, and is regarded as the most common solid lubricant in copper-based friction materials. The addition of graphite to the copper-based friction material can reduce metal-metal direct contact between friction pairs and form a graphite-rich transfer layer between the friction pairs to improve the working stability, scratch resistance, seizure resistance, adhesion resistance and wear resistance of the friction material. However, the density difference between graphite and copper is very different, the two powders are uniformly mixed by a traditional method, the graphite and the copper are not mutually soluble in a solid phase and a liquid phase, and the characteristic of mutual non-wetting can cause poor bonding strength of the graphite and the copper interface in the sintered composite material and reduce the mechanical property and the frictional wear property of the graphite-copper-based composite material. According to the reports of the relevant literatures, the most common method for solving the problems at present is graphite surface metallization, such as applying a Cu layer, a Ni layer and other metal coatings on the graphite surface. However, this method is often only effective in improving the bonding strength of graphite with smaller size and copper, such as spheroidal graphite, graphite powder or graphite fiber. When the graphite size is larger than a certain value, the method can not effectively improve the interface bonding strength as the surface metallization of the small-size graphite. Therefore, the structure of the flake graphite needs to be designed to improve the bonding strength with the copper matrix.
Disclosure of Invention
The invention aims to provide metal-sandwiched flake graphite to improve the bonding strength of the flake graphite and a copper matrix.
In order to solve the technical problem, the invention provides a preparation method of metal layer-sandwiched crystalline flake graphite, which comprises the following steps:
carrying out sensitization and activation treatment on the layered flake graphite in sequence, so that metal Pd is adsorbed on the surface and the interlayer of the flake graphite, and a nucleation site is formed on the metal Pd; and
and plating metal layers on the surfaces and the layers of the layered flake graphite by a chemical plating method to obtain the metal-sandwiched flake graphite.
Further, the layered flake graphite is prepared by the following steps:
uniformly mixing natural crystalline flake graphite with mixed acid and an oxidant, and stirring and reacting for 1-2 hours at the temperature of 30-40 ℃; and after the reaction is finished, washing the natural crystalline flake graphite, filtering, drying, and then preserving heat at 300-400 ℃ for 1-2 min to obtain the layered crystalline flake graphite.
Further, the size of the natural crystalline flake graphite is 100-300 mu m.
Further, the mixed acid is formed by mixing perchloric acid and phosphoric acid, and the volume ratio of the perchloric acid to the phosphoric acid is 3-6: 0.5-1.5; the oxidant is potassium permanganate.
Furthermore, the content ratio of the mixed acid, the potassium permanganate and the natural crystalline flake graphite is (3.5-7.5 ml), (0.2-0.6 g) and (3-5 g).
In the invention, the activation is to make the surface of the flake graphite adsorb a layer of metal Pd, wherein the Pd is a strong catalytic active metal, and in the chemical plating metal plating process, the metal plating layer takes the Pd as a center to nucleate and grow up, so that the chemical plating process can be smoothly carried out; the adsorption of metal Pd is realized by adsorbing Pd on the surface of the carbon fiber after sensitization treatment by virtue of Sn (OH) Cl colloid2+Reducing the obtained product. Further, the formulation of the sensitizing solution is: SnCl220-30 g/L; 37wt% of HCl, 30-50 mL/L; the rest is deionized water; the formula of the activating solution is as follows: PdCl20.1-0.3 g/L; 37wt% of HCl, 3-6 mL/L; the remainder was deionized water.
Furthermore, the metal layer is made of one of Cu, Ni, Co and Ag.
Further, the formula of the electroless Cu plating solution is as follows: 14-18 g/L of copper sulfate pentahydrate; 20-30 g/L of disodium ethylene diamine tetraacetate; 15-25 g/L of potassium sodium tartrate; formaldehyde solution of 12-16 mL/L; the balance of deionized water; the pH regulator is 50wt.% NaOH solution, and the pH value of the solution is regulated to 13.5-14; the temperature of chemical plating Cu is 30-45 ℃;
the chemical Ni-plating solution comprises the following components: 25-35 g/L of nickel sulfate hexahydrate; 18-22 g/L sodium hypophosphite; 20-30 g/L of sodium citrate; 18-22 g/L of ammonium chloride; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 8-9; the temperature of chemical plating Ni is 65-80 ℃;
the formula of the chemical Co plating solution is as follows: 15-25 g/L of cobalt sulfate; 20-40 g/L sodium hypophosphite; 20-35 g/L of sodium citrate; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 8-13; the temperature of the chemical Co plating is 75-85 ℃;
the chemical Ag plating solution formula is as follows: silver nitrate, 12-18 g/L; 10-15 g/L of potassium hydroxide; 15-25 g/L of glucose; 40-60 mL/L ethanol; 15-25 g/L of potassium sodium tartrate; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 13.5-14; the chemical Ag plating temperature is 30-40 ℃.
Further, the method also comprises the steps of cleaning and drying the metal-sandwiched layer crystalline flake graphite obtained after chemical plating in an alcohol solution.
The invention also provides the metal-sandwiched layer crystalline flake graphite prepared by the method.
The invention also provides application of the metal-sandwiched layer crystalline flake graphite in preparation of a copper-based composite material.
The invention has the beneficial effects that:
the preparation method of the invention can apply metal layers on the surface of the flake graphite and between flake graphite layers, thereby solving the problem that the coating is easy to separate from the graphite because the traditional flake graphite only applies a metal coating on the surface; meanwhile, the invention has simple process and low preparation cost, and is suitable for industrial scale use.
Drawings
FIG. 1 is an SEM topography of a raw material flake graphite;
FIG. 2 is an SEM topography of the layered flake graphite prepared in example 1;
FIG. 3 is an SEM topography of the intercalated metal layer flake graphite prepared in example 1;
fig. 4 is an EDS image of the graphite surface intercalated with metallic copper layer flakes prepared in example 1.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
The embodiment discloses a preparation method of metal-sandwiched copper flake graphite, which comprises the following steps:
the first step is as follows: preparation of layered flake graphite
(1) Under the room temperature environment, 5ml perchloric acid and 1ml phosphoric acid are put into a glass beaker and mixed evenly to obtain mixed acid, then 0.4g potassium permanganate is added and stirred slowly to dissolve the mixed acid, and finally 4g crystalline flake graphite is added and stirred fully to mix evenly. Placing a glass beaker filled with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite into a constant-temperature water bath box with the water temperature of 40 ℃ for reaction for 60min, and continuously stirring during the reaction to ensure uniform reaction. After the reaction is finished, washing with water for many times, filtering out the precipitated crystalline flake graphite and drying at 60 ℃. And finally, putting the obtained crystalline flake graphite into a muffle furnace, heating the muffle furnace to 300 ℃, and preserving the heat for 60 s. And turning off a power supply of the muffle furnace, and taking the crystalline flake graphite out of the muffle furnace when the temperature in the muffle furnace is reduced to be below 100 ℃ to obtain the layered crystalline flake graphite. The original morphology of the flake graphite is shown in fig. 1, and the morphology of the obtained layered flake graphite is shown in fig. 2.
The second step is that: layered flake graphite sensitization and activation treatment
And (3) putting the crystalline flake graphite obtained by the first step of treatment into a sensitizing solution, continuously stirring, taking out after 15min, cleaning by using deionized water, and airing at room temperature. The proportion of the sensitizing solution is as follows: SnCl220 g/L; 37wt% HCl, 40 mL/L; the remainder was deionized water. Putting the sensitized crystalline flake graphite into an activation solution, continuously stirring, taking out after 15min, cleaning by deionized water, and airing at room temperature; the activating solution is prepared by the following steps: PdCl20.2 g/L; 37wt% HCl, 5 mL/L; the remainder was deionized water.
The third step: preparation of graphite with copper flakes
And plating a metal copper layer on the surface of the layered flake graphite and between graphite layers by adopting a chemical plating method. The chemical plating Cu solution is composed of copper sulfate pentahydrate, 16 g/L; 25g/L of ethylene diamine tetraacetic acid disodium salt; 20g/L of potassium sodium tartrate; formaldehyde solution, 13mL/L, and the balance of deionized water. And heating the constant-temperature water bath tank to 35 ℃, preserving heat for 10 minutes, then adding 50wt.% of NaOH solution to adjust the pH value of the solution to 13.5-14, preserving heat for 30 minutes and continuously stirring.
The fourth step: post-plating treatment
And taking the metal layer-sandwiched flake graphite obtained in the third step out of the water bath box, immediately putting the metal layer-sandwiched flake graphite into an ethanol solution for ultrasonic cleaning, and drying the metal layer-sandwiched flake graphite in a drying box.
The morphology of the obtained metal-sandwiched copper flake graphite is shown in fig. 3, and it can be seen from the figure that the surface of the flake graphite is coated by a metal coating. Referring to fig. 4, EDS analysis of the flake graphite surface shows that the metal coating on the flake graphite surface is copper coating.
Example 2
The embodiment discloses a preparation method of metal-sandwiched copper flake graphite, which comprises the following steps:
the first step is as follows: preparation of layered flake graphite
(1) Under the room temperature environment, 3ml perchloric acid and 1.5ml phosphoric acid are put into a glass beaker and mixed evenly to obtain mixed acid, then 0.5g potassium permanganate is added and stirred slowly to dissolve the mixed acid, and finally 3g crystalline flake graphite is added and stirred fully to mix evenly. Placing a glass beaker filled with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite into a constant-temperature water bath box with the water temperature of 40 ℃ for reaction for 60min, and continuously stirring during the reaction to ensure uniform reaction. After the reaction is finished, washing with water for many times, filtering out the precipitated crystalline flake graphite and drying at 60 ℃. And finally, putting the obtained crystalline flake graphite into a muffle furnace, heating the muffle furnace to 300 ℃, and preserving the heat for 60 s. And turning off a power supply of the muffle furnace, and taking the crystalline flake graphite out of the muffle furnace when the temperature in the muffle furnace is reduced to be below 100 ℃ to obtain the layered crystalline flake graphite.
The second step is that: layered flake graphite sensitization and activation treatment
And (3) putting the crystalline flake graphite obtained by the first step of treatment into a sensitizing solution, continuously stirring, taking out after 15min, cleaning by using deionized water, and airing at room temperature. The proportion of the sensitizing solution is as follows: SnCl220 g/L; 37wt% HCl, 40 mL/L; the remainder was deionized water. Putting the sensitized crystalline flake graphite into an activation solution, continuously stirring, taking out after 15min, cleaning by deionized water, and airing at room temperature; activity deviceThe chemical solution is prepared by the following steps: PdCl20.2 g/L; 37wt% HCl, 5 mL/L; the remainder was deionized water.
The third step: preparation of graphite with copper flakes
And plating a metal copper layer on the surface of the layered flake graphite and between graphite layers by adopting a chemical plating method. The chemical copper plating solution comprises the following components: copper sulfate pentahydrate, 18 g/L; disodium ethylene diamine tetraacetate, 22 g/L; 20g/L of potassium sodium tartrate; formaldehyde solution, 15mL/L, and the balance of deionized water. And heating the constant-temperature water bath tank to 35 ℃, preserving heat for 10 minutes, then adding 50wt.% of NaOH solution to adjust the pH value of the solution to 13.5-14, preserving heat for 30 minutes and continuously stirring.
The fourth step: post-plating treatment
And taking the metal layer-sandwiched flake graphite obtained in the third step out of the water bath box, immediately putting the metal layer-sandwiched flake graphite into an ethanol solution for ultrasonic cleaning, and drying the metal layer-sandwiched flake graphite in a drying box.
Example 3
The embodiment discloses a preparation method of metal-sandwiched nickel flake graphite, which comprises the following steps:
the first step is as follows: preparation of layered flake graphite
(1) Under the room temperature environment, 5ml perchloric acid and 1ml phosphoric acid are put into a glass beaker and mixed evenly to obtain mixed acid, then 0.4g potassium permanganate is added and stirred slowly to dissolve the mixed acid, and finally 4g crystalline flake graphite is added and stirred fully to mix evenly. Placing a glass beaker filled with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite into a constant-temperature water bath box with the water temperature of 40 ℃ for reaction for 60min, and continuously stirring during the reaction to ensure uniform reaction. After the reaction is finished, washing with water for many times, filtering out the precipitated crystalline flake graphite and drying at 60 ℃. And finally, putting the obtained crystalline flake graphite into a muffle furnace, heating the muffle furnace to 300 ℃, and preserving the heat for 60 s. And turning off a power supply of the muffle furnace, and taking the crystalline flake graphite out of the muffle furnace when the temperature in the muffle furnace is reduced to be below 100 ℃ to obtain the layered crystalline flake graphite.
The second step is that: layered flake graphite sensitization and activation treatment
The flake graphite obtained by the first step of treatmentPutting into sensitizing solution, stirring, taking out after 15min, cleaning with deionized water, and air drying at room temperature. The proportion of the sensitizing solution is as follows: SnCl220 g/L; 37wt% HCl, 40 mL/L; the remainder was deionized water. Putting the sensitized crystalline flake graphite into an activation solution, continuously stirring, taking out after 15min, cleaning by deionized water, and airing at room temperature; the activating solution is prepared by the following steps: PdCl20.2 g/L; 37wt% HCl, 5 mL/L; the remainder was deionized water.
The third step: preparation of metal-sandwiched nickel flake graphite
And plating a metal nickel layer on the surface of the layered flake graphite and between graphite layers by adopting a chemical plating method. The chemical nickel plating solution comprises 30g/L of nickel sulfate hexahydrate; sodium hypophosphite, 20 g/L; 25g/L of sodium citrate; ammonium chloride, 20 g/L; the balance of deionized water. And heating the constant-temperature water bath tank to 75 ℃, preserving heat for 10 minutes, then adding an ammonia water solution to adjust the pH value of the solution to 8-9, preserving heat for 30 minutes and continuously stirring.
The fourth step: post-plating treatment
And taking the metal layer-sandwiched flake graphite obtained in the third step out of the water bath box, immediately putting the metal layer-sandwiched flake graphite into an ethanol solution for ultrasonic cleaning, and drying the metal layer-sandwiched flake graphite in a drying box.
Example 4
The embodiment discloses a preparation method of metal-sandwiched cobalt flake graphite, which comprises the following steps:
the first step is as follows: preparation of layered flake graphite
(1) Under the room temperature environment, 5ml perchloric acid and 1ml phosphoric acid are put into a glass beaker and mixed evenly to obtain mixed acid, then 0.4g potassium permanganate is added and stirred slowly to dissolve the mixed acid, and finally 4g crystalline flake graphite is added and stirred fully to mix evenly. Placing a glass beaker filled with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite into a constant-temperature water bath box with the water temperature of 40 ℃ for reaction for 60min, and continuously stirring during the reaction to ensure uniform reaction. After the reaction is finished, washing with water for many times, filtering out the precipitated crystalline flake graphite and drying at 60 ℃. And finally, putting the obtained crystalline flake graphite into a muffle furnace, heating the muffle furnace to 300 ℃, and preserving the heat for 60 s. And turning off a power supply of the muffle furnace, and taking the crystalline flake graphite out of the muffle furnace when the temperature in the muffle furnace is reduced to be below 100 ℃ to obtain the layered crystalline flake graphite.
The second step is that: layered flake graphite sensitization and activation treatment
And (3) putting the crystalline flake graphite obtained by the first step of treatment into a sensitizing solution, continuously stirring, taking out after 15min, cleaning by using deionized water, and airing at room temperature. The proportion of the sensitizing solution is as follows: SnCl220 g/L; 37wt% HCl, 40 mL/L; the remainder was deionized water. Putting the sensitized crystalline flake graphite into an activation solution, continuously stirring, taking out after 15min, cleaning by deionized water, and airing at room temperature; the activating solution is prepared by the following steps: PdCl20.2 g/L; 37wt% HCl, 5 mL/L; the remainder was deionized water.
The third step: preparation of metal-sandwiched cobalt flake graphite
And plating a metal cobalt layer on the surface of the layered flake graphite and between graphite layers by adopting a chemical plating method. The chemical nickel plating solution is prepared from 20g/L of cobalt sulfate; 30g/L of sodium hypophosphite; 28g/L of sodium citrate; the balance of deionized water. And heating the constant-temperature water bath tank to 85 ℃, preserving heat for 10 minutes, then adding an ammonia water solution to adjust the pH value of the solution to 8-13, preserving heat for 30 minutes and continuously stirring.
The fourth step: post-plating treatment
And taking the metal layer-sandwiched flake graphite obtained in the third step out of the water bath box, immediately putting the metal layer-sandwiched flake graphite into an ethanol solution for ultrasonic cleaning, and drying the metal layer-sandwiched flake graphite in a drying box.
Example 5
The embodiment discloses a preparation method of graphite with metal silver flakes, which comprises the following steps:
the first step is as follows: preparation of layered flake graphite
(1) Under the room temperature environment, 5ml perchloric acid and 1ml phosphoric acid are put into a glass beaker and mixed evenly to obtain mixed acid, then 0.4g potassium permanganate is added and stirred slowly to dissolve the mixed acid, and finally 4g crystalline flake graphite is added and stirred fully to mix evenly. Placing a glass beaker filled with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite into a constant-temperature water bath box with the water temperature of 40 ℃ for reaction for 60min, and continuously stirring during the reaction to ensure uniform reaction. After the reaction is finished, washing with water for many times, filtering out the precipitated crystalline flake graphite and drying at 60 ℃. And finally, putting the obtained crystalline flake graphite into a muffle furnace, heating the muffle furnace to 300 ℃, and preserving the heat for 60 s. And turning off a power supply of the muffle furnace, and taking the crystalline flake graphite out of the muffle furnace when the temperature in the muffle furnace is reduced to be below 100 ℃ to obtain the layered crystalline flake graphite.
The second step is that: layered flake graphite sensitization and activation treatment
And (3) putting the crystalline flake graphite obtained by the first step of treatment into a sensitizing solution, continuously stirring, taking out after 15min, cleaning by using deionized water, and airing at room temperature. The proportion of the sensitizing solution is as follows: SnCl220 g/L; 37wt% HCl, 40 mL/L; the remainder was deionized water. Putting the sensitized crystalline flake graphite into an activation solution, continuously stirring, taking out after 15min, cleaning by deionized water, and airing at room temperature; the activating solution is prepared by the following steps: PdCl20.2 g/L; 37wt% HCl, 5 mL/L; the remainder was deionized water.
The third step: preparation of graphite with metal silver flakes
And plating a metal nickel layer on the surface of the layered flake graphite and between graphite layers by adopting a chemical plating method. The chemical silver plating solution is 15g/L silver nitrate; 12g/L of potassium hydroxide; glucose, 20 g/L; ethanol, 30 mL/L; 20g/L of potassium sodium tartrate; the balance of deionized water. And heating the constant-temperature water bath tank to 30 ℃, preserving heat for 10 minutes, then adding an ammonia water solution to adjust the pH value of the solution to 13.5-14, preserving heat for 30 minutes and continuously stirring.
The fourth step: post-plating treatment
And taking the metal layer-sandwiched flake graphite obtained in the third step out of the water bath box, immediately putting the metal layer-sandwiched flake graphite into an ethanol solution for ultrasonic cleaning, and drying the metal layer-sandwiched flake graphite in a drying box.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. The preparation method of the metal layer-sandwiched flake graphite is characterized by comprising the following steps of:
carrying out sensitization and activation treatment on the layered flake graphite in sequence, so that metal Pd is adsorbed on the surface and the interlayer of the layered flake graphite, and a nucleation site is formed on the metal Pd; and
plating metal layers on the surfaces and the layers of the layered flake graphite by a chemical plating method to obtain the flake graphite with the sandwiched metal layer;
wherein, the layered flake graphite is prepared by the following steps:
uniformly mixing natural crystalline flake graphite with mixed acid and an oxidant, and stirring and reacting for 1-2 hours at the temperature of 30-40 ℃; after the reaction is finished, washing the natural crystalline flake graphite, filtering, drying, and then preserving heat at 300-400 ℃ for 1-2 min to obtain the layered crystalline flake graphite; the size of the natural crystalline flake graphite is 100-300 mu m; the mixed acid is formed by mixing perchloric acid and phosphoric acid, and the volume ratio of the perchloric acid to the phosphoric acid is 3-6: 0.5-1.5; the oxidant is potassium permanganate; the content ratio of the mixed acid, the potassium permanganate and the natural crystalline flake graphite is (3.5-7.5 ml), (0.2-0.6 g) and (3-5 g).
2. The method for preparing metal-intercalated flake graphite as claimed in claim 1, wherein the sensitizing solution is prepared from the following components in parts by weight: SnCl220-30 g/L; 37wt% of HCl, 30-50 mL/L; the rest is deionized water;
the formula of the activating solution is as follows: PdCl20.1-0.3 g/L; 37wt% of HCl, 3-6 mL/L; the remainder was deionized water.
3. The method for preparing metal-intercalated flake graphite according to claim 1, wherein said metal layer material is one selected from the group consisting of Cu, Ni, Co and Ag.
4. The method for preparing metal-intercalated flake graphite as claimed in claim 3,
the formula of the chemical Cu plating solution is as follows: 14-18 g/L of copper sulfate pentahydrate; 20-30 g/L of disodium ethylene diamine tetraacetate; 15-25 g/L of potassium sodium tartrate; formaldehyde solution of 12-16 mL/L; the balance of deionized water; the pH regulator is 50wt.% NaOH solution, and the pH value of the solution is regulated to 13.5-14; the temperature of chemical plating Cu is 30-45 ℃;
the chemical Ni-plating solution comprises the following components: 25-35 g/L of nickel sulfate hexahydrate; 18-22 g/L sodium hypophosphite; 20-30 g/L of sodium citrate; 18-22 g/L of ammonium chloride; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 8-9; the temperature of chemical plating Ni is 65-80 ℃;
the formula of the chemical Co plating solution is as follows: 15-25 g/L of cobalt sulfate; 20-40 g/L sodium hypophosphite; 20-35 g/L of sodium citrate; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 8-13; the temperature of the chemical Co plating is 75-85 ℃;
the chemical Ag plating solution formula is as follows: silver nitrate, 12-18 g/L; 10-15 g/L of potassium hydroxide; 15-25 g/L of glucose; 40-60 mL/L ethanol; 15-25 g/L of potassium sodium tartrate; the balance of deionized water; the pH regulator is ammonia water, and the pH value of the solution is regulated to 13.5-14; the chemical Ag plating temperature is 30-40 ℃.
5. The method for preparing metal-intercalated layer crystalline flake graphite as claimed in claim 1, further comprising the steps of washing and drying the metal-intercalated layer crystalline flake graphite obtained after electroless plating in an alcohol solution.
6. The metal-intercalated layer flake graphite prepared by the method of any one of claims 1 to 5.
7. Use of the metal-intercalated layer crystalline flake graphite of claim 6 in the preparation of copper-based composites.
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