CN114774993B - Method for preparing nanometer copper powder by electrodeposition - Google Patents
Method for preparing nanometer copper powder by electrodeposition Download PDFInfo
- Publication number
- CN114774993B CN114774993B CN202210441855.2A CN202210441855A CN114774993B CN 114774993 B CN114774993 B CN 114774993B CN 202210441855 A CN202210441855 A CN 202210441855A CN 114774993 B CN114774993 B CN 114774993B
- Authority
- CN
- China
- Prior art keywords
- copper
- compound
- solution
- copper powder
- electrodeposition
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Abstract
The invention relates to a method for preparing nanometer copper powder by electrodeposition, which takes benzotriazole as a raw material to synthesize a compound C, wherein the compound C has the characteristics of oxidation resistance and agglomeration resistance; graphite or platinum sheet is used as anode, stainless steel or red copper is used as cathode, and is placed in copper salt solution containing compound C to make electrodeposition reaction, centrifugal and vacuum drying so as to obtain the nano copper powder whose average grain size is 30-60nm and copper content is not less than 98wt%. The copper powder prepared by the method has uniform particle size, and the preparation method is simple and saves cost.
Description
Technical Field
The invention belongs to the technical field of metal material preparation, and relates to a method for preparing nanometer copper powder by electrodeposition.
Background
The nano copper has the advantages of low resistivity, high electromigration resistance, good weldability, low cost and the like, is often applied to various fields such as electric conduction, heat conduction, catalysis, antibiosis and the like, but is easy to agglomerate and oxidize, and due to the existence of oxides and agglomerates, the stability of the copper nano product is greatly reduced, and the electric conduction and heat transfer effects of the nano copper powder are weakened.
The current preparation method of the nanometer copper powder comprises the following steps: mechanical polishing, vapor phase evaporation, liquid phase reduction, electrodeposition, and the like. Wherein, the powder prepared by the mechanochemical method is easy to agglomerate, has wide particle size distribution range and is easy to mix with impurities in the grinding process; the gas-phase steam method has high equipment requirement, high-temperature operation and high cost, and the prepared powder has poor dispersibility, is not modified and protected, and is easy to oxidize in the air; the liquid phase reduction method is generally used for reducing agents such as sodium borohydride, formaldehyde, hydrazine hydrate and the like, which are toxic and not environment-friendly; the electrodeposition method has the advantages of mild reaction conditions, simple instruments and equipment, green and environment-friendly preparation process and the like, and is an effective means for synthesizing the nano material.
Patent CN201210428910.0 discloses a method for preparing nano copper powder by electrodeposition, which uses copper salt solution containing mixed acid and surfactant as electrolyte, uses copper plate as positive electrode, stainless steel as negative electrode, and applies direct current, deposits nano copper powder on stainless steel plate, uses distilled water and ethanol for cleaning, and vacuum dries to obtain nano copper powder. The nanometer copper powder needs to be prepared at a higher current density (maximally up to 100 mA/cm) 2 ) After the reaction is finished, hydrogen evolution side reaction is easy to occur; and copper ions consumed by cathode deposition are supplied by adopting a sacrificial copper anode, so that the anode dissolution rate is far greater than the cathode deposition rate, the concentration of copper ions in the solution is increased, copper powder is aggregated and grown in the electrodeposition process, the particle size of the obtained copper powder is 50-100nm, and the particle size distribution is uneven.
Patent CN201310609893.5 discloses a method for preparing nanometer copper powder by electrodeposition of low-eutectic ionic liquid, which comprises heating urea and choline chloride for 2 hours at 80 ℃ according to a molar ratio of 1:2-4, adding cuprous oxide as copper precursor into the electrolyte, adding stainless steel, nickel sheet or titanium sheet as cathode, graphite or platinum sheet as anode, stirring at 30-50 ℃ at a stirring rate of 100-300r/min and a cell pressure of 2-2.5V or lower current density (2-8 mA/cm) 2 ) And electrodepositing for 1-3 hours with the electrode spacing of 1cm, and obtaining 30-50nm copper powder with uniform particle size at the cathode. The problem of hydrogen evolution side reaction is solved by adopting a nonaqueous solvent and carrying out electrodeposition under low current, and additives such as a dispersing agent, a surfactant and the like are not needed, but in order to prevent copper powder from oxidizing, electrodeposition is carried out in an inert atmosphere, and expensive cuprous oxide is directly used as a raw material, so that the cost is greatly increased, and the industrial application is not facilitated.
Patent CN201810666978.X discloses a method for preparing nanometer copper powder by adopting fluorocarbon surfactant, which comprises CuSO 4 ·5H 2 Mixing O, anionic fluorocarbon surfactant, nonionic surfactant, adjuvant and water, stirring to obtain microemulsion, taking red copper as cathode plate, titanium alloy as anode plate, and current density of 0.05-0.2A/cm 2 Electrodepositing the microemulsion with the electrode plate spacing of 10-30mm, electrifying for 10-30min, centrifuging, filtering, drying in a vacuum drying oven at 40-80 ℃ for 30-60min to obtain nano copper powder with the particle size of 20-100nm, and finally sealing and packaging the nano copper powder by an aluminum foil bag filled with nitrogen or argon. Although the problems that the nanometer copper powder prepared by the patent CN201210428910.0 is easy to adhere to a cathode, difficult to scrape and collect, and incapable of realizing self-desorption, so that copper powder is accumulated and grown, and nanometer copper particles are uneven are solved, the used anionic fluorocarbon surfactant is very expensive, difficult to degrade and enrich, and the dosage of the surfactant is large (up to 25 g/L), so that the cost is increased, and the large-scale industrial application is not facilitated.
Therefore, in order to solve the problems that the particle size distribution is uneven, the raw materials are expensive and are not favorable for industrial application in the prior art for preparing the nano copper powder by adopting an electrodeposition method, and in order to further improve the dispersibility and the oxidation resistance of the nano copper powder, the development of a novel method for preparing the nano copper powder by adopting electrodeposition is necessary.
In addition, in order to prevent oxidation corrosion of metals, corrosion inhibitors are often doped in coatings for protecting metals, the corrosion inhibitors are gathered between the metals and electrolyte solutions, and the oxidation resistance effect is achieved by coating the surfaces of the metals through physical or chemical adsorption or film formation. Patent CN201610345539.X discloses a preparation method of antioxidant nanometer copper powder, which adopts a liquid phase reduction method, takes hydrazine hydrate as a reducing agent, is dripped into copper sulfate solution doped with corrosion inhibitor benzotriazole and surfactant PVP (K30), and is subjected to vacuum drying treatment after cleaning to obtain 80-600nm nanometer copper powder, wherein the copper powder prepared by the method has uneven particle size distribution and larger particle size difference. Although the electrodeposition technology is an effective method for preparing copper powder with smaller particle size, no report exists in the prior art that nanometer copper powder with oxidation resistance, high dispersion and uniform particle size distribution is prepared in a corrosion inhibitor solution by utilizing the electrodeposition technology.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing nano copper powder by electrodeposition in order to solve the problems existing in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing nanometer copper powder by electrodeposition, which specifically comprises the following steps:
(1) Adding benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, placing the mixture into ice water after microwave irradiation treatment, filtering, and recrystallizing to obtain a compound A;
dissolving the compound A in an N, N-dimethylformamide solvent, then adding hydrazine hydrate, uniformly mixing, adding 10% hydrochloric acid after microwave irradiation treatment, washing for three times by using chloroform, and drying to obtain a compound B;
uniformly mixing the compound B with dimethyl sulfate and potassium carbonate, adding 10% sodium hydroxide aqueous solution after microwave irradiation treatment, extracting with chloroform for three times, and drying to obtain a compound C;
(2) Preparing electrolyte, dissolving the compound C in ethanol or acetone solvent to obtain solution C, then preparing copper salt aqueous solution with the concentration of 0.1-1mol/L, adding sodium sulfate with the mass of 0.01-0.5% of copper salt, adding the mixed copper salt aqueous solution into the solution C, regulating the pH of the solution by using buffer solution, and uniformly stirring by using ultrasonic waves;
(3) And (3) electrodepositing graphite or platinum sheets serving as anodes and stainless steel or red copper serving as cathodes in the electrolyte in the step (2), centrifuging the obtained electrolyte to obtain copper nano particles, washing with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder.
The invention uses copper salt solution containing self-made compound C as electrolyte, graphite or platinum sheet as anode, stainless steel or red copper as cathode, and adopts electrodeposition technique to prepare nanometer copper powder. The invention not only solves the problems of uneven particle size distribution of copper powder caused by easy hydrogen evolution side reaction and incapability of realizing self-desorption in the prior art for preparing copper powder by electrodeposition, but also simplifies the preparation method, does not need to carry out electrodeposition in inert atmosphere, can realize the preparation of antioxidant and anti-agglomeration nanometer copper powder in air, reduces the production cost and is beneficial to industrial production.
The reaction mechanism of the invention is as follows: the compound C of the invention has positively charged ammonium ions and can be adsorbed on the cathode region of the microbattery on the surface of the nanometer copper powder, thus preventing H + The cathode surface is closed and discharged, so that hydrogen evolution side reaction is difficult to occur; the N atoms in the compound C have lone pair electrons and can carry out complex reaction with copper ions, so that the N atoms are wrapped around the copper ions, and the copper powder is effectively prevented from being oxidized during cathode deposition; the compound C belongs to a methyl ammonium sulfate compound, has surface activity, reduces the surface tension of copper powder through adsorption, and the steric hindrance on the structure of the compound C ensures that the copper powder is not easy to aggregate and agglomerate in the electrodeposition process, so that the nucleation process of the copper is blocked, and the particle size of the copper powder is more uniform and more dispersed.
In addition, the structural formula of the compound C in the step (1) is as follows:
the compound C has a methyl ammonium sulfate structure, has cationic surface activity, reduces the surface tension of copper powder through adsorption, ensures that generated copper powder particles are not easy to agglomerate, has a steric hindrance structure, ensures that the nucleation process of copper is hindered, further ensures that copper powder is not easy to agglomerate and grow to agglomerate in the electrodeposition process, ensures that the prepared copper powder particles can be dispersed into an electrolyte system while being generated, overcomes the problem that the particle size distribution of copper powder is uneven due to the fact that self-desorption cannot be realized on an electrode plate in the preparation process of nano copper powder, and ensures that the particle size of copper powder obtained through electrodeposition is more uniform and more dispersed;
in addition, the compound C is positively charged and can be adsorbed on the cathode region of the microbattery on the surface of the nanometer copper powder, thereby preventing H + The cathode surface is closed and discharged, so that hydrogen evolution side reaction is difficult to occur; the structure of the compound C is rich in N atoms, and the lone pair electron energy thereofThe copper-free compound has coordination with copper ion empty orbits in copper salt to surround the copper ions, effectively isolates oxygen to prevent copper powder from being oxidized, and further ensures that copper powder is not oxidized due to the compound C and reducing diamine groups.
As described above, the reaction molecules are activated by the action of the microwave irradiation treatment in the step (1), and the reaction time is shortened. The microwave radiation excites the rotation of the reaction molecules, so that the energy obtained by the reaction molecules is changed into a metastable state with extremely active molecular state, the mutual effective collision frequency between the reaction molecules is promoted, and the reaction is easy to carry out.
And, in the step (1), potassium carbonate is a base catalyst.
Preferably, in the step (1), the molar volume ratio of benzotriazole to dichloroethane in the solution 1 is 0.45-0.5mol:3mL, the molar volume ratio of potassium carbonate to dichloroethane in the solution 2 is 0.45-0.5mol:3mL, the molar volume ratio of compound A to potassium carbonate and N, N-dimethylformamide solvent is 0.05-0.06mol:1mL, the molar ratio of compound A to hydrazine hydrate is 1:3-5, and the molar ratio of compound B to dimethyl sulfate and potassium carbonate is 0.06:0.7-0.75:0.8.
Further preferably, the microwave irradiation treatment power for preparing the compound A is 350W, the microwave irradiation treatment power for preparing the compound B is 250W, the microwave irradiation treatment power for preparing the compound C is 350W, and the microwave irradiation treatment time is 5-8 min.
Preferably, in the step (2), the molar volume ratio of the compound C, copper salt, ethanol or acetone solvent to water is 0.1-0.5mol:0.2-5mol:30-50mL:100mL; the pH value of the solution is regulated to 6-8 by using a buffer solution, and the buffer solution is 0.1mol/L sodium borate, 0.1mol/L sodium phosphate buffer, 0.2mol/LTris-HCl buffer or 0.2mol/L disodium hydrogen phosphate-sodium dihydrogen phosphate buffer.
Further, the copper salt at least comprises one of copper sulfate, anhydrous copper sulfate, copper chloride, copper nitrate, cuprous chloride, copper acetate, anhydrous copper acetate, copper lactate, copper oleate, copper laurate, copper glycine, copper citrate, copper tartrate, copper malate dihydrate and copper octadecenoate.
Further, the sodium sulfate in the step (2) is used for increasing the free mobile ion concentration of the electrolyte and improving the conductivity of the electrolyte. Sodium sulfate ionizes in water into sodium cations and sulfate anions, enhancing conductivity through movement of the anions and cations.
Preferably, in step (3), the electrodeposition process parameters are as follows:
at 30-50deg.C, current density of 5-20mA/cm 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 25-60min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 300-500W.
Further, the vacuum drying temperature is 45-80 ℃, the drying time is 3-6h, and the rotating speed of ion separation is 5000-8000rpm.
Furthermore, in the step (3), the ultrasonic treatment is to eliminate concentration polarization in the electrolyte, the stirring effect of the ultrasonic wave causes the thickness of a diffusion layer to be reduced, concentration gradient is destroyed, the surface concentration of a cathode electrode is close to that of the electrolyte, copper ions are increased to discharge at a cathode, copper deposition is accelerated, and meanwhile, jet flow generated on the surface of the cathode by ultrasonic vibration causes copper powder particles deposited at the cathode to shake down and suspend and disperse in the electrolyte, so that generated copper powder is prevented from piling up together.
In addition, the current density is set to be 5-20mA/cm in the step (3) 2 The current density affects the metal deposition rate, which is proportional to the current density and has an important effect on nucleation and growth of crystals during deposition. The preferred current density is 10-15mA/cm 2 Within this range, the larger the current density, the smaller the copper powder particle size, and the more dispersed the copper powder particles; if the current density is continuously increased, the deposition speed of copper ions is increased, the deposition amount of the cathode is increased, atoms provided by large crystal nucleus length are increased, the prepared copper powder particles are stacked and become large, and further screening and other processes are needed to obtain copper powder with uniform particle size, so that the process is complicated; if it is less than this current density range, the efficiency of copper powder production will be greatly reduced, increasing the time cost.
In addition, the invention also claims a nanometer copper powder prepared by the electrodeposition method, wherein the average particle size of the nanometer copper powder is 30-60nm, the copper content is not less than 98wt%, and the balance is adsorbed compound C. The prepared nanometer copper powder has good oxidation resistance, and can be stored for 45 days at room temperature without oxidation.
Compared with the prior art, the method for preparing the nano copper powder by electrodeposition has the following excellent effects:
according to the invention, through adopting an electrodeposition technology, a compound C with antioxidation, surface activity and reducibility is added into electrolyte containing copper salt, additives such as dispersing agents, surfactants and the like are not required to be added, so that nano copper powder with good dispersibility, uniform particle size and good oxidation resistance can be prepared, the problems that hydrogen evolution side reaction is easy to occur and copper particle size distribution is uneven due to incapability of realizing self-desorption when the nano copper powder is prepared by adopting the electrodeposition technology in the prior art are solved, the preparation method is simplified, electrodeposition in inert atmosphere is not required, the preparation of antioxidation and agglomeration-resistant nano copper powder can be realized in air, the production cost is reduced, and the nano copper powder is beneficial to industrial production, and has an average particle size of 30-60nm and a copper content of not less than 98wt%.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a method for preparing nanometer copper powder by electrodeposition.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
(1) Adding a certain amount of benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing a certain amount of potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, performing 350W microwave irradiation treatment for 6min, placing the solution in ice water, filtering and recrystallizing to obtain a compound A, wherein the molar volume ratio of the benzotriazole to the dichloroethane is 0.45mol:3 mL;
dissolving a compound A in an N, N-dimethylformamide solvent, uniformly mixing the compound A with potassium carbonate and the N, N-dimethylformamide solvent in a molar volume ratio of 0.05mol to 1mL and a molar ratio of the compound A to hydrazine hydrate of 1 to 3.5, performing microwave irradiation treatment for 6min at 250W, adding 10% hydrochloric acid to remove the hydrazine hydrate, washing with chloroform for three times, and drying to obtain a compound B;
and (3) uniformly mixing the compound B with dimethyl sulfate and potassium carbonate according to the molar ratio of 0.06:0.7:0.8, performing 350W microwave irradiation treatment for 6min, adding a 10% sodium hydroxide aqueous solution, extracting for three times by using chloroform, and drying to obtain a compound C.
(2) Preparing an electrolyte, dissolving a certain amount of compound C in an ethanol solvent to obtain a C solution, preparing a copper sulfate aqueous solution with the concentration of 0.5mol/L, adding sodium sulfate with the mass of copper salt of 0.2%, adding the C solution, regulating the pH value of the solution to 8 by using a buffer solution, and uniformly stirring by ultrasonic, wherein the molar volume ratio of the compound C to the copper sulfate to the ethanol solvent to the water is 0.3mol:0.4mol:40 mL.
(3) Graphite is used as an anode, stainless steel is used as a cathode and is placed in the electrolyte in the step (2), and the current density is 10mA/cm at the temperature of 35 DEG C 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 60min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 400W.
And (3) centrifugally separating the obtained electrolyte at the rotating speed of 6000rpm to obtain copper nano particles, washing the copper nano particles with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder with the average particle size of 50-60nm and the purity of 99.2 wt%.
Example 2
(1) Adding a certain amount of benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing a certain amount of potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, performing 350W microwave irradiation treatment for 7min, placing the solution in ice water, filtering and recrystallizing to obtain a compound A;
dissolving a compound A in an N, N-dimethylformamide solvent, uniformly mixing the compound A with potassium carbonate and the N, N-dimethylformamide solvent in a molar volume ratio of 0.06mol to 1mL and a molar ratio of the compound A to hydrazine hydrate of 1:4.5, performing microwave irradiation treatment for 7min at 250W, adding 10% hydrochloric acid to remove the hydrazine hydrate, washing with chloroform for three times, and drying to obtain a compound B;
and (3) uniformly mixing the compound B with dimethyl sulfate and potassium carbonate according to the molar ratio of 0.06:0.75:0.8, performing 350W microwave irradiation treatment for 7min, adding a 10% sodium hydroxide aqueous solution, extracting for three times by using chloroform, and drying to obtain a compound C.
(2) Preparing an electrolyte, dissolving a certain amount of compound C in an ethanol solvent to obtain a C solution, preparing a copper chloride aqueous solution with the concentration of 0.6mol/L, adding sodium sulfate with the mass of copper salt of 0.4%, adding the C solution, regulating the pH value of the solution to be 6 by using a buffer solution, and uniformly stirring by ultrasonic, wherein the molar volume ratio of the compound C to the copper chloride to the ethanol solvent to the water is 0.5mol:2.5mol:40 mL.
(3) Taking a platinum sheet as an anode and red copper as a cathode, placing the platinum sheet into the electrolyte in the step (2), and controlling the temperature to 40 ℃ and the current density to 14mA/cm 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 50min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 450W.
And (3) centrifugally separating the obtained electrolyte at the rotating speed of 7000rpm to obtain copper nano particles, washing with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder with the average particle size of 40-50nm and the purity of 99.3 wt%.
Example 3
(1) Adding a certain amount of benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing a certain amount of potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, performing 350W microwave irradiation treatment for 7min, placing the solution in ice water, filtering and recrystallizing to obtain a compound A, wherein the molar volume ratio of the benzotriazole to the dichloroethane is 0.45mol:3 mL;
dissolving a compound A in an N, N-dimethylformamide solvent, uniformly mixing the compound A with potassium carbonate and the N, N-dimethylformamide solvent in a molar volume ratio of 0.05mol to 1mL and a molar ratio of the compound A to hydrazine hydrate of 1:5, performing microwave irradiation treatment for 7min at 250W, adding 10% hydrochloric acid to remove the hydrazine hydrate, washing with chloroform for three times, and drying to obtain a compound B;
and (3) uniformly mixing the compound B with dimethyl sulfate and potassium carbonate according to the molar ratio of 0.06:0.7:0.8, performing 350W microwave irradiation treatment for 7min, adding a 10% sodium hydroxide aqueous solution, extracting for three times by using chloroform, and drying to obtain a compound C.
(2) Preparing electrolyte, dissolving a certain amount of compound C in an acetone solvent to obtain a C solution, preparing a copper acetate aqueous solution with the concentration of 0.6mol/L, adding sodium sulfate with the mass of copper salt of 0.4%, adding the C solution, regulating the pH value of the solution to 7 by using a buffer solution, and uniformly stirring by ultrasonic, wherein the molar volume ratio of the compound C, the copper acetate, the acetone solvent and water is 0.4mol:2.5mol:40mL:100mL.
(3) Placing a platinum sheet serving as an anode and stainless steel serving as a cathode into the electrolyte in the step (2), wherein the temperature is 45 ℃ and the current density is 15mA/cm 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 50min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 350W.
And (3) centrifugally separating the obtained electrolyte at the rotating speed of 7000rpm to obtain copper nano particles, washing with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder with the average particle size of 35-45nm and the purity of 98.5 wt%.
Example 4
(1) Adding a certain amount of benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing a certain amount of potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, performing 350W microwave irradiation treatment for 7min, placing the solution in ice water, filtering and recrystallizing to obtain a compound A;
dissolving a compound A in an N, N-dimethylformamide solvent, uniformly mixing the compound A with potassium carbonate and the N, N-dimethylformamide solvent in a molar volume ratio of 0.06mol to 1mL and a molar ratio of the compound A to hydrazine hydrate of 1:3, performing microwave irradiation treatment for 6min at 250W, adding 10% hydrochloric acid to remove the hydrazine hydrate, washing with chloroform for three times, and drying to obtain a compound B;
and (3) uniformly mixing the compound B with dimethyl sulfate and potassium carbonate according to the molar ratio of 0.06:0.75:0.8, performing 350W microwave irradiation treatment for 6min, adding a 10% sodium hydroxide aqueous solution, extracting for three times by using chloroform, and drying to obtain a compound C.
(2) Preparing an electrolyte, dissolving a certain amount of compound C in an ethanol solvent to obtain a C solution, preparing a copper nitrate aqueous solution with the concentration of 0.5mol/L, adding sodium sulfate with the mass of copper salt of 0.4%, adding the C solution, regulating the pH value of the solution to 7.5 by using a buffer solution, and uniformly stirring by ultrasonic, wherein the molar volume ratio of the compound C, the copper nitrate, the ethanol solvent and water is 0.3mol:3mol:40mL:100mL.
(3) Graphite is used as an anode, red copper is used as a cathode, and is placed in the electrolyte in the step (2), and the current density is 13mA/cm at the temperature of 40 DEG C 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 50min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 500W.
And (3) centrifugally separating the obtained electrolyte at the rotating speed of 7000rpm to obtain copper nano particles, washing the copper nano particles with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder with the average particle size of 38-46nm and the purity of 99.5 wt%.
To further verify the excellent effects of the modification methods disclosed in the present invention, the inventors also conducted the following comparative tests:
comparative example 1
The method of example 1 in CN201210428910.0 was used to prepare nano copper powder, which was as follows:
(1) Adding a copper sulfate solution with the concentration of 0.4mol/L into distilled water, and adding 200mL of mixed acid and 2g of dispersing agent sodium dodecyl sulfate into each liter of solution after copper sulfate is completely dissolved;
(2) Placing a copper plate serving as a positive electrode and a stainless steel plate serving as a negative electrode into the solution prepared in the step (1), and electrifying direct current with a current density of 15mA/cm 2 Depositing nano copper powder on the cathode stainless steel plate for 20 min;
(3) Taking down the nano copper powder deposited on the cathode, and cleaning the nano copper powder with distilled water and then ethanol for 3 times;
(4) And (3) placing the cleaned nano copper powder into a vacuum drying oven, drying at 60 ℃ to obtain copper powder with the particle size of 50-70nm, wherein the purity is 94.5wt%, and oxidizing the copper powder in air within one week.
Comparative example 2
The method of example 2 in cn201810666978.X was used to prepare the nano copper powder, the specific method is as follows:
(1) Weighing 0.5g of sulfonate anionic fluorocarbon surfactant, 806g of non-ionic surfactant Tween-806 g of glycol auxiliary agent and 50g of anhydrous copper sulfate according to the proportion of each liter of microemulsion, dissolving the sulfonate anionic fluorocarbon surfactant, tween-80 and glycol in 200mL of water, mechanically stirring for 30min to obtain a composite surfactant solution, and adding the anhydrous copper sulfate to obtain a copper sulfate solution; adding a copper sulfate solution into the composite surfactant solution, adding water to prepare a 1L solution, and adding sulfuric acid to adjust the pH to 2; performing ultrasonic dispersion for 1h to prepare microemulsion;
(2) Heating the microemulsion at 25deg.C, placing an electrodeposition device which is a multi-layer polar plate, red copper as cathode plate, titanium alloy as anode plate, and current density of 0.1A/cm with spacing of 50mm 2 Electrifying electrodeposition, wherein the electrodeposition time is 30min, and taking out the multilayer electrodeposition device;
(3) And (3) centrifuging the electrodeposited microemulsion, adding a proper amount of alcohol into the extract to obtain a mixed solution, performing ultrasonic dispersion and centrifugal treatment on the mixed solution for 3 times, performing suction filtration, and then drying in a vacuum drying oven at 40 ℃ for 50min to obtain nano copper powder with the purity of 99wt% and the average particle size of 50-100nm, wherein the corrosion rate of a cathode plate in the electrodepositing process is 0.13%.
In the preparation method, in examples 1 to 4, the compound C with oxidation resistance, surface activity and reducibility is added in copper salt solution, the average particle diameter of the copper powder obtained by the test of a laser particle sizer and the test of a scanning electrochemical microscope is 30 to 60nm, the purity of the copper powder obtained by the test of an inductively coupled plasma emission spectrometry (refer to modern measurement and laboratory management, 2014 (6): 9. ") is not less than 98wt percent, and the copper powder is not oxidized when stored for 45 days under the conditions of room temperature (25 ℃) and humidity of 40 to 50 percent, therefore, the copper powder prepared by the method has good dispersibility, uniform diameter and good oxidation resistance, the prepared nano copper powder has the advantages of lower purity than the copper powder prepared by the method of the invention, poor oxidation resistance and dispersibility, partial agglomeration phenomenon, and the composite surfactant is added in comparative example 2, compared with the preparation of the nano copper powder, the preparation method has the steps of complex nano copper powder, and a plurality of surfactants are not good in post-treatment, and especially the fluorocarbon surfactant is easy to be enriched, and the prepared nano copper powder has poor oxidation resistance, and the copper powder has poor oxidation resistance. In a word, compared with the comparative example, the preparation method of the high-dispersion nanometer copper powder has the advantages of simple process, cleanness, high efficiency, oxidation resistance and high dispersion.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing nanometer copper powder by electrodeposition, which is characterized by comprising the following steps:
(1) Adding benzotriazole into dichloroethane, stirring uniformly to obtain a solution 1, mixing potassium carbonate and dichloroethane uniformly to obtain a solution 2, mixing the solution 1 and the solution 2 uniformly at room temperature, placing the mixture into ice water after microwave irradiation treatment, filtering, and recrystallizing to obtain a compound A;
dissolving the compound A in an N, N-dimethylformamide solvent, then adding hydrazine hydrate, uniformly mixing, adding 10% hydrochloric acid after microwave irradiation treatment, washing for three times by using chloroform, and drying to obtain a compound B;
uniformly mixing the compound B with dimethyl sulfate and potassium carbonate, adding 10% sodium hydroxide aqueous solution after microwave irradiation treatment, extracting with chloroform for three times, and drying to obtain a compound C;
(2) Preparing electrolyte, dissolving the compound C in ethanol or acetone solvent to obtain solution C, then preparing copper salt aqueous solution with the concentration of 0.1-1mol/L, adding sodium sulfate with the mass of 0.01-0.5% of copper salt, adding the mixed copper salt aqueous solution into the solution C, regulating the pH of the solution by using buffer solution, and uniformly stirring by using ultrasonic waves;
(3) And (3) electrodepositing graphite or platinum sheets serving as anodes and stainless steel or red copper serving as cathodes in the electrolyte in the step (2), centrifuging the obtained electrolyte to obtain copper nano particles, washing with absolute ethyl alcohol for three times, and carrying out vacuum drying treatment to obtain the nano copper powder.
2. The method according to claim 1, wherein in the step (1), the molar volume ratio of benzotriazole to dichloroethane in the solution 1 is 0.45-0.5 mol/3 ml, the molar volume ratio of potassium carbonate to dichloroethane in the solution 2 is 0.45-0.5 mol/3 ml, the molar volume ratio of compound a to potassium carbonate, N-dimethylformamide solvent is 0.05-0.06 mol/1 ml, the molar ratio of compound a to hydrazine hydrate is 1:3-5, and the molar ratio of compound B to dimethyl sulfate, potassium carbonate is 0.06:0.7-0.75:0.8.
3. The method for preparing nano copper powder by electrodeposition according to claim 1 or 2, wherein the microwave irradiation treatment power for preparing the compound a is 350W, the microwave irradiation treatment power for preparing the compound B is 250W, the microwave irradiation treatment power for preparing the compound C is 350W, and the microwave irradiation treatment time is 5 to 8min.
4. The method for preparing nano copper powder by electrodeposition according to claim 1, wherein in the step (2), the molar volume ratio of the compound C, copper salt, ethanol or acetone solvent to water is 0.1-0.5mol:0.2-5mol:30-50ml:100ml; the pH value of the solution is regulated to 6-8 by using a buffer solution, and the buffer solution is 0.1mol/L sodium borate, 0.1mol/L sodium phosphate buffer, 0.2mol/LTris-HCl buffer or 0.2mol/L disodium hydrogen phosphate-sodium dihydrogen phosphate buffer.
5. The method of preparing nano-copper powder according to claim 1 or 4, wherein the copper salt comprises at least one of copper sulfate, anhydrous copper sulfate, copper chloride, copper nitrate, cuprous chloride, copper acetate, anhydrous copper acetate, copper lactate, copper oleate, copper laurate, copper glycinate, copper citrate, copper tartrate, copper malate dihydrate, and copper octadecenoate.
6. The method for preparing nano copper powder by electrodeposition according to claim 1, wherein in the step (3), electrodeposition process parameters are as follows:
at 30-50deg.C, current density of 5-20mA/cm 2 Under the condition that the distance between the electrode plates is 1cm, the electrodeposition time is 25-60min, the ultrasonic treatment is carried out in the electrodeposition process, and the ultrasonic power is 300-500W.
7. The method for preparing nano copper powder by electrodeposition according to claim 1 or 6, wherein the vacuum drying temperature is 45-80 ℃, the drying time is 3-6 hours, and the rotation speed of ion separation is 5000-8000rpm.
8. A nano copper powder prepared by the method according to any one of claims 1 to 7, wherein the average particle size of the nano copper powder is 30 to 60nm, and the copper content is not less than 98wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210441855.2A CN114774993B (en) | 2022-04-25 | 2022-04-25 | Method for preparing nanometer copper powder by electrodeposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210441855.2A CN114774993B (en) | 2022-04-25 | 2022-04-25 | Method for preparing nanometer copper powder by electrodeposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114774993A CN114774993A (en) | 2022-07-22 |
| CN114774993B true CN114774993B (en) | 2023-06-27 |
Family
ID=82433196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210441855.2A Active CN114774993B (en) | 2022-04-25 | 2022-04-25 | Method for preparing nanometer copper powder by electrodeposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114774993B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115874170B (en) * | 2022-12-07 | 2024-03-26 | 西南交通大学 | Long-acting antibacterial titanium/titanium alloy material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978667A (en) * | 2012-10-25 | 2013-03-20 | 烟台大学 | Preparation method for nanometer copper powder through electro-deposition |
| CN103639420A (en) * | 2013-11-27 | 2014-03-19 | 昆明理工大学 | Method for utilizing low co-fusion type ionic liquid electro-deposition to manufacture nanometer copper powder |
| CN105945302A (en) * | 2016-05-20 | 2016-09-21 | 金陵科技学院 | Preparation method for antioxidant copper nanopowder |
| CN108728871A (en) * | 2018-06-26 | 2018-11-02 | 中南大学 | A method of copper nanoparticle is prepared using fluorocarbon surfactant |
-
2022
- 2022-04-25 CN CN202210441855.2A patent/CN114774993B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978667A (en) * | 2012-10-25 | 2013-03-20 | 烟台大学 | Preparation method for nanometer copper powder through electro-deposition |
| CN103639420A (en) * | 2013-11-27 | 2014-03-19 | 昆明理工大学 | Method for utilizing low co-fusion type ionic liquid electro-deposition to manufacture nanometer copper powder |
| CN105945302A (en) * | 2016-05-20 | 2016-09-21 | 金陵科技学院 | Preparation method for antioxidant copper nanopowder |
| CN108728871A (en) * | 2018-06-26 | 2018-11-02 | 中南大学 | A method of copper nanoparticle is prepared using fluorocarbon surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114774993A (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110235292B (en) | Prussian blue cathode material with high sodium content, preparation method and application thereof, and sodium-ion battery | |
| US8815338B2 (en) | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced by same | |
| CN100544861C (en) | The preparation method of superfine cupper powder | |
| WO2016155313A1 (en) | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor | |
| WO2020228709A1 (en) | Method for preparing alloy powder material | |
| CN114774993B (en) | Method for preparing nanometer copper powder by electrodeposition | |
| CN108336345A (en) | A kind of preparation method of nano-micro structure silicium cathode material | |
| Yiwei et al. | Preparation of spherical silver particles for solar cell electronic paste with gelatin protection | |
| KR100767703B1 (en) | Preparation method of silver nano-powder using electrolysis | |
| CN111342069B (en) | Surface gold-modified high-load carbon-supported platinum-cobalt catalyst and preparation method and application thereof | |
| WO2024060510A1 (en) | Recovery method and preparation method for prussian positive electrode material | |
| CN108728871B (en) | A method of copper nanoparticle is prepared using fluorocarbon surfactant | |
| CN115224264B (en) | Protective lithium battery positive electrode material and preparation method thereof | |
| CN105322160B (en) | The boride prepared using microemulsion method is the alkaline secondary cell of negative material | |
| CN110600754A (en) | Pt-rare earth alloy material and preparation method and application thereof | |
| CN111252753A (en) | Three-dimensional ordered porous nitrogen-doped graphene and preparation method and application thereof | |
| CN114455647A (en) | Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material | |
| JP2003306707A (en) | Superfine-particle metal tin, and method and equipment for manufacturing it | |
| CN109368701B (en) | Preparation method of rare earth-containing ammonium paratungstate composite powder | |
| CN112242512A (en) | Preparation method of vanadium dioxide and graphene oxide composite material | |
| CN110947979B (en) | Method for synthesizing superfine single crystal nickel powder by solvothermal method | |
| Yin et al. | Highly surface-roughened quasi-spherical silver powders in back electrode paste for silicon solar cells | |
| CN115321609B (en) | Multi-metal fluoride positive electrode material, preparation method thereof and lithium ion battery | |
| CN113461055B (en) | Oxygen vacancy defect-rich Cu 3 V 2 O 8 Preparation method of nano bead | |
| CN113548720B (en) | Ti 3 C 2 T x MXene quantum dot/active semicoke electrode, preparation method and application |
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 |