CN119263337A - Spherical copper oxide powder, copper powder and preparation method - Google Patents
Spherical copper oxide powder, copper powder and preparation method Download PDFInfo
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Abstract
本公开提供了一种球形氧化铜粉体的制备方法、球形铜粉的制备方法、球形氧化铜粉体和球形铜粉，涉及粉体材料技术领域。该球形氧化铜粉体的制备方法包括：配置铜盐水溶液和弱碱水溶液；其中，铜盐水溶液包含分散剂；将铜盐水溶液转化为铜盐气溶胶，并将铜盐气溶胶加入至弱碱水溶液中，以得到含铜化合物的悬浮液；对含铜化合物的悬浮液进行均相水热反应，以得到铜前驱体悬浮液；对铜前驱体悬浮液进行固液分离，并对得到的固体物质进行干燥处理，以得到球形氧化铜粉体。本公开可以降低球形氧化铜粉体和铜粉的制备成本。
The present disclosure provides a preparation method of spherical copper oxide powder, a preparation method of spherical copper powder, spherical copper oxide powder and spherical copper powder, and relates to the technical field of powder materials. The preparation method of the spherical copper oxide powder comprises: preparing a copper salt aqueous solution and a weak alkali aqueous solution; wherein the copper salt aqueous solution contains a dispersant; converting the copper salt aqueous solution into a copper salt aerosol, and adding the copper salt aerosol to the weak alkali aqueous solution to obtain a suspension containing copper compounds; subjecting the suspension containing copper compounds to a homogeneous hydrothermal reaction to obtain a copper precursor suspension; subjecting the copper precursor suspension to solid-liquid separation, and drying the obtained solid matter to obtain spherical copper oxide powder. The present disclosure can reduce the preparation cost of spherical copper oxide powder and copper powder.
Description
Technical Field
The disclosure relates to the technical field of powder materials, in particular to a preparation method of spherical copper oxide powder, a preparation method of spherical copper powder, spherical copper oxide powder and spherical copper powder.
Background
Copper oxide is a brown-black metal oxide powder, soluble in dilute acid, insoluble in water and ethanol. The catalyst has the characteristics of large specific surface area, high chemical activity, high electron mobility, high heat conductivity, strong adsorption capacity, strong selectivity and the like, has special electric, optical, catalytic and other properties, is widely applied to catalytic reactions such as oxidation, reduction, hydrogenation and the like, and is suitable for the fields of lithium ion batteries, energetic materials, gas sensors, printing and dyeing, glass, ceramics, medicines and the like.
Copper powder is a purplish brown or brown powder, is widely used in the production of microelectronic devices and the manufacture of terminals for multilayer ceramic capacitors, and can be used as a catalyst in the reaction process of synthesizing methanol from carbon dioxide and hydrogen, as well as in petroleum lubricants and in the industries of medicine, electroplating, paint, etc.
At present, the preparation of copper oxide powder and copper powder generally has the problem of high cost.
It should be noted that the information disclosed in the above background section is only for enhancing understanding of the background of the present disclosure and thus may include information that does not constitute prior art known to those of ordinary skill in the art.
Disclosure of Invention
The purpose of the present disclosure is to provide a method for producing spherical copper oxide powder, a method for producing spherical copper powder, spherical copper oxide powder and spherical copper powder, and further overcome the problem of high production costs of copper oxide powder and copper powder at least to some extent.
According to a first aspect of the present disclosure, there is provided a method for preparing spherical copper oxide powder, comprising preparing an aqueous copper salt solution and an aqueous weak base solution, wherein the aqueous copper salt solution contains a dispersant, converting the aqueous copper salt solution into an aerosol of copper salt, and adding the aerosol of copper salt to the aqueous weak base solution to obtain a suspension of a copper-containing compound, subjecting the suspension of the copper-containing compound to a homogeneous hydrothermal reaction to obtain a copper precursor suspension, subjecting the copper precursor suspension to solid-liquid separation, and subjecting the obtained solid matter to a drying treatment to obtain spherical copper oxide powder.
Optionally, the copper salt in the copper salt aqueous solution is copper acetate or copper chloride, the copper ion concentration in the copper salt aqueous solution is 40g/L to 70g/L, the dispersing agent is one or a mixture of more of cetyltrimethylammonium bromide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate, the mass percent of the dispersing agent is 1% to 5%, the weak base in the weak base aqueous solution is sodium carbonate or ammonium bicarbonate, and the alkali concentration in the weak base aqueous solution is 50g/L to 100g/L.
Optionally, converting the copper salt aqueous solution into the copper salt aerosol comprises converting the copper salt aqueous solution into the copper salt aerosol by utilizing an atomization device, wherein the liquid inlet amount of the copper salt aqueous solution in the atomization device is set to be 110-350 mL/h, and the gas flow rate of the atomization device is set to be 5-20L/min.
Alternatively, the suspension of the copper-containing compound is subjected to a homogeneous hydrothermal reaction to obtain a copper precursor suspension, which comprises placing the suspension of the copper-containing compound in a reaction vessel and sealing, and carrying out the homogeneous hydrothermal reaction at a temperature of 60 ℃ to 100 ℃ for a reaction time of 4 hours to 10 hours to obtain the copper precursor suspension.
Optionally, carrying out solid-liquid separation on the copper precursor suspension and drying the obtained solid matters to obtain spherical copper oxide powder, wherein the method comprises the steps of carrying out solid-liquid separation on the copper precursor suspension by adopting a suction filtration or centrifugation mode, and drying the obtained solid matters by adopting a vacuum drying or freeze drying mode to obtain the spherical copper oxide powder.
According to a second aspect of the present disclosure, there is provided a method for producing spherical copper oxide powder, comprising preparing an aqueous copper salt solution and an aqueous weak base solution, wherein the aqueous copper salt solution contains a dispersant, converting the aqueous weak base solution into an aerosol of weak base, and adding the aerosol of weak base to the aqueous copper salt solution to obtain a suspension of a copper-containing compound, subjecting the suspension of the copper-containing compound to a homogeneous hydrothermal reaction to obtain a copper precursor suspension, subjecting the copper precursor suspension to solid-liquid separation, and subjecting the obtained solid matter to a drying treatment to obtain spherical copper oxide powder.
Optionally, the copper salt in the copper salt aqueous solution is copper acetate or copper chloride, the copper ion concentration in the copper salt aqueous solution is 40g/L to 70g/L, the dispersing agent is one or a mixture of more of cetyltrimethylammonium bromide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate, the mass percent of the dispersing agent is 1% to 5%, the weak base in the weak base aqueous solution is sodium carbonate or ammonium bicarbonate, and the alkali concentration in the weak base aqueous solution is 50g/L to 100g/L.
Optionally, converting the aqueous weak base solution into the weak base aerosol comprises converting the aqueous weak base solution into the weak base aerosol by using an atomization device, wherein the liquid inlet amount of the aqueous weak base solution in the atomization device is set to be 110-350 mL/h, and the air flow of the atomization device is set to be 5-20L/min.
Alternatively, the suspension of the copper-containing compound is subjected to a homogeneous hydrothermal reaction to obtain a copper precursor suspension, which comprises placing the suspension of the copper-containing compound in a reaction vessel and sealing, and carrying out the homogeneous hydrothermal reaction at a temperature of 60 ℃ to 100 ℃ for a reaction time of 4 hours to 10 hours to obtain the copper precursor suspension.
Optionally, carrying out solid-liquid separation on the copper precursor suspension and drying the obtained solid matters to obtain spherical copper oxide powder, wherein the method comprises the steps of carrying out solid-liquid separation on the copper precursor suspension by adopting a suction filtration or centrifugation mode, and drying the obtained solid matters by adopting a vacuum drying or freeze drying mode to obtain the spherical copper oxide powder.
According to a third aspect of the present disclosure, there is provided a method for producing spherical copper oxide powder, comprising producing spherical copper oxide powder by using any one of the above methods for producing spherical copper oxide powder, and subjecting the spherical copper oxide powder to hydrogen reduction treatment to obtain spherical copper powder.
Optionally, heating to 180-300 ℃ at a heating rate of 5-10 ℃ per minute, carrying out hydrogen reduction treatment on the spherical copper oxide powder, and preserving heat for 30-2 hours to obtain the spherical copper powder.
According to a fourth aspect of the present disclosure, there is provided a spherical copper oxide powder prepared by any one of the above methods for preparing spherical copper oxide powder.
According to a fifth aspect of the present disclosure, there is provided a spherical copper powder prepared by any one of the above methods for preparing spherical copper powder.
In the scheme of the exemplary embodiment of the disclosure, on one hand, by configuring the combined process of aerosol, homogeneous phase hydrothermal and the like, the nucleation and growth process can be effectively regulated and controlled, and the three-dimensional spherical copper oxide powder and copper powder are obtained, so that the cost is low, the process is simple and convenient to implement, and the process condition is easy to control. On the other hand, the reactant solution is converted into aerosol and then the gas-liquid phase reaction is carried out, so that the dispersibility of the powder can be effectively regulated and controlled, and the agglomeration phenomenon of particles is avoided. In yet another aspect, the scheme disclosed by the invention has the advantages of low energy consumption, environment-friendly process and the like, and is suitable for industrial production.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure. It will be apparent to those of ordinary skill in the art that the drawings in the following description are merely examples of the disclosure and that other drawings may be derived from them without undue effort.
Fig. 1 schematically shows a flowchart of a method of producing spherical copper oxide powder according to an embodiment of the present disclosure.
Fig. 2 schematically shows a flow chart of a method of preparing spherical copper oxide powder according to another embodiment of the present disclosure.
Fig. 3 schematically shows a flow chart of a method of preparing spherical copper powder according to an embodiment of the present disclosure.
Fig. 4 schematically shows an SEM (Scanning Electron Microscope ) image of the prepared spherical copper powder of example 1 of the present disclosure.
Fig. 5 schematically shows an SEM image of the spherical copper powder prepared in example 2 of the present disclosure.
Fig. 6 schematically shows an SEM image of the spherical copper powder prepared in example 3 of the present disclosure.
Fig. 7 schematically shows an SEM image of the spherical copper powder prepared in example 4 of the present disclosure.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments may be embodied in many forms and should not be construed as limited to the examples set forth herein, but rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the present disclosure. One skilled in the relevant art will recognize, however, that the aspects of the disclosure may be practiced without one or more of the specific details, or with other methods, processes, steps, etc. In other instances, well-known technical solutions have not been shown or described in detail to avoid obscuring aspects of the present disclosure.
Furthermore, the drawings are merely schematic illustrations of the present disclosure and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. The flow diagrams depicted in the figures are exemplary only and not necessarily all steps are included. For example, some steps may be decomposed, and some steps may be combined or partially combined, so that the order of actual execution may be changed according to actual situations.
The preparation method of the copper oxide material can comprise a solvothermal method, a pyrolysis method, a microwave method, a wet chemical method, a magnetron sputtering method, a solid-liquid reaction method and the like. However, these preparation methods are costly to prepare and the resulting nanoparticle morphology is irregular.
In addition, the global productivity is rapidly increasing for chip type multilayer ceramic capacitors (Multi-LAYER CERAMIC Capacitors, MLCCs) which are widely used in various fields of consumer electronics, communication industry, automobile industry, military equipment, etc. Copper is used as an MLCC terminal electrode material, and has a plurality of excellent performances such as wide sources, low price, conductivity similar to silver, excellent migration resistance and the like. However, copper has very active chemical properties, is easily oxidized in air at normal temperature, particularly, the oxidation speed of ultrafine/nano copper powder with larger specific surface area is higher, and the generated copper oxide has no conductivity, so that the conductivity of the MLCC is greatly reduced, and therefore, sintering is required in nitrogen or reducing atmosphere, and the complexity and cost of the process are correspondingly increased. In addition, in some schemes, the high-temperature sintering (for example, at a temperature of more than 850 ℃) of the copper end electrode slurry has the problems of high sintering temperature, large stress and the like, and especially in high-capacity MLCC products, internal cracks are easily generated due to residual stress, so that the element is invalid. However, the copper end electrode slurry sintered at low temperature (for example, less than 800 ℃) always has the problem of insufficient compactness.
The superfine copper powder for the MLCC electrode is mainly prepared by a chemical method. However, the preparation method of ultrafine copper powder is still in the exploring experimental stage mostly, but is not perfect, such as expensive raw material gas, complicated equipment, high cost and smaller yield required by the vapor phase evaporation method. The copper powder prepared by the mechanochemical method has wide particle size distribution and is easy to introduce impurities. These disadvantages limit the spread of the relevant preparation methods.
The liquid phase reduction method for preparing the superfine copper powder has unique advantages such as simple equipment, short process flow, easy industrialized production and the like. The reducing agents such as formaldehyde, ascorbic acid, sodium hypophosphite, sodium borohydride, hydrated scale and the like are simple and easy to obtain, but meanwhile, due to the factors such as virulence, reaction capacity, cost and the like, more suitable reducing agents are required to be further searched for to research a more ideal reaction system.
Aiming at the situation, the present disclosure provides a new spherical copper oxide powder and a preparation scheme of the spherical copper powder in order to at least solve the problem of high preparation cost.
Fig. 1 schematically shows a flowchart of a method of producing spherical copper oxide powder according to an embodiment of the present disclosure. Referring to fig. 1, the method of preparing spherical copper oxide powder according to an embodiment of the present disclosure may include the steps of:
and S12, preparing a copper salt aqueous solution and a weak base aqueous solution, wherein the copper salt aqueous solution contains a dispersing agent.
In exemplary embodiments of the present disclosure, in one aspect, copper salts, deionized water, and dispersants may be employed to formulate an aqueous copper salt solution. Alternatively, the aqueous precipitant solution may be prepared using a weak base and deionized water.
Specifically, the copper salt in the copper salt aqueous solution is copper acetate or copper chloride, the concentration of copper ions in the copper salt aqueous solution is 40g/L to 70g/L, the dispersing agent is one or a mixture of more of cetyltrimethylammonium bromide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate, the mass percent of the dispersing agent is 1% to 5%, the weak base in the weak base aqueous solution is sodium carbonate or ammonium bicarbonate, and the concentration of alkali in the weak base aqueous solution is 50g/L to 100g/L.
S14, converting the copper salt aqueous solution into copper salt aerosol, and adding the copper salt aerosol into weak base aqueous solution to obtain a suspension containing the copper compound.
In exemplary embodiments of the present disclosure, the aqueous copper salt solution may be converted to a copper salt aerosol by means of a high pressure gas stream. In particular, the aqueous copper salt solution may be converted to an aerosol of copper salt by an atomizing device (e.g., an atomizing spray gun, etc.). Wherein, the liquid inlet amount of the copper salt aqueous solution in the atomizing equipment can be set to be 110mL/h to 350mL/h, and the air flow of the atomizing equipment can be set to be 5L/min to 20L/min.
Next, the copper salt aerosol may be added to a weak base aqueous solution to obtain a suspension of the copper-containing compound.
And S16, carrying out homogeneous phase hydrothermal reaction on the suspension containing the copper compound to obtain a copper precursor suspension.
In exemplary embodiments of the present disclosure, a suspension of a copper-containing compound may be sealed in a reaction vessel, and a homogeneous hydrothermal reaction may be performed at a temperature of 60 ℃ to 100 ℃ for a reaction time of 4 hours to 10 hours to obtain a copper precursor suspension.
S18, carrying out solid-liquid separation on the copper precursor suspension, and drying the obtained solid substance to obtain spherical copper oxide powder.
Specifically, the copper precursor suspension may be subjected to solid-liquid separation by suction filtration or centrifugation. And drying the obtained solid substance by adopting a vacuum drying or freeze drying mode to obtain spherical copper oxide powder. In the case of vacuum drying, the temperature may be set to 60 to 80 ℃.
Fig. 2 schematically shows a flow chart of a method of preparing spherical copper oxide powder according to another embodiment of the present disclosure. Referring to fig. 2, a method of preparing spherical copper oxide powder according to another embodiment of the present disclosure may include the steps of:
S22, preparing a copper salt aqueous solution and a weak base aqueous solution, wherein the copper salt aqueous solution contains a dispersing agent;
S24, converting the weak base aqueous solution into weak base aerosol, and adding the weak base aerosol into the copper salt aqueous solution to obtain a suspension containing a copper compound;
S26, carrying out homogeneous phase hydrothermal reaction on the suspension containing the copper compound to obtain copper precursor suspension;
s28, carrying out solid-liquid separation on the copper precursor suspension, and drying the obtained solid matters to obtain spherical copper oxide powder.
Step S22, step S26 and step S28 correspond to step S12, step S16 and step S18, respectively, and are not described in detail.
For step S24, the aqueous weak base solution may also be converted into a weak base aerosol by means of a high pressure gas stream. In particular, the aqueous weak base solution may be converted to a weak base aerosol by an atomizing device (e.g., an atomizing spray gun, etc.). Wherein, the liquid inlet amount of the weak alkali aqueous solution in the atomizing device can be set to be 110mL/h to 350mL/h, and the air flow of the atomizing device can be set to be 5L/min to 20L/min. Next, a weak base aerosol may be added to the copper salt aqueous solution to obtain a suspension of the copper-containing compound.
The detection shows that the primary particle size of the spherical copper oxide prepared by the preparation process disclosed by the disclosure is 20nm to 30nm, and the secondary particle size is 200nm to 500nm.
Based on the preparation process, the embodiment of the disclosure further provides a preparation method of the spherical copper powder.
Fig. 3 schematically shows a flow chart of a method of preparing spherical copper powder according to an exemplary embodiment of the present disclosure. Referring to fig. 3, a method of preparing spherical copper powder according to an embodiment of the present disclosure may include the steps of:
S32, preparing spherical copper oxide powder.
Specifically, the spherical copper oxide powder may be prepared by the preparation method of the steps S12 to S18 or the steps S22 to S28.
S34, carrying out hydrogen reduction treatment on the spherical copper oxide powder to obtain spherical copper powder.
For the hydrogen reduction treatment process, specifically, the temperature may be raised to 180 ℃ to 300 ℃ at a temperature raising rate of 5 ℃ to 10 ℃ per minute, and the temperature may be kept for 30min to 2 hours, to obtain spherical copper powder from spherical copper oxide powder.
The copper powder obtained by the embodiment of the disclosure is spherical superfine copper powder, and the thickness of the powder laying material layer is 5mm to 20mm. In addition, the size of the prepared spherical superfine copper powder is 150nm to 400nm.
According to the scheme, the atomization method is adopted to effectively control irregular agglomeration of the copper precursor in the nucleation growth process, meanwhile, in the low-temperature hydrothermal process, the copper precursor is decomposed into high-dispersity spherical copper oxide particles in situ, and the process flow is simplified while the sphericity, the dispersity and the uniformity of the particles are ensured.
Based on the preparation scheme disclosed by the invention, the copper crystal grain is uniform in size and shape, controllable in granularity, dispersible and sphericity. The present disclosure first converts the reactant solution to an aerosol prior to the hydrothermal process, performing a defined area of gas-liquid phase reaction. Compared with the direct addition or dropwise addition of the solution, the aerosol is easier to diffuse, has smaller average granularity and higher specific surface area, greatly accelerates the transmission rate of copper salt and a precipitated phase in the reaction process, effectively improves the reaction rate and increases the nucleation number, and meanwhile, the gas-liquid phase reaction in a limited area can inhibit aggregation and growth of copper-containing compounds, thereby effectively regulating and controlling sphericity and dispersibility of copper precursor particles and avoiding aggregation phenomenon of the particles. The method can decompose copper precursor particles into high-dispersion spherical copper oxide ultrafine powder in situ in the hydrothermal process. The synthesis method of the three-dimensional spherical superfine copper powder has the advantages of low cost, simple process, low energy consumption, continuous operation and easily controlled process conditions.
The three-dimensional spherical superfine copper powder prepared by the method has high purity, good crystallinity, good sphericity, uniform morphology and good dispersity, and can obtain a series of three-dimensional spherical copper particles formed by self-assembly of nano particles with controllable granularity, wherein the granularity range is 30nm to 1 mu m. Under the conditions of low cost and low energy consumption, the method effectively obtains the copper particles with high sphericity, accords with the granularity, uniformity and fluidity of the superfine copper powder required by the end electrode slurry for the MLCC, and is favorable for preparing the end electrode slurry for the high-performance MLCC.
The copper powder preparation process of the present disclosure is illustrated by the following examples.
Example 1
First, copper salt and weak base were formulated into aqueous copper salt solution and aqueous weak base solution having concentrations of 70g/L and 100g/L, respectively. Wherein, 1% polyethylene glycol is used as a dispersing agent and added into copper salt aqueous solution.
Next, the prepared aqueous alkali solution was converted into a weakly basic aerosol, the weakly basic aerosol was added to the aqueous copper salt solution in an amount of 200mL/h and a gas flow of 15L/min, and a suspension containing the copper compound was obtained by collecting.
Subsequently, the obtained suspension was transferred to a high-pressure reaction kettle for sealing, and a homogeneous hydrothermal reaction was performed at a reaction temperature of 70 ℃ for a reaction time of 6 hours to obtain a copper precursor suspension. And after the reaction kettle is cooled to room temperature, carrying out solid-liquid separation and washing on the copper precursor suspension obtained after the reaction, and putting the filter cake into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain dark brown copper oxide powder.
And then carrying out hydrogen reduction on the dried dark brown copper oxide powder, wherein the heating rate is 5 ℃ per minute, the reaction temperature is 220 ℃, the temperature is kept for 1.5 hours, and the thickness of a powder laying layer is 20mm, so that the three-dimensional spherical superfine copper powder is obtained.
In the embodiment, the atomization method is adopted to effectively control the irregular agglomeration phenomenon of the copper precursor in the nucleation growth process, meanwhile, in the low-temperature hydrothermal process, the copper precursor is decomposed into high-dispersity spherical copper oxide particles in situ, the sphericity, the dispersity and the uniformity of the particles are ensured, the energy consumption caused by roasting the copper precursor is effectively reduced, and the process flow is simplified.
Fig. 4 schematically shows an SEM image of the spherical copper powder prepared in example 1 of the present disclosure. As can be seen from fig. 4, the copper powder prepared in example 1 of the present disclosure has good sphericity, good dispersibility, particle size of 200nm to 500nm, and no obvious agglomeration phenomenon.
Example 2
First, copper salt and weak base were formulated into aqueous copper salt solution and aqueous weak base solution having concentrations of 70g/L and 100g/L, respectively. Wherein 5% polyethylene glycol is used as a dispersing agent and added into the copper salt aqueous solution.
Next, the prepared aqueous alkali solution was converted into a weakly basic aerosol, the weakly basic aerosol was added to the aqueous copper salt solution in an amount of 110mL/h and an air flow rate of 5L/min, and a suspension containing the copper compound was obtained by collecting.
Subsequently, the obtained suspension was transferred to a high-pressure reaction kettle for sealing, and a homogeneous hydrothermal reaction was performed at a reaction temperature of 60 ℃ for 4 hours to obtain a copper precursor suspension. And after the reaction kettle is cooled to room temperature, carrying out solid-liquid separation and washing on the copper precursor suspension obtained after the reaction, and putting the filter cake into a vacuum drying oven for drying treatment at the temperature of 80 ℃ to obtain dark brown copper oxide powder.
And then carrying out hydrogen reduction on the dried dark brown copper oxide powder, wherein the heating rate is 5 ℃ per minute, the reaction temperature is 200 ℃, the temperature is kept for 1h, and the thickness of a powder laying material layer is 20mm, so that the three-dimensional spherical superfine copper powder is obtained.
Fig. 5 schematically shows an SEM image of the spherical copper powder prepared in example 2 of the present disclosure. As can be seen from fig. 5, the copper powder prepared in example 2 of the present disclosure has good sphericity, good dispersibility, uniform particle size, about 120nm particle diameter, and no obvious agglomeration phenomenon.
Example 3
First, copper salt and weak base were formulated into an aqueous solution of copper salt and an aqueous solution of weak base at concentrations of 40g/L and 50g/L, respectively. Wherein 5% cetyl trimethylammonium bromide is added as a dispersant to the copper salt aqueous solution.
Next, the prepared aqueous alkali solution was converted into a weakly basic aerosol, the weakly basic aerosol was added to the aqueous copper salt solution in an amount of 350mL/h and an air flow rate of 20L/min, and a suspension containing the copper compound was obtained by collecting.
Subsequently, the obtained suspension was transferred to a high-pressure reaction kettle and sealed, and a homogeneous hydrothermal reaction was performed at a reaction temperature of 100 ℃ for 10 hours to obtain a copper precursor suspension. And after the reaction kettle is cooled to room temperature, carrying out solid-liquid separation and washing on the copper precursor suspension obtained after the reaction, and putting the filter cake into a vacuum drying oven for drying treatment at the temperature of 80 ℃ to obtain dark brown copper oxide powder.
And then carrying out hydrogen reduction on the dried dark brown copper oxide powder, wherein the heating rate is 10 ℃ per minute, the reaction temperature is 180 ℃, the temperature is kept for 2 hours, and the thickness of a powder laying material layer is 15mm, so that the three-dimensional spherical superfine copper powder is obtained.
Fig. 6 schematically shows an SEM image of the spherical copper powder prepared in example 3 of the present disclosure. As can be seen from fig. 6, the copper powder prepared in example 3 of the present disclosure has good sphericity, good dispersibility, uniform particle size, particle diameter of about 200nm, and no obvious agglomeration phenomenon.
Example 4
First, copper salt and weak base were formulated into 50g/L and 80g/L copper salt aqueous solution and weak base aqueous solution, respectively. Wherein 5% sodium dodecyl benzene sulfonate is added as dispersant into copper salt water solution.
Next, the prepared aqueous copper salt solution was converted into an aerosol of copper salt, the aerosol of copper salt was added to a weakly alkaline aqueous solution in an amount of 350mL/h and an air flow of 20L/min, and a suspension containing a copper compound was obtained.
Subsequently, the obtained suspension was transferred to a high-pressure reaction kettle and sealed, and a homogeneous hydrothermal reaction was performed at a reaction temperature of 75 ℃ for a reaction time of 6 hours to obtain a copper precursor suspension. And after the reaction kettle is cooled to room temperature, carrying out solid-liquid separation and washing on the copper precursor suspension obtained after the reaction, and putting the filter cake into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain dark brown copper oxide powder.
And then carrying out hydrogen reduction on the dried dark brown copper oxide powder, wherein the heating rate is 5 ℃ per minute, the reaction temperature is 300 ℃, the temperature is kept for 30 minutes, and the thickness of a powder laying material layer is 20mm, so that the three-dimensional spherical superfine copper powder is obtained.
Fig. 7 schematically shows an SEM image of the spherical copper powder prepared in example 4 of the present disclosure. As can be seen from fig. 7, the copper powder prepared in example 4 of the present disclosure has good sphericity, good dispersibility, uniform particle size, about 300nm particle diameter, and no obvious agglomeration phenomenon.
Further, the embodiment of the disclosure also provides a spherical copper oxide powder, which is prepared by adopting the preparation method of the spherical copper oxide powder.
Further, the embodiment of the disclosure also provides spherical copper powder, which is prepared by adopting the preparation method of the spherical copper powder.
It should be noted that although the steps of the methods in the present disclosure are depicted in the accompanying drawings in a particular order, this does not require or imply that the steps must be performed in that particular order, or that all illustrated steps be performed, to achieve desirable results. Additionally or alternatively, certain steps may be omitted, multiple steps combined into one step to perform, and/or one step decomposed into multiple steps to perform, etc.
Furthermore, the above-described figures are only schematic illustrations of processes included in the method according to the exemplary embodiments of the present disclosure, and are not intended to be limiting. It will be readily appreciated that the processes shown in the above figures do not indicate or limit the temporal order of these processes. In addition, it is also readily understood that these processes may be performed synchronously or asynchronously, for example, among a plurality of modules.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This application is intended to cover any adaptations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It is to be understood that the present disclosure is not limited to the precise arrangements and instrumentalities shown in the drawings, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.
Claims (10)
1. The preparation method of the spherical copper oxide powder is characterized by comprising the following steps:
preparing a copper salt aqueous solution and a weak base aqueous solution, wherein the copper salt aqueous solution comprises a dispersing agent;
Converting the copper salt aqueous solution into a copper salt aerosol, and adding the copper salt aerosol to the weak base aqueous solution to obtain a suspension of a copper-containing compound;
Performing a homogeneous hydrothermal reaction on the suspension of copper-containing compounds to obtain a copper precursor suspension;
And carrying out solid-liquid separation on the copper precursor suspension, and drying the obtained solid substance to obtain spherical copper oxide powder.
2. The preparation method according to claim 1, wherein the copper salt in the copper salt aqueous solution is copper acetate or copper chloride, and the copper ion concentration in the copper salt aqueous solution is 40g/L to 70g/L;
the dispersing agent is one or more of cetyl trimethyl ammonium bromide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate, and the mass fraction of the dispersing agent is 1-5%;
the weak base in the weak base aqueous solution is sodium carbonate or ammonium bicarbonate, and the concentration of the alkali in the weak base aqueous solution is 50g/L to 100g/L.
3. The method of preparing according to claim 1, wherein converting the aqueous copper salt solution into a copper salt aerosol comprises:
converting the copper salt aqueous solution into a copper salt aerosol using an atomizing device;
Wherein the liquid inlet amount of the copper salt aqueous solution in the atomizing equipment is set to be 110mL/h to 350mL/h, and the air flow of the atomizing equipment is set to be 5L/min to 20L/min.
4. The method of preparation according to claim 1, characterized in that the suspension of copper-containing compound is subjected to a homogeneous hydrothermal reaction to obtain a copper precursor suspension comprising:
and (3) placing the suspension containing the copper compound into a reaction kettle for sealing, and performing homogeneous hydrothermal reaction at the temperature of 60-100 ℃ for 4-10 hours to obtain a copper precursor suspension.
5. The method according to claim 1, wherein the copper precursor suspension is subjected to solid-liquid separation and the obtained solid matter is subjected to drying treatment to obtain spherical copper oxide powder, comprising:
Carrying out solid-liquid separation on the copper precursor suspension by adopting a suction filtration or centrifugation mode;
and drying the obtained solid substance by adopting a vacuum drying or freeze drying mode to obtain spherical copper oxide powder.
6. The preparation method of the spherical copper oxide powder is characterized by comprising the following steps:
preparing a copper salt aqueous solution and a weak base aqueous solution, wherein the copper salt aqueous solution comprises a dispersing agent;
Converting the aqueous weak base solution into a weak base aerosol and adding the weak base aerosol to the aqueous copper salt solution to obtain a suspension of a copper-containing compound;
Performing a homogeneous hydrothermal reaction on the suspension of copper-containing compounds to obtain a copper precursor suspension;
And carrying out solid-liquid separation on the copper precursor suspension, and drying the obtained solid substance to obtain spherical copper oxide powder.
7. A method for preparing spherical copper powder, comprising the steps of:
preparing spherical copper oxide powder by the preparation method of the spherical copper oxide powder according to any one of claims 1 to 6;
And carrying out hydrogen reduction treatment on the spherical copper oxide powder to obtain spherical copper powder.
8. The method of producing a spherical copper powder according to claim 7, wherein the hydrogen reduction treatment is performed on the spherical copper oxide powder to obtain the spherical copper powder, comprising:
heating to 180-300 ℃ at the heating rate of 5-10 ℃ per minute, carrying out hydrogen reduction treatment on the spherical copper oxide powder, and preserving heat for 30-2 hours to obtain the spherical copper powder.
9. A spherical copper oxide powder prepared by the method of any one of claims 1 to 6.
10. A spherical copper powder prepared by the method of claim 7 or 8.
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