A method for preparing copper selenide micro / nanoparticles

Abstract

This invention relates to the field of powder metallurgy, specifically to a method for preparing copper selenide micro / nanoparticles. The method includes the following steps: preparing an ultrafine selenium nanoparticle suspension according to a design; uniformly coating the suspension onto a bright copper substrate surface using spin coating or blade coating; heating the copper substrate; and collecting the powder after the substrate cools down to obtain the copper selenide micro / nanoparticles. This invention achieves rapid chemical reaction between the copper substrate and the ultrafine selenium nanoparticles at the micro / nano scale, not only maintaining the uniform size of the copper selenide powder at the micro / nano level but also greatly simplifies the preparation process, enabling one-step preparation of copper selenide ultrafine / nanoparticles and further shortening the preparation time. The raw materials required for this preparation method are readily available and low-cost. Furthermore, the process is simple, the particle size is adjustable, the process is efficient and safe, and the preparation speed is extremely fast, making it very suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of powder metallurgy technology, specifically to a method for preparing copper selenide micro / nanoparticles. Background Technology

[0002] With the gradual development of the energy industry, significant progress has been made in the development and utilization of new energy sources such as solar and wind power. Metal selenides, with their excellent properties, have shown great application potential in fields such as optoelectronics, catalysis, new energy, and sensors, attracting widespread attention. Among them, copper selenide, a p-type conductive semiconductor, is attracting attention due to its potential applications in solar cells, filters, and superionic materials. Furthermore, micro- and nano-sized copper selenide particles not only possess the band gap characteristics of large particles but also the advantages of nanomaterials. Micro- and nano-sized copper selenide particles have higher specific area and activity, effectively improving the catalytic effect in catalytic processes. Moreover, existing research indicates that copper selenide with different particle sizes may have different band gaps, further expanding the application areas and potential of copper selenide.

[0003] In current research, Huang Hong et al. (authorization announcement number CN115347174A) prepared porous octahedrons of copper selenide with a diameter of 2-3 μm by calcining Cu-MOF with selenium powder under a protective atmosphere for 2-8 hours, which improved the rate performance of sodium-ion batteries; He Ping et al. (authorization announcement number CN115025748A) obtained large-particle copper selenide flakes by dissolving selenium powder in sodium hydroxide, adding copper sulfate solution and heating for 24 hours, washing with water and ethanol multiple times, and drying at 60℃ for 12 hours; Liang Changhao et al. (authorization announcement number CN114590832A) obtained non-stoichiometric nano-copper selenide by laser irradiating selenium solution, adding copper foil to the solution and reacting for 24-72 hours, and then centrifuging and drying.

[0004] The above search reveals that current technologies mainly employ precursor thermal decomposition, solvothermal synthesis, and laser irradiation methods. These methods not only require complex processes and take several to tens of hours to prepare, but also necessitate lengthy drying processes to obtain the powder. Furthermore, it is difficult to precisely control the particle size of copper selenide powder to nanometer or micrometer scale under the same process. Therefore, current technologies struggle to meet the demands of low-cost, high-volume, and industrialized production lines for commercially available copper selenide micro / nanoparticles with a wide range of particle sizes. Summary of the Invention

[0005] This invention discloses a method for preparing copper selenide micro / nanoparticles to solve any of the above-mentioned and other potential problems in the prior art.

[0006] To solve the above-mentioned technical problems, the technical solution of the present invention is: a method for preparing copper selenide micro / nanoparticles, which specifically includes the following steps:

[0007] S1) Prepare a solution of nano-selenium particles;

[0008] S2) The nano-selenium particle solution obtained in S1) is uniformly coated on the surface of the copper substrate.

[0009] S3) The copper substrate coated with selenium particles obtained in S2) is heated, kept at the temperature for a period of time, cooled to room temperature, and the powder on the surface of the copper substrate is collected to obtain copper selenide micro-nano particles.

[0010] Furthermore, the specific steps of S1) are as follows:

[0011] S1.1) First, mix the selenium particles and solvent at a mass ratio of 1:10 to 1:100 to obtain a mixed solution;

[0012] S1.2) The mixed solution obtained in S1.1) is ultrasonically stirred to obtain a nano-selenium particle solution.

[0013] Furthermore, the particle size of the selenium particles in S1.1) is 1-1000 nm or 1-1000 μm; the solvent is an inorganic solvent or an organic solvent.

[0014] Furthermore, the specific process parameters for ultrasonic stirring in S1.2) are: stirring speed of 50-500 rpm and ultrasonic power of 5-20 kW.

[0015] Furthermore, the solvent includes organic solvents and inorganic solvents; the inorganic solvent includes pure water and ultrapure water; the organic solvent includes methanol, ethanol, propanol, acetone, dimethylamide, and toluene.

[0016] Furthermore, the coating method in S2) includes spin coating and blade coating; the coating thickness is 10μm to 1cm.

[0017] Furthermore, the surface of the copper substrate in S2) should be pre-treated for cleaning before coating. The pre-treatment for cleaning can be a variety of methods such as grinding and polishing, acid washing, and ultrasonic cleaning.

[0018] Furthermore, the heating temperature in S3) is ±20 degrees Celsius of the boiling point of the solvent in the nano-selenium particle solution, and the holding time is 5 to 10 minutes.

[0019] Furthermore, the heating method in S3) includes resistive and inductive methods.

[0020] Furthermore, the particle size of the copper selenide micro / nanoparticles is 1 nm to 1000 μm.

[0021] A copper selenide micro / nanoparticle is prepared using the method described above.

[0022] The beneficial effects of this invention are:

[0023] 1. The method described in this invention overcomes the safety hazards of the solvothermal high-pressure reaction of existing copper selenide particles, and prepares copper selenide micro and nano particles through atmospheric pressure reaction throughout the process. The process is simple and conducive to large-scale commercial production.

[0024] 2. The method described in this invention can be applied to the preparation of nano- and micro-sized copper selenide micro- and nano-sized particles, and even millimeter- or centimeter-sized large copper selenide particles. It has the characteristic of meeting multiple size requirements in one, thereby reducing the construction requirements and costs of the industrial copper selenide multi-scale particle industrial chain.

[0025] 3. The method described in this invention overcomes the shortcomings of existing synthesis technologies, which are time-consuming and involve many steps. By utilizing an integrated coating-evaporation-reaction technology, the reaction and conversion of selenium and copper, as well as powder drying, can be achieved simultaneously. The preparation of copper selenide micro-nano particles and powder collection can be realized within 5 to 10 minutes, which is time-efficient and can effectively reduce the time and economic costs of large-scale industrialization.

[0026] 4. The method described in this invention uses inexpensive raw materials and solvents that are widely available, which greatly reduces the preparation cost of copper selenide micro / nanoparticles. The preparation process is environmentally friendly and in line with the national policy of green and sustainable development. Attached Figure Description

[0027] Figure 1 This is a flowchart of an ultrafast preparation method for copper selenide micro / nanoparticles according to the present invention.

[0028] Figure 2 The image shows the morphology and elemental energy distribution of copper selenide nanoparticles prepared in Example 1 of this invention.

[0029] Figure 3 This is a size distribution diagram of the copper selenide nanoparticles prepared in Example 1 of the present invention.

[0030] Figure 4 This is a diagram showing the morphology and size distribution of copper selenide micron particles prepared in Example 2 of the present invention.

[0031] Figure 5 This is a diagram showing the morphology and size distribution of copper selenide micron particles prepared in Comparative Example 1 of this invention. Detailed Implementation

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0033] like Figure 1As shown, the present invention discloses an ultrafast preparation method for copper selenide micro / nanoparticles, characterized in that the method specifically includes the following steps:

[0034] S1) Prepare a solution of nano-selenium particles;

[0035] The specific steps are as follows:

[0036] S1.1) First, mix the selenium particles and solvent at a mass ratio of 1:10 to 1:100 to obtain a mixed solution;

[0037] S1.2) The mixed solution obtained in S1.1) is ultrasonically stirred to obtain a nano-selenium particle solution.

[0038] S2) The nano-selenium particle solution obtained in S1) is uniformly coated on the surface of the copper substrate.

[0039] S3) The copper substrate coated with selenium particles obtained in S2) is heated, kept at the temperature for a period of time, cooled to room temperature, and the powder on the surface of the copper substrate is collected to obtain copper selenide micro-nano particles.

[0040] The size of the selenium particles in S1) can be 1–1000 nm or 1–1000 μm;

[0041] In S1), the ratio of selenium particles to solvent is 1:10 to 1:100 by mass.

[0042] The solvent in S1) can be an inorganic solvent such as pure water or ultrapure water, or an organic solvent such as methanol, ethanol, propanol, acetone, dimethylamide, or toluene.

[0043] The stirring speed in S1) is 50-500 rpm, and the ultrasonic power is 5-20 kW.

[0044] The coating method of S2) can be a variety of coating methods such as spin coating and blade coating;

[0045] The coating thickness of S2) ranges from 10 μm to 1 cm;

[0046] The surface of the copper substrate in S2) should be cleaned and pretreated to ensure sufficient contact between the nano-selenium particles and the copper substrate.

[0047] The copper substrate heating method in S3) can be resistive or inductive.

[0048] The heating temperature of the copper substrate in S3) should be controlled within ±20 degrees of the boiling point temperature of the solvent in the nano-selenium particle solution to improve the preparation speed of ultrafine copper selenide nanopowder.

[0049] The heating time of the copper substrate in S3) is approximately 5 to 10 minutes;

[0050] The final cooling temperature of the copper substrate in S3) can be controlled between 25 and 50°C according to the actual production speed requirements.

[0051] The particle size of the copper selenide micro / nanoparticles can be controlled between 1 nm and 1000 μm.

[0052] Example 1

[0053] (1) Preparation of nano-selenium suspension: Nano-selenium particles with a size in the range of 1 to 500 nm were added to ethanol at a mass ratio of 1:50. The mixture was stirred at 200 rpm for 3 minutes and then ultrasonicated with an ultrasonic cleaner at a power of 10 kW for 2 minutes to obtain a uniformly mixed nano-selenium suspension.

[0054] (2) Preparation of copper selenide nanoparticles: The nano-selenium suspension obtained in the previous step was uniformly coated on the surface of a cleaned copper substrate after acid washing by spin coating. The coating thickness was 50 μm. Then, the temperature of the copper substrate was rapidly raised to 70 °C by resistance heating. After heating for 5 minutes, the powder on the surface of the copper substrate was collected to obtain copper selenide nanoparticles.

[0055] (3) The copper selenide nanoparticles prepared in the examples have a D50 of 352 nm and are mainly spherical in shape. The test results are shown in the attached figure. Figure 2 and 3 As shown.

[0056] Example 2

[0057] (1) Preparation of micron selenium suspension: Micron selenium particles with a size in the range of 1 to 10 μm are added to water at a mass ratio of 1:90. The mixture is stirred at 450 rpm for 5 minutes and then ultrasonicated with an ultrasonic cleaner at a power of 15 kW for 2 minutes to obtain a uniformly mixed micron selenium suspension.

[0058] (2) Preparation of copper selenide nanoparticles: The micron selenium suspension obtained in the previous step was uniformly coated on the surface of a cleaned copper substrate after ultrasonic cleaning by a scraping method. The coating thickness was 100 μm. Then, the temperature of the copper substrate was rapidly raised to 105 °C by inductive heating. After heating for 9 minutes, the powder on the surface of the copper substrate was collected to obtain copper selenide micron particles.

[0059] (3) The copper selenide micron particles prepared in the example have a D50 of 3.885 μm and are mainly spherical in shape. The test results are shown in the attached figure. Figure 4 As shown.

[0060] The above description represents a preferred embodiment of the present invention and is not intended to limit the invention. It is merely used to illustrate the detailed preparation process of the present invention and does not imply that the invention is limited to the above-described preparation process. Those skilled in the art should understand that any simple improvements and modifications to the technology of the present invention without departing from its scope are within the protection scope of the present invention.

[0061] Comparative Example 1

[0062] (1) Preparation of nano-selenium suspension: Nano-selenium particles with a size in the range of 1 to 500 nm were added to ethanol at a mass ratio of 1:5. The mixture was stirred at a speed of 10 rpm for 1 minute and then ultrasonicated with an ultrasonic cleaner at a power of 10 kW for 2 minutes to obtain the nano-selenium suspension.

[0063] (2) Preparation of copper selenide nanoparticles: The nano-selenium suspension obtained in the previous step was uniformly coated on the surface of a cleaned copper substrate after acid washing by a scraping method. The coating thickness was 1 cm. Then, the temperature of the copper substrate was rapidly raised to 70°C by resistance heating. After heating for 20 minutes, the powder on the surface of the copper substrate was collected.

[0064] (3) The copper selenide particles prepared in the example have a D50 of 4.442 μm, which does not meet the nanoscale requirement of particle size <1 μm. The test results are attached. Figure 5 As shown.

[0065] The preparation method of copper selenide micro / nanoparticles provided in the embodiments of this application has been described in detail above. The description of the above embodiments is only for the purpose of helping to understand the method and core idea of ​​this application; at the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the idea of ​​this application. Therefore, the content of this specification should not be construed as a limitation of this application.

[0066] Certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that hardware manufacturers may use different names to refer to the same component. This specification and claims do not distinguish components based on differences in name, but rather on differences in function. The terms "comprising" and "including" used throughout the specification and claims are open-ended and should be interpreted as "comprising / including but not limited to". "Approximately" means that within an acceptable margin of error, those skilled in the art can solve the technical problem and substantially achieve the technical effect within a certain margin of error. The following descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of illustrating the general principles of this application and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims.

[0067] It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a product or system comprising a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a product or system. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the product or system that includes said element.

[0068] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0069] The foregoing description illustrates and describes several preferred embodiments of this application. However, as previously stated, it should be understood that this application is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the application concept described herein through the foregoing teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this application should be within the protection scope of the appended claims.

Claims

1. A method for preparing copper selenide micro / nanoparticles, characterized in that, The preparation method specifically includes the following steps: S1) Prepare a solution of nano-selenium particles; S2) The nano-selenium particle solution obtained in S1) is uniformly coated on the surface of the copper substrate; S3) The copper substrate coated with selenium particles obtained in S2) is heated, kept at the temperature for a period of time, cooled to room temperature, and the powder on the surface of the copper substrate is collected to obtain copper selenide micro-nano particles. The heating temperature is ±20 degrees Celsius of the boiling point of the solvent in the nano-selenium particle solution, and the holding time is 5~10 minutes.

2. The preparation method according to claim 1, characterized in that, The specific steps of S1) are as follows: S1.1) First, mix the selenium particles and solvent at a mass ratio of 1:10 to 1:100 to obtain a mixed solution; S1.2) The mixed solution obtained in S1.1) is ultrasonically stirred to obtain a nano-selenium particle solution.

3. The preparation method according to claim 2, characterized in that, The selenium particles in S1.1) have a particle size of 1~1000 nm or 1~1000 μm; the solvent is an inorganic solvent or an organic solvent.

4. The preparation method according to claim 2, characterized in that, The specific process parameters for ultrasonic stirring in S1.2) are: stirring speed of 50~500 rpm and ultrasonic power of 5~20 kW.

5. The preparation method according to claim 2, characterized in that, The solvents include organic solvents and inorganic solvents; the inorganic solvents include pure water and ultrapure water; the organic solvents include methanol, ethanol, propanol, acetone, dimethylamide, and toluene.

6. The preparation method according to claim 1, characterized in that, The coating method in S2) includes spin coating and blade coating; the coating thickness is 10μm~1cm.

7. The preparation method according to claim 1, characterized in that, The heating methods in S3) include resistance heating and inductive heating.

8. The preparation method according to claim 1, characterized in that, The copper selenide micro / nanoparticles have a particle size of 1 nm to 1000 μm.

9. A copper selenide micro / nanoparticle, characterized in that, The copper selenide micro / nanoparticles are prepared using the preparation method described in any one of claims 1-8.

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