CN113084186A - Flower-shaped copper particle and preparation method thereof - Google Patents
Flower-shaped copper particle and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002245 particle Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940081974 saccharin Drugs 0.000 claims abstract description 14
- 235000019204 saccharin Nutrition 0.000 claims abstract description 14
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000005498 polishing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000004070 electrodeposition Methods 0.000 abstract description 5
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
本发明提供一种花形态铜颗粒，其尺寸为0.5μm～6μm，由20片～50片纳米片组成，纳米片的厚度为30nm～200nm。花形态铜颗粒的制备方法包括如下步骤：步骤S1：将无机铜盐溶解在蒸馏水中，加入聚乙二醇和糖精为添加剂，搅拌均匀，得到电解液；步骤S2：将石墨圆片进行打磨抛光处理，依次用无水乙醇和蒸馏水清洗，得到生长基底；步骤S3：将电解液倒入电解反应池，将阳极和生长基底分别连接直流稳压电源的正极和负极，并竖直插入电解反应池中的电解液中，进行电解；步骤S4：电解完成，将生长基底取出后，清洗、干燥，在生长基底表面得到所述花形态铜颗粒。本发明寻找到了一种利用电沉积法制备花形态铜颗粒的新方法。
The invention provides a flower-shaped copper particle, the size of which is 0.5 μm to 6 μm, and is composed of 20 to 50 nanosheets, and the thickness of the nanosheets is 30 nm to 200 nm. The preparation method of flower-shaped copper particles includes the following steps: step S1: dissolving inorganic copper salt in distilled water, adding polyethylene glycol and saccharin as additives, and stirring evenly to obtain an electrolyte; step S2: grinding and polishing the graphite disc , wash with absolute ethanol and distilled water in turn to obtain a growth substrate; Step S3: Pour the electrolyte into the electrolysis reaction cell, connect the anode and the growth base to the positive and negative electrodes of the DC power supply respectively, and insert them vertically into the electrolysis reaction cell In the electrolyte solution, electrolysis is performed; Step S4: after the electrolysis is completed, the growth substrate is taken out, cleaned and dried, and the flower-shaped copper particles are obtained on the surface of the growth substrate. The invention finds a new method for preparing flower-shaped copper particles by electrodeposition.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a flower-shaped copper particle and a preparation method thereof.
Background
Because of excellent performances in the aspects of heat, electricity, catalysis and the like, environmental friendliness and low price, research and preparation of copper micro-nano particles increasingly attract attention of researchers, and the copper micro-nano particles are widely applied to the aspects of microelectronics, semiconductors, catalysis, batteries, bacteriostasis, sterilization and the like.
By controlling the structural characteristics and the morphological characteristics of the copper particles, the performance of the copper particles can be regulated, controlled and optimized. At present, the form of micro-nano copper particles mainly comprises: a polyhedron; sheet-shaped; a rod shape; spherical; linear shape; dendritic, etc., with less reported grain morphology. The flower-shaped particles have the characteristic of large specific surface area, have the contact area with other substances which is several times larger than that of other forms, and have more active sites and better performance in the processes of reaction, test (such as Raman scattering) and the like.
At present, the preparation method of micro-nano copper particles mainly comprises the following steps: physical chemical deposition; mechanical grinding; electro-deposition; carrying out hydrothermal reduction; ultraviolet irradiation; ultrasonic synthesis, and the like. Many methods have the problems of high requirement on environment or environmental pollution, long experimental period, many process parameters, single prepared particle form (only one type can be prepared), and the like, such as: chinese patent 201810380253.4 discloses a method for preparing free flower-shaped copper particles without a template, which successfully prepares flower-shaped copper particles, but the steps are complicated, and have special requirements (such as vacuum) on the environment, the used instruments are expensive, and only the flower shape can be prepared. Zhang wenfeng et al disclose a method for preparing flower-like nano-copper by liquid phase chemical reduction in the preparation and antibacterial properties of flower-like nano-copper, which shows excellent antibacterial and bacteriostatic properties, but the reaction period is longer, the prepared nano-copper petals are less, and the specific surface area is not increased sufficiently. The electrodeposition method is widely applied to the synthesis of copper particles as a mature preparation method, and is simple and easy to operate. Meanwhile, the micro-nano particles are easy to agglomerate in the preparation process due to high surface energy. Aiming at the problems, the invention aims to provide a flower-shaped copper particle and an electrodeposition preparation method thereof, wherein the preparation method is simple and easy to operate, has no special requirement on environment, and the prepared particle petals are rich.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides a flower-shaped copper particle and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a flower-shaped copper particle, characterized in that: the flower-shaped copper particles have the size of 0.5-6 mu m and consist of 20-50 nanosheets, and the thickness of the nanosheets is 30-200 nm.
A preparation method of flower-shaped copper particles is characterized by comprising the following steps:
step S1: dissolving inorganic copper salt in distilled water, adding polyethylene glycol and saccharin as additives, and uniformly stirring to obtain electrolyte;
step S2: polishing the graphite wafer, and sequentially cleaning with absolute ethyl alcohol and distilled water to obtain a growth substrate;
step S3: pouring the electrolyte into an electrolytic reaction tank, respectively connecting an anode and a growth substrate with a positive electrode and a negative electrode of a direct current stabilized voltage power supply, vertically inserting the anode and the growth substrate into the electrolyte in the electrolytic reaction tank, and electrolyzing;
step S4: and (4) after the electrolysis is finished, taking out the growth substrate, cleaning and drying to obtain the flower-shaped copper particles on the surface of the growth substrate.
Further, in step S1, the inorganic copper salt is one or more of copper sulfate, copper nitrate or copper chloride.
Further, the concentration of each component in the electrolyte obtained in step S1 is: cu2+In the concentration range of200 mmol/L-400 mmol/L, polyethylene glycol concentration range of 20 mmol/L-30 mmol/L, and saccharin concentration range of 0.5 g/L-1 g/L.
Further, in step S2, the mode of the grinding and polishing process is: the side surfaces of the graphite wafer were polished with 400 mesh, 1000 mesh, 2000 mesh, 4000 mesh and 10000 mesh silicon carbide sandpaper in this order, and then polished to a mirror surface.
Further, in step S2, one side surface of the graphite wafer is polished, the other side surface of the graphite wafer is insulated with a photoresist, and then washed with absolute ethyl alcohol and distilled water in sequence to obtain a growth substrate.
Further, in step S2, the graphite wafer has a diameter of 5mm to 10mm and a thickness of 2mm to 4 mm.
Further, in step S3, the electrolysis process is a constant voltage electrolysis process or a constant current electrolysis process.
Further, in step S3, during the electrolysis, the electrolysis parameters are: the voltage is 15V-20V, the current is 1A-2A, the time is 4 min-6 min, the temperature is room temperature, and the atmosphere is air.
Further, in step S3, the anode and the growth substrate are spaced apart by a distance of 4cm to 6 cm.
Further, the anode is an inert electrode or a copper electrode. The inert electrode is made of a material which does not lose electrons and does not react with the electrolyte during electrolysis, and the electrolyte contains inorganic copper salt, so that the inert electrode comprises metals (such as Pt, Au, W and the like) which are not as active as copper in a metal activity sequence table, a non-metal electrode (such as a graphite electrode) and the like; the copper electrode can supplement Cu in the electrolyte2+。
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention uses graphite wafer as growing base to connect power negative pole, uses polyethylene glycol and saccharin as additive, finds a new method for preparing flower-shaped copper particles by electrodeposition method, the obtained flower-shaped copper particles have higher specific surface area than other common copper particles with shape structure, and have more petals and surface area than the published flower-shaped copper particles.
Drawings
FIG. 1 is a high resolution scanning electron micrograph of flower-shaped copper particles prepared according to example 1;
FIG. 2 is a low resolution scanning electron micrograph of the flower-shaped copper particles prepared in example 1;
FIG. 3 is a high resolution scanning electron micrograph of non-flower shaped copper particles prepared according to example 3;
FIG. 4 is a low resolution scanning electron micrograph of the non-flower shaped copper particles prepared in example 3.
Detailed Description
Example 1
Step S1: dissolving inorganic copper salt in distilled water, adding polyethylene glycol and saccharin as additives, and uniformly stirring to obtain electrolyte; the concentration of each component in the electrolyte is as follows: cu2+The concentration of the saccharin is 200mmol/L, the concentration range of the polyethylene glycol is 20mmol/L, and the concentration range of the saccharin is 0.5 g/L;
step S2: grinding one side surface of the graphite wafer by using 400-mesh, 1000-mesh, 2000-mesh, 4000-mesh and 10000-mesh silicon carbide abrasive paper in sequence, then polishing the side surface to a mirror surface, performing insulation treatment on the other side surface of the graphite wafer by using a photoresist, and then cleaning by using absolute ethyl alcohol and distilled water in sequence to obtain a growth substrate; the diameter of the graphite wafer is 5mm, and the thickness of the graphite wafer is 2 mm;
step S3: pouring the electrolyte into an electrolytic reaction tank, respectively connecting an anode and a growth substrate with a positive electrode and a negative electrode of a direct current stabilized voltage power supply, vertically inserting the anode and the growth substrate into the electrolyte in the electrolytic reaction tank, and electrolyzing; the anode is a tungsten electrode; the spacing distance between the anode and the growth substrate is 4cm, the electrolysis process is a constant-voltage electrolysis process, and the electrolysis parameters are as follows: voltage 15V, current 1A, time 6min, temperature room temperature, atmosphere is air.
Step S4: and (4) after the electrolysis is finished, taking out the growth substrate, cleaning and drying to obtain the flower-shaped copper particles on the surface of the growth substrate.
Fig. 1 and 2 are high-and low-resolution scanning electron micrographs of flower-shaped copper particles prepared in example 1 of the present invention, the size of the flower-shaped copper particles being 1 to 6 μm, the thickness of the nanosheets constituting the copper particles being 50 to 200nm, each copper particle being composed of about 20 to 50 nanosheets.
Example 2
Step S1: dissolving inorganic copper salt in distilled water, adding polyethylene glycol and saccharin as additives, and uniformly stirring to obtain electrolyte; the concentration of each component in the electrolyte is as follows: cu2+The concentration range of the saccharin is 400mmol/L, the concentration range of the polyethylene glycol is 30mmol/L, and the concentration range of the saccharin is 1 g/L;
step S2: sequentially grinding two side surfaces of the graphite wafer by using 400-mesh, 1000-mesh, 2000-mesh, 4000-mesh and 10000-mesh silicon carbide abrasive paper, polishing the two side surfaces to a mirror surface, and sequentially cleaning by using absolute ethyl alcohol and distilled water to obtain a growth substrate; the diameter of the graphite wafer is 10mm, and the thickness of the graphite wafer is 4 mm;
step S3: pouring the electrolyte into an electrolytic reaction tank, respectively connecting an anode and a growth substrate with a positive electrode and a negative electrode of a direct current stabilized voltage power supply, vertically inserting the anode and the growth substrate into the electrolyte in the electrolytic reaction tank, and electrolyzing; the anode is a tungsten electrode; the spacing distance between the anode and the growth substrate is 6cm, the electrolysis process is a constant-voltage electrolysis process, and the electrolysis parameters are as follows: voltage 20V, current 2A, time 4min, temperature room temperature, atmosphere is air.
Step S4: and (4) after the electrolysis is finished, taking out the growth substrate, cleaning and drying to obtain the flower-shaped copper particles on the surface of the growth substrate.
The flower-shaped copper particles prepared in example 2 have a size of 0.5 to 6 μm, and the thickness of the nanosheets constituting the copper particles is 30 to 50nm, each copper particle being composed of about 20 to 50 nanosheets.
Example 3
Step S1: dissolving inorganic copper salt in distilled water, adding gelatin as an additive, and uniformly stirring to obtain an electrolyte; the concentration of each component in the electrolyte is as follows: cu2+The concentration range of (1) is 200mmol/L, and the concentration of the gelatin is 1 g/L;
step S2: grinding one side surface of the graphite wafer by using 400-mesh, 1000-mesh, 2000-mesh, 4000-mesh and 10000-mesh silicon carbide abrasive paper in sequence, then polishing the side surface to a mirror surface, performing insulation treatment on the other side surface of the graphite wafer by using a photoresist, and then cleaning by using absolute ethyl alcohol and distilled water in sequence to obtain a growth substrate; the diameter of the graphite wafer is 5mm, and the thickness of the graphite wafer is 2 mm;
step S3: pouring the electrolyte into an electrolytic reaction tank, respectively connecting an anode and a growth substrate with a positive electrode and a negative electrode of a direct current stabilized voltage power supply, vertically inserting the anode and the growth substrate into the electrolyte in the electrolytic reaction tank, and electrolyzing; the anode is a tungsten electrode; the spacing distance between the anode and the growth substrate is 4cm, the electrolysis process is a constant-voltage electrolysis process, and the electrolysis parameters are as follows: voltage 15V, current 1A, time 6min, temperature room temperature, atmosphere is air.
Step S4: and (4) after the electrolysis is finished, taking out the growth substrate, cleaning and drying to obtain the copper particles in the non-flower shape on the surface of the growth substrate.
FIGS. 3 and 4 are high-and low-resolution scanning electron micrographs of non-flower-shaped copper particles prepared according to example 3 of the present invention, the copper particles having a size of 400nm to 800nm, which do not exhibit flower morphology.
For the sake of non-misunderstanding, it is said that "the anode and the growth substrate are connected to the anode and the cathode of the dc regulated power supply respectively" means "the anode is connected to the anode of the dc regulated power supply, and the growth substrate is connected to the cathode of the dc regulated power supply".
The experiments of the embodiment 1 and the embodiment 2 show that the graphite wafer is used as a growth substrate, connected with a power supply negative electrode, and electrolyzed by using polyethylene glycol and saccharin as additives, so that flower-shaped copper particles can grow, the size of the flower-shaped copper particles is 0.5-6 μm, the flower-shaped copper particles are composed of 20-50 nanosheets, and the thickness of the nanosheets is 30-200 nm. Example 3 as a comparative example to example 1, it differs from example 1 only in that example 3 uses gelatin as an additive, whereas the electrodeposited product is a non-flower-shaped copper particle.
Claims (10)
1. A flower-shaped copper particle, characterized in that: the flower-shaped copper particles have the size of 0.5-6 mu m and consist of 20-50 nanosheets, and the thickness of the nanosheets is 30-200 nm.
2. A method for producing flower-shaped copper particles according to claim 1, comprising the steps of:
step S1: dissolving inorganic copper salt in distilled water, adding polyethylene glycol and saccharin as additives, and uniformly stirring to obtain electrolyte;
step S2: polishing the graphite wafer, and sequentially cleaning with absolute ethyl alcohol and distilled water to obtain a growth substrate;
step S3: pouring the electrolyte into an electrolytic reaction tank, respectively connecting an anode and a growth substrate with a positive electrode and a negative electrode of a direct current stabilized voltage power supply, vertically inserting the anode and the growth substrate into the electrolyte in the electrolytic reaction tank, and electrolyzing;
step S4: and (4) after the electrolysis is finished, taking out the growth substrate, cleaning and drying to obtain the flower-shaped copper particles on the surface of the growth substrate.
3. The method for preparing flower-shaped copper particles according to claim 2, wherein in step S1, the inorganic copper salt is one or more of copper sulfate, copper nitrate or copper chloride.
4. The method for producing flower-shaped copper particles according to claim 2, wherein the electrolyte obtained in step S1 contains the following components in concentrations: cu2+The concentration range of the saccharin is 200 mmol/L-400 mmol/L, the concentration range of the polyethylene glycol is 20 mmol/L-30 mmol/L, and the concentration range of the saccharin is 0.5 g/L-1 g/L.
5. The method for producing flower-shaped copper particles according to claim 2, wherein in step S2, the polishing process is performed by: the side surfaces of the graphite wafer were polished with 400 mesh, 1000 mesh, 2000 mesh, 4000 mesh and 10000 mesh silicon carbide sandpaper in this order, and then polished to a mirror surface.
6. The method for producing flower-shaped copper particles as claimed in claim 2, wherein in step S2, one side surface of the graphite wafer is subjected to a grinding and polishing treatment, the other side surface of the graphite wafer is subjected to an insulating treatment with a photoresist, and thereafter, the wafer is washed with absolute ethyl alcohol and distilled water in this order to obtain a growth substrate.
7. The method for producing flower-shaped copper particles according to claim 2, wherein in step S2, the graphite wafer has a diameter of 5mm to 10mm and a thickness of 2mm to 4 mm.
8. The method for producing flower-shaped copper particles according to claim 2, wherein in step S3, the electrolysis process is a constant-voltage electrolysis process or a constant-current electrolysis process.
9. The method for producing flower-shaped copper particles according to claim 2, wherein in step S3, the electrolysis parameters during electrolysis are: the voltage is 15V-20V, the current is 1A-2A, the time is 4 min-6 min, the temperature is room temperature, and the atmosphere is air.
10. The method for producing flower-shaped copper particles according to claim 2, wherein the anode is spaced apart from the growth substrate by a distance of 4cm to 6cm in step S3.
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