A device for preparing metal particles by continuous electrochemical deposition

Abstract

A device for preparing metal particles by continuous electrochemical deposition, the device mainly includes: an electrodeposition tank (anode, electrolyte, cathode), a cleaning tank, a collection tank (collection component), etc. The advantages of this device are: the entire electrodeposition collection process is completed in one device, the cathode is designed as a reciprocating strip, and is organically combined with the collection device, and the modular design prevents the two processes from interfering with each other; the metal particles are collected by mechanical stripping, avoiding a large amount of surfactants in traditional chemical synthesis methods; the electrolyte in the entire synthesis process can be reused, does not require a large amount of organic additives, and has excellent environmental benefits; the device has good universality and is suitable for a variety of metals.

Description

Technical Field

[0001] The present invention relates to the field of metal particle synthesis, and in particular, to low-contact-force metal particles and a device for preparing corresponding metal particles by regulating their particle size through continuous electrochemical deposition. Background Art

[0002] Metal particle materials are an important component of metal materials. In recent years, with the discovery of various novel properties of metal particles, the field of metal particles has achieved vigorous development and has become a key basic material for the preparation of various new functional materials.

[0003] The development of methods for preparing metal particles is the foundation for the development of metal science. There are two main ways to prepare metal particles traditionally: one is chemical method, including liquid phase reduction method and high temperature pyrolysis method. Liquid phase reduction method includes hydrothermal method, solvent thermal method and other methods. Liquid phase reduction method can well control the morphology and growth process of particles, but the yield of liquid phase synthesis reaction is very low. A large amount of surfactant needs to be added during the synthesis process, which is easy to contaminate the surface of synthesized particles and subsequently produce a large amount of wastewater. High temperature pyrolysis method and arc evaporation condensation method are also common methods for synthesizing metal particles, but this method is energy-intensive, and the synthesized metal particles often have a wide particle size distribution, which is mostly suitable for micron-sized particles.

[0004] Another commonly used approach is the physical method. Commonly used physical crushing methods and evaporation condensation methods, such as ball milling, mechanical crushing, and ultrasonic crushing, are used to subdivide and crush bulk metal raw materials to prepare particles. However, the particle size is often large and unevenly distributed, and the obtained material has many defects.

[0005] In general, the chemical method for preparing metal particles has low energy consumption, simple process, and good product morphology uniformity; the physical method produces metal particles with clean surface and fewer impurities, but the cost is high and the production efficiency is low.

[0006] Metal electrodeposition refers to the use of electrochemical principles to deposit metal ions in the solution onto the cathode surface in a suitable electrolyte by forming an electrodeposition circuit with an anode and a cathode under the action of a DC electric field or a pulsed electric field.

[0007] Traditional metal electrodeposition is often used to prepare thin film materials for decorative, wear-resistant, anti-corrosion and other protective applications, or to prepare new functional coatings, such as electrical performance coatings, semiconductor performance coatings, etc. By controlling the nucleation and growth process of the electrodeposition process, particles can be prepared by electrodeposition. However, the limited electroplating particle materials that have been publicly reported and synthesized are very limited, and most of them are only limited to the synthesis of a small amount of materials or the modification of the substrate surface.

[0008] CN201710098703.6 discloses a method and device for preparing metal powder by electrodeposition, wherein graphite felt or carbon felt is used as anode material to electrolyze electrolyte, and the shape and size of the metal powder deposited at the cathode can be adjusted by adjusting the working current. Since the method uses graphite felt or carbon felt as the anode, its extremely large specific surface area can enable the anode to obtain a large working current at a very small current density, showing characteristics different from those of traditional planar electrodes, and can overcome the "air curtain" and electro-corrosion phenomena of traditional dense anode materials; the change in cathode current density causes the cathode product to change from dense to loose, the shape changes from blocks and sheets to particles and powders, and the shape changes from large to small, and powdered metal can be obtained. It can be seen that this method requires the use of special anode materials and requires a large cathode current density. Although this method can realize the continuous production of metal powder prepared by electrodeposition, the production cost is high and the industrialization prospect is difficult.

[0009] CN201720061248.8 discloses a device for preparing electrolytic silver powder, including an electrodeposition tank, a chain plate, a chain and a scraper, and a transmission motor for driving the chain plate to rotate. The electrodeposition tank has a powder sinking bottom surface for depositing electrolytic silver powder, and a powder outlet inclined surface that connects the powder sinking bottom surface and the powder outlet and is gradually inclined. The chain is continuously arranged along the powder sinking bottom surface and the powder outlet inclined surface to the vicinity of the powder outlet, and is driven by a number of chain plates arranged along the chain to form a rotary conveyor chain that runs back and forth along the powder sinking bottom surface to the vicinity of the powder outlet. A number of scrapers are distributed along the length direction of the chain, and each scraper is close to the powder sinking bottom surface or the powder outlet inclined surface when it runs on the chain to the lower conveying surface of the rotary conveyor chain. The device can achieve rapid powder discharge, but its essence is the adjustment after the electrolysis process, and does not involve the control of the electrolysis process.

[0010] Therefore, how to design a reasonable electrolysis or electrodeposition device to achieve continuous production of metal particles while effectively controlling the particle size and quickly collecting the resulting metal particles has always been a research difficulty in the field of metal particle preparation. Summary of the invention

[0011] In response to the problems in the prior art, the purpose of the present invention is first to provide a device for preparing metal particles by continuous electrodeposition. The device deposits metal particles on the cathode by adjusting the moving speed of the cathode. The contact force between the metal particles and the cathode is very small, and the metal particles are easily separated from the cathode. At the same time, the size of the metal particles can be effectively controlled.

[0012] A device for preparing metal particles by continuous electrodeposition by controlling the cathode speed, wherein the contact force between the prepared metal particles and the cathode is less than 25nN, or the shear strength is less than 1MPa, the device comprising:

[0013] (a) a power source, an electrodeposition tank, a cleaning tank, and a collecting tank, wherein the electrodeposition tank, the cleaning tank, and the collecting tank are connected in sequence, the power source adjusts the electrochemical deposition parameters, and performs constant current or constant voltage mode electrodeposition, and the current density range during the constant current mode is 0 to 10 mA / cm 2 , the voltage range during constant voltage mode is 0~10V;

[0014] (b) an anode and a cathode disposed opposite to each other in an electrodeposition cell;

[0015] (c) The cathode is a conductive strip material with a polished surface, which passes through an electrodeposition tank, a cleaning tank, and a collection tank continuously and sequentially;

[0016] (d) the cleaning tank has a liquid inlet and a liquid outlet for the cleaning liquid;

[0017] (e) There is a brush in the collecting tank, the diameter of the brush is 5-10 cm, and the length of the bristles is about 1-2 cm.

[0018] Preferably, the cathode is a continuous, circulating conductive strip material, which continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank, and circulates from the collecting tank to the electrodeposition tank.

[0019] Preferably, the cathode is a stainless steel belt, a titanium belt, or a copper belt, and is driven by rollers in the electrodeposition tank, the cleaning tank, and the collecting tank to achieve continuous and cyclic motion.

[0020] Preferably, the width of the cathode is 1 to 15 cm.

[0021] Preferably, the width of the cathode is 2 to 10 cm.

[0022] Preferably, the rollers include a power roller and a driven roller.

[0023] Preferably, a roller support is provided in the electrodeposition tank, the cleaning tank and the collecting tank.

[0024] Preferably, air knives are provided in the electrodeposition tank, the cleaning tank and the collecting tank, and the air knives respectively perform air blowing treatment on the cathode after electrodeposition, the cathode after cleaning and the cathode after scraping off the electrodeposited metal particles.

[0025] Preferably, the brush is an electric brush.

[0026] Preferably, according to the demand for electrodeposited metal particles, the technical solution of the present invention can omit the cleaning tank. That is, the cathode directly enters the collecting tank after the metal particles are electrodeposited in the electrodeposition tank, and the metal particles are separated from the cathode. At the same time, the spatial arrangement of the electrodeposition tank, the cleaning tank, and the collecting tank of the present invention can be arranged in the same plane or in different planes above and below, and there is no need for special restrictions.

[0027] According to the device of the present invention, it is possible to realize continuous preparation of metal particles, that is, a method for preparing metal particles by continuous electrodeposition by controlling the speed of the cathode substrate, wherein the contact force between the prepared metal particles and the cathode substrate is less than 25nN, or the shear strength is less than 1MPa, and the preparation method comprises:

[0028] (1) preparing electrolyte;

[0029] (2) Selecting a cathode substrate that can move continuously, the surface of which is polished;

[0030] (3) Adjust the electrochemical deposition parameters to perform constant current or constant voltage mode electrodeposition. The current density range during the constant current mode is 0 to 10 mA / cm 2 , the voltage range during constant voltage mode is 0~10V;

[0031] (4) The cathode substrate continuously and sequentially passes through the electrodeposition area, the cleaning area, and the stripping area;

[0032] (5) In the electrodeposition zone, the cathode substrate moves continuously in the electrolyte at a speed of 0.03 cm / s to 30 cm / s, and metal particles are deposited on the cathode substrate. The average particle size of the metal particles is 10 nm to 500 nm;

[0033] (6) In the cleaning area, the metal particles deposited on the surface of the cathode substrate are cleaned;

[0034] (7) In the stripping area, the metal particles deposited on the surface of the cathode substrate are stripped and collected using physical friction methods.

[0035] Preferably, the contact force between the prepared metal particles and the cathode is 2-23 nN, preferably 5-15 nN, or the shear strength is 0.1-0.7 MPa, preferably 0.2-0.5 MPa.

[0036] Preferably, the moving speed of the cathode is 0.5-30 cm / s, and the average particle size of the metal particles is 20-400 nm.

[0037] Preferably, the moving speed of the cathode is 1-20 cm / s, and the average particle size of the metal particles is 25-280 nm.

[0038] Preferably, the moving speed of the cathode is 1.5-10 cm / s, and the average particle size of the metal particles is 60-270 nm.

[0039] Preferably, the moving speed of the cathode is 2 cm / s, and the average particle size of the metal particles is 126 nm.

[0040] Preferably, the particle density at the particle deposition site on the cathode is 0.8×10 8 / cm2 -9×10 8 / cm 2 Preferably, the particle density is 1.0×10 8 / cm 2 -4×10 8 / cm 2 .

[0041] Preferably, the residence time of the particle deposition site of the cathode in the electrolyte is 0.5-490 s.

[0042] Preferably, the residence time of the particle deposition site of the cathode in the electrolyte is 1-300 s.

[0043] Preferably, the residence time of the particle deposition site of the cathode in the electrolyte is 5-50 s.

[0044] Preferably, the length of the portion of the cathode immersed in the electrolyte along the moving direction is greater than 5 cm.

[0045] Preferably, the length of the portion of the cathode immersed in the electrolyte is 10-50 cm along the moving direction.

[0046] Preferably, the current density range during the constant current mode is 0.2-3 mA / cm 2 , the voltage range during the constant voltage mode is 0.3~3V.

[0047] Preferably, the current density range during the constant current mode is 0.5-1 mA / cm 2 , the voltage range during the constant voltage mode is 1 to 2.5V.

[0048] Preferably, the metal particles include silver particles, nickel particles, copper particles, gold particles, and copper-nickel alloy particles.

[0049] Preferably, the electrolyte of the electrodeposition tank is one of the following electrolytes: (1) silver electrolyte, a mixed solution of 1-15 g / L AgNO3, 5-75 g / L Na2S2O3·5H2O, 1-15 g / L K2SO3 and 2-15 g / L H3BO3; (2) nickel electrolyte, a mixed solution of 10-50 g / L NiSO4·6H2O, 1.5-7 g / L NiCl2·6H2O, and 5-20 g / L H3BO3; (3) copper electrolyte, a 1-10 g / L CuSO4·5H2O solution, the pH value of which is adjusted to 1 using H2SO4; (4) gold electrolyte, a mixed solution of 10-30 g / L ammonium citrate, 2.5-10 g / L chloroauric acid and 10-15 g / L (5) Cobalt-nickel alloy electrolyte, a mixed solution of 5-10 g / L NiSO4·6H2O, 5-10 g / L CoSO4·7H2O, 2.5-10 g / L H3BO3 and 0-1 g / L KCl.

[0050] Preferably, the electrolyte of the electrodeposition tank is one of the following electrolytes: (1) silver electrolyte, a mixed solution of 2-8 g / L AgNO3, 15-35 g / L Na2S2O3·5H2O, 3-10 g / L K2SO3 and 2-10 g / L H3BO3; (2) nickel electrolyte, a mixed solution of 20-30 g / L NiSO4·6H2O, 2.5-4 g / L NiCl2·6H2O, and 8-15 g / L H3BO3; (3) copper electrolyte, a 2-8 g / L CuSO4·5H2O solution, the pH value of which is adjusted to 1 using H2SO4; (4) gold electrolyte, a mixed solution of 15-25 g / L ammonium citrate, 4-7 g / L chloroauric acid and 12-14 g / L Na2SO3; (5) cobalt-nickel alloy electrolyte, a mixed solution of 6-8 g / L A mixed solution of NiSO4·6H2O, 5.5~7g / L CoSO4·7H2O, 4~6g / L H3BO3 and 0.3~0.7g / L KCl.

[0051] Preferably, the electrolyte of the electrodeposition tank is one of the following electrolytes: (1) silver electrolyte, a mixed solution of 5g / L AgNO3, 25g / L Na2S2O3·5H2O, 5g / L K2SO3 and 5g / L H3BO3; (2) nickel electrolyte, a mixed solution of 25g / L NiSO4·6H2O, 3.75g / L NiCl2·6H2O, and 10g / L H3BO3; (3) copper electrolyte, a 5g / L CuSO4·5H2O solution, the pH value of which is adjusted to 1 using H2SO4; (4) gold electrolyte, a mixed solution of 20g / L ammonium citrate, 5g / L chloroauric acid and 13.7g / L Na2SO3; (5) cobalt-nickel alloy electrolyte, 6.75g / L NiSO4·6H2O, 6.25g / L CoSO4·7H2O, 5g / L A mixed solution of H3BO3 and 0.5g / L KCl.

[0052] Preferably, the cathode continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, so that the cathode forms a continuous and cyclic movement.

[0053] Preferably, the physical friction method in the collection tank is to use a brush to rub and collect the metal particles through the non-woven fabric. Taking silver particles as particles, the maximum particle density (surface density) of silver particles is about 4×10 8 / cm 2 , the contact area between the brush and the cathode (such as stainless steel belt) is less than 6cm 2 , so the force required to brush all particles at the same time is less than 10N, which is much smaller than the brushing force that a general brush can provide. Therefore, since the contact force between the metal particles obtained by electrodeposition and the cathode is small, the present invention can separate the electrodeposited metal particles from the cathode by using physical friction similar to a brush, and the separation effect is far better than other existing methods.

[0054] Preferably, in the cleaning tank, residual electrolyte on the cathode surface is removed by water washing, and if necessary, the metal particles deposited on the cathode surface can be functionally modified. That is to say, the present invention does not limit the other treatment and modification of the metal particles deposited on the cathode surface while cleaning the cathode.

[0055] According to the technical solution of the present invention, when negative pressure is applied to the cathode during the electrodeposition process, the metal ions in the electrolyte are reduced to elemental metals on the cathode surface. The cathode in the present invention can move relative to the anode, and the metal particles obtained by electrodeposition on the movable cathode surface are evenly distributed. By controlling the moving speed of the cathode, adjusting the residence time of the cathode in the electrolyte, controlling the particle size of the electrodeposited metal particles, and the contact force between the particles and the cathode, the continuous preparation of easily separable metal particles with controllable particle size is achieved.

[0056] The deposition and growth process of metal particles can be understood through the electrochemical aggregation growth mechanism. First, under the influence of the applied potential, small single-crystalline primary nanoclusters grow on the cathode by direct attachment and random distribution. Subsequently, the small nanoclusters diffuse on the substrate, aggregate, and grow further by recrystallization.

[0057] At the same time, in the technical solution of the present invention, according to the cognition of the inventors of the present invention, the cathode moves continuously while adjusting the electrodeposition parameters so that certain side reactions occur on the surface of the electrode substrate, such as hydrogen evolution reaction. The movement of the cathode shortens the moving distance of the metal ions during the electrodeposition process to a certain extent, realizes rapid diffusion and aggregation, and reduces the contact area between the electrodeposited metal and the surface to weaken its bonding force with the substrate.

[0058] According to the technical solution of the present invention, the adhesion force (i.e., contact force) between a single metal particle on the cathode and the cathode is less than 25 nN. All metal particles electrodeposited on the substrate can be collected by simple physical friction, so that the cathode is restored to cleanliness and can be reused for electrodeposition, thus realizing continuous and cyclic electrodeposition of metal particles.

[0059] The metal particles prepared according to the present invention are evenly dispersed and can be prepared into a highly conductive slurry, which is applied to fields such as printed electronics. The prepared printed circuit has excellent flexibility.

[0060] At the same time, the metal particles can be surface modified according to the requirements of their performance. Such surface modification can be carried out in the metal particle cleaning tank, after the cleaning tank, or after the metal particles are separated, without any special restrictions.

[0061] Beneficial effects achieved by the present invention:

[0062] 1. The present invention controls the contact force (i.e., adhesion) between the electrodeposited metal particles and the cathode by controlling the movement of the cathode. The contact force between the electrodeposited metal particles and the cathode is very small, and the electrodeposited metal particles can be peeled off from the cathode by simple physical friction. This peeling method is better than the existing ultrasonic de-powdering method, requires low energy consumption, and avoids the impact on the reuse of the cathode, thereby realizing the continuous and cyclic use of the cathode.

[0063] 2. The present invention realizes the continuous production of metal particles prepared by electrodeposition. Through the continuous and cyclic movement of the cathode, continuous electrodeposition and continuous particle collection are realized. It can be applied on a large scale and is easy to industrialize.

[0064] 3. The present invention realizes effective control of the particle size of metal particles during the electrodeposition process. By selecting the moving speed of the cathode and the electrodeposition parameters, the deposition speed and deposition time of the metal particles can be reasonably regulated, and the particle size of the obtained metal particles can be effectively regulated within the range of 10nm to 500nm, and the particle size distribution is uniform.

[0065] 4. The present invention is suitable for preparing various metal particles and alloy particles and has a wide range of applications.

[0066] The advantages of the device of the present invention are: the entire electrodeposition collection process is completed in one device, the cathode is designed to be a reciprocating strip and is organically combined with the collection device, and the modular design prevents the two processes from interfering with each other; the metal particles are collected by mechanical stripping, avoiding the large amount of surfactants in the traditional chemical synthesis method; the electrolyte in the entire synthesis process can be reused, does not require a large amount of organic additives, and has excellent environmental benefits; the device has good universality and is suitable for a variety of metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0068] 1. Anode lead, 2. Power supply, 3. Drain port of electrodeposition tank, 4. Anode, 5. Electrodeposition tank, 6. Liquid outlet of cleaning tank, 7. Cleaning tank, 8. Collection tank, 9. Roller bracket in tank, 10. Electric brush, 11. Collection port, 12. Roller bracket, 13. Driven roller, 14. Air knife, 15. Cover, 16. Cathode, 17. Power roller

[0069] Figure 1 The invention relates to a device for continuous electrochemical deposition of metal particles.

[0070] Figure 2 It is a schematic diagram of the layout of the continuous electrochemical deposition metal particle device of the present invention.

[0071] Among them, the spatial layout of the electrodeposition tank, the cleaning tank, and the collecting tank can be adjusted according to actual needs, and the cleaning tank can also be omitted, so that only the electrodeposition tank and the collecting tank are used.

[0072] Figure 3 This is the morphology of the electrodeposited silver particles in Example 2.

[0073] Figure 4 This is the morphology of the electrodeposited silver particles in Example 3 (v=2 cm / s, 1 cm / s, 0.1 cm / s).

[0074] Figure 5 (a) is a graph showing the relationship between the particle size of the silver particles in Example 2 and the moving speed of the substrate; and (b) is an XRD spectrum of the silver particles in Example 2.

[0075] Figure 6 The figure below is the lateral force test curve of the electrodeposited silver nanoparticles in Example 2. The left figure is a schematic diagram of the relationship between the lateral force and the moving distance. The right figure is a diagram of the relationship between the lateral force and the moving distance of a single specific silver nanoparticle of different particle sizes (the particle size d in the figure is the particle size of the test particle, not the average particle size of the product obtained in Example 1). The lateral force is equivalent to the contact force.

[0076] Figure 7 The morphology and XRD of the metal particles electrodeposited in Examples 4-7 are: (a) nickel particles; (b) copper particles; (c) gold particles; (d) cobalt-nickel alloy particles. DETAILED DESCRIPTION

[0077] The contact force between the metal particles and the substrate in the present invention is tested by an atomic force microscope. The probe of the microscope is brought into contact with each nanoparticle, and the contact force of each particle is tested by directly moving the single nanoparticle. The contact force changes as follows: Figure 6 shown.

[0078] The calculation formula of shear strength is as follows:

[0079]

[0080] Among them, F A is the value obtained by the test, F f is the friction force when no load is applied, A particle is the contact area between the particle and the substrate.

[0081] The present invention will be further described below in conjunction with specific embodiments. These embodiments are only used to illustrate the present invention and should not be construed as limiting the present invention. In addition, it should be understood that after reading the contents disclosed in the present invention, those skilled in the relevant art may make various modifications to the present invention, and these equivalent forms are also within the scope of the claims attached to the present invention.

[0082] Example 1

[0083] A device for preparing metal particles by continuous electrodeposition by controlling the cathode speed, wherein the contact force between the prepared metal particles and the cathode is less than 25nN, or the shear strength is less than 1MPa, such as Figure 1 As shown, the device comprises:

[0084] (a) a power source (2), an electrodeposition tank (5), a cleaning tank (7), and a collecting tank (8), wherein the electrodeposition tank (5), the cleaning tank (7), and the collecting tank (8) are connected in sequence, and the power source (2) adjusts the electrochemical deposition parameters to perform constant current or constant voltage mode electrodeposition, and the current density range during the constant current mode is 0 to 10 mA / cm 2, the voltage range during constant voltage mode is 0~10V;

[0085] (b) an anode (4) and a cathode (16) arranged opposite to each other in an electrodeposition tank (5); the anode (4) is connected to a power source (2) via an anode lead (1), and the cathode (16) is connected to a cathode lead via a cathode lead;

[0086] (c) the cathode (16) is a conductive strip material with a polished surface, and passes through the electrodeposition tank (5), the cleaning tank (7), and the collecting tank (8) continuously and sequentially;

[0087] The cathode (16) is a stainless steel belt, a titanium belt or a copper belt, and is driven by rollers in the electrodeposition tank (5), the cleaning tank (7) and the collecting tank (8) to achieve continuous and cyclic motion;

[0088] The rollers include a power roller (17) and a driven roller (13); corresponding roller brackets (9) are arranged in the electrodeposition tank (5), the cleaning tank (7) and the collecting tank (8);

[0089] An air knife (14) is arranged in each of the electrodeposition tank (5), the cleaning tank (7) and the collecting tank (8), and the air knife (14) respectively performs air blowing treatment on the cathode (16) after electrodeposition, the cathode (16) after cleaning and the cathode (16) after scraping off the electrodeposited metal particles;

[0090] (d) the cleaning tank (8) has a liquid inlet (not shown) and a liquid outlet (6) for the cleaning liquid;

[0091] (e) An electric brush (10) is provided in the collecting tank. The diameter of the electric brush is 5-10 cm and the length of the bristles is about 1-2 cm.

[0092] Example 2

[0093] Silver particles were prepared by electrodeposition in constant voltage mode using the apparatus of Example 1.

[0094] (1) preparing an electrolyte solution, a mixed solution of 5 g / L AgNO3, 25 g / L Na2S2O3·5H2O, 5 g / L K2SO3 and 5 g / L H3BO3;

[0095] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0096] (3) adjusting the electrochemical deposition parameters and performing constant voltage mode electrochemical deposition. The electrochemical workstation used was CHENHUA760, and the voltage range during the constant voltage mode was 0.4 V;

[0097] (4) The cathode stainless steel belt continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, and the cathode forms a continuous and cyclic movement;

[0098] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte, the length of the portion of the cathode stainless steel strip immersed in the electrolyte along the moving direction is 10 cm, the average moving speed is 0.02 cm / s, 0.2 cm / s, 0.5 cm / s, 1 cm / s, 2 cm / s, 10 cm / s, and metallic silver particles are deposited on the cathode stainless steel strip;

[0099] (6) In the cleaning tank, the metallic silver particles deposited on the surface of the cathode stainless steel strip are cleaned with a cleaning liquid, wherein the cleaning liquid is deionized water;

[0100] (7) In the collection tank, the metal silver particles deposited on the surface of the cathode stainless steel strip are peeled off and collected by using a physical friction method such as brush friction.

[0101] The contact force was measured using a scanning probe microscope (AFM).

[0102] Table 1 Performance parameters of silver particles prepared in Example 2

[0103]

[0104] Example 3

[0105] Silver particles were prepared by electro-deposition in constant current mode using the device of Example 1

[0106] (1) preparing an electrolyte solution, a mixed solution of 5 g / L AgNO3, 25 g / L Na2S2O3·5H2O, 5 g / L K2SO3 and 5 g / L H3BO3;

[0107] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0108] (3) Adjust the electrochemical deposition parameters and perform constant current mode electrodeposition. The current density range during the constant current mode is 1 mA / cm 2 ;

[0109] (4) The cathode stainless steel strip continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collection tank;

[0110] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte. The length of the portion of the cathode stainless steel strip immersed in the electrolyte is 10 cm along the moving direction. The average moving speed is 0.1 cm / s, 1 cm / s, and 2 cm / s. Metal particles are deposited on the cathode stainless steel strip.

[0111] (6) In the cleaning tank, the metallic silver particles deposited on the surface of the cathode stainless steel strip are cleaned with a cleaning liquid, wherein the cleaning liquid is deionized water;

[0112] (7) In the collection tank, use physical friction methods such as a brush to peel off and collect the metallic silver particles deposited on the cathode surface.

[0113] The morphology of the obtained metallic silver particles is as follows Figure 4 shown.

[0114] Example 4

[0115] Nickel particles were prepared by electrodeposition in constant voltage mode using the apparatus of Example 1.

[0116] (1) preparing an electrolyte solution, namely, a mixed solution of 25 g / L NiSO4·6H2O, 3.75 g / L NiCl2·6H2O, and 10 g / L H3BO3;

[0117] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0118] (3) adjusting the electrochemical deposition parameters to perform constant voltage mode electrodeposition, wherein the voltage during the constant voltage mode is 1.5 V;

[0119] (4) The cathode stainless steel belt continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, and the cathode forms a continuous and cyclic movement;

[0120] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte. The length of the portion of the cathode stainless steel strip immersed in the electrolyte is 10 cm along the moving direction. The average moving speed is 2 cm / s. Metal nickel particles are deposited on the cathode stainless steel strip.

[0121] (6) In the cleaning tank, the metal nickel particles deposited on the surface of the cathode stainless steel strip are cleaned with a cleaning liquid, wherein the cleaning liquid is deionized water;

[0122] (7) In the collection tank, use physical friction methods such as brushes to peel off and collect the metal nickel particles deposited on the cathode surface.

[0123] Example 5

[0124] Copper particles were prepared by electroplating in constant voltage mode using the apparatus of Example 1

[0125] (1) preparing an electrolyte solution of 5 g / L CuSO4·5H2O solution, and then adjusting the pH value to 1 with H2SO4;

[0126] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0127] (3) adjusting the electrochemical deposition parameters to perform constant voltage mode electrodeposition, wherein the voltage during the constant voltage mode is 1.5 V;

[0128] (4) The cathode stainless steel belt continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, and the cathode forms a continuous and cyclic movement;

[0129] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte. The length of the portion of the cathode stainless steel strip immersed in the electrolyte is 10 cm along the moving direction. The average moving speed is 2 cm / s. Metal copper particles are deposited on the cathode stainless steel strip.

[0130] (6) In the cleaning tank, a cleaning liquid is used to clean the metal copper particles deposited on the surface of the cathode stainless steel strip, and the cleaning liquid is anhydrous ethanol;

[0131] (7) In the collection tank, use physical friction methods such as brushes to peel off and collect the metal copper particles deposited on the surface of the cathode stainless steel strip.

[0132] Example 6

[0133] Gold particles were prepared by electroplating in constant voltage mode using the apparatus of Example 1

[0134] (1) preparing an electrolyte solution, preparing a mixed solution of 20 g / L ammonium citrate, 5 g / L chloroauric acid and 13.7 g / L Na2SO3;

[0135] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0136] (3) adjusting the electrochemical deposition parameters to perform constant voltage mode electrodeposition, wherein the voltage during the constant voltage mode is 2.5 V;

[0137] (4) The cathode stainless steel belt continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, and the cathode forms a continuous and cyclic movement;

[0138] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte. The length of the portion of the cathode stainless steel strip immersed in the electrolyte is 10 cm along the moving direction. The average moving speed is 2 cm / s. Metallic gold particles are deposited on the cathode stainless steel strip.

[0139] (6) In the cleaning tank, the metal gold particles deposited on the surface of the cathode stainless steel strip are cleaned with a cleaning liquid, wherein the cleaning liquid is deionized water;

[0140] (7) In the collection tank, use physical friction methods such as a brush to peel off and collect the metal gold particles deposited on the surface of the cathode stainless steel strip.

[0141] Example 7

[0142] Cobalt-nickel particles were prepared by electrodeposition in constant voltage mode using the apparatus of Example 1.

[0143] (1) preparing an electrolyte solution, namely, a mixed solution of 6.75 g / L NiSO4·6H2O, 6.25 g / L CoSO4·7H2O, 5 g / L H3BO3 and 0.5 g / L KCl;

[0144] (2) Select a cathode that can move continuously, and the cathode is made of a stainless steel belt, and the surface of the cathode stainless steel belt is polished;

[0145] (3) adjusting the electrochemical deposition parameters to perform constant voltage mode electrodeposition, wherein the voltage during the constant voltage mode is 1.5 V;

[0146] (4) The cathode stainless steel belt continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank and then directly returns to the electrodeposition tank, and the cathode forms a continuous and cyclic movement;

[0147] (5) In the electrodeposition tank, the cathode stainless steel strip moves continuously in the electrolyte. The length of the portion of the cathode stainless steel strip immersed in the electrolyte is 10 cm along the moving direction. The average moving speed is 2 cm / s. Metal cobalt and nickel particles are deposited on the cathode stainless steel strip.

[0148] (6) In the cleaning tank, the metal cobalt and nickel particles deposited on the surface of the cathode stainless steel strip are cleaned with a cleaning liquid, wherein the cleaning liquid is deionized water;

[0149] (7) In the collection tank, use physical friction methods such as brushes to peel off and collect the metal cobalt and nickel particles deposited on the surface of the cathode stainless steel strip.

[0150] Table 2 Performance parameters of metal particles prepared in Examples 4-7

[0151] Example 3 Example 4 Example 5 Example 6 Cathode moving speed (cm / s) 2 2 2 2 Dwell time(s) 5 5 5 5 Average particle size (nm) 30 27 38 45

Claims

1. A device for preparing metal particles by continuous electrodeposition by controlling the cathode speed, wherein the contact force between the prepared metal particles and the cathode is less than 25nN, or the shear strength is less than 1MPa, and the average particle size of the metal particles is 10nm to 500nm, the device comprising: (a) a power source, an electrodeposition tank, a cleaning tank, and a collecting tank, wherein the electrodeposition tank, the cleaning tank, and the collecting tank are connected in sequence, the power source adjusts the electrochemical deposition parameters, and performs constant current or constant voltage mode electrodeposition, and the current density during the constant current mode is greater than 0A / cm 2 And less than or equal to 10mA / cm 2 , during the constant voltage mode, the voltage is greater than 0V and less than or equal to 10V; (b) an anode and a cathode disposed opposite to each other in an electrodeposition tank, wherein the electrodeposition tank is used to contain an electrolytic solution; (c) The cathode is a conductive strip material with a polished surface, which passes through an electrodeposition tank, a cleaning tank, and a collection tank continuously and sequentially; (d) the cleaning tank has a liquid inlet and a liquid outlet for the cleaning liquid; (e) There is a brush in the collecting tank, the diameter of the brush is 5-10 cm, and the length of the bristles is 1-2 cm.

2. The device according to claim 1, characterized in that The cathode is a continuous, circulating conductive strip material, which continuously and sequentially passes through the electrodeposition tank, the cleaning tank, and the collecting tank, and circulates from the collecting tank to the electrodeposition tank.

3. The device according to claim 1 or 2, characterized in that: The cathode is a stainless steel belt, a titanium belt, or a copper belt, and is driven by rollers in an electrodeposition tank, a cleaning tank, and a collecting tank to achieve continuous and cyclic motion.

4. The device according to claim 1 or 2, characterized in that: The width of the cathode is 1 to 15 cm.

5. The device according to claim 3, characterized in that The rollers include a power roller and a driven roller.

6. The device according to claim 1 or 2, characterized in that: Roller supports are arranged in the electrodeposition tank, the cleaning tank and the collecting tank.

7. The device according to claim 1 or 2, characterized in that: Air knives are arranged in the electrodeposition tank, the cleaning tank and the collecting tank, and the air knives respectively perform air blowing treatment on the cathode after electrodeposition, the cathode after cleaning and the cathode after scraping off the metal particles of the electrodeposition.

8. The device according to claim 1 or 2, characterized in that: The brush is an electric brush.

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