Special-shaped electrode for electro-deposition 3D printing and electro-deposition 3D printing method

Abstract

The invention relates to a special-shaped electrode for electro-deposition 3D printing and an electro-deposition 3D printing method, and aims to solve the problems of non-uniform material deposition growth speed, poor forming structure precision, quality defects and the like in printing caused by unstable ion mass transfer in existing electro-deposition 3D printing. The near-cathode end of a tool anode is designed into a certain special-shaped surface, a micropore channel structure is designed in the anode, and dynamic circulation of electrolyte is combined, so that dynamic and stable control over an ion concentration field around a cathode growth nuclear point is achieved. The method obviously improves the printing precision, efficiency and material utilization rate, and can be widely applied to the fields of aerospace, automobile manufacturing, medical instruments and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical 3D printing, and in particular to a special-shaped electrode for electrodeposition 3D printing and an electrodeposition 3D printing method. Background Art

[0002] Electrodeposition 3D printing is an additive manufacturing technology that uses electric fields to drive ion deposition. It is known for its simple process and low cost, but the traditional planar electrode design limits the control of ion mass transfer, resulting in uneven deposition and unstable printing quality. With the advancement of additive manufacturing technology, 3D printing has expanded from prototyping to the production of functional parts, and electrodeposition 3D printing has attracted much attention due to its unique advantages. This technology uses metal ions to reduce and deposit under the action of an electric field to build the target structure layer by layer. It is used in aerospace, automotive, medical and other fields. The current problems of electrodeposition 3D printing technology include: (1) Unstable ion mass transfer: The traditional planar electrode design makes it difficult to form a stable ion concentration field, resulting in fluctuations in the deposition rate during the printing process, which directly affects the printing accuracy and product quality. The ion migration process is affected by the electric field distribution and diffusion mechanism, and the uneven deposition rate often leads to defects in the printed structure. For example, when printing complex geometric shapes, the electric field edge effect causes excessive or insufficient ion deposition in certain parts. (2) Low deposition efficiency: Due to the uneven ion mass transfer and the limitation of the diffusion process, the speed of electrodeposition 3D printing is usually slow. The gradual thickening of the diffusion layer limits the effective mass transfer of ions, and the printing time is significantly extended. At the same time, the grain structure of the metal deposition layer is easily disturbed, affecting the printing speed. (3) Microstructural defects: Due to the fluctuation of the ion concentration field during the deposition process, traditional electrodeposition technology is difficult to control the growth direction and speed of microscopic grains, resulting in reduced structural strength. In the production of complex parts, microscopic defects may cause mechanical performance problems, limiting the application scope of high-precision and high-performance parts. (4) Limited to planar electrodes: Traditional methods mostly use planar anode and cathode electrode designs, lacking precise control over ion migration paths and electric field distribution. In large-scale or complex geometric printing, the electric field distribution is difficult to evenly cover the entire printing area, resulting in increased shape errors of the printed parts.

[0003] In order to overcome the above problems, researchers have proposed some improved methods. For example, in the invention patent CN112813465B, the conductive area on the surface of the anode is controlled by a light source to accurately guide the ion deposition path. The local deposition performance has been improved, but the overall ion concentration field stability has not been fundamentally solved. The utility model patent CN213538126U combines laser processing with electrodeposition technology to achieve local efficient deposition. This method is still limited in its application to large areas or complex parts, especially for the overall stability of multi-core point deposition. In the invention patent application CN116005215A, the deposition process is accelerated and efficiency is improved by spraying electrolyte. This method is suitable for rapid deposition, but its effect is limited in high-precision printing, and its ability to control the uniformity of the material surface is insufficient.

[0004] Current technological improvements are mostly focused on optimizing local deposition areas, but there is still a lack of effective solutions to the dynamic stability of the ion concentration field during the overall deposition process. At the same time, the limitations of traditional electrode design are still significant and cannot meet the needs of high-precision and complex structure printing. Therefore, it is particularly important to develop an innovative technology that dynamically regulates the ion concentration field by optimizing the electrode design and electrolyte supply system. Summary of the invention

[0005] Aiming at the problems existing in the application of the existing chemical nickel plating coating, the present invention provides a special-shaped electrode for electrodeposition 3D printing and an electrodeposition 3D printing method.

[0006] Implementation method of the present invention: A shaped electrode for electrodeposition 3D printing, the shaped electrode is in the shape of a hollow column, one end of the shaped electrode is designed as a concave shaped surface, the concave shaped surface is a conductive area and is provided with a microporous channel; the other end of the shaped electrode is a plane end; the other parts of the shaped electrode except the concave shaped surface are non-functional surfaces, and the non-functional surface of the shaped electrode is covered by an insulating layer; a conductive connecting part is provided at the center of the plane end of the shaped electrode; a partition is axially arranged at the center of the shaped electrode, a gap is provided between the end of the partition close to the concave shaped surface and the concave shaped surface, the other end of the partition is connected to the plane end of the shaped electrode, the plane end of the shaped electrode is respectively provided with an electrolyte inlet and an electrolyte outlet, the electrolyte inlet and the electrolyte outlet are respectively arranged on both sides of the partition, the electrolyte inlet, the electrolyte outlet, the electrolyte between the partition and the cavity of the shaped electrode constitute an electrolyte circulation system; the electrolyte flow rate in the electrolyte circulation system is adjustable.

[0007] Preferably, the special-shaped surface is a hemispherical surface, a conical surface or a combination thereof.

[0008] Preferably, the pore size of the microporous channel ranges from 1 um to 50 um.

[0009] Preferably, the electrolyte flow rate control range in the electrolyte circulation system is 0.1m / s-2.0m / s.

[0010] Preferably, the microporous channels on the shaped surface of the shaped electrode are evenly distributed, and the pore density is 10-50 per square millimeter.

[0011] Preferably, the resistivity of the conductive connection portion is less than 10-6 Ω·cm, and is made of one of gold, silver and copper having excellent conductive properties.

[0012] Preferably, the insulating layer material of the non-functional surface of the special-shaped electrode is one of polytetrafluoroethylene and epoxy resin, and the thickness of the insulating layer is 0.1-1.0 mm.

[0013] The above-mentioned electrodeposition 3D printing method of a shaped electrode for electrodeposition 3D printing comprises the following steps: (1) selecting a shaped electrode that is compatible with the material to be printed, connecting the shaped electrode to the positive electrode of a power source through a conductive connection portion, connecting the selected cathode to the negative electrode of the power source, and placing the shaped electrode and the cathode in an electrolytic cell to form an electrical circuit; the electrolyte in the electrolytic cell does not contain cations to be electrodeposited and only has a conductive effect. (2) The electrolyte is input into the electrolyte circulation system from the electrolyte inlet, and the electrolyte flow rate is controlled to ensure that the electrolyte flows continuously at the set flow rate. The electrolyte in the electrolyte circulation system passes through the microporous channel of the shaped electrode to form a stable ion concentration on the surface of the shaped surface, ensuring that the ion concentration is the same as the ion concentration in the electrolyte in the electrolyte circulation system during the continuous process of electrodeposition 3D printing; the electrolyte in the shaped electrode is used to provide the metal ions to be deposited; (3) A DC voltage is applied between the shaped electrode and the relative cathode, and the DC voltage applied between the shaped electrode and the relative cathode is controlled to be 3V-7V, the electrodeposition process is started, and the 3D printing parameters are adjusted to control the shaped electrode to maintain a rate of 0.02mm / h perpendicular to the cathode surface and move away from the cathode surface; (4) After 30-120min of electrodeposition 3D printing, the deposited layer of the printed part is cleaned and dried to complete the printing.

[0014] The electrodeposition 3D printing of the present invention is based on the principle that metal ions migrate to the cathode and are reduced under the action of an electric field, and a three-dimensional structure is manufactured by layer-by-layer deposition. Traditional methods usually use a planar anode, and the electric field and ion concentration field are unevenly distributed, resulting in the instability of the ion migration path and the concentration field, which in turn affects the deposition quality. The present invention solves this problem through the following technical principles: (1) Special-shaped electrodes limit ion mass transfer: The special-shaped electrodes limit and optimize the ion mass transfer path by designing geometric structures and microporous channels that match the ion concentration field on the anode surface. Microporous channels are designed on the electrode surface to increase the local fluidity of the electrolyte, thereby maintaining the stability of the ion concentration field near the anode. The design of the special-shaped electrode overcomes the problem of ion mass transfer fluctuations caused by the uneven diffusion layer of the traditional planar electrode, making the ion concentration field more uniform around the cathode growth core point, and significantly improving the electrodeposition growth accuracy during printing. (2) Dynamic control of the electrolyte circulation system: The electrolyte circulation system is integrated inside the special-shaped electrode to ensure the dynamic stability of the ion concentration field. By dynamically adjusting the flow rate and concentration, the relationship between the ion consumption at the cathode growth point and the anode replenishment is balanced. The electrolyte circulation system forms a stable concentration gradient between the anode and the cathode, which increases the deposition rate and eliminates local deposition defects caused by ion depletion. (3) Dynamic stability of the ion concentration field: Combining the special-shaped electrode design and the electrolyte circulation system, a dynamically stable ion concentration field is formed by optimizing the electric field distribution and the ion mass transfer path. The electric field parameters are optimized experimentally to reduce the edge effect of the electric field. The ion diffusion path is simulated to establish a stable ion supply network on the anode surface, thereby forming a concentration field around the cathode core point with a concentration gradient that gradually tends to be stable. This method significantly improves the unevenness of the growth rate during the crystal growth process and ensures the microscopic uniformity and mechanical properties of the printed structure.

[0015] The beneficial effects of the present invention include: (1) Improved printing accuracy: The design of special-shaped electrodes and the control of the stability of the ion concentration field reduce the error in printing dimensions. (2) Improved deposition efficiency: The deposition rate is increased through the dynamic supply of the electrolyte circulation system. (3) Enhanced microstructure uniformity: The stability of crystal growth is significantly improved, the appearance growth size is significantly improved, and the mechanical properties of the printed parts are improved compared with traditional methods. (4) Dynamic flow rate regulation is achieved by controlling the flow rate of the electrolyte in the electrolyte circulation system to meet the needs of different materials and deposition conditions; the electrolyte flow rate, ion concentration and temperature are monitored in real time during the electroplating printing process to ensure the dynamic stability of the ion concentration field. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the structure of a special-shaped electrode for electrodeposition 3D printing in which the special-shaped surface is a hemispherical surface according to the present invention.

[0017] Figure 2This is a schematic diagram of the structure of a special-shaped electrode for electrodeposition 3D printing in which the special-shaped surface is a conical surface according to the present invention.

[0018] Figure 3 This is a schematic diagram of the structure of a special-shaped electrode for electrodeposition 3D printing in which the special-shaped surface is a hemispherical surface combined with a conical surface.

[0019] Figure 4 This is a schematic diagram of the electrodeposition 3D printing of a special-shaped electrode for electrodeposition 3D printing of the present invention.

[0020] Among them, 1. special-shaped electrode; 101. special-shaped surface; 102. plane end; 103. partition; 104. electrolyte outlet; 105. electrolyte inlet; 106. micro-control channel; 2. conductive connection part; 3. power supply; 4. electrolytic cell; 5. cathode; 6. deposition layer. DETAILED DESCRIPTION

[0021] The following is combined with Figure 1-4 The specific embodiments of the present invention are described in detail, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. Example

[0022] like Figure 1 As shown, a shaped electrode for electrodeposition 3D printing, the shaped electrode 1 is in the shape of a hollow column, one end of the shaped electrode 1 is designed as a concave shaped surface 101, the concave shaped surface 101 is a conductive area, and a microporous channel 106 is provided; the other end of the shaped electrode 1 is a plane end 102; the other parts of the shaped electrode 1 except the concave shaped surface 101 are non-functional surfaces, and the non-functional surface of the shaped electrode 1 is covered by an insulating layer; a conductive connecting portion 2 is provided at the center of the plane end 102 of the shaped electrode 1; the center of the shaped electrode 1 is axially A partition 103 is provided, and a gap is provided between one end of the partition 103 close to the concave shaped surface 101 and the concave shaped surface 101, and the other end of the partition 103 is connected to the plane end 102 of the shaped electrode 1, and the plane end 102 of the shaped electrode 1 is respectively provided with an electrolyte inlet 105 and an electrolyte outlet 104, and the electrolyte inlet 105 and the electrolyte outlet 104 are respectively arranged on both sides of the partition 103, and an electrolyte circulation system is formed between the electrolyte inlet 105, the electrolyte outlet 104, the partition 103 and the cavity of the shaped electrode 1.

[0023] The above-mentioned electrodeposition 3D printing method of a special-shaped electrode for electrodeposition 3D printing has a deposition circuit diagram as shown in Figure 4As shown, the process comprises the following steps: (1) selecting a shaped electrode 1 that is compatible with the material to be printed, connecting the shaped electrode 1 to the positive electrode of the power source 3 through the conductive connection part 2, connecting the selected cathode 5 to the negative electrode of the power source 3, and placing the shaped electrode 1 and the cathode 5 in an electrolytic cell to form an electrical circuit; (2) inputting the electrolyte from the electrolyte inlet 105 into the electrolyte circulation system, and controlling the electrolyte flow rate to ensure that the electrolyte flows continuously at the set flow rate, and the electrolyte in the electrolyte circulation system passes through the microporous channel 106 of the shaped electrode 1 to form a stable ion concentration on the surface of the shaped surface 101. Ensure that the ion concentration is the same as the ion concentration in the electrolyte in the electrolyte circulation system during the continuous process of electrodeposition 3D printing; (3) Apply a DC voltage between the shaped electrode 1 and the relative cathode 5, and control the DC voltage applied between the shaped electrode 1 and the relative cathode 5 to 5V, start the electrodeposition process, and adjust the 3D printing parameters to control the shaped electrode 1 to maintain a rate of 0.02mm / h perpendicular to the surface of the cathode 5 and move away from the surface of the cathode 5; (4) After 60 minutes of electrodeposition 3D printing, the deposited layer 6 of the printed part is cleaned and dried to complete the printing.

[0024] In this embodiment, the profiled surface 101 is a hemispherical surface, the profiled electrode 1 is made of pure copper material, and is covered with an insulating layer except for the conductive area. The insulating layer is polytetrafluoroethylene with a thickness of 0.5 mm; the resistivity of the conductive connecting portion 2 is less than 10 -6 Ω·cm, using gold with excellent conductivity; the electrolyte in the shaped electrode 1 is used to provide metal cations to be deposited, and the electrolyte flow rate is controlled to be 1.0m / s; the pore size of the microporous channel 106 is 10um, and the density of the microporous channel 106 is 20 per square millimeter. The electrolyte components in the shaped electrode 1 are: 0.05mol / L of copper sulfate pentahydrate, 0.15mol / L of 5,5-dimethylhydantoin, 0.15mol / L of sodium citrate, and 0.15mol / L of potassium carbonate. After the above components are mixed, the pH of the mixed solution is adjusted to 9 using a high concentration potassium carbonate solution. The electrolyte in the electrolytic cell 4 is only used for conducting electricity, and its components do not contain metal ions to be deposited. The electrolyte components of the electrolytic cell 4 are: 0.05 mol / L potassium sulfate, 0.15 mol / L 5,5-dimethylhydantoin, 0.15 mol / L sodium citrate, and 0.15 mol / L potassium carbonate. After the above components are mixed, a high concentration potassium carbonate solution is used to adjust the pH of the mixed solution to 9.

[0025] The cathode 5 in this method is a copper plate with a size of 50×50×5mm and a surface polishing treatment. A copper deposition layer is formed on the cathode 5 by electrodeposition. Through scanning electron microscopy observation of the copper deposition layer, the surface of the obtained copper deposition layer is uniform, and no significant coarse and fine changes and nodulation phenomenon are observed. Through the current density uniformity test during the electrodeposition 3D printing process, it is shown that the current density fluctuation range is within the range of ±10%, indicating that the rate of ion reduction during the electrodeposition 3D printing process is basically stable, and there is no large rate fluctuation in the ion supply and electrochemical reduction process. From the electrochemical layer, the stability of the growth rate of the microstructure of the electrodeposition 3D printing is confirmed. Example

[0026] like Figure 2 As shown, a shaped electrode for electrodeposition 3D printing, the shaped electrode 1 is in the shape of a hollow column, one end of the shaped electrode 1 is designed as a concave shaped surface 101, the concave shaped surface 101 is a conductive area, and a microporous channel 106 is provided; the other end of the shaped electrode 1 is a plane end 102; the other parts of the shaped electrode 1 except the concave shaped surface 101 are non-functional surfaces, and the non-functional surface of the shaped electrode 1 is covered by an insulating layer; a conductive connecting portion 2 is provided at the center of the plane end 102 of the shaped electrode 1; the center of the shaped electrode 1 is axially A partition 103 is provided, and a gap is provided between one end of the partition 103 close to the concave shaped surface 101 and the concave shaped surface 101, and the other end of the partition 103 is connected to the plane end 102 of the shaped electrode 1, and the plane end 102 of the shaped electrode 1 is respectively provided with an electrolyte inlet 105 and an electrolyte outlet 104, and the electrolyte inlet 105 and the electrolyte outlet 104 are respectively arranged on both sides of the partition 103, and an electrolyte circulation system is formed between the electrolyte inlet 105, the electrolyte outlet 104, the partition 103 and the cavity of the shaped electrode 1.

[0027] The above-mentioned electrodeposition 3D printing method of a special-shaped electrode for electrodeposition 3D printing has a deposition circuit diagram as shown in Figure 4As shown, the method comprises the following steps: (1) selecting a shaped electrode 1 that is compatible with the material to be printed, connecting the shaped electrode 1 to the positive electrode of the power source 3 through the conductive connecting portion 2, connecting the selected cathode 5 to the negative electrode of the power source 3, and placing the shaped electrode 1 and the cathode 5 in an electrolytic cell to form an electrical circuit; (2) inputting the electrolyte from the electrolyte inlet 105 into the electrolyte circulation system, and controlling the electrolyte flow rate to ensure that the electrolyte flows continuously at the set flow rate, and the electrolyte in the electrolyte circulation system passes through the microporous channel 106 of the shaped electrode 1 to form a stable ion concentration on the surface of the shaped surface 101, thereby ensuring The ion concentration is kept the same as the ion concentration in the electrolyte in the electrolyte circulation system during the continuous process of electrodeposition 3D printing; (3) a DC voltage is applied between the shaped electrode 1 and the relative cathode 5, and the DC voltage applied between the shaped electrode 1 and the relative cathode 5 is controlled at 3V, the electrodeposition process is started, and the 3D printing parameters are adjusted to control the shaped electrode 1 to maintain a rate of 0.02mm / h perpendicular to the surface of the cathode 5 and move away from the surface of the cathode 5; (4) after 120 minutes of electrodeposition 3D printing, the deposited layer 6 of the printed part is cleaned and dried to complete the printing.

[0028] In this embodiment, the profiled surface 101 is a conical surface, the profiled electrode 1 is made of titanium-supported iridium oxide, and is coated with an insulating layer except for the conductive area. The insulating layer is epoxy resin with a thickness of 0.1 mm; the resistivity of the conductive connecting portion 2 is less than 10 -6 Ω·cm, silver with excellent conductivity is used; the electrolyte in the shaped electrode 1 is used to provide the metal cations to be deposited, and the electrolyte flow rate is controlled to be 0.1m / s. The diameter of the microporous channel 106 is 1um, and the density of the microporous channel 106 is 50 per square millimeter. The electrolyte components in the shaped electrode 1 are: 0.05mol / L of copper sulfate pentahydrate, 0.15mol / L of 5,5-dimethylhydantoin, 0.15mol / L of sodium citrate, and 0.15mol / L of potassium carbonate. After the above components are mixed, the pH of the mixed solution is adjusted to 9 using a high concentration potassium carbonate solution. The electrolyte in the electrolytic cell 4 is only used for conducting electricity, and its components do not contain metal ions to be deposited. The electrolyte components of the electrolytic cell 4 are: 0.05 mol / L potassium sulfate, 0.15 mol / L 5,5-dimethylhydantoin, 0.15 mol / L sodium citrate, and 0.15 mol / L potassium carbonate. After the above components are mixed, a high concentration potassium carbonate solution is used to adjust the pH of the mixed solution to 9.

[0029] The cathode 5 described in this method is graphite, with a size of 50×50×5mm. In this embodiment, a copper deposition layer is formed on the cathode 5 by electrodeposition using a special-shaped electrode 1 with a concave cone surface. The surface of the copper deposition layer obtained by scanning electron microscopy observation is uniform, and no significant coarse and fine changes and nodulation are observed. The current density uniformity test during the electrodeposition 3D printing process shows that the current density fluctuation range is within the range of ±10%, indicating that the rate of ion reduction during the electrodeposition 3D printing process is basically stable, and there is no large rate fluctuation in the ion supply and electrochemical reduction process. From the electrochemical layer, the stability of the growth rate of the microstructure of the electrodeposition 3D printing is confirmed. Example

[0030] like Figure 3 As shown, a shaped electrode for electrodeposition 3D printing, the shaped electrode 1 is in the shape of a hollow column, one end of the shaped electrode 1 is designed as a concave shaped surface 101, the concave shaped surface 101 is a conductive area, and a microporous channel 106 is provided; the other end of the shaped electrode 1 is a plane end 102; the other parts of the shaped electrode 1 except the concave shaped surface 101 are non-functional surfaces, and the non-functional surface of the shaped electrode 1 is covered by an insulating layer; a conductive connecting portion 2 is provided at the center of the plane end 102 of the shaped electrode 1; the center of the shaped electrode 1 is axially A partition 103 is provided, and a gap is provided between one end of the partition 103 close to the concave shaped surface 101 and the concave shaped surface 101, and the other end of the partition 103 is connected to the plane end 102 of the shaped electrode 1, and the plane end 102 of the shaped electrode 1 is respectively provided with an electrolyte inlet 105 and an electrolyte outlet 104, and the electrolyte inlet 105 and the electrolyte outlet 104 are respectively arranged on both sides of the partition 103, and an electrolyte circulation system is formed between the electrolyte inlet 105, the electrolyte outlet 104, the partition 103 and the cavity of the shaped electrode 1.

[0031] The above-mentioned electrodeposition 3D printing method of a special-shaped electrode for electrodeposition 3D printing has a deposition circuit diagram as shown in Figure 4As shown, the process comprises the following steps: (1) selecting a shaped electrode 1 that is compatible with the material to be printed, connecting the shaped electrode 1 to the positive electrode of the power source 3 through the conductive connection part 2, connecting the selected cathode 5 to the negative electrode of the power source 3, and placing the shaped electrode 1 and the cathode 5 in an electrolytic cell to form an electrical circuit; (2) inputting the electrolyte from the electrolyte inlet 105 into the electrolyte circulation system, and controlling the electrolyte flow rate to ensure that the electrolyte flows continuously at the set flow rate, and the electrolyte in the electrolyte circulation system passes through the microporous channel 106 of the shaped electrode 1 to form a stable ion concentration on the surface of the shaped surface 101. Ensure that the ion concentration is the same as the ion concentration in the electrolyte in the electrolyte circulation system during the continuous process of electrodeposition 3D printing; (3) Apply a DC voltage between the shaped electrode 1 and the relative cathode 5, and control the DC voltage applied between the shaped electrode 1 and the relative cathode 5 to 7V, start the electrodeposition process, and adjust the 3D printing parameters to control the shaped electrode 1 to maintain a rate of 0.02mm / h perpendicular to the surface of the cathode 5 and move away from the surface of the cathode 5; (4) After 30 minutes of electrodeposition 3D printing, the deposited layer 6 of the printed part is cleaned and dried to complete the printing.

[0032] In this embodiment, the profiled surface 101 is a combination of a conical surface and a hemispherical surface, the conical surface portion gradually increases toward the cathode 5 end, and the hemispherical surface portion is located at the tip of the conical surface; the profiled electrode 1 is made of platinum metal, and is coated with an insulating layer except for the conductive area, and the insulating layer is polytetrafluoroethylene with a thickness of 1 mm; the resistivity of the conductive connecting portion 2 is less than 10 -6 Ω·cm, copper with excellent conductivity is used; the electrolyte in the shaped electrode 1 is used to provide metal cations to be deposited, and the electrolyte flow rate is controlled to be 2m / s. The microporous channel 106 has a pore size of 50um and a density of 10 microporous channels per square millimeter.

[0033] The electrolyte components in the shaped electrode 1 are: 0.05 mol / L copper sulfate pentahydrate, 0.15 mol / L 5,5-dimethylhydantoin, 0.15 mol / L sodium citrate, and 0.15 mol / L potassium carbonate. After the above components are mixed, a high-concentration potassium carbonate solution is used to adjust the pH of the mixed solution to 9. The electrolyte in the electrolytic cell 4 is only used for conduction, and its components do not contain metal ions to be deposited. The electrolyte components of the electrolytic cell 4 are: 0.05 mol / L potassium sulfate, 0.15 mol / L 5,5-dimethylhydantoin, 0.15 mol / L sodium citrate, and 0.15 mol / L potassium carbonate. After the above components are mixed, a high-concentration potassium carbonate solution is used to adjust the pH of the mixed solution to 9.

[0034] The cathode 5 in the method is a stainless steel plate with a size of 50×50×5 mm and a polished surface.

[0035] In this embodiment, the conical surface portion gradually becomes larger toward the cathode 5 end, and a copper deposition layer is formed on the cathode 5. Through scanning electron microscopy observation of the copper deposition layer, the surface of the obtained copper deposition layer is uniform, and no significant changes in thickness and nodulation are observed. Through the current density uniformity test during the electrodeposition 3D printing process, it is shown that the current density fluctuation range is within the range of ±9%, indicating that the rate of ion reduction in the electrodeposition 3D printing process is basically stable, and there is no large rate fluctuation in the ion supply and electrochemical reduction process. From the electrochemical layer, the stability of the growth rate of the electrodeposition 3D printing microstructure is confirmed.

Claims

1. A special-shaped electrode for electrodeposition 3D printing, characterized in that: The shaped electrode is in the shape of a hollow column, one end of which is designed to be a concave shaped surface, which is a conductive area and is provided with a microporous channel; the other end of the shaped electrode is a plane end; the other parts of the shaped electrode except the concave shaped surface are non-functional surfaces, which are covered by an insulating layer; a conductive connecting part is provided at the center of the plane end of the shaped electrode; a partition is axially arranged at the center of the shaped electrode, one end of the partition close to the concave shaped surface is provided with a gap between the concave shaped surface, the other end of the partition is connected to the plane end of the shaped electrode, the plane end of the shaped electrode is respectively provided with an electrolyte inlet and an electrolyte outlet, the electrolyte inlet and the electrolyte outlet are respectively arranged on both sides of the partition, the electrolyte inlet, the electrolyte outlet, the electrolyte between the partition and the cavity of the shaped electrode constitute an electrolyte circulation system, and the electrolyte flow rate in the electrolyte circulation system is adjustable.

2. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The special-shaped surface is a hemispherical surface, a conical surface or a combination thereof.

3. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The microporous channel has a pore size ranging from 1 um to 50 um.

4. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The electrolyte flow rate control range in the electrolyte circulation system is 0.1m / s-2.0m / s.

5. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The microporous channels on the special-shaped surface of the special-shaped electrode are evenly distributed, and the hole density is 10-50 per square millimeter.

6. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The resistivity of the conductive connection portion is less than 10 -6 Ω·cm, using one of the excellent conductive properties of gold, silver, and copper.

7. The special-shaped electrode for electrodeposition 3D printing according to claim 1, characterized in that: The insulating layer material of the non-functional surface of the special-shaped electrode is one of polytetrafluoroethylene and epoxy resin, and the thickness of the insulating layer is 0.1-1.0 mm.

8. The method for electrodeposition 3D printing of a special-shaped electrode for electrodeposition 3D printing according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: (1) selecting a shaped electrode that is compatible with the material to be printed, connecting the shaped electrode to the positive electrode of a power source through a conductive connection, connecting the selected cathode to the negative electrode of the power source, and placing the shaped electrode and the cathode in an electrolytic cell to form an electrical circuit; (2) inputting an electrolyte from an electrolyte inlet into an electrolyte circulation system, and controlling the electrolyte flow rate to ensure that the electrolyte flows continuously at a set flow rate, and the electrolyte in the electrolyte circulation system passes through the microporous channel of the shaped electrode to form a stable ion concentration on the surface of the shaped surface, thereby ensuring that the ion concentration is stable during the electrodeposition. During the continuous process of 3D printing, the ion concentration in the electrolyte is the same as that in the electrolyte circulation system; (3) a DC voltage is applied between the shaped electrode and the relative cathode, and the DC voltage applied between the shaped electrode and the relative cathode is controlled at 3V-7V to start the electrodeposition process, and the 3D printing parameters are adjusted to control the shaped electrode to maintain a rate of 0.02mm / h perpendicular to the cathode surface and move away from the cathode surface; (4) after 30-120min of electrodeposition 3D printing, the deposited layer of the printed part is cleaned and dried to complete the printing.

Images