Metal column electrochemical deposition additive preparation device and preparation method

Abstract

The invention provides a metal column electrochemical deposition additive preparation device and method.The preparation device comprises an electrolytic bath and an insulated electrode support, the insulated electrode support comprises a first plate, a second plate and a plurality of connecting rods, the connecting rods are arranged at intervals in a surrounding mode along a first circle, and annular anodes are arranged on the radial inner sides of the connecting rods; the first plate and the second plate are respectively provided with a first clamping part and a second clamping part, the first clamping part and the second clamping part are respectively and correspondingly clamped at the two ends of the substrate cathode metal wire, so that the central axis of the substrate cathode metal wire coincides with the central axis of the annular anode, and the annular anode is electrically connected with the power supply anode; and the substrate cathode metal wire is electrically connected with the power supply cathode. According to the method, atomic-scale metallurgical bonding is realized, extremely high bonding strength between the deposition layer and the core body is ensured, stripping of the deposition layer and the core body is completely eradicated, and the solid metal column with the straightness and roundness reaching the standard and high material uniformity and density can be prepared easily.

Description

TECHNICAL FIELD

[0001] The present disclosure belongs to the technical field of metal column electrolytic preparation, and particularly relates to a metal column electrochemical deposition additive preparation device and a preparation method. BACKGROUND

[0002] In the field of metal conductor manufacturing, there is an increasing demand for high-precision and high-performance metal copper columns / rods, which are applied in precise electronic component connection, vacuum equipment lining, high-power heat dissipation medium, and special electromagnetic device carrier, etc. Currently, the large-scale production of such products mainly relies on the melting-casting-plastic deformation process, i.e., through melting and casting to obtain a blank, and then applying hot extrusion, multi-pass cold drawing and annealing. Although this mode can realize basic supply, it faces the core difficulties of complex process, high energy consumption, and insufficient comprehensive utilization rate of materials of less than 70%. More importantly, due to the physical nature of high-temperature solidification and mechanical deformation, this method is difficult to precisely control the microstructure of the material, is prone to casting defects, and when preparing ultra-high purity (such as ≥5N), ultra-large length-diameter ratio or functional copper rods with directional crystal structure, it faces significant technical bottlenecks and economic challenges.

[0003] Electrochemical deposition technology provides a theoretical possibility for solving the above problems due to its characteristic of directly reducing metal ions to solid metal. The existing widely industrialized electroplating technology system mainly presents two ways: one is the traditional continuous electroplating aiming at producing independent films (represented by electrolytic copper foil), and the other is the surface treatment electroplating aiming at modifying existing workpieces (thickening and repairing type).

[0004] The electrolytic copper foil technology realizes the large-scale continuous production of copper foil through high-speed electrodeposition on the surface of a rotating cathode roller and then peeling off. Although it is indispensable in the field of electronic substrates, the technical core and the demand for rod manufacturing are different in dimension. The ultimate product of this process is an independent two-dimensional film that must be peeled off from the cathode substrate. This "peeling" step is a necessary part of the process, but it cannot form a three-dimensional integral structure that is permanently metallurgically combined with the substrate. Essentially, it does not have the ability to manufacture integrated solid rods. The obtained copper foil is designed as a flexible and bendable sheet, which completely depends on laminating on an insulating substrate to form a composite material for use. This is completely different from the self-supporting solid rod that can be directly used as a conductive and heat-conductive strip or a structural functional piece in terms of mechanical and functional property requirements. The entire system (including the rotating cathode roller, the peeling mechanism, and the mass transfer and power supply optimized for thin layer deposition) serves the goal of peelable thin foil. Its technical logic cannot adapt to the process path of electroplating into a metal column.

[0005] Surface treatment electroplating aims to repair the dimensions or enhance the surface properties of pre-existing workpieces. Its "dependent processing" nature imposes the following limitations: the process relies entirely on a pre-formed solid workpiece with fixed geometry as the cathode substrate. It lacks the ability to manufacture "from scratch," and cannot autonomously construct a completely new, independent product entity. In such applications, the deposited layer is an additional part serving the main workpiece, its thickness and morphology strictly constrained by the initial shape of the substrate and the repair requirements. The deposited layer itself does not constitute the main body of the product; the endpoint of the process is to complete surface modification or repair, not to manufacture an independent product. The final performance is a combination of the substrate and coating properties, with a clear physical and chemical interface between them. This heterogeneous structure can become a performance bottleneck or failure source under extreme thermal and mechanical loads. This technology struggles to achieve free growth of the deposited material in three-dimensional space, unconstrained by the original shape of the substrate. For example, it cannot undisturbedly and uniformly grow solid metal pillars with diameters tens of times larger than the initial substrate and consistent length radially on a thin filament substrate.

[0006] In summary, existing electroplating technologies and equipment, regardless of whether their purpose is functional enhancement or surface decoration and protection, are limited to "applying a thin film to the surface of an existing object" and cannot be applied to the preparation of metal pillars with high performance requirements such as straightness, roundness, and uniformity of structure. Summary of the Invention

[0007] Therefore, this disclosure provides an electrochemical deposition additive manufacturing apparatus and method for metal pillars, which can overcome the shortcomings of electroplating technology systems and equipment in related technologies that are not suitable for the preparation of metal pillars with high performance requirements such as straightness, roundness, and uniformity of structure.

[0008] To address the aforementioned problems, this disclosure provides a metal column electrochemical deposition additive manufacturing apparatus, comprising an electrolytic cell for holding an electrolyte and an insulating electrode support with at least a portion of its structure located within the electrolytic cell. The insulating electrode support includes a first plate, a second plate, and multiple connecting rods. The first plate and the second plate are arranged parallel to each other and spaced apart, and each connecting rod is detachably supporting and connecting the first plate and the second plate. Each connecting rod is spaced along a first circle, and an annular anode is provided on the radially inner side of each connecting rod. A first clamping component is provided on the first plate, and a second clamping component is provided on the second plate. The first clamping component and the second clamping component respectively clamp the two ends of a substrate cathode wire so that the central axis of the substrate cathode wire coincides with the central axis of the annular anode. The annular anode is electrically connected to a power supply anode, and the substrate cathode wire is electrically connected to a power supply cathode.

[0009] In some embodiments, the electrolytic cell is a cylindrical body with an open top, the inlet of the electrolytic cell is located in the lower region of the cylindrical body, and the open top forms the overflow port of the electrolytic cell; and / or, the electrolytic cell is a cylindrical body, and in the state where the insulating electrode support is assembled with the electrolytic cell, the second plate is located inside the electrolytic cell, the second plate is a circular plate, and the outer diameter of the circular plate is equal to the inner diameter of the cylindrical body; and / or, the radially outer side of each connecting rod is in contact with the inner wall of the cylindrical body.

[0010] In some embodiments, a liquid inlet cavity is formed between the second plate and the bottom wall of the electrolytic cell, the liquid inlet is formed on the cavity wall of the liquid inlet cavity, and a plurality of liquid equalization holes are formed on the second plate, penetrating its two end faces, and each of the liquid equalization holes is evenly spaced around the substrate cathode metal wire; and / or, the first plate is located outside the top opening.

[0011] In some embodiments, each of the connecting rods has a protruding section extending from the end face of the second plate near the bottom wall of the electrolytic cell, the free end of each of the protruding sections abutting against the bottom wall of the electrolytic cell; and / or, it further includes an annular cover plate that can be selectively placed on the second plate to adjust the on / off state of the liquid equalization hole.

[0012] In some embodiments, the metal column electrochemical deposition additive manufacturing apparatus further includes a heat exchange tank and a circulation pump. The heat exchange tank is provided with heat exchange components to adjust the temperature of the electrolyte and keep it at a preset temperature. The electrolytic cell is located in the heat exchange tank. The circulation pump is used to drive the electrolyte from the heat exchange tank into the electrolytic cell through the inlet.

[0013] In some embodiments, the metal column electrochemical deposition additive manufacturing apparatus further includes two auxiliary cathode end rings, each of which is located radially inside the connecting rod and at both ends of the annular anode. Each auxiliary cathode end ring is coaxially arranged with the annular anode and has an insulating structure between its end faces opposite to the annular anode. The auxiliary cathode end rings are electrically connected to the power cathode, and during use, the current density formed in the auxiliary cathode end rings is less than the current density formed in the substrate cathode wire; and / or, the first clamping component includes a clamping part for clamping the substrate cathode wire and a tension adjustment part threadedly connected to the first plate.

[0014] In some embodiments, the insulating structure is an insulating ring sandwiched between the auxiliary cathode end ring and the corresponding end face of the annular anode.

[0015] In some embodiments, each of the connecting rods is provided with a plurality of threaded holes spaced apart along its length, each threaded hole penetrating the radial inner and outer sides of the connecting rod, and a radial push screw is screwed into each threaded hole.

[0016] In some embodiments, the axial height of the annular anode is H, the length of the substrate cathode wire is L, H≥L, preferably, H / L=1:1~1.5:1, and the substrate cathode wire is within the height projection range of the annular anode along its radial projection; and / or, the cross-section of the substrate cathode wire is circular, the diameter of the substrate cathode wire is greater than 0.01mm, and when the substrate cathode wire is made of a different material than the deposition layer, the diameter of the substrate cathode wire is less than D / 20, where D is the outer diameter of the metal column to be prepared.

[0017] This disclosure also provides a method for preparing metal pillars by electrochemical deposition additive manufacturing, using the aforementioned metal pillar electrochemical deposition additive manufacturing apparatus, comprising the following steps:

[0018] Select matching materials for the annular anode, substrate cathode wire, and auxiliary cathode end ring according to the required materials of the metal column to be prepared, and assemble the annular anode, substrate cathode wire, and auxiliary cathode end ring on the insulating electrode support, ensuring that the annular anode, substrate cathode wire, and auxiliary cathode end ring are coaxial and that the substrate cathode wire is in a straightened state;

[0019] The second plate of the assembled insulating electrode holder is placed inside the electrolytic cell;

[0020] Select a suitable electrolyte according to the electrochemical deposition requirements and add additives to the electrolyte. After the temperature of the electrolyte is adjusted to a preset temperature, control the electrolyte to enter the electrolytic cell from the heat exchange tank and overflow through the top opening of the electrolytic cell to form a circulation. Then, control the current mode of the annular anode, the substrate cathode wire and the auxiliary cathode end ring and the electrolyte flow rate according to the requirements to prepare a metal cylinder that is integrated with the substrate cathode wire.

[0021] The metal column electrochemical deposition additive manufacturing apparatus and method disclosed herein have the following beneficial effects:

[0022] A ring anode is used and placed radially outside a straightened substrate cathode wire. When energized, a radial electric field is formed between the two, and uniform radial deposition additive manufacturing is carried out with the substrate cathode wire as the seed. Metal ions in the electrolyte are reduced to target metal atoms and deposited on the outer wall of the substrate cathode wire to form a metal bond between the two, achieving atomic-scale metallurgical bonding. This ensures extremely high bonding strength between the deposited layer and the core (i.e., the substrate cathode wire), preventing the deposited layer from peeling off from the core. This method is conducive to preparing solid metal columns with straightness, roundness, material uniformity, and high density. It realizes a high-purity and high-utilization manufacturing path from ions in the electrolyte to finished materials, providing a reliable experimental device for the research and preparation of high-performance metal columnar samples. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments or related technologies of this disclosure, the accompanying drawings used in the description of the embodiments or related technologies will be briefly introduced below. The accompanying drawings described below are merely exemplary, and those skilled in the art can derive other embodiment drawings from the provided drawings without creative effort.

[0024] Figure 1 This is a three-dimensional structural schematic diagram of the metal column electrochemical deposition additive manufacturing apparatus in the embodiments of this disclosure;

[0025] Figure 2 yes Figure 1 A three-dimensional structural schematic diagram of the metal column electrochemical deposition additive manufacturing device from a first-view perspective;

[0026] Figure 3 yes Figure 2 Cross-sectional view of AA in the middle;

[0027] Figure 4 yes Figure 1 Top view of the metal column electrochemical deposition additive manufacturing apparatus;

[0028] Figure 5 yes Figure 1 A three-dimensional structural diagram of the insulating electrode support in the image;

[0029] Figure 6 This is a scanning electron microscope image of a partial cross-section of a copper column prepared according to Example 1 of this disclosure.

[0030] The attached figures are labeled as follows:

[0031] 1. Electrolytic cell; 11. Liquid inlet; 12. Liquid inlet chamber; 2. Insulating electrode support; 21. First plate; 22. Second plate; 221. Liquid equalization hole; 222. Annular cover plate; 23. Connecting rod; 231. Extended section; 232. Threaded hole; 31. First clamping component; 32. Second clamping component; 41. Annular anode; 411. Anode conductor; 42. Substrate cathode wire; 43. Auxiliary cathode end ring; 431. Auxiliary cathode conductor; 44. Insulating structure. Detailed Implementation

[0032] The technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this disclosure or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without creative effort are within the scope of protection of this disclosure.

[0033] In the description of this disclosure, it should be understood that the orientation or positional relationship indicated by directional terms such as "front, back, up, down, left, right", "horizontal, vertical, horizontal" and "top, bottom" is generally based on the orientation or positional relationship shown in the accompanying drawings and is only for the convenience of describing this disclosure and simplifying the description. Unless otherwise stated, these directional terms do not indicate or imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the scope of protection of this disclosure; the directional terms "inner" and "outer" refer to the inner and outer contours relative to the outline of each component itself.

[0034] For ease of description, spatial relative terms such as "above," "on top of," "on the upper surface of," "above," etc., are used herein to describe the spatial positional relationship of a device or feature as shown in the figures to other devices or features. It should be understood that spatial relative terms are intended to encompass different orientations in use or operation beyond the orientation of the device as described in the figures. For example, if the device in the figures were inverted, a device described as "above" or "on top of" other devices or structures would subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90° or in other orientations), and the spatial relative descriptions used herein will be interpreted accordingly.

[0035] Furthermore, it should be noted that the use of terms such as "first" and "second" to define components is merely for the purpose of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this disclosure.

[0036] See also Figures 1 to 5 As shown, according to an embodiment of this disclosure, a metal column electrochemical deposition additive manufacturing apparatus is provided, including an electrolytic cell 1 for holding an electrolyte and at least a portion of the structure (e.g., Figure 3 The first plate 21 (not located within the electrolytic cell 1) is located within the insulating electrode support 2 inside the electrolytic cell 1. The insulating electrode support 2 includes a first plate 21, a second plate 22, and multiple connecting rods 23. The first plate 21 and the second plate 22 are arranged parallel to each other, and each connecting rod 23 is detachably supporting and connecting the first plate 21 and the second plate 22. This makes the first plate 21, the second plate 22, and each connecting rod 23 form a whole. Each connecting rod 23 is arranged at intervals along a first circle, objectively forming an electrode mounting area within the radial direction of each connecting rod 23. An annular anode 41 is provided on the radially inner side of each connecting rod 23. A first clamping component 31 is provided on the first plate 21, and a second clamping component 32 is provided on the second plate 22. The first clamping component 31 and the second clamping component 32 are respectively clamped to both ends of the substrate cathode metal wire 42 so that the central axis of the substrate cathode metal wire 42 coincides with the central axis of the annular anode 41. That is, in specific use, the annular anode 41... The annular anode 41 and the substrate cathode wire 42 are coaxially arranged, and the substrate cathode wire 42 should be straightened (i.e., taut and straightened at both ends by the aforementioned first clamping member 31 and second clamping member 32). It is understood that both the annular anode 41 and the substrate cathode wire 42 are located within the aforementioned electrode mounting area. The annular anode 41 is electrically connected to the power anode, and the substrate cathode wire 42 is electrically connected to the power cathode. Specifically, the annular anode 41 is electrically connected to the power anode via an anode conductor 411, and the substrate cathode wire 42 is electrically connected to the power cathode via a corresponding cathode conductor (not labeled in the figure). In a preferred embodiment, for the purpose of simplifying the structural design, in one embodiment, one of the aforementioned first clamping member 31 or second clamping member 32 simultaneously forms the aforementioned cathode conductor. That is, one of the aforementioned first clamping member 31 or second clamping member 32 serves as both the end clamping and straightening structure of the substrate cathode wire 42 and the cathode conductor of the substrate cathode wire 42. Figure 1In the specific embodiment shown, the aforementioned first clamping component 31 is also used as a cathode conductor. It is understood that the aforementioned first clamping component 31 and the second clamping component 32 have an insulating layer on their outer peripheral walls. Of course, when they are not used as the aforementioned cathode conductors, they can be made of insulating materials. In specific applications, considering the specific conditions of the electrolyte, the aforementioned first clamping component 31 and the second clamping component 32 should generally be treated with acid-resistant and high-temperature-resistant insulation or made of acid-resistant and high-temperature-resistant insulating materials (when they do not need to be used as cathode conductors).

[0037] In this technical solution, an annular anode 41 is used and placed radially outside a straightened substrate cathode wire 42. After energization, a radial electric field is formed between the two, and uniform radial deposition additive manufacturing is carried out with the substrate cathode wire 42 as the seed. Metal ions in the electrolyte are reduced to target metal atoms and deposited on the outer wall of the substrate cathode wire 42 to form a metal bond between the two, realizing atomic-scale metallurgical bonding. This ensures that the deposition layer and the core (i.e., the substrate cathode wire 42) have extremely high bonding strength, preventing the deposition layer from peeling off from the core. This is conducive to the preparation of solid metal columns with straightness, roundness, material uniformity, and high density. It realizes a high-purity and high-utilization manufacturing path from ions in the electrolyte to finished materials, providing a reliable experimental device for the research and preparation of high-performance metal columnar samples. It should be noted that after the metal pillar is prepared, the aforementioned substrate cathode metal wire 42 and the deposited layer will be reliably integrated into an organic whole due to metal bonding. That is, the substrate cathode metal wire 42 will be an organic part of the metal pillar and cannot be peeled off after preparation.

[0038] It is understandable that the specific materials chosen for the electrolyte, the annular anode 41, and the substrate cathode wire 42 will vary depending on the specific materials used to prepare the metal column.

[0039] In some embodiments, the substrate cathode wire 42 is made of any metal, including but not limited to copper, nickel, and iron. Metals, as excellent conductors, can efficiently and uniformly transmit current from the power source to the entire surface to be deposited, which is a prerequisite for initiating and maintaining the electrodeposition reaction (non-metallic materials cannot fulfill this role). The essence of electrodeposition is the reduction of metal ions into metal atoms by gaining electrons on the cathode surface. Using a metal core material allows the newly formed atoms to directly form metallic bonds with the substrate metal atoms, achieving atomic-scale metallurgical bonding and ensuring extremely high bonding strength between the deposited layer and the core, preventing delamination. The crystal structure of the metal core material provides a good crystalline substrate for epitaxial deposition, guiding the orderly growth of the deposited layer and facilitating the formation of a dense, low-stress microstructure, which is crucial for manufacturing pillars used as structural components.

[0040] In some embodiments, the cross-section of the aforementioned substrate cathode wire 42 is circular. The radius of the circular cross-section is equal in any direction from the center to the edge, without any sharp edges or points. At the sharp edges, electric field lines will be concentrated, resulting in excessively high current density, excessively fast deposition, and the formation of dendrites or rough nodules. In an ideal configuration of a ring anode (i.e., the aforementioned annular anode 41), the electric field lines can be uniformly and vertically directed to the cathode surface from all sides, which provides a naturally uniform driving force for the deposition of metal ions on the surface of the wire. The circular cross-section of the substrate cathode wire 42 also allows the internal stress generated during the electrodeposition process to be symmetrically distributed on the circular cross-section, which greatly reduces the risk of cracking, warping, or peeling off from the substrate due to uneven stress. This is the key to ensuring that the coating, which is several millimeters or even centimeters thick, is firmly bonded to the core and forms an integrated rod. The uniform electric field and mass transport conditions are conducive to forming a concentric ring-shaped, fine-grained, and isotropic deposition structure. This structure is very beneficial for the uniformity of electrical / thermal conductivity, mechanical properties, and subsequent hot and cold processing.

[0041] Referring to the foregoing, since the substrate cathode wire 42 in this disclosure will be an organic part of the metal pillar after the metal pillar is prepared, when the material of the substrate cathode wire 42 is different from the material of the metal pillar (i.e., the material of the deposited layer), in order not to adversely affect the overall performance of the metal pillar and to ensure its reliable stability in the straightened state (preventing breakage), in some embodiments, the diameter of the aforementioned substrate cathode wire 42 is generally greater than 0.01 mm and less than D / 20 (where D is the outer diameter of the metal pillar to be prepared), so as to ensure the performance stability of the metal pillar when the materials of the deposited layer and the wire are different (for example, when the outer diameter of the prepared metal pillar is 20 mm, the corresponding outer diameter of the substrate cathode wire 42 does not exceed 1 mm). It is important to note that metals smaller than 0.01 mm are extremely prone to breakage during the straightening tension process and cannot withstand the basic tension required by the process. The resistance of the ultra-fine wire increases significantly, and it is prone to local overheating or even melting when the current required for electroplating is passed through it. At the same time, its contact area with the cathode conductor is too small, resulting in unstable current input, which will reduce the initial uniformity of the deposited layer. In addition, the ultra-fine wire is easily swayed by fluid disturbance in the electrolyte, making it difficult to maintain precise concentricity and position, thus rendering the surrounding electric field design aimed at uniform thickening ineffective.

[0042] In some embodiments, the axial height of the annular anode 41 is H, and the length of the substrate cathode wire 42 is L, where H ≥ L. The purpose of the wire length being less than the height of the annular anode 41 is to precisely define the effective working area for deposition additive manufacturing, thereby ensuring the uniformity of the finished product and the controllability of the process. This ensures that the entire section of the wire to be thickened is always within the uniform annular electric field generated by the anode, which helps to eliminate the "edge effect" caused by the concentration of electric field lines at both ends, and avoids excessive deposition at the ends of the wire to form bulges or dendrites. In some embodiments, H / L = 1:1 to 1.5:1, and along the radial projection of the annular anode 41, the substrate cathode wire 42 is within the height projection range of the annular anode 41. Limiting the height ratio of the effective working length of the annular anode 41 to the effective working length of the substrate cathode wire 42 to the aforementioned range allows for precise control of the electric field distribution to achieve uniform radial electrodeposition. Here, 1:1 is the theoretical ideal value for the electric field to completely and uniformly cover the cathode, while 1.5:1 is the engineering optimal value that, after considering assembly tolerances and edge effects, ensures the best uniformity of the entire length of the column in actual production. If the ratio is too small (e.g., the anode is too short), the two ends of the substrate cathode will be at the edge of the electric field, and the current density will increase dramatically, resulting in a dog-bone-shaped conical thickening of the deposited layer, which destroys the geometric uniformity. If the ratio is too large (e.g., the anode is too long), the excess anode will hardly contribute to effective deposition, instead causing material waste and increasing costs.

[0043] The material of the annular anode 41 includes, but is not limited to, copper, lead-antimony alloy, lead-silver alloy, and coated titanium cylinder. The coating in the coated titanium cylinder is selected from iridium-tantalum, lead dioxide, ruthenium dioxide, and iridium dioxide. The material selection of the annular anode 41 is based on a comprehensive trade-off between solubility, stability, and economy. When the prepared metal column is a copper column (or copper rod), a soluble pure copper anode can actively replenish copper ions in the electrolyte and maintain a stable concentration. The aforementioned lead-antimony and lead-silver alloys serve as classic insoluble anodes. Due to the dense lead dioxide passivation film formed on their surface, they are corrosion-resistant, dimensionally stable, and have low cost in acidic plating solutions. Among them, the lead-silver alloy has better conductivity, further reducing energy consumption. The titanium substrate in the coated titanium cylinder anode is lightweight and strong, and the noble metal oxide coating can achieve a pure oxygen evolution reaction at extremely high current densities, ensuring the purity of the plating solution and the ultimate quality of the coating.

[0044] In some embodiments, the electrolytic cell 1 is a cylindrical body with an open top, the liquid inlet 11 of the electrolytic cell 1 is located in the lower region of the cylindrical body, and the open top forms the overflow port of the electrolytic cell 1.

[0045] In this technical solution, the electrolytic cell 1 is a cylindrical body with an open top, and the liquid inlet 11 of the electrolytic cell 1 is located in the lower region of the cylindrical body, forming a liquid inlet method of overflow from top to bottom, which can ensure the full amount of electrolyte in the electrolytic cell 1, thereby ensuring the reliable and stable electrochemical deposition.

[0046] In some embodiments, the electrolytic cell 1 is a cylindrical body. When the insulating electrode support 2 is assembled with the electrolytic cell 1, the second plate 22 is located inside the electrolytic cell 1. The second plate 22 is a circular plate, and the outer diameter of the circular plate is equal to the inner diameter of the cylindrical body, that is, the second plate 22 is in contact with the inner wall of the cylindrical body, and / or, the radial outer side of each connecting rod 23 is in contact with the inner wall of the cylindrical body.

[0047] In this technical solution, the radial outer side of the second plate 22 and / or each connecting rod 23 is in contact with the inner wall of the cylinder, which can ensure that the insulating electrode support 2 is in a stable position in the electrolytic cell 1, and prevent the straightness, roundness and uniformity of the metal column from being reduced due to the change of the position of each electrode during the electrolytic deposition process.

[0048] In some embodiments, three connecting rods 23 are provided, and the three connecting rods 23 are evenly spaced in the semicircular area. In this way, the radial inner sidewall of the three connecting rods 23 can form a single-sided support for the annular anode 41, while also facilitating the insertion of the annular anode 41 from the other side of the semicircular area where the three connecting rods 23 are located, thus facilitating the assembly of the annular anode 41 with the insulating electrode support 2.

[0049] In some embodiments, a liquid inlet cavity 12 is formed between the second plate 22 and the bottom wall of the electrolytic cell 1. The liquid inlet 11 is formed on the cavity wall of the liquid inlet cavity 12. A plurality of liquid equalization holes 221 are formed on the second plate 22, penetrating both end faces of the plate. Each liquid equalization hole 221 is evenly spaced around the substrate cathode wire 42. That is, each liquid equalization hole 221 corresponds to the annular electric field between the annular anode 41 and the substrate cathode wire 42. It is understood that the flow direction of each liquid equalization hole 221 is parallel to the length direction of the substrate cathode wire 42.

[0050] In this technical solution, an inlet chamber 12 is provided in the lower region of the electrolytic cell 1, and multiple liquid equalization holes 221 are provided on the second plate 22. This allows the electrolyte entering the electrolytic cell 1 to flow in along the length direction of the substrate cathode metal wire 42, which can effectively reduce the disturbance of the metal wire caused by the inlet liquid, thereby ensuring the uniform and stable formation of the deposition layer. At the same time, the uniform spacing of each liquid equalization hole 221 can also ensure the uniformity of the concentration and flow rate of the electrolyte 1 entering the annular electric field region, which can further ensure the uniform and stable formation of the deposition layer.

[0051] In some embodiments, the first plate 21 is positioned outside the top opening. Due to the spacing of the connecting rods 23, the top opening of the electrolytic cell 1 is essentially completely open, ensuring smooth overflow of the electrolyte and thus ensuring sufficient electrolyte flow and improving deposition uniformity. Furthermore, it is worth emphasizing that the first plate 21 being positioned outside the top opening also decouples the portion of the first clamping member 31 electrically connected to the power cathode from contact with the electrolyte, significantly reducing the difficulty of insulation protection at that location.

[0052] In some embodiments, each of the connecting rods 23 has a protruding section 231 that protrudes from the end face of the second plate 22 near the bottom wall of the electrolytic cell 1, and the free end of each of the protruding sections 231 (i.e., Figure 3 The bottom end (as shown in the diagram) abuts against the bottom wall of the electrolytic cell 1.

[0053] In this technical solution, the second plate 22 objectively forms an upper and lower layer of the cylindrical structure of the electrolytic cell 1, thereby forming the aforementioned liquid inlet chamber 12, while the protruding section 231 of each connecting rod 23 forms an abutment support with the bottom wall of the electrolytic cell 1, simplifying the structural design inside the electrolytic cell 1.

[0054] In some embodiments, the metal column electrochemical deposition additive manufacturing apparatus further includes an annular cover plate 222, which can be selectively placed on the second plate 22 to adjust the on / off state of the liquid equalization holes 221. This allows for control of the electrolyte flow rate into the radial electric field region by adjusting the number of liquid equalization holes 221 while ensuring the pump liquid pressure remains constant. This reduces the difficulty of selecting a circulating pump. It is understood that under the same pump liquid pressure (i.e., the same circulating pump operating power), the fewer liquid equalization holes 221 in the flow state, the higher the electrolyte flow rate, and vice versa. Thus, before assembling the insulating electrode support 2, an annular cover plate 222 with a suitable radial width (ring width) can be placed on the top surface of the second plate 22 to block some of the liquid equalization holes 221. Of course, depending on actual needs, the aforementioned annular cover plate 222 may not be placed. That is, the aforementioned annular cover plate 222 is an optional accessory and has multiple specifications with different radial widths available.

[0055] The aforementioned electrolytic cell 1, insulating electrode support 2, and annular cover plate 222 can all be made of acid-resistant materials such as PP and PVC.

[0056] In some embodiments, the metal column electrochemical deposition additive manufacturing apparatus further includes a heat exchange tank (not shown in the figure) and a circulation pump (not shown in the figure). The heat exchange tank is equipped with heat exchange components to adjust the temperature of the electrolyte and maintain it at a preset temperature (the preset temperature varies depending on the actual deposition material). The electrolytic cell 1 is located in the heat exchange tank. The circulation pump is used to drive the electrolyte from the heat exchange tank into the electrolytic cell 1 through the inlet 11. The aforementioned heat exchange components can specifically be spiral coil type or plate type heat exchangers, which can be placed on the side wall and / or bottom wall of the heat exchange tank. Specifically, they can form a forced circulation of cooling medium with an external chiller unit, thereby achieving the purpose of heat exchange and temperature regulation of the electrolyte in the heat exchange tank. The aforementioned electrolyte can flow through the heat exchange surface of the aforementioned heat exchange components through natural convection or slight forced circulation to achieve the increase, decrease, or constant temperature maintenance of the electrolyte.

[0057] In some embodiments, the metal column electrochemical deposition additive manufacturing apparatus further includes two auxiliary cathode end rings 43. Each auxiliary cathode end ring 43 is located radially inside each connecting rod 23 and at both ends of the annular anode 41. Each auxiliary cathode end ring 43 is coaxially arranged with the annular anode 41, and an insulating structure 44 is provided between the end faces opposite to the annular anode 41. The auxiliary cathode end rings 43 are electrically connected to the power cathode, and during use, the current density formed in the auxiliary cathode end rings 43 is less than the current density formed in the substrate cathode metal wire 42. Each auxiliary cathode end ring 43 is specifically connected to the corresponding power cathode through a correspondingly provided auxiliary cathode conductor 431. The material of the auxiliary cathode end rings 43 includes, but is not limited to, any one of metals such as copper, nickel, and iron. In specific applications, the auxiliary cathode end rings 43 and the substrate cathode metal wire 42 can be controlled separately using different power supplies, or they can be connected in parallel with the same power supply to control the current distribution (with the help of a corresponding series resistor).

[0058] In this technical solution, by setting an auxiliary cathode end ring 43 at each end of the annular anode 41, the auxiliary cathode end ring 43 actively attracts and diverts the excess electric lines naturally gathered at both ends of the substrate cathode metal wire 42, thereby further eliminating the "edge effect" and preventing bulging at the end of the column due to excessive current density. This achieves precise fine-tuning of the local electric field, ensuring high axial uniformity of the deposition process. It is an indispensable part of obtaining a straight metal column with a consistent diameter and meeting geometric accuracy standards. It is understandable that the aforementioned auxiliary cathode end ring 43 objectively plays the role of an "electric field shaper". Specifically, the equipotential connection between the auxiliary cathode end ring 43 and the main cathode (i.e., the substrate cathode wire 42) means that the auxiliary cathode end ring 43 is in an equipotential state with the substrate cathode wire 42 (the aforementioned equipotential state refers to the state in which the potential difference between the two is controlled within a range that will not cause significant interference electric fields). This ensures that the auxiliary cathode end ring 43 can effectively perform the "electric field shaping" function, rather than "current competition". If the potential of the auxiliary cathode end ring 42 is different from that of the main cathode, a new, uncontrolled potential difference and electric field will be generated between the two, which will severely distort the originally designed ring symmetrical electric field, leading to increased deposition non-uniformity, or even the opposite effect. If the potential of the auxiliary cathode, i.e., the potential of the auxiliary cathode end ring 43, is too much lower than the potential of the substrate and the wire 42, it will violently "steal" the current that should be deposited on the copper wire, rapidly depositing and thickening itself and destroying the geometry.

[0059] Generally speaking, the inner diameter of the aforementioned auxiliary cathode end ring 43 is less than or equal to the inner diameter of the annular anode 41, and the axial length is less than the length of the substrate cathode metal wire 42.

[0060] In some embodiments, the insulating structure 44 is an insulating ring sandwiched between the corresponding end faces of the auxiliary cathode end ring 43 and the annular anode 41. The axial thickness of the insulating ring can be reasonably selected according to actual needs. By sandwiching the insulating ring between the corresponding end faces of the auxiliary cathode end ring 43 and the annular anode 41, a relatively stable annular electric field region can be objectively formed on the radial inner side of the annular anode 41 and the auxiliary cathode end ring 43, ensuring that the electrolyte flowing out of each of the aforementioned liquid equalization holes 221 flows parallel along the length direction of the auxiliary cathode end ring 43, further ensuring the stable formation and uniformity of the deposited layer.

[0061] In some embodiments, each connecting rod 23 is provided with a plurality of threaded holes 232 spaced apart along its length. Each threaded hole 232 penetrates the radial inner and outer sides of the connecting rod 23. A radial push screw (or bolt, not shown in the figure) is screwed into each threaded hole 232. In order to ensure that the radial outer side of each connecting rod 23 fits against the inner wall of the aforementioned cylinder, in a specific embodiment, a receiving groove is formed at the radial outer opening of each threaded hole 232, and the screw head of each radial push screw is received in each receiving groove.

[0062] In this technical solution, by screwing corresponding radial push screws into each threaded hole 232, the annular anode 41 and / or the auxiliary cathode end ring 43 can be radially pushed by turning each radial push screw. This allows for precise adjustment (fine-tuning) of the radial position of the annular anode 41 and the auxiliary cathode end ring 43 in the assembled state, thereby ensuring strict coaxiality between the annular anode 41 and the auxiliary cathode end ring 43 and the aforementioned substrate cathode metal wire 42. Furthermore, it is worth emphasizing that the centering action of each radial push screw also simultaneously achieves centering locking of the annular anode 41 and the auxiliary cathode end ring 43, ensuring stable and reliable positioning.

[0063] The first clamping component 31 includes a clamping part (not labeled in the figure) for clamping the substrate cathode metal wire 42 and a tension adjustment part (not labeled in the figure) threadedly connected to the first plate 21. Similarly, the aforementioned second clamping component 32 may also include the aforementioned clamping part and a connecting part connected to the second plate 22. The structure of the aforementioned clamping part can be varied, such as a chuck (jaw) or the like. The connecting part of the second clamping component 32 can be a threaded connecting post or a welded structure.

[0064] In this technical solution, the tension adjustment part of the first clamping component 31 is threadedly connected to the first plate 21. After the substrate cathode wire 42 is clamped by the upper and lower clamping components and the position of the bottom second clamping component 32 and the second plate 22 is locked, the tension adjustment part of the first clamping component 31 can be screwed in and out, thereby changing the relative position between the first clamping component 31 and the first plate 21, and thus changing the tension force on the substrate cathode wire 42. This ensures that the substrate cathode wire 42 can be stably kept in a straight and taut state without plastic deformation during use. It is understood that the tension applied to the substrate cathode wire 42 can be adjusted adaptively when the material of the substrate cathode wire 42 is different. For example, when the material of the substrate cathode wire 42 is copper, the corresponding tension can be 0.005N.

[0065] According to embodiments of this disclosure, a method for preparing metal pillars by electrochemical deposition additive manufacturing is also provided, using the aforementioned metal pillar electrochemical deposition additive manufacturing apparatus, comprising the following steps:

[0066] Select matching materials for the annular anode 41, substrate cathode metal wire 42, and auxiliary cathode end ring 43 according to the required metal column material, and assemble the annular anode 41, substrate cathode metal wire 42, and auxiliary cathode end ring 43 onto the insulating electrode support 2, ensuring that the annular anode 41, substrate cathode metal wire 42, and auxiliary cathode end ring 43 are coaxial (for example, by adjusting the aforementioned radial push screws) and ensuring that the substrate cathode metal wire 42 is in a straightened state (by screwing the first clamping component 31, and ensuring that the metal wire does not undergo plastic tensile deformation).

[0067] The second plate 22 of the assembled insulating electrode support 2 is placed inside the electrolytic cell 1. During the placement process, since the outer circle of the second plate 22 and the radial outer side of each connecting rod 23 are in contact with the inner wall of the cylindrical electrolytic cell 1, the insulating electrode support 2 can be stably and reliably locked in the radial direction after it is placed in place.

[0068] Select a suitable electrolyte according to the electrochemical deposition requirements and add additives to the electrolyte. After the temperature of the electrolyte is adjusted to a preset temperature, control the electrolyte to enter the electrolytic cell 1 from the heat exchange tank and overflow through the top opening of the electrolytic cell 1 to form a circulation. Then, control the current mode of the annular anode 41, the substrate cathode wire 42 and the auxiliary cathode end ring 43 and the electrolyte flow rate according to the requirements to prepare a metal cylinder that is integrated with the substrate cathode wire 42.

[0069] Specifically, the aforementioned energizing current modes include DC mode and pulse mode. As a specific example, when using DC mode, the current density is 0.1 A / dm. 2 ~100A / dm 2 When pulse mode is used, the peak current density range is 10 A / dm². 2 ~500A / dm 2The on-off time of one pulse cycle is 0.1ms to 1000ms and 100ms to 5000ms, respectively. The preset temperature is generally 5℃ to 70℃. The aforementioned DC mode is suitable for conventional applications with high deposition rate requirements but not extremely stringent requirements on the ultimate physical properties of the coating. The pulse mode adjusts parameters such as the on-time, off-time, and peak current density of the pulse current, which can precisely control the crystallization process, thereby achieving significant grain refinement, reduced internal stress, reduced impurity content, and more uniform thickness distribution. More preferably, the coating produced by the pulse mode has a finer equiaxed crystal structure, and its mechanical properties (strength, toughness), physical properties (conductivity uniformity), and chemical properties (corrosion resistance) are generally superior to the columnar crystal structure of the DC mode. The pulse mode can effectively suppress dendrite growth, allowing operation at higher average current densities without producing rough deposits, thereby improving production efficiency potential while ensuring quality.

[0070] The preset temperature control modes include one or a combination of constant, rising, and falling modes. The choice of temperature control mode lies in how to optimize the microstructure and internal stress by regulating deposition kinetics. The constant mode ensures stable parameters throughout the process, resulting in a uniform microstructure. Temperature programming primarily addresses the increased mass transfer limitations in thick-layer deposition by improving ion diffusion to prevent defects and alleviate stress. Temperature programming promotes nucleation and refines grains to enhance final hardness. From the perspective of production stability and controllability, the constant temperature mode is preferred, as it is more conducive to achieving product consistency. When depositing other samples requiring specific conditions, a combination of "constant temperature + rising temperature" or "constant temperature + falling temperature" modes can be considered for targeted optimization.

[0071] The electrolyte flow rate is 0.01 m. 3 / h~8m 3 / h; The aforementioned additives also contain electroplating-grade additives, mainly brighteners, leveling agents, positioning agents, and stress relievers. The use of these additives can include one or more combinations of the above, specifically adjusting one or more of the electrolysis time, current density, temperature, flow rate, and additives according to actual needs to control the diameter and surface quality of the deposited metal pillars. It is worth noting that, through their synergistic effects of leveling, refining grains, and relieving stress, the additives can precisely control the electrochemical microprocesses at the deposition interface, thereby suppressing dendrites and obtaining a smooth surface and a fine, uniform equiaxed grain structure.

[0072] It should be noted that before assembling the aforementioned substrate cathode metal wire 42 onto the insulating electrode support 2, steps such as alkaline washing, acid washing, water washing, and drying should be performed. Among them, alkaline washing aims to thoroughly remove grease, organic contaminants, and some oxides that have adhered to the metal wire during production and storage, providing a clean interface for subsequent processing. The core function of acid washing is to activate the surface by chemically etching away stubborn oxide films and exposing fresh, highly active pure metal lattices, which directly determines whether subsequent deposition layers can form a strong atomic-level metallurgical bond with it. Thorough water washing is used to completely remove residual chemical agents from each step, preventing them from contaminating the core electroplating solution and ensuring deposition purity and solution stability. Finally, drying can eliminate surface moisture.

[0073] Taking electrolytic (electrochemical deposition) of a copper column as an example, this embodiment provides the aforementioned preparation apparatus. During electrolytic deposition (i.e., electrochemical deposition) of a copper column, the annular anode iridium-tantalum-titanium (i.e., the aforementioned annular anode 41) is placed radially inside each connecting rod 23 of the intermediate support (i.e., the aforementioned insulating electrode support 2). One end of the substrate cathode copper wire (i.e., the aforementioned substrate cathode metal wire 42), after acid pickling and other treatments, is fixed to the second plate 22 using the second clamping component 32, and the other end is fixed using the first clamping component 31 (passing through the annular anode). The upper and lower clamping components are moved and adjusted along the height direction so that the copper wire is located radially inside the annular anode iridium-tantalum-titanium. The tension of the substrate cathode copper wire is 0.005N, which keeps the copper wire vertical. Bolts (i.e., the aforementioned radial push screws) are used to adjust it to keep it coaxial with the copper wire. This is crucial for the upright electrolytically deposited copper column. The apparatus is configured with copper... When the ring, also known as the aforementioned auxiliary cathode end ring 43, is used, before fixing the aforementioned copper wire, it is necessary to place the copper ring at both ends of the annular anode iridium-tantalum-titanium of the intermediate support, and adjust the radial push screw to keep it coaxial with the copper wire. The copper wire and the copper ring are respectively connected to the negative terminal of the power supply, and the conductive strip connected to the iridium-tantalum-titanium (i.e., the aforementioned anode conductive strip 411) is connected to the positive terminal of the power supply. The electrolytic cell 1 is placed in the heat exchange tank, and the bottom inlet of the electrolytic cell is connected to the circulation pump. After the solution containing sulfuric acid and copper ions is heated in the heat exchange tank, it enters the electrolytic cell cavity through the bottom inlet (i.e., the aforementioned inlet 11), passes through the inlet chamber 12 and each liquid equalization hole 221 into the annular space between the annular anode iridium-tantalum-titanium and the copper wire, and overflows out from the top opening of the electrolytic cell back to the heat exchange tank to complete the solution circulation. Similarly, when using the preparation setting of the electrolytic metal column provided in this embodiment to electrolytically deposit other metals, a similar operation is also used.

[0074] The metal columns obtained using the aforementioned technical solution have a diameter range of 12μm to 20000μm and an axial height greater than 10mm. Besides copper columns, the aforementioned metal columns can also be pure metal columns such as nickel columns, or alloy metal columns can be prepared.

[0075] The following experimental examples and comparative examples further illustrate this point.

[0076] Example 1

[0077] This embodiment uses the aforementioned preparation apparatus of this disclosure to perform DC electrolytic deposition of copper pillars, as detailed below:

[0078] Electrolyte composition: The base solution is mainly composed of 300g / L CuSO4·5H2O, 100g / L H2SO4 and deionized water. The electrolyte also contains electroplating grade additives, including brighteners and leveling agents.

[0079] The substrate cathode (i.e., the aforementioned substrate cathode metal wire 42) is made of 0.1 mm diameter copper wire (99.99% purity) and 100 mm in length. It is acid-washed and water-washed, and held by upper and lower clamps (i.e., the aforementioned first clamping assembly 31 and second clamping assembly 32) with a tension of 0.005 N. The annular anode (i.e., the aforementioned annular anode 41) is made of iridium-tantalum coated titanium, and the auxiliary cathode (i.e., the aforementioned auxiliary cathode end ring 43) is made of copper ring. The cathode, anode, and auxiliary cathode are placed coaxially by bolts (i.e., the aforementioned radial push screws) on the intermediate support (i.e., the aforementioned insulating electrode support 2). The distance between the cathode and anode is 25 mm, and the effective area ratio is 1:1. The auxiliary cathode is 10 mm high and 5 mm away from the anode. The liquid inlet (i.e., the aforementioned liquid equalization hole 221) has a diameter of 50 mm.

[0080] Electrolysis time is controlled by the power supply; electrolysis temperature is controlled by the heat exchange tank; a circulating pump with a power of 2W is used to circulate the electrolyte; the total electrolyte volume of the device is 3L; and a constant current density of 3A / dm³ is selected. 2 Temperature 25℃, flow rate 1m 3 Electrolysis was carried out at a time of 133 hours to obtain a copper column of uniform thickness.

[0081]

[0082] Comparative Example 1:

[0083] A conventional electrolytic deposition apparatus was used for DC electrolytic deposition of copper pillars (without using the coaxially arranged electrodes described in this application, without an auxiliary cathode, and without straightened metal wires), as detailed below:

[0084] Electrolyte composition: The base solution mainly consists of 300 g / L CuSO4·5H2O, 100 g / L H2SO4, and deionized water. The electrolyte also contains electroplating-grade additives, primarily brighteners and leveling agents.

[0085] The cathode is made of 0.1mm diameter copper wire (99.99% purity) with a length of 100mm, which is acid-washed and water-washed. The anode is an iridium-tantalum coated titanium plate. The distance between the cathode and anode is 25mm, and the ratio of the effective area of ​​the cathode to the anode is 1:1.

[0086] The total electrolyte volume of the device is 13L, and the pump power is 35W. Here, taking the constant current method as an example, a current density of 3A / dm³ is selected. 2 An electrolytic reaction was carried out at a temperature of 25℃ for 133 hours to obtain a copper column.

[0087]

[0088] Comparative Example 2:

[0089] The copper pillar was deposited using a conventional electrolytic deposition apparatus via direct current electrolysis, as detailed below:

[0090] Electrolyte composition: The base solution mainly consists of 300 g / L CuSO4·5H2O, 100 g / L H2SO4, and deionized water. The electrolyte also contains electroplating-grade additives, primarily brighteners and leveling agents.

[0091] The cathode is made of 0.1mm diameter copper wire (99.99% purity) with a length of 100mm, which is acid-washed and water-washed. The anode is made of annular iridium-tantalum coated titanium. The distance between the cathode and anode is 25mm, and the ratio of the effective area of ​​the cathode to the anode is 1:1.

[0092] The total electrolyte volume of the device is 13L, and the pump power is 35W. Here, taking the constant current method as an example, a current density of 3A / dm³ is selected. 2 An electrolytic reaction was carried out at a temperature of 25℃ for 133 hours to obtain a copper column.

[0093]

[0094] In Comparative Example 1, the flat anode and the copper wire are extremely asymmetrical, with a strong electric field on only one side and a very weak electric field on the back side. The cross-section is semi-cylindrical or teardrop-shaped, with one side extremely thick and the other extremely thin. The lack of an auxiliary cathode leads to severe concentration of the electric field at both ends, forming a large bulge. Due to the absence of tension regulation and axial flow equalization holes, the high-speed flowing electrolyte generates asymmetrical and random fluid impact forces on the copper wire, causing it to oscillate irregularly in the anode chamber, ultimately resulting in some deformation. After electroplating into a copper pillar, it exhibits a bent state. The insufficient solution flow also leads to uneven adsorption of additives and the appearance of copper nodules on the surface. In Comparative Example 2, although a ring anode is used, there are no concentric rings. The adjustment components resulted in a slight eccentricity of the copper wire, creating an asymmetrical electric field—stronger near the anode and weaker further away. This resulted in an elliptical cross-section, with the eccentricity at both ends contributing to a more complex and distorted bulge shape. In contrast, the copper pillar prepared in Example 1 exhibited a better surface condition and uniform, controllable thickness. This was primarily due to tension control ensuring the verticality of the substrate cathode, crucial for the upright copper pillar. Bolts on the support allowed for adjustment of the annular anode and auxiliary cathode, ensuring they were concentric with the copper wire—a key factor for the uniformity of the copper pillar. The auxiliary cathode corrected the electric field distribution; it did not participate in the main productive deposition but provided a crucial electric field environment to ensure the deposition of a uniform and straight copper pillar from the main cathode copper wire. The uniform liquid distribution holes allowed for even solution entry into the electrolytic cell, resulting in more uniform adsorption of additives and a superior surface condition.

[0095] In addition, scanning electron microscopy tests were performed on the cross-section of Example 1, such as... Figure 6 As shown, columnar crystals extend outward from the copper wire substrate interface in a direction roughly perpendicular to the surface. Obvious elongated grains are visible penetrating multiple micrometers or even millimeters in thickness, with grain boundaries parallel to the growth direction. The formation of columnar crystals is a typical characteristic of diffusion-controlled electrodeposition, indicating a significant preferred orientation in crystal growth under DC mode, resulting in a columnar structure. Additives such as brighteners and leveling agents promote this oriented growth, forming a dense but columnar microstructure. The dense, continuous columnar crystals demonstrate the reliability and stability of the preparation device and the good control of the preparation process. The deposited layer has high purity, few defects, and excellent conductivity along the length of the columnar crystals, proving the high directionality and continuity of the deposition process, resulting in excellent axial conductivity and a certain strength. To further improve the overall mechanical properties of the copper pillars, especially their lateral properties, grain refinement can be promoted by adjusting the current mode and additive formulation, achieving microstructural control from columnar crystals to equiaxed crystals.

[0096] In summary, the metal column electrochemical deposition additive manufacturing apparatus and method of this disclosure can controllably produce solid copper columns with straightness and roundness that meet the standards, high uniformity, and high density. This overcomes the limitations of traditional casting-rolling processes, which are long and energy-intensive, as well as the inability of conventional electroplating to produce integral materials. It provides a revolutionary technological path for the short-process, low-cost preparation of high-purity, complex-structure, and high-performance copper materials required in fields such as semiconductors and high-energy physics.

[0097] It will be readily understood by those skilled in the art that, without conflict, the advantageous technical features of the above-mentioned methods can be freely combined and superimposed.

[0098] The above description is merely a preferred embodiment of this disclosure and is not intended to limit this disclosure. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this disclosure should be included within the protection scope of this disclosure. The above description is only a preferred embodiment of this disclosure. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of this disclosure, and these improvements and modifications should also be considered within the protection scope of this disclosure.

Claims

1. A metal column electrochemical deposition additive manufacturing apparatus, characterized in that, The device includes an electrolytic cell (1) for holding an electrolyte and an insulating electrode support (2) with at least a portion of its structure located within the electrolytic cell (1). The insulating electrode support (2) includes a first plate (21), a second plate (22), and multiple connecting rods (23). The first plate (21) and the second plate (22) are arranged parallel to each other and spaced apart. Each of the connecting rods (23) is detachably supporting and connecting the first plate (21) and the second plate (22). Each of the connecting rods (23) is spaced apart along a first circle, and the diameter of each of the connecting rods (23) is... An annular anode (41) is provided on the inner side. A first clamping component (31) is provided on the first plate (21) and a second clamping component (32) is provided on the second plate (22). The first clamping component (31) and the second clamping component (32) are respectively clamped at both ends of the substrate cathode wire (42) so that the central axis of the substrate cathode wire (42) coincides with the central axis of the annular anode (41). The annular anode (41) is electrically connected to the power anode and the substrate cathode wire (42) is electrically connected to the power cathode.

2. The metal column electrochemical deposition additive manufacturing apparatus according to claim 1, characterized in that, The electrolytic cell (1) is a cylindrical body with an open top. The inlet (11) of the electrolytic cell (1) is located in the lower region of the cylindrical body, and the open top forms the overflow port of the electrolytic cell (1). Or, the electrolytic cell (1) is a cylindrical body. When the insulating electrode support (2) is assembled with the electrolytic cell (1), the second plate (22) is located inside the electrolytic cell (1). The second plate (22) is a circular plate, and the outer diameter of the circular plate is equal to the inner diameter of the cylindrical body. Or, the radial outer side of each connecting rod (23) is in contact with the inner wall of the cylindrical body.

3. The metal column electrochemical deposition additive manufacturing apparatus according to claim 2, characterized in that, A liquid inlet cavity (12) is formed between the second plate (22) and the bottom wall of the electrolytic cell (1). The liquid inlet (11) is formed on the cavity wall of the liquid inlet cavity (12). A plurality of liquid equalization holes (221) are formed on the second plate (22) and penetrate its two end faces. Each of the liquid equalization holes (221) is evenly spaced around the substrate cathode wire (42); and / or, the first plate (21) is located outside the top opening.

4. The metal column electrochemical deposition additive manufacturing apparatus according to claim 3, characterized in that, Each of the connecting rods (23) has an extension section (231) protruding from the end face of the second plate (22) near the bottom wall of the electrolytic cell (1), and the free end of each extension section (231) abuts against the bottom wall of the electrolytic cell (1); and / or, it also includes an annular cover plate (222), which can be selectively placed on the second plate (22) to adjust the on / off state of the liquid equalization hole (221).

5. The metal column electrochemical deposition additive manufacturing apparatus according to claim 2, characterized in that, It also includes a heat exchange tank and a circulation pump. The heat exchange tank is equipped with heat exchange components to adjust the temperature of the electrolyte and keep it at a preset temperature. The electrolytic cell (1) is located in the heat exchange tank. The circulation pump is used to drive the electrolyte from the heat exchange tank into the electrolytic cell (1) through the liquid inlet (11).

6. The metal column electrochemical deposition additive manufacturing apparatus according to claim 2, characterized in that, It also includes two auxiliary cathode end rings (43), each of which is located radially inside each of the connecting rods (23) and at both ends of the annular anode (41). Each of the auxiliary cathode end rings (43) is coaxially arranged with the annular anode (41) and has an insulating structure (44) between its end face and the annular anode (41). The auxiliary cathode end rings (43) are electrically connected to the power cathode, and during use, the current density formed in the auxiliary cathode end rings (43) is less than the current density formed in the substrate cathode wire (42); and / or, the first clamping component (31) includes a clamping part for clamping the substrate cathode wire (42) and a tension adjustment part threadedly connected to the first plate (21).

7. The metal column electrochemical deposition additive manufacturing apparatus according to claim 6, characterized in that, The insulating structure (44) is an insulating ring sandwiched between the auxiliary cathode end ring (43) and the corresponding end face of the annular anode (41).

8. The metal column electrochemical deposition additive manufacturing apparatus according to claim 6, characterized in that, Each of the connecting rods (23) is provided with a plurality of threaded holes (232) spaced apart along its length. Each of the threaded holes (232) passes through the radial inner and outer sides of the connecting rod (23), and a radial push screw is screwed into each of the threaded holes (232).

9. The metal column electrochemical deposition additive manufacturing apparatus according to claim 1, characterized in that, The axial height of the annular anode (41) is H, and the length of the substrate cathode wire (42) is L, where H ≥ L. Preferably, H / L = 1:1 to 1.5:1, and the substrate cathode wire (42) is within the height projection range of the annular anode (41) along its radial projection; and / or, the cross-section of the substrate cathode wire (42) is circular, the diameter of the substrate cathode wire (42) is greater than 0.01 mm, and when the substrate cathode wire (42) is different from the material of the deposition layer, the diameter of the substrate cathode wire (42) is less than D / 20, where D is the outer diameter of the metal column to be prepared.

10. A method for preparing metal pillars by electrochemical deposition additive manufacturing, characterized in that, The metal column electrochemical deposition additive manufacturing apparatus according to any one of claims 2 to 8 is used, comprising the following steps: Select a matching annular anode (41), substrate cathode wire (42), and auxiliary cathode end ring (43) based on the material of the metal column to be prepared, and assemble the annular anode (41), substrate cathode wire (42), and auxiliary cathode end ring (43) on the insulating electrode support (2) to ensure that the annular anode (41), substrate cathode wire (42), and auxiliary cathode end ring (43) are coaxial and that the substrate cathode wire (42) is in a straightened state; The second plate (22) of the assembled insulating electrode support (2) is placed inside the electrolytic cell (1); Select a matching electrolyte according to the electrochemical deposition requirements and add additives to the electrolyte. After the temperature of the electrolyte is adjusted to a preset temperature, control the electrolyte to enter the electrolytic cell (1) from the heat exchange tank and overflow through the top opening of the electrolytic cell (1) to form a circulation. Then, control the current mode of the ring anode (41), the substrate cathode wire (42) and the auxiliary cathode end ring (43) and the electrolyte flow rate according to the requirements to prepare a metal cylinder that is integrated with the substrate cathode wire (42).

Images