US20240060202A1

US20240060202A1 - Optimized method and device for insoluble anode acid sulfate copper electroplating process

Info

Publication number: US20240060202A1
Application number: US18/270,494
Authority: US
Inventors: Tao Ye; Yiting YE
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-12-31
Filing date: 2021-12-30
Publication date: 2024-02-22
Also published as: TW202229649A; CN116685721A; TWI806328B; WO2022143860A1

Abstract

The present invention provided an optimized method for an insoluble anode acid sulfate copper electroplating process, comprising following steps: providing an insoluble anode made of coated titanium in the form of a mesh or a perforated plate; providing at least one liquid outlet pipe/port on the side of the insoluble anode away from the cathode, to generate a liquid flow of an electroplating solution by overflow and/or power driven suction at the liquid outlet pipe/port; initiating an electroplating process by switching on an electroplating power supply, while the electroplating solution flows away due to the overflow and/or power driven suction at the liquid outlet pipe/port, the electroplating solution in the electroplating cell forms a liquid flow towards the liquid outlet pipe/port, and accordingly, adding electroplating solution to the electroplating cell to maintain the liquid volume in the cell until the electroplating process is completed and the electroplated cathode is removed.

Description

TECHNICAL FIELD

The disclosure relates to the field of copper electroplating. More specifically, the disclosure relates to an optimized method and a device for an insoluble anode acid sulfate copper electroplating process.

DESCRIPTION OF RELATED ART

Copper electroplating is one of the most common processes in the electroplating industry. Generally, to coat a nickel, gold, silver or tin metal layer on a surface of various metal parts, an intermediate copper layer is required to improve the adhesion between metal parts and their exterior plated layer.
Existing acid sulfate copper electroplating processes involve an electroplating solution that comprises an aqueous solution of sulfuric acid and copper sulfate as its main component. Such processes can be divided into two types: a soluble anode process and an insoluble anode process. The soluble anode copper electroplating process uses phosphorus copper as the soluble anode material; while the insoluble anode copper electroplating process refers to an electroplating process in which the anode does not dissolve or extremely slightly dissolves during the electroplating reaction, that is, an insoluble anode material is used. For the latter, insoluble titanium-based coated anodes are commonly seen in the prior art.
The electrochemical reactions at the anode for the two types of acid sulfate copper electroplating processes are as follows:
(1) Copper electroplating process with soluble anode
Cu−2e⁻→Cu²⁺
(2) Copper electroplating process with insoluble anode
H₂O−2e⁻→1/2O₂↑+2H⁺
Compared to the soluble anode copper electroplating process, the insoluble anode copper electroplating process produces hydrogen ions and oxygen gas from water electrolysis at the anode, and copper ions in the electroplating solution are reduced to metallic copper on the surface of the cathode (the part to be coated), resulting in a more uniform, smoother and denser copper metal layer on the cathode due to the relatively stable anode size as well as more controllable and more stable electroplating solution composition during the electroplating process. Besides direct current electroplating, pulse electroplating is also applicable to the insoluble anode copper electroplating process, and the productivity can be significantly increased by increasing the anode current density.
At the same time, as technology development has fully entered the 5G era in recent years, the market demand for high-precision circuit boards is increasing, and the requirements of copper electroplated through-hole aspect ratio (i.e. hole length to hole diameter ratio of a through-hole) of multilayer circuit boards are also reaching a high level. Therefore, insoluble anode copper electroplating process is more and more common in circuit board manufacturing to enhance the production quality and efficiency of copper electroplating of circuit board products.
For double-sided electroplating of circuit boards with large aspect ratios of copper plated through-holes, the existing insoluble anode copper electroplating process uses reverse pulse current to convert the electroplated cathode into anode to allow copper dissolution; such operation not only optimizes the uniformity and flatness of the plated layer, improves the dispersion of the electroplating solution and enhances the bonding of the plated layer, but also results in good hole-electroplating of the copper plated through-holes.
However, the existing insoluble anode copper electroplating process has the following disadvantages.
1. Oxygen bubbles are generated on the anode during the electroplating process, which are distributed between the anode and cathode, thus forming a barrier to the electroplating current and affecting the electric discharge uniformity, as well as reducing the uniformity of the plated layer. At the same time, while in the conventional vertical electroplating process, the oxygen bubbles generated during the process form a bubble layer from the bottom to the top with certain gradient on the surface of the anode, which further leads to uneven current distribution, and thus seriously affects the plating quality in vertical electroplating.
To solve the above problem in vertical electroplating, horizontal electroplating is applied in the prior art to minimize the effect of the bubble layer. But the equipment for horizontal electroplating is more complex in structure and the space in the electroplating cell is very limited, so the plated parts are usually thin sheets only and cannot meet the copper electroplating requirements of products with different shapes and sizes.
2. During the reverse pulse electroplating process, the original insoluble anode is converted to a cathode while applying reverse pulse, the polarity change of the insoluble anode causes hydrogen generation on its surface, leading to the titanium oxide on the surface of the insoluble titanium-based coated anode changing into titanium hydride, resulting in flaking and damage of the coating of the insoluble anode.
3. In the existing insoluble anode copper electroplating process, an organic electroplating additive, i.e. a brightening additive, is usually added to the electroplating solution to obtain a flatter and brighter electroplating layer. The anodes used in the insoluble anode copper electroplating process are coated with a precious metal coating, which shows a catalytic effect in decomposition of the electroplating additives and directly decomposes the electroplating additives in the electroplating solution. In addition, when insoluble anodes are used for acid copper electroplating, decomposition of the electroplating additives is accelerated by some new-formed oxidants. Therefore, the existing insoluble anode copper electroplating processes consume far more electroplating additives than the copper electroplating processes with soluble anodes. The additional consumption of electroplating additives leads to increased production costs.
In summary, process optimization is still necessary, despite the advantages of good plating flatness and high efficiency of insoluble anode copper electroplating process compared to soluble anode copper electroplating process.

SUMMARY

A first objective of the present disclosure is to provide an optimized method for an insoluble anode acid sulfate copper electroplating process. The method can effectively improves the uniformity of the electroplated copper layer and the electroplating quality.
A second objective of the present disclosure is to provide a device to carry out the aforementioned optimized method for an insoluble anode acid sulfate copper electroplating process.
The first objective can be achieved by the following technical solution.
An optimized method for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell, an electroplating power supply, an insoluble anode, a cathode, and an acid sulfate copper electroplating solution, wherein the method comprises the following steps.
Step 1: Providing an insoluble anode made of coated titanium in the form of a mesh or a perforated plate, and then the insoluble anode and a cathode are placed in the electroplating cell; providing at least one liquid outlet pipe/port on the side of the insoluble anode away from the cathode, to generate a liquid flow of an electroplating solution by overflow and/or power driven suction at the liquid outlet pipe/port.
Step 2: Initiating an electroplating process by switching on an electroplating power supply, while the electroplating solution flows away due to the overflow and/or power driven suction at the liquid outlet pipe/port, the electroplating solution in the electroplating cell forms a liquid flow towards the liquid outlet pipe/port, and accordingly, adding another electroplating solution to the electroplating cell to maintain the liquid volume in the cell until the electroplating process is completed and the electroplated cathode is removed.
In the present disclosure, the shape of the insoluble anode as a mesh or a perforated plate provides a hole, or holes distributed randomly or regularly, that penetrates through both sides of the anode; the hole of the insoluble anode cooperates with at least one liquid outlet pipe/port located on the side of the anode away from the cathode, to generate a liquid flow in the vicinity of the insoluble anode that flows away from the cathode and through the hole of the anode by overflow and/or power driven suction. Therefore, the oxygen bubbles generated on the surface of the anode during the electroplating process can pass through the holes formed by the mesh or the perforated plate structure of the insoluble anode with the liquid flow, and be carried away from the area between the anode and the cathode for external discharge. The method helpfully reduces the build-up of oxygen bubbles that results in the formation of an oxygen bubble shield on the surface of the anode facing the cathode during the electroplating process, and thus improves the plating uniformity and electroplating efficiency.
Preferably, the liquid outlet pipe/port utilizes a power driven device to produce a liquid flow in the vicinity of the insoluble anode that flows away from the cathode and through the holes of the anode. The power driven device is at least one pump that allows pressurized drainage and/or negative pressure suction.
In the present disclosure, the electroplating solution added to the electroplating cell to maintain the liquid volume in the cell is an additionally added new electroplating solution and/or a supplementary electroplating solution, and/or a circulated electroplating solution using a fluid circulating system.
The fluid circulating system of the present disclosure mainly consists of a pump and a connecting pipe, with one end connecting to the liquid outlet pipe/port and the other end connecting to the electroplating cell. The fluid circulating system is utilized to make the electroplating solution flow away from the liquid outlet pipe/port and return to the electroplating cell, forming a liquid flow in the electroplating cell towards the liquid outlet pipe/port near the anode, in a circular manner. The fluid circulating system can be made by adding a connecting pipe, which is connected to the electroplating cell, to the above-mentioned case that the liquid outlet pipe/port utilizes a power driven device to force the liquid in the vicinity of the insoluble anode to create a flow away from the cathode and through the anode holes.
The method of the present disclosure is applicable to both vertical electroplating and horizontal electroplating; it can be used in conjunction with either ordinary direct current power supplies, or reverse pulse power supplies. Particularly for vertical electroplating, the method of the present disclosure can effectively solve the problem of oxygen bubbles forming a current blocking shield on the surface of the anode facing the cathode in the existing processes, achieving good electroplating results with insoluble anodes and the vertical electroplating equipment which has simple structure and can be easily maintained.
The present disclosure can be improved as follows.
At least one liquid ejecting pipe/port is provided on a side of the insoluble anode facing the cathode. The liquid ejecting pipe/port connects to an external liquid ejecting pipeline to spray liquid towards the anode; and in conjunction with the liquid outlet pipe/port, produces a more stable and more controllable liquid flow in the vicinity of the insoluble anode that flows away from the cathode, thus better enabling the oxygen bubbles generated on the anode during the electroplating process to pass smoothly through the holes of the insoluble anode and leave the area between the anode and the cathode. The external liquid ejecting pipeline comprises a pipe with a pump, the other end of the pipe connects to a container containing the electroplating solution, providing a constant supply of the electroplating solution for the liquid ejecting pipe/port.
Preferably, the liquid ejecting pipe/port is provided at the bottom of the electroplating cell on the side of the insoluble anode facing the cathode. Therefore, the liquid ejecting pipe/port and the liquid outlet pipe/port cooperate to produce a bottom-up liquid flow, so that the oxygen bubbles generated on the anode are forced away from the cathode as soon as possible through the holes of the insoluble anode, avoiding eddies in the electroplating solution in the area between the anode and the cathode which may affect the current distribution in the electroplating solution.
The present disclosure can also be improved by modifying the feed structure of the insoluble anode, preferably by providing feed lines at both sides of the edge of the insoluble anode to reduce the difference in current density between the upper and lower parts of the insoluble anode, so that the conductivity of the gas-liquid mixture between the gas-generating anode and the cathode tends to be uniform. In this case, the present disclosure overcomes the disadvantage of feeding from the top of the anode that the current density at the upper part of the anode is higher than that at the lower part of the anode, which results in an extremely uneven distribution of the electroplating current in the electroplating solution.
The present disclosure can be further improved by providing a gas-liquid separator in the fluid circulating system, so that the gas-liquid mixture from the electroplating cell is discharged via the liquid outlet pipe/port and a connecting pipe into the gas-liquid separator. The gas-liquid separator is a device for diverting the oxygen bubbles generated on the anode during the electroplating process together with the electroplating solution into a larger space, slowing down the liquid flow to allow gas release from the liquid. The gas in the gas-liquid mixture is released inside the gas-liquid separator and the liquid is then diverted back to the electroplating cell for circulation.
Preferably, the oxygen released in the gas-liquid separator is collected for reuse.
The present disclosure can further provide an electroplating cell divider in the electroplating cell, dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone; the electroplating solutions in the electroplating anode zone and the electroplating cathode zone can be the same or different. That is, the electroplating solution in the electroplating anode zone is also called an anolyte, which is specifically composed of an aqueous solution comprises at least one inorganic acid and/or at least one inorganic salt, or an acid sulfate copper electroplating solution; the electroplating solution in the electroplating cathode zone is also called a catholyte, which is an acid sulfate copper electroplating solution. During the electroplating process, the insoluble anode and the cathode are placed separately in the electroplating anode zone and electroplating cathode zone. In this preferred embodiment of the present disclosure, since the oxygen bubbles only present within the area in the electroplating anode zone that between the anode and the cathode, the liquid outlet pipe/port of the present disclosure is provided in the electroplating anode zone, creating a liquid flow away from the cathode and through the holes of the anode only within the electroplating anode zone. To further provide a liquid ejecting pipe/port on the side of the insoluble anode facing the cathode, the liquid ejecting pipe/port is also located within the electroplating anode zone.
The electroplating cell divider separates the oxygen and hydroxyl radicals generated on the anode from the electroplating solution in the area near the cathode, in order to reduce the chance of the oxygen and hydroxyl radicals entering the acid sulfate copper electroplating solution near the cathode and reacting with the electroplating additives, thus reducing the additional loss of the electroplating additives in the acid sulfate copper electroplating solution. It also facilitates the centralized exhausting of the oxygen from the anode surface during the electroplating process.
Preferably, the electroplating cell divider is at least one selected from the group consisting of a cation exchange membrane, an anion exchange membrane, a bipolar membrane, a reverse osmosis membrane, a filter cloth, an ultrafiltration membrane, a ceramic filter plate and a PE filter plate.
When a cation exchange membrane is selected to be used alone as the electroplating cell divider, as the electrochemical reactions proceed, the copper ions in the acid sulfate copper electroplating solution within the electroplating cathode zone are reduced to metallic copper on the surface of the cathode, while the cations from the anolyte in the electroplating anode zone pass through the electroplating cell divider and enter the electroplating cathode zone.
When an anion exchange membrane is selected to be used alone as the electroplating cell divider, as the electrochemical reactions proceed, the copper ions in the acid sulfate copper electroplating solution within the electroplating cathode zone are reduced to metallic copper on the surface of the cathode, while the anions from the acid sulfate copper electroplating solution in the electroplating cathode zone pass through the electroplating cell divider and enter the electroplating anode zone.
When only ultra-filtration membranes and/or ceramic filter plates and/or PE filter plates and/or filter cloths are selected to be used as the electroplating cell divider(s), as the electrochemical reactions proceed, the copper ions from the acid sulfate copper electroplating solution in the electroplating cathode zone are reduced to metallic copper on the surface of the cathode, while some of the cations from the anolyte in the electroplating anode zone enter the electroplating cathode zone through the small holes of the electroplating cell divider(s), and some of the anions from the acid sulfate copper electroplating solution in the electroplating cathode zone also enter the electroplating anode zone through the small holes of the electroplating cell divider(s).
When a bipolar membrane is selected to be used alone as the electroplating cell divider, as the electrochemical reactions proceed, the copper ions from the acid sulfate copper electroplating solution in the electroplating cathode zone are reduced to metallic copper on the surface of the cathode, while hydrogen ions are generated via water electrolysis within the bipolar membrane and enter the electroplating cathode zone.
When a reverse osmosis membrane is selected to be used alone as the electroplating cell divider, as the electrochemical reactions proceed, the copper ions from the acid sulfate copper electroplating solution in the electroplating cathode zone are reduced to metallic copper on the surface of the cathode. If hydrogen ions exist in the anolyte in the electroplating anode zone, the hydrogen ions also pass through the electroplating cell divider and enter the electroplating cathode zone.
Preferably, the anolyte is composed of an aqueous solution of sulfuric acid and/or copper sulfate. More preferably, the anolyte is a sulfuric acid solution.
In the case of providing a gas-liquid separator in the fluid circulating system, the gas-liquid mixture from the electroplating anode zone is discharged via the liquid outlet pipe/port and a connecting pipe into the gas-liquid separator. The gas in the gas-liquid mixture is released inside the gas-liquid separator and the liquid is then diverted back to the electroplating anode zone for circulation.
As an improved embodiment of the present disclosure, the electroplating anode zone is in the form of an anode box inside the electroplating cell, dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone. Particularly, the anode box is shaped as a cubic box, in which the insoluble anode is provided; the side of the anode box facing the cathode is the electroplating cell divider, making the inner space of the anode box to be the electroplating anode zone, and the space in the electroplating cell outside the anode box to be the electroplating cathode zone. In this preferred embodiment, the liquid outlet pipe/port of the present disclosure is provided at the anode box, specifically in the area inside the anode box or on the wall of the anode box on the side of the insoluble anode away from the cathode; furthermore, a liquid ejecting pipe/port is provided inside the anode box, specifically in the area inside the anode box between the anode and a nearby wall of the anode box on side of the insoluble anode facing the cathode. Preferably, the liquid ejected from the liquid ejecting pipe/port in the anode box is from the gas-liquid separator.
Preferably, an electroplating solution ejecting pipe is provided at the side edges of the anode box on the side facing the cathode to eject an electroplating solution at the cathode, so that the electroplating solution can be poured deeply into the holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed, thus improving the electroplating quality deep inside the holes of the cathode.
More preferably, when more than one anode boxes are provided, the ejecting action of the electroplating solution ejecting pipes located outside the anode boxes are controlled as programmed according to time and/or flow rate. Using the difference in time and/or flow rate to avoid collision of the liquid ejecting streams from the anode boxes on both sides of the cathode, in order to improve the filling effect of the electroplating solution in the holes of the cathode.
In the present disclosure, the insoluble anode is provided with a reverse-pulse protective screen. The reverse-pulse protective screen is made of uncoated titanium in the form of a protrusion, or a protruding mesh or bar, or any electrode structure that facilitates electric discharge, protruding from the surface of the insoluble anode facing the cathode and directly connecting to the titanium substrate of the insoluble anode. The protrusion can be in any one of the form of a bump, a spike, a vertical bar; the protruding mesh or bar can be a mesh or bar extending towards the cathode with its supporting foot fixed on the side of the anode facing the cathode, or a mesh or bar formed by interconnecting the upper part of any above-mentioned protrusions, the plane surface formed by the protruding mesh or bar is parallel or substantially parallel to the anode surface.
By specifically modifying the structure of the insoluble anode as described above, while in an electroplating process using a reverse-pulse power supply, the advantages in electroplating quality of the present disclosure becomes more obvious. The reverse-pulse protective screen protects the insoluble anode in a reverse-pulse electrolysis process, by using the valve metal property of titanium that it conduct electrons unidirectionally during an electrochemical reaction in an aqueous electrolyte solution. That is, when the uncoated titanium of the reverse-pulse protective screen takes part in an electrochemical reaction of an aqueous electrolyte solution as an anode, an oxide layer is formed on its surface stopping the uncoated titanium from participating the electrochemical reaction; but when the uncoated titanium of the reverse-pulse protective screen takes part in an electrochemical reaction as a cathode, it discharges normally. Therefore, while an insoluble anode with a reverse-pulse protective screen acts as an anode in an electroplating process, the reverse-pulse protective screen hardly participates in the electrochemical reaction, whereas the main electrochemical reactions of the electroplating process are carried out at the coated titanium anode body. However, when the current direction is reversed, the original cathode is converted to an anode for electrolytic dissolution of copper metal, the insoluble anode is converted to a cathode, and the reverse-pulse protective screen is involved in the electrochemical reactions for electric discharge. Since the reverse-pulse protective screen is protruding from the surface of the insoluble anode and is thus closer to the cathode, according to the principle of potential difference in the electric field, the reverse-pulse protective screen is more effective in attracting the electroplating current and allows the main current to pass through it and then the titanium substrate inside the insoluble anode. Hydrogen generates directly on the reverse-pulse protective screen, instead of mainly on the coating of the insoluble anode as in the prior art. The reverse-pulse protective screen therefore effectively reduces the electrochemical reaction of hydrogen generation on the surface of the insoluble anode coating, and thus effectively extends the service life of the insoluble anode. When the reverse-pulse protective screen is in the form of protrusions, the more numerous and more uniformly distributed the protrusions are, the better the protection of the insoluble anode coating.
The present disclosure further provides a fixed frame at the edges of the insoluble anode, which enhances the planar mechanical rigidity of the insoluble anode and reduces the effect of uneven electric discharge due to anode deformation. The fixed frame has a greater thickness than the insoluble anode, and/or a greater width than the no-hole part of the insoluble anode, and/or a greater mechanical rigidity than the insoluble anode, and/or a stabilizing structure that enhances the mechanical rigidity of the insoluble anode.
The fixed frame can be made of any material that is insoluble as an anode, heat-resisting, acid-resisting and relatively rigid.
When the insoluble anode of the present disclosure is provided with a reverse-pulse protective screen and an uncoated or coated titanium fixed frame, the reverse-pulse protective screen can be connected to either the titanium substrate of the insoluble anode or the titanium of the fixed frame, or to both. Since the thicker the conductor, the lower the resistance, as a preferred embodiment, the fixed frame results in a reasonable current distribution of the insoluble anode during an electroplating process, and also introduce the main current into the fixed frame as a bypass current during the reverse pulse electrolysis, further protecting the coating of the insoluble anode.
Preferably, the fixed frame is selected from a conductive material, connecting to the positive electrode of the electroplating power supply via the titanium substrate of the insoluble anode, or to both the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply, or to the positive electrode of the reverse pulse electroplating power supply.
More preferably, the fixed frame is selected to be uncoated titanium, connecting to the positive electrode of the electroplating power supply via the titanium substrate of the insoluble anode, or to both the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply, or to the positive electrode of the reverse pulse electroplating power supply, to obtain an improved feed structure in combination with the insoluble anode.
The present disclosure can be improved as follows.
In an electroplating process, a supplementary solution or a raw material of the electroplating solution is added to the electroplating cell according to the analytic results of the concentration of components in the electroplating solution, in order to maintain a stable ratio between the components in the electroplating solution.
The present disclosure can be improved as follows.
The electroplating cell can be connected to an electroplating solution regenerating device, either directly or through a transfer tank, to set up a controllable recycling system according to the process for the replenishment of the electroplating copper source, which helps to achieve green and clean production and reduction in production costs.
The present disclosure can be improved as follows.
A conductor connected to the positive electrode of the electroplating power supply is attached to the insoluble anode on the side away from the cathode, using the bypass current through conductor to increase the electric discharge uniformity of the insoluble anode in an electroplating process, thus improving the electroplating quality of the plated layers. The conductor can be any one of a conductive rod, a conductive plate, and a conductive mesh, and the conductor is connected to the fixed frame so that the insoluble anode discharges more uniformly during electroplating.
Preferably, the conductive plate is an uncoated titanium plate with a mesh or a perforated structure, and the conductive mesh is an uncoated titanium mesh.
The present disclosure can be further modified as follows.
The reverse-pulse protective screen is provided on the conductor, and it extends out of the surface of the insoluble anode through the holes of the anode and towards the cathode. Two ways of connection are specified below.
(1) The reverse-pulse protective screen is welded to the titanium substrate of the insoluble anode as it extends through the anode, enabling reverse pulse current to pass through the extended part of reverse-pulse protective screen out of the surface of the insoluble anode during electroplating, and be shunted to the conductor as well as the titanium substrate of the insoluble anode respectively, hence reducing hydrogen production on the insoluble anode.
(2) The reverse-pulse protective screen is not electrically connected to the insoluble anode when extending through the anode, which further reduces the current through the insoluble anode during reverse pulse electroplating, thereby further reducing hydrogen production.
Preferably, the reverse-pulse protective screen is not electrically connected to the insoluble anode, and the insoluble anode and/or the fixed frame is welded to the conductive plate or conductive mesh via a titanium plate or mesh.
More preferably, the fixed frame is connected to the conductive plate or conductive mesh around the perimeter by welding titanium plates or meshes. This allows a more uniform current discharge on the insoluble anode in an electroplating process, and further reduces hydrogen production at the insoluble anode by shunting the main current with bypassing the reverse pulse protective screen, the fixed frame and/or the conductive plate or mesh while the insoluble anode is converted to a cathode in a reverse pulse process.
The present disclosure can be improved as follows.
In the case of an insoluble anode with a reverse-pulse protective screen, a fixed frame and a conductor, at least one liquid outlet pipe/port is provided on the side of the conductor away from the cathode; and by connecting the insoluble anode to the conductive plate or conductive mesh around the perimeter through a titanium fixed frame, the main liquid flow from a liquid ejecting pipe/port carries the oxygen bubbles generated at the anode and flows through the holes of the insoluble anode, as well as the holes of the conductive plate or conductive mesh behind the anode, and flows out from the liquid outlet pipe/port.
Preferably, an insoluble anode with a reverse-pulse protective screen, a fixed frame and a conductor, together with the insoluble anode accessories including a liquid outlet pipe/port and a liquid ejecting pipe/port are provided in an anode box as an anode box assembly.
The present disclosure can be improved as follows.
When a cathode needs to be electroplated in multiple directions or has different electroplating area on different sides, using one power supply connected to two or more insoluble anodes which are reasonably distributed around the cathode for the electrochemical reactions of electroplating; or, using two or more power supplies co-connected to the cathode, along with more than one reasonably distributed insoluble anodes; or, using two or more power supplies respectively connected to one or more insoluble anodes according to the required electrochemical reaction amount and co-connected to the cathode, precisely adjusting the output current intensity of each electroplating power supply in accordance to the electroplating surface area on different sides of the cathode and the requirements of the process, in order to improve the electroplating quality of the cathode.
The second objective of the present disclosure is achieved by the following technical solution.
An optimized device for an insoluble anode acid sulfate copper electroplating process, wherein the device comprises an electroplating cell, an insoluble anode, a cathode, and an electroplating power supply, wherein:

- the electroplating cell is provided with at least one liquid outlet pipe/port on the side of the insoluble anode away from the cathode, to generate a liquid flow in the electroplating cell by overflow and/or power driven suction of an electroplating solution at the liquid outlet pipe/port;
- the insoluble anode is made of coated titanium in the form of a mesh or a perforated plate;
- the positive and negative electrodes of the electroplating power supply are respectively connected to the insoluble anode and the cathode in an electroplating process.

The present disclosure can be improved as follows.
The device is provided with a fluid circulating system, which mainly consists of a power driven device and a connecting pipe, with one end connecting to the liquid outlet pipe/port and the other end connecting to the electroplating cell. The fluid circulating system is utilized to make the electroplating solution flow away from the liquid outlet pipe/port and return to the electroplating cell, forming a liquid flow in the electroplating cell towards the liquid outlet pipe/port at the anode, in a circular manner. The fluid circulating system can be made by adding a connection pipe to the above-mentioned case that the liquid outlet pipe/port utilizes a power driven device to force the liquid near the insoluble anode to create a flow away from the cathode and through the anode holes.
The present disclosure can be improved as follows.
The electroplating cell is provided with at least one liquid jet pipe/port, which is located in the area on the side of the insoluble anode facing the cathode and between the anode and the cathode. The liquid ejecting pipe/port connects to an external liquid ejecting pipeline to spray liquid towards the anode; and in conjunction with the liquid outlet pipe/port, produces a more stable and more controllable liquid flow in the vicinity of the insoluble anode that flows away from the cathode. The external liquid ejecting pipeline comprises a pipe with a pump, the other end of the pipe connects to a container containing the electroplating solution, providing a constant supply of electroplating solution for the liquid ejecting pipe/port.
Preferably, the liquid ejecting pipe/port is provided at the bottom of the electroplating cell on the side of the insoluble anode facing the cathode, ejecting liquid towards the insoluble anode.
The present disclosure can be improved as follows.
The liquid outlet pipe/port is connected to a gas-liquid separator via a connection pipe. The gas-liquid separator is a relatively large container, diverting the oxygen bubbles generated on the anode during the electroplating process together with the electroplating solution to it, utilizing its relatively large space to slow down the liquid flow to allow the gas to release from it. The gas-liquid separator can also be connected to the electroplating cell via a pump and a connection pipe to form a fluid circulating system, which returns the gas-released liquid back into the electroplating cell for circulation.
The present disclosure can be improved as follows.
Providing an electroplating cell divider in the electroplating cell, dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone.
Preferably, an anode box is provided inside the electroplating cell, dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone: the anode box is shaped as a cubic box, in which the insoluble anode is provided; the side of the anode box facing the cathode is the electroplating cell divider, making the inner space of the anode box to be the electroplating anode zone, and the space in the electroplating cell outside the anode box to be the electroplating cathode zone. The liquid outlet pipe/port of the present disclosure is provided at the anode box, specifically in the area inside the anode box or on the wall of the anode box on the side of the insoluble anode away from the cathode; furthermore, a liquid ejecting pipe/port is provided inside the anode box, specifically in the area inside the anode box between the anode and the nearby wall of the anode box on side of the insoluble anode facing the cathode.
Preferably, the liquid outlet of the gas-liquid separator is connected to the liquid ejecting pipeline and the liquid ejecting pipe/port. That is, the connecting pipe between the gas-liquid separator and the liquid ejecting pipe/port is provided with a pump, combining the liquid returning pipe and the liquid ejecting pipeline into one. Therefore, the anode electroplating solution with oxygen bubbles is driven by the pump, flowing quickly through the holes of the insoluble anode and the liquid outlet pipe/port to the gas-liquid separator for gas-liquid separation.
The present disclosure can be improved as follows.
An electroplating solution ejecting pipe is provided at the side edge of the anode box on the side facing the cathode, and each electroplating solution ejecting pipe is equipped with a flow regulator to adjust the ejection effect of an electroplating solution towards the cathode.
More preferably, more than one anode boxes are provided in the electroplating cell, and the ejecting action of the electroplating solution ejecting pipes located outside the anode boxes is programmed and controlled to avoid collision of the liquid ejecting streams from the electroplating solution ejecting pipes attached to the anode boxes during operation that hinders hole filling optimization.
In the present disclosure, the insoluble anode is provided with a reverse-pulse protective screen, which is made of uncoated titanium protruding from the surface of the insoluble anode facing the cathode and directly connecting to the titanium substrate of the insoluble anode. The reverse-pulse protective screen can be in any one of the form of a bump, a spike, a vertical bar, or a mesh or bar connected to any above-mentioned protrusions, or any electrode structure that facilitates electric discharge.
The present disclosure can be improved as follows.
The insoluble anode is further provided with a fixed frame at its edges.
Preferably, the fixed frame is made of uncoated titanium, connecting to the positive electrode of the electroplating power supply via the titanium substrate of the insoluble anode, or to both the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply.
The present disclosure can be improved as follows.
A conductor connected to the positive electrode of the electroplating power supply is attached to the insoluble anode on the side away from the cathode, to allow uniform electric discharge of the insoluble anode. Preferably, the conductor is an uncoated titanium plate with a mesh or a perforated structure, that is, a conductive plate or a conductive mesh.
The present disclosure can be improved as follows.
Modifying the feed structure of the insoluble anode, preferably by providing feed lines at both sides of the edge of the insoluble anode, so that the conductivity of the gas-liquid mixture between the gas-generating anode and the cathode tends to be uniform, overcoming the disadvantage of conventional feeding from up to down that results in a bubble layer with gradient on the surface of the anode.
The present disclosure can be improved as follows:
An insoluble anode with a reverse-pulse protective screen, a fixed frame and a conductor, together with the insoluble anode accessories including a liquid outlet pipe/port and a liquid ejecting pipe/port are provided in an anode box as an anode box assembly, making the electroplating device more compact.
The present disclosure can be improved as follows.
When the cathode has different electroplating area on different sides, using a electroplating process system consisting of one power supply connected to two or more insoluble anodes which are reasonably distributed around the cathode; or, using a electroplating process system consisting of two or more power supplies co-connected to the cathode, along with two or more insoluble anodes which are reasonably distributed around the cathode. The operation status of the power supplies are programmed and controlled according to the process requirements, so that the expected electroplating quality of the cathode can be achieved.
The present disclosure can be improved as follows.
To meet the electroplating quality requirements of the cathode, a reverse pulse power supply can be used, utilizing the reverse pulse electroplating process to achieve better electroplating quality and efficiency with the insoluble anode of the present disclosure.
The present disclosure can be improved as follows.
A stirring device is provided in the electroplating cell to help each component of the electroplating solution to be evenly distributed. The stirring device is any one of a liquid circulating device, a stirring blade, a pneumatic stirring device or any combination thereof; the liquid circulating device comprises a liquid outlet pipe, a pump, and a return pipe. The pneumatic stirring device is a device that could introduce gas into the electroplating solution to generated liquid flow.
The present disclosure can be improved as follows.
A current regulator is attached to the electroplating power supply, or the electroplating power supply is inherently provided with a current regulator, wherein the current regulator adjusts an output current of the electroplating power supply, or controls on/off of the electroplating power supply.
The present disclosure can be improved as follows.
The electroplating cell is provided with a detection device, including one or more of a level gauge, a hydrometer, an acidity meter, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer, to detect the corresponding process parameters of the liquid in the electroplating cell.
Preferably, the detection device is connected to an automatic detection and replenishment controller, the automatic detection and replenishment controller can control the process according to time and/or the measurement results of the detection device: adding a supplementary electroplating solution and/or a chemical material and/or water to the electroplating cell, and/or controlling adjustment of an output current of the electroplating power supply or on/off of the electroplating power supply.
The present disclosure can be improved as follows.
A filtering device is provided to be connected to the electroplating cell through a pipe, in order to remove copper sludge that may be present in the electroplating solution and/or impurities brought by the use of electrodes.
The present disclosure can be improved as follows.
A gas exhaust system is provided above the electroplating cell to extract the gas generated on the anode and/or cathode during the electroplating process, avoiding gas accumulation and ensuring safe production.
The present disclosure can be improved as follows.
The electroplating cell is connected to an electroplating solution regenerating device, setting up a controlled recycling system according to the process for the replenishment of the electroplating copper source.
The present disclosure can be improved as follows.
A temporary storage tank is additionally connected to the electroplating cell, for temporary storing the liquid flowing from the electroplating cell and/or the liquid to be added to the electroplating cell, and/or for other chemical reactions of the electroplating solution.
The present disclosure can be improved as follows.
A cool-heat exchanger is provided in the electroplating cell and/or the gas-liquid separator to stabilize the temperature of the electroplating solution.
Compared with the prior art, the beneficial effects of the present disclosure are as follows.
1. In present disclosure, an insoluble anode in the form of a mesh or a perforated plate structure is provided with a liquid outlet pipe/port on the side of the insoluble anode away from the cathode, effectively overcoming the problem of oxygen bubbles accumulation on the surface of the anode forming an oxygen bubble shield and affecting the uniformity of electroplating in the prior art, making the electroplating layer more uniform and flat, and significantly improving the quality of electroplating. The liquid ejecting pipe/port provided at the bottom of the electroplating cell on the side of the insoluble anode facing the cathode, together with the liquid outlet pipe/port, generates a liquid flow from the bottom up and away from the cathode, so that the oxygen bubbles generated on the anode can enter the liquid outlet pipe/port through the holes of the insoluble anode as soon as possible, and at the same time, avoid the electroplating solution in the area between the anode and the cathode to produce eddies that affect the current distribution of the electroplating solution.
The method of the present disclosure can also obtain uniform plated layer with high quality in a vertical electroplating process, so it can be promoted to the conventional vertical electroplating process, and avoid the process problems that are difficult to overcome for an irregularly shaped cathode in a horizontal electroplating line with an insoluble anode.
2. In the present disclosure, a fixed frame is provided at the edge of the insoluble anode, which can effectively enhance the planar mechanical rigidity of the insoluble anode, reducing the electric discharge unevenness caused by anode distortion, improving the quality of the plated cathode, and obtaining products with high flatness and uniformity.
The present disclosure further provides a fixed frame made of uncoated titanium or coated titanium, connected to the titanium substrate of the anode and/or the reverse-pulse protective screen, or provides a conductor on the side of the insoluble anode away from the cathode, in order to effectively increase the electric discharge uniformity of the insoluble anode during electroplating and thus improve the protection effect of the coating and electroplating quality.
3. The present invention provides a reverse-pulse protective screen on the side of the insoluble anode facing the cathode, which can effectively reduce the damage of the coating on the surface of the insoluble anode due to hydrogen generation during the reverse-pulse process, thereby extending the service life of the insoluble anode and reducing production costs.
Moreover, the present disclosure provides a fixed frame made of uncoated titanium or coated titanium, which is connected to the titanium substrate of the insoluble anode and/or the reverse-pulse protective screen and/or the positive electrode of the reverse pulse electroplating power supply, so that the main current can be effectively led into the fixed frame for bypass during the reverse-pulse electrolysis, thus further improving the protection effect of the coating on the surface of the insoluble anode and reducing the damage of the insoluble anode.
Therefore, the process of the present disclosure can effectively ensure the through-hole electroplating quality of copper electroplating, i.e., better electroplating quality, as well as greatly reduce the damage of insoluble anode and extend the service life of the insoluble anode during the reverse pulse electroplating process.
4. The present disclosure provides an electroplating solution ejecting pipe outside the anode box to eject an electroplating solution towards the cathode, so that the electroplating solution can be poured deeply into the small holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed, thus further improving the through-hole penetration quality of the cathode.
5. The present disclosure can effectively reduce the additional loss of electroplating additives in the acid sulfate copper electroplating solution by dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone using an electroplating cell divider, thus reducing the production cost; therein, the consumption rate of electroplating additives in the present disclosure is ⅓ of the existing technology.
6. In the present disclosure, an insoluble anode with a reverse-pulse protective screen, a fixed frame and a conductor, together with the insoluble anode accessories including a liquid outlet pipe/port and a liquid ejecting pipe/port are provided in an anode box as an anode box assembly. And by reasonably connecting multiple insoluble anodes around the cathode, not only the problems of uneven electric discharge of anode and hydrogen generation are solved, but also the electroplating quality of irregularly shaped cathode is improved.
7. The device of the present disclosure can be used with an electroplating solution regenerating device. The electroplating cell is connected to the electroplating solution regenerating device, forming a controlled recycling system for the replenishment of the electroplating copper source through combining with a control system, helpfully reducing phosphorus copper pollution to achieve green and clean production, and reducing production costs at the same time.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure will be further described with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 1 of the present disclosure.

FIG. 2 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 2 of the present disclosure.

FIG. 3 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 3 of the present disclosure.

FIG. 4 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 4 of the present disclosure.

FIG. 5 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 5 of the present disclosure.

FIG. 6 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 6 of the present disclosure.

FIG. 7 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 7 of the present disclosure.

FIG. 8 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 8 of the present disclosure.

FIG. 9 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 9 of the present disclosure.

FIG. 10 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 10 of the present disclosure.

FIG. 11 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 11 of the present disclosure.

FIG. 12 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 12 of the present disclosure.

FIG. 13 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 13 of the present disclosure.

FIG. 14 is a schematic diagram of a device for insoluble anode acid copper electroplating process according to comparative example 1 of the prior art.

FIG. 15 is a schematic diagram of a device for insoluble anode acid copper electroplating process according to comparative example 2 of the prior art.

FIG. 16 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 14 of the present disclosure.

FIG. 17 is a schematic diagram of an optimized device for an insoluble anode acid sulfate copper electroplating process according to embodiment 15 of the present disclosure.

FIG. A is a schematic diagram of the insoluble anode of embodiment 1 of the present disclosure.

FIG. B is a schematic diagram of the insoluble anode in embodiment 2 of the present disclosure.

FIG. C is a schematic diagram of the insoluble anode in embodiment 3 of the present disclosure.

FIG. D is a schematic diagram of the insoluble anode in embodiment 4 of the present disclosure.

FIG. E is a schematic diagram of the insoluble anode in embodiment 5 of the present disclosure.

FIG. F is a schematic diagram of the insoluble anode in embodiment 6 of the present disclosure.

FIG. G is a schematic diagram of the structure of the insoluble anode cartridge in

embodiments

7 and 11 of the present disclosure.

FIG. H is a schematic diagram of the insoluble anode cartridge structure in embodiment 8 of the present disclosure.

FIG. J is a schematic diagram of the insoluble anode cartridge structure in

embodiments

9 and 12 of the present disclosure.

FIG. K is a schematic diagram of the insoluble anode cartridge structure in

embodiments

10 and 13 of the present disclosure.

Reference signs: 1—insoluble anode; 1-1—hole of insoluble anode; 2—liquid liquid outlet pipe/port; 3—feed line installation hole; 4—cathode; 5—electroplating cell; 6—electroplating power supply; 7—acid sulfate copper electroplating solution; 8—gas-liquid separator; 9—liquid returning circulation pipe; 10—liquid ejecting pipe/port; 11—electroplating cell divider; 12—anolyte; 13—anode box; 14—electroplating solution ejecting pipe; 15—reverse-pulse protective screen; 16—fixed frame; 17—conductor (in the form of rod/mesh/plate); 18—fixing device; 19—reverse-pulse electroplating power supply; 20—electroplating solution regenerating device; 21—detection device; 22—liquid circulation pipe; 23—corrosion resistant pump; 24—stirring device; 25—gas extraction hood; 26-28—electroplating additives; 29—inverter pump; 30—liquid flow regulator with pump; 31—copper metal block; 32—temporary storage tank; 33—solid-liquid separation filter; 34—automatic detection and replenishment controller; 35—flow meter; 36—cool-heat exchanger; 37—anode coating; 38—overflow tank; 39—titanium basket.

DESCRIPTION OF THE EMBODIMENTS

The disclosure is further described by the following embodiments.
In the following embodiments, the copper sulfate used is a commercially available copper sulfate product. The sulfuric acid used is preferably produced by Guangzhou Chemical Reagent Factory. The titanium-based coated electroplating anode and the electroplating cell used are produced by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd. The ion exchange membrane used is produced by Membranes International Inc. The bipolar membrane used is produced by Guochu Technology. The ultrafiltration membrane, the filter cloth, the ceramic filter plate, the PE filter plate and the reverse osmosis membrane are commercially available products. The microscope used is preferably a computer microscope produced by Guangzhou Optical Instrument Co., Ltd. The electroplating power supply and reverse-pulse electroplating power supply used are produced by Guangzhou Guangxing Electroplating Equipment Factory. The acid copper electroplating additive is the produced by Foshan Gaoli Group Company. In addition to the above-listed products, those of skill in the art can also select products and equipment with similar properties to those listed herein to achieve the objective of the current disclosure.

Embodiment 1

As shown in FIG. 1 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an insoluble anode 1, a liquid outlet pipe 2, a cathode 4, an electroplating power supply 6, and a gas-liquid separator 8.
The electroplating cell 5 is provided with a liquid outlet pipe 2, which is located on the side of the insoluble anode 1 away from the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 through a connecting pipe, and the other end of the gas-liquid separator 8 is connected to the electroplating cell 5 through a pipe and a pump 23, so that the gas-liquid mixture is discharged from the electroplating cell through the liquid outlet pipe 2 and the connecting pipe and release gas in the gas-liquid separator, and the gas-released liquid returns back into the electroplating cell for circulation.
The insoluble anode 1 is provided with the structure shown in FIG. A, which is a perforated plate made of coated titanium, and a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
The cathode 4 is a flat copper plate.
An optimized method for an insoluble anode acid sulfate copper electroplating process, wherein the method comprises the following steps:

- (1) The electroplating solution was prepared as specified in Table 1 and poured into the electroplating cell;
- (2) The insoluble anode was installed in the electroplating cell a liquid outlet pipe provided on the side of the insoluble anode away from the cathode; the positive electrode of the electroplating power supply was connected to the insoluble anode, and the negative electrode of the electroplating power supply was connected to the cathode;
- (3) An appropriate amount of electroplating additives was added to the electroplating solution; the electroplating power supply was turned on to initiate electroplating production using the acid sulfate copper electroplating solution;
- (4) After electroplating was completed, the electroplating cathode (i.e., the cathode electroplating product) was removed; the electroplating cathode 14 was washed with water and dried with hot air; the surface of the coating was observed using a computer microscope and the observation results were recorded in Table 1.

During the electroplating process, the structure of the insoluble anode cooperate with the liquid outlet pipe located on the side of the anode away from the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by overflow. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode for external discharge.
The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.

Embodiment 2

As shown in FIG. 2 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 1 as follows.
The insoluble anode 1 is provided with the structure shown in FIG. B, which is a mesh made of coated titanium, and welded to a fixed frame 16 made of coated titanium around the four sides of the insoluble anode; feed lines are provided through the feed line installation holes on both sides of the anode for structural modification.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.

Embodiment 3

As shown in FIG. 3 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an insoluble anode 1, a cathode 4, an electroplating power supply 6, a gas-liquid separator 8, and a solid-liquid separation filter 33, wherein:
The electroplating cell 5 is provided with a liquid outlet port 2, a liquid ejecting pipe 10, a stirring blade 24.2 and a pneumatic stirring device 24.1; the liquid outlet port 2 is located on the wall of the electroplating cell 5 and on the side of the insoluble anode 1 away from the cathode 4; the liquid ejecting pipe 10 is provided in the space between the insoluble anode 1 and the cathode 4; the liquid outlet port 2 is connected to the gas-liquid separator 8 via a pipe and a pump; the gas-liquid separator 8 is further connected to a solid-liquid separation filter 33 and the liquid ejecting pipe 10 through a liquid returning circulation pipe 9, so that the gas-released liquid is able to return to the electroplating cell 5 after filtration via the liquid ejecting pipe 10.
The insoluble anode 1 is provided with the structure shown in FIG. C, which is a perforated plate made of coated titanium, and welded to a fixed frame 16 made of uncoated titanium around the four sides of the insoluble anode; a reverse-pulse protective screen 15 consisting of uncoated titanium spikes is provided and connected to the insoluble anode 1 and the fixed frame 16; a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process. The cathode 4 is a flat copper plate.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1 and Table 2.
During the electroplating process, the perforated structure of the insoluble anode cooperates with the liquid outlet port located on the side of the anode away from the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode and discharged to the gas-liquid separator for gas release. And the remaining liquid returns back into the electroplating cell for circulation.

Embodiment 4

As shown in FIG. 4 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an insoluble anode 1, a liquid outlet pipe 2, a cathode 4, a reverse pulse electroplating power supply 19, and a gas-liquid separator 8.
The electroplating cell 5 is provided with a liquid outlet pipe 2 and a liquid ejecting pipe 10; the liquid outlet pipe 2 is located on the side of the insoluble anode 1 away from the cathode 4; the liquid ejecting pipe 10 is installed in the space between the insoluble anode 1 and the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 via a pipe and pump 23, so that the liquid treated in the gas-liquid separator 8 can be returned to the electroplating cell via a liquid return circulation pipe 9.
The insoluble anode 1 is provided with the structure shown in FIG. D, which is a perforated plate made of coated titanium. A reverse-pulse protective screen 15 is provided on the side of the insoluble anode 1 facing the cathode, connecting directly to the titanium substrate of the insoluble anode 1. The reverse-pulse protective screen consists of uncoated titanium protrusions in the form of spikes and vertical bars, and a mesh formed by interconnecting the upper part of the protrusions. A conductor 17, which is a conducting rod, is attached to the insoluble anode 1 on the side away from the cathode. A feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
The cathode 4 is a flat copper plate with small through-holes.
The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
In the electroplating process, the perforated structure of the insoluble anode cooperates with and the liquid outlet port located on the side of the anode away from the cathode and the liquid ejecting pipe on the side of the anode facing the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode and discharged to the gas-liquid separator for gas release. And the remaining liquid returns back into the electroplating cell for circulation. During reverse pulse electroplating, the reverse-pulse protective screen can effectively reduce the electrochemical reaction of hydrogen generation on the surface of the insoluble anode coating.

Embodiment 5

As shown in FIG. 5 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an insoluble anode 1, a liquid outlet pipe 2, a cathode 4, and a reverse pulse electroplating power supply 19.
The electroplating cell 5 is provided with an electroplating cell divider 11 separating it into an electroplating anode zone and an electroplating cathode zone; the electroplating cell divider 11 is specifically a combination of an ultrafiltration membrane and a filter cloth. The electroplating anode zone is provided with a liquid outlet pipe 2 and a liquid ejecting port 10; the liquid ejecting port 10 is installed at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, and is connected to the electroplating anode zone on the side away from the electroplating cathode zone via a pipe and a pump 23.1. The liquid outlet pipe 2 is provided with two liquid outlet ports and is located on the side of the insoluble anode 1 away from the cathode 4. The liquid outlet pipe 2 is connected to a pipe with a pump 23.2 to divert the liquid with oxygen bubbles to area in the electroplating anode zone away from the cathode 4 for gas release.
As shown in FIG. E, the insoluble anode 1 in the electroplating anode zone is a coated titanium mesh; the insoluble anode 1 is also welded to a fixed frame 16 made of uncoated titanium around its four sides; the conductor 17, provided on the side of the insoluble anode 1 away from the cathode 4, is a bypass structure conductor in the shape of a mesh, and is welded to the fixed frame 16 around the four sides of the frame via titanium meshes. The fixed frame 16 and the conductor 17 are welded together as plates and frames, and welded surrounding the edges of the insoluble anode 1 on the side of the anode away from the cathode 4, forming a cubic box with two sides of mesh in parallel and connecting electrically. The conductor 17 is provided with a reverse-pulse protective screen 15, which is welded to the conductor 17; the reverse-pulse protective screen 15 consists of uncoated titanium spikes that extend through the mesh holes of the insoluble anode 1 without contacting with it. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for feeding from the top of the anode.
The cathode 4 is a flat copper plate with small holes, and is provided in the electroplating cathode zone.
The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
An optimized method for an insoluble anode acid sulfate copper electroplating process, wherein the method comprises the following steps:

- (1) The electroplating solutions including the anolyte and the catholyte were prepared as specified in Table 1 and poured into the electroplating anode zone and the electroplating cathode zone respectively;
- (2) The insoluble anode was installed in the electroplating cell a liquid outlet pipe provided on the side of the insoluble anode away from the cathode; the positive electrode of the electroplating power supply was connected to the insoluble anode, and the negative electrode of the electroplating power supply was connected to the cathode;
- (3) An appropriate amount of electroplating additives was added to the electroplating solution; the electroplating power supply was turned on to initiate electroplating production;
- (4) After electroplating was completed, the electroplating cathode (i.e., the cathode electroplating product) was removed; the electroplating cathode 14 was washed with water and dried with hot air; the surface of the coating was observed using a computer microscope and the observation results were recorded in Table 1.

During the electroplating process, the mesh structure of the insoluble anode cooperates with the liquid outlet port located on the side of the anode away from the cathode and the liquid ejecting pipe located at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode and the conductive mesh by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the conductive mesh more concentratedly with the liquid flow, and be carried away from the cathode and released. In the case of reverse pulse electrolysis, the spikes of the reverse-pulse protective screen have no contact with the insoluble anode, so that the reverse pulse current is diverted from the upper part of the spikes into the conductor as a bypass current, effectively reducing electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, and hence preventing the coating of the insoluble anode from falling off. The design of the electroplating cell divider also effectively reduces the consumption of electroplating additives.

Embodiment 6

As shown in FIG. 6 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 5 as follows.
The electroplating cell divider 11 is specifically a combination of a PE filter plate and a ceramic filter plate.
The liquid ejecting pipe 10 is designed to have an oblate flared mouth, and is installed at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4. The liquid ejecting pipe 10 is connected to the electroplating anode zone on the side away from the electroplating cathode zone via a pipe and a pump 23.1. The liquid outlet pipe 2 with a flared mouth is located on the side of the insoluble anode 1 away from the cathode 4; the liquid outlet pipe 2 drains the liquid with oxygen bubbles through a pipe connected to the pump 23.2 to the area away from the cathode 4 in the electroplating anode zone for gas release.
As shown in FIG. F, the insoluble anode 1 in the electroplating anode zone is a coated titanium plate with through holes, and is welded to a fixed frame 16 around its edges. The fixed frame is made of uncoated titanium. The conductor 17, provided on the side of the insoluble anode 1 away from the cathode 4, is a titanium plate with through holes and is welded to the fixed frame 16 around its edges as a bypass conductor. The insoluble anode 1 is electrically connected to the fixed frame 16 and the conductor 17, forming a cubic box with two sides of perforated titanium plate in parallel and the other four sides of enclosed structure. The conductor 17 is also provided with a reverse-pulse protective screen 15, which is welded to the conductor 17; the reverse-pulse protective screen 15 consists of uncoated titanium spikes that extend through the holes of the insoluble anode 1 without contacting with it. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for feeding from the top of the anode.
The cathode 4 is a flat copper plate with small holes, and is provided in the electroplating cathode zone.
The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, the perforated structure of the insoluble anode cooperates with the liquid outlet pipe with a flared mouth located on the side of the anode away from the cathode and the liquid ejecting pipe with an oblate flared mouth located at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the conductor by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode more concentratedly with the liquid flow, and be carried away from the cathode and released. In the case of reverse pulse electrolysis, the spikes of the reverse-pulse protective screen have no contact with the insoluble anode, so that the reverse pulse current is diverted from the upper part of the spikes into the conductor as a bypass current, effectively reducing electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, and hence preventing the coating of the insoluble anode from falling off. The design of the electroplating cell divider also effectively reduces the consumption of electroplating additives.

Embodiment 7

As shown in FIG. 7 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an anode box 13, a cathode 4, a gas-liquid separator 8, and a reverse pulse electroplating power supply 19.
The electroplating cell 5 is provided with an anode box 13, the side of the anode box 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a cation exchange membrane; the inner space of the anode box 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode box 13 is the electroplating cathode zone.
As shown in FIG. G, the anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port 10 inside it; the liquid outlet pipe 2 is provided with four liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 through a pipe and a pump 23, and the gas-liquid separator 8 is then connected to the liquid ejecting port 10 through a liquid returning circulation pipe 9 to return the gas-released liquid to the anode box 13.
The insoluble anode 1 of the present embodiment is provided with the structure shown in FIG. D, which is a coated titanium plate with a perforated structure. The insoluble anode 1 is provided with a reverse-pulse protective screen 15 on the side facing the cathode; the reverse-pulse protective screen consists of uncoated titanium protrusions connecting directly to the titanium substrate of the insoluble anode 1, and a conductive mesh formed by interconnecting the upper part of the protrusions using titanium wire. The insoluble anode 1 is connected to the reverse pulse electroplating power supply 19 during the electroplating process. The insoluble anode 1 is also provided with a conductor 17, which is a conductive rod, on the side of the anode away from the cathode. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The above-mentioned anode assembly is provided in the anode box 13 as shown in FIG. G.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, the liquid outlet pipe located in the anode box on the side of the anode away from the cathode cooperates with and the liquid ejecting port located at the bottom of the anode box on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives.

Embodiment 8

As shown in FIG. 8 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 7 as follows.
The electroplating cell divider 11 is specifically a combination of a reverse osmosis membrane and a filter cloth.
As shown in FIG. H, the anode box 13 is connected to a liquid outlet pipe 2 and a liquid ejecting pipe 10. The liquid outlet pipe 2 is provided with a large flared mouth, and the liquid ejecting pipe 10 is provided with several liquid outlets set in a line.
The anode assembly provided in the present embodiment is the same as that in embodiment 5, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. E, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. H. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. H, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the conductive mesh by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the conductive mesh with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.

Embodiment 9

As shown in FIG. 9 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 7 as follows.
The present embodiment further comprises an electroplating solution ejecting pipe 14.
The electroplating cell divider 11 is specifically a combination of an anion exchange membrane and a filter cloth.
As shown in FIG. J, the anode box 13 is connected to a liquid outlet pipe 2 and a liquid ejecting pipe 10; inside the anode box, the liquid outlet pipe 2 is provided with a large flared mouth, and the liquid ejecting pipe 10 is provided with several liquid outlets set in lines. The liquid outlet pipe 2 is connected to a gas-liquid separator 8 via a pipe and a pump 23.1, and the gas-liquid separator 8 is then connected to the liquid ejecting pipe 10 through a liquid returning circulation pipe 9 to return the treated liquid to the anode box 13; An electroplating solution ejecting pipe 14 is provided at the side edges of the anode box 13 on the side facing the cathode, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2, to eject an electroplating solution at the cathode 4.
The anode assembly provided in the present embodiment is the same as that in embodiment 6, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. F, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. J. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the catholyte was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. J, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the perforated conductor by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the perforated conductor with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.

Embodiment 10

As shown in FIG. 10 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 7 as follows.
The present embodiment further comprises an electroplating solution ejecting pipe 14.
The electroplating cell divider 11 is specifically a combination of a bipolar membrane and a filter cloth;
As shown in FIG. K, the anode box 13 is connected to a liquid outlet pipe 2, and a liquid ejecting port 10 provided inside the box; the liquid outlet pipe 2 has 4 liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4. The liquid outlet pipe 2 is connected to a gas-liquid separator 8 through a pipe and a pump 23.1, and the gas-liquid separator 8 is then connected to the liquid ejecting port 10 through a liquid returning circulation pipe 9 to return the treated liquid to the anode box 13. An electroplating solution ejecting pipe 14 is provided at the side edges of the anode box 13 on the side facing the cathode, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2, to eject an electroplating solution at the cathode 4.
The anode assembly provided in the present embodiment is the same as that in embodiment 3, comprising an insoluble anode 1, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. C, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. K. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the catholyte was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. K, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.

Embodiment 11

As shown in FIG. 11 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, anode boxes 13, cathodes 4, an electroplating power supply 6, and a gas-liquid separator 8.
The electroplating cell 5 is provided with three anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a cation exchange membrane; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone.
As shown in FIG. G, the structure of the anode box 13 is the same as in embodiment 7 that each anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port inside it. The liquid outlet pipe 2 of each anode box 13 is connected to a pump, and then a gas-liquid separator 8; the gas-liquid separator 8 is provided above the surface of the electroplating solution, and is connected to the liquid ejecting port 10 of each anode box 13 through liquid returning circulation pipes 9 to return the gas-released liquid to each anode box 13.
The electroplating cathode zone is provided with a detection device 21 and a stirring device 24. The detection device 21 comprises a hydrometer, a photoelectric colourimeter and an acidity meter, and the stirring device 24 is a liquid circulating device. The electroplating cathode zone is connected to an overflow tank 38, a pump 23.4, a filter 33.1, an electroplating solution regenerating device 20, a liquid flow regulator with pump 30 and a filter 33.2 in order, forming a liquid circulation system; the catholyte in the electroplating cathode zone overflows into the overflow tank 38 and is pumped to the electroplating solution regenerating device 20 by the pump 23.4 after treated by filter 33.1. The feeding action of the liquid flow regulator with pump 30 is controlled by an automatic detection and replenishment controller 34, according to the results detected by the detection device 21, so that the catholyte is replenished with a copper source. A gas extraction hood 25 is provided above the electroplating cell 5.
The anode assembly provided in the present embodiment is the same as that in embodiment 4, comprising an insoluble anode 1, a conductor 17, and a reverse-pulse protective screen 15; as shown in FIG. D, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. G. The insoluble anode 1 is connected to the positive electrode of the electroplating power supply 6 during the electroplating process.
The cathode 4 is a flat copper plate provided in the electroplating cathode zone, and is connected to the negative electrode of the electroplating power supply 6 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, the liquid outlet pipe located in the anode box on the side of the anode away from the cathode cooperates with and the liquid ejecting port located at the bottom of the anode box on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the gas-liquid separator with the liquid flow for gas release. The gas-released liquid is then return to the anode box 13. The design of the anode box with the electroplating cell divider separates the anolyte and the catholyte, effectively reducing the consumption of electroplating additives. In addition, the gas released from the gas-liquid separator can be collected for further processing.

Embodiment 12

As shown in FIG. 12 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, anode boxes 13, cathodes 4, a gas-liquid separator 8, and a reverse pulse electroplating power supply 19.
The electroplating cell 5 is provided with six anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a combination of an anion exchange membrane and a filter cloth; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone. The electroplating cathode zone is provided with a detection device 21, which comprises a level gauge, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer. The detection device 21 is connected to an automatic detection and replenishment controller 34, to control the liquid level of the electroplating cell, temperature adjustment, power output current, concentration detection of the electroplating solution, electroplating time and other process parameters so that the electroplating process is carried out according to the process requirements.
The structure of the anode box 13 is as shown in FIG. J. Same as the structure of the anode box 13 of embodiment 9, each anode box 13 is connected with a liquid outlet pipe 2 and a liquid ejecting pipe 10. The liquid outlet pipe 2 in each anode box 13 is respectively connected to a pump 23 through a pipe, and is then connected to a temporary storage tank 32; wherein the pumps 23.1, 23.2, and 23.3 are utilized to pump the liquid into the temporary storage tank 32.1, and the pumps 23.4, 23.5, 23.6 are utilized to pump the liquid into the temporary storage tank 32.2. The liquid from the two temporary storage tanks is transferred with oxygen bubbles through a pump 23.7 and pipes to the gas-liquid separator 8 which contains copper metal 31, to make full use of the sulfuric acid and oxygen in the anolyte and allow them participating in the chemical reaction of converting copper metal to copper sulfate. The anolyte is chemically reacted in the gas-liquid separator 8, and has gas released in the gas-liquid separator 8 before being diverted to the liquid ejecting pipe 10 of each anode box 13 via a pump 23.8 and a liquid return circulation pipe 9, and is pumped into the anode box 13. Each anode box 13 is provided with an electroplating solution ejecting pipe 14 at the side edges on the side facing the cathode 4, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone. The liquid ejection motions of the electroplating solution ejecting pipes 14 towards the cathodes 4 are controlled as programmed.
The anode assembly provided in the present embodiment is the same as that in embodiment 6, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen net 15; as shown in FIG. F, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification. The anode assembly is provided in an anode box 13, as shown in FIG. J. The insoluble anode 1 is connected to the positive electrode of the electroplating power supply 19 during the electroplating process.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, a liquid flow is generated in the vicinity of the insoluble anode in each anode box, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the two temporary storage tanks with the liquid flow, and pumped to the gas-liquid separator 8 for the chemical reaction of copper metal. The liquid in the gas-liquid separator 8 is pumped back to each anode box after gas release. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, the electroplating solution inside the holes can be replenished and renewed, and the electroplating solution is also stirred. During the electroplating process, the cathode can be moved parallelly in one direction or back and forth in both directions to achieve a more uniform layer. In addition, the design of the anode box with the electroplating cell divider prevents the catholyte from entering the electroplating anode zone, which effectively reduces the consumption of electroplating additives and facilitates the collection of anolyte with bubbles from the anode box for use in the chemical reaction of copper metal in the temporary storage tank to produce more copper sulfate.

Embodiment 13

As shown in FIG. 13 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, anode boxes 13, cathodes 4, a gas-liquid separator 8, and two reverse pulse electroplating power supplies 19.
The electroplating cell 5 is provided with six anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is a combination of a bipolar film and a filter cloth; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone. The electroplating cathode zone is provided with a detection device 21, which comprises a level gauge, a hydrometer and an acidity meter. The detection device 21 is connected to an automatic detection and replenishment controller 34, which controls the electroplating current as well as the electroplating solution parameters of the process and alarms according to the detected results of the detection device 21.
As shown in FIG. K, the structure of the anode box 13 is the same as in embodiment 10 that each anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port inside it. Each liquid outlet pipe 2 is provided with four liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4. Each liquid outlet pipe 2 is connected via a pipe to the gas-liquid separator 8, into which the overflow liquid is diverted for gas release. The gas-released liquid in the gas-liquid separator 8 is pumped through the solid-liquid separator 33 by a pump 23.1 and into a liquid returning circulation pipe 9, which is connected to the liquid ejecting port 10 of each anode box 13 to return the treated liquid to the anode boxes 13. Each anode box 13 is provided with an electroplating solution ejecting pipe 14 at the side edges on the side facing the cathode 4, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2. The liquid ejection motions of the electroplating solution ejecting pipes 14 towards the cathodes 4 are controlled by the set program of the automatic detection and replenishment controller 34.
The anode assembly provided in the present embodiment is the same as that in embodiment 3, comprising an insoluble anode 1, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. C, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification. The anode assembly is provided in an anode box 13, as shown in FIG. K.
The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone.
During the electroplating process, the titanium substrates of the insoluble anodes 1 are connected to the positive electrode of the corresponding one of the two reverse pulse electroplating power supplies 19, whereas the four cathodes 4 are co-connected to the negative electrodes of the two reverse pulse electroplating power supplies.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
During the electroplating process, a liquid flow is generated in the vicinity of the insoluble anode in each anode box, which flows away from the cathode and through the holes of the insoluble anode due to power driven ejection of liquid from the liquid ejecting port. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the gas-liquid separator with the liquid flow for gas release. The gas-released liquid is then return to each anode box of the electroplating cell. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, the electroplating solution inside the holes can be replenished and renewed. During the electroplating process, the cathodes move parallelly in one direction or back and forth in both directions, and the output current of each electroplating power supply is adjusted according to the quality requirements of the cathode electroplating process, to achieve a better cathode electroplating layer. In addition, the design of the anode boxes with the electroplating cell divider can effectively reduce the consumption of electroplating additives.

Embodiment 14

As shown in FIG. 16 , the present embodiment is a basic example of an optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell 5, an insoluble anode 1, a liquid outlet pipe 2, a cathode 4 and an electroplating power supply 6.
The electroplating cell 5 is provided with a liquid outlet pipe 2, which is located on the side of the insoluble anode 1 away from the cathode 4, and the insoluble anode 1 is a coated titanium mesh.
The insoluble anode 1 is provided with the structure shown in FIG. A, which is a perforated plate made of coated titanium, and a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
The cathode 4 is a flat copper plate.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.

Embodiment 15

As shown in FIG. 17 , the present embodiment is an optimized device for an insoluble anode acid sulfate copper electroplating process, which differs from the device of embodiment 1 as follows.
A reverse pulse electroplating power supply 19 is used instead of the electroplating power supply 6.
As shown in FIG. C, the insoluble anode 1 is a perforated plate made of coated titanium, and is welded to a fixed frame 16 made of non-conductive material; a reverse-pulse protective screen 15 consisting of electric discharge spikes is provided and connected to the insoluble anode 1 and the fixed frame 16; a feed line is provided through the feed line installation holes at the upper part of the anode for structural modification.
The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and cathode 4 during the electroplating process.
The cathode 4 is a flat copper plate.
According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.

Comparative Example 1

As shown in FIG. 14 , the present comparative example is a device for insoluble anode acid sulfate copper electroplating process of the prior art, comprising a electroplating cell 5, an insoluble anode 1, a cathode 4, and a reverse pulse electroplating power supply 19.
The electroplating cell 5 is provided with an insoluble anode 14 and a cathode 4.
The insoluble anode 1 is made of coated titanium, and the cathode 4 is a flat copper plate with small holes.
The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19, and the cathode 4 is connected to the negative electrode of the power supply 19.
According to each parameter specified in Table 1, the reverse pulse electroplating power supply 19 was turned on to initiate electroplating production, and the results were recorded in Table 1. The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
In the present comparative example, the presence of a large number of oxygen bubbles in the electroplating solution between the cathode and the insoluble anode affected the current distribution in the electric field, and hydrogen generates massively on the surface of the insoluble anode coating during reverse pulse electrolysis. Both of these factors lead to uneven plating and damage to the anode coating.

Comparative Example 2

As shown in FIG. 15 , the present comparative example is a device for insoluble anode acid sulfate copper electroplating process of the prior art, which differs from the device of comparative example 1 in that it further comprises an electroplating cell divider 11, a stirring device 24, and a titanium basket 39.
The electroplating cell 5 is provided with a titanium basket 39, inside which an insoluble anode 1 is placed; the titanium basket is wrapped around by a neutral filter membrane 11, making the inner space enclosed by the titanium basket 39 and the neutral filter membrane 11 is the electroplating anode zone and the remaining space in the electroplating cell is the electroplating cathode zone; the electroplating cell 5 is also provided with a stirring device 24 and a cathode 4.
The insoluble anode 1 is made of coated titanium, and the cathode 4 is a flat copper plate with small holes.
The insoluble anode 1 and the titanium basket 39 are connected to the positive electrode of the reverse pulse electroplating power supply 19, and the cathode 4 is connected to the negative electrode of the reverse pulse electroplating power supply 19.
According to each parameter specified in Table 1, the stirring device 24 and the reverse pulse electroplating power supply 19 were turned on to initiate electroplating production, and the results were recorded in Table 1.
In the present comparative example, the presence of a large number of oxygen bubbles in the electroplating solution between the cathode and the anode affected the current distribution in the electric field, and hydrogen generates massively on the surface of the anode coating during reverse pulse electrolysis. Both of these factors lead to uneven plating and damage to the anode coating.
The process conditions for the embodiments and the comparative examples of the present disclosure are as follows:

- (1) the electroplating current was 2 A/dm²;
- (2) the reverse pulsed power supply operated with a forward current of 2 A/dm²and a reverse pulsed current of 6 A/dm², with a time ratio of 20:1 between the forward current and the reverse pulsed current;
- (3) the electroplating time was 40 minutes, and the working temperature was 30° C.;
- (4) the acid sulfate copper electroplating solution comprised:
- CuSO₄200 g/L;
- H₂SO₄60 g/L;
- Cl⁻70 g/L;

Commercially available Gaoli brand copper electroplating additive 9 mg/L.
Method of identifying the condition and uniformity of the electroplating layer.
After electroplating operation, three points on the electroplated cathode chosen uniformly from top to bottom were cut out and polished, and the electroplating layer of the cut-out samples were observed and measured in thickness using a microscope; for cathodes with small holes, the condition and the copper electroplating layer inside the holes were also observed; the measured results and the conclusions were recorded in Table 1.
Method of identifying the condition of the anode coating.
After electroplating operation, the anode coating was visually observed, and lightly brushed to test whether the coating would be peeled off; the conclusions were recorded in Table 1.
Method of identifying of the consumption of electroplating additives.
The COD value of the electroplating solution or catholyte was analyzed before and after the electroplating operation using the COD analytical method mentioned in the national standard, and the consumption of the electroplating additives was evaluated through the difference in the COD values of the electroplating solution or catholyte before and after the electroplating operation; the conclusions were recorded in Table 2.

TABLE 1

	Thickness of plated		Condition
Electroplating	layer (μm)	Surface quality of	of anode

System	solution	top	middle	bottom	plated layer	coating

Embodiment	Acid copper	15.5	14.9	14.3	Uniform and flat	In perfect
1	electroplating					condition
	solution
Embodiment	Acid copper	15.1	15.0	15.1	Uniform and flat	In perfect
2	electroplating					condition
	solution
Embodiment	Acid copper	15	15	15	Uniform and flat	In perfect
3	electroplating					condition
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
4	Acidic copper				holes with 0.2 mm	condition
	sulfate				diameter and 2 mm
	solution;				depth fully plated
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
5	Acidic copper				holes with 0.2 mm	condition
	sulfate				diameter and 2 mm
	solution;				depth fully plated
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte: Acid	15	15	15	Uniform and flat, small	In perfect
6	copper				holes with 0.2 mm	condition
	electroplating				diameter and 2 mm
	solution;				depth fully plated
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
7	Sulfuric acid				holes with 0.2 mm	condition
	solution;				diameter and 2 mm
	Catholyte:				depth fully plated
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
8	Acidic copper				holes with 0.2 mm	condition
	sulfate				diameter and 2 mm
	solution;				depth fully plated
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte: Acid	15	15	15	Uniform and flat, small	In perfect
9	copper				holes with 0.2 mm	condition
	electroplating				diameter and 2 mm
	solution;				depth fully plated
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
10	Sulfuric acid				holes with 0.2 mm	condition
	solution;				diameter and 2 mm
	Catholyte:				depth fully plated
	Acid copper
	electroplating
	solution
Embodiment	Anolyte: Acid	15	15	15	Uniform and flat	In perfect
11	copper					condition
	electroplating
	solution;
	Catholyte:
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
12	Acidic copper				holes with 0.2 mm	condition
	sulfate				diameter and 2 mm
	solution;				depth fully plated with
	Catholyte:				high quality
	Acid copper
	electroplating
	solution
Embodiment	Anolyte:	15	15	15	Uniform and flat, small	In perfect
13	Sulfuric acid				holes with 0.2 mm	condition
	solution;				diameter and 2 mm
	Catholyte:				depth fully plated with
	Acid copper				high quality
	electroplating
	solution
Embodiment	Acid copper	15.6	14.8	14.3	Uniform and flat	In perfect
14	electroplating					condition
	solution
Embodiment	Acid copper	15.2	15.0	14.8	Uniform and flat	Anode
15	electroplating					coating at
	solution					upper part
						slightly fell
						off when
						lightly
						brushed
Comparative	Acid copper	14.1	15.3	16.4	Rough plated surface,	Anode
Example 1	electroplating				small holes with 0.2 mm	coating
	solution				diameter and 2 mm	obviously
					depth not fully plated	fell off
						when
						lightly
						brushed
Comparative	Anolyte: Acid	13.6	15.2	16.9	Rough plated surface,	Anode
Example 2	copper				small holes with 0.2 mm	coating
	electroplating				diameter and 2 mm	obviously
	solution;				depth not fully plated	fell off
	Catholyte:					when
	Acid copper					lightly
	electroplating					brushed
	solution

	TABLE 2

	COD value of electroplating
	solution (mg/L)

	Before elec-	After elec-	Differ-
System	troplating	troplating	ence	Conclusion

Comparative	5122	4889	233	Relatively large
Example 1				consumption of
				electroplating additives
Embodiment	4933	4721	212	Relatively large
1				consumption of
				electroplating additives
Embodiment	5320	5111	209	Relatively large
4				consumption of
				electroplating additives
Embodiment	4902	4837	65	Small consumption of
9				electroplating additives
Embodiment	5076	5002	74	Small consumption of
10				electroplating additives

It can be concluded from Table 1 that, when comparing the electroplating quality obtained in embodiments 1-15 with that obtained in comparative examples 1-2 of the prior art, the plated layer obtained in embodiments 1-15 showed a more even thickness at three points (top, middle and bottom) than in comparative example 1. Since a fixed frame or a conductor with connection points was provided in embodiments 2-13 acting as a feed line, the plated layer obtained were uniform in overall thickness and flat, with small holes fully plated. Whereas in comparative examples 1-2, the current distribution in the electroplating solution was affected by the bubbles during electroplating, resulting in a plated layer with rough surface, uneven thickness, and unsatisfactory electroplating quality inside the small holes. It can be summarized that the plated layer obtained in the process of the present disclosure is more uniform and flat, with a higher electroplating quality of through-holes, showing that the present disclosure can effectively improve the electroplating quality and meet the requirements of the electroplating industry for high quality products after optimizing the insoluble anode copper electroplating process with gas generation.
It can also be concluded from Table 1 that, when comparing the anode coating condition in embodiments 4-10, embodiments 12-13 and embodiment 15 with comparative examples 1-2 of the prior art: the insoluble anode was provided with a reverse-pulse protective screen in embodiments 4-10, embodiments 12-13 and embodiment 15, wherein the anode coating in embodiments 4-10 and embodiments 12-13 were in perfect condition after electroplating, and the anode coating in embodiment 15 had its upper part slightly fell off after light brushing due to the lack of bypass design; whereas the insoluble anode in comparative examples 1-2 were provided without a reverse-pulse protective screen which protects anode coating, the coating after electroplating obviously fell off when it was brushed lightly. It can be summarized that the insoluble anode of the present disclosure provided with a reverse-pulse protective screen can effectively reduce the electrochemical formation of hydrogen on the surface of the insoluble anode coating, thus extending the service life of the insoluble anode.
Since the electroplating additives used in the industry are organic compounds, their consumption can be reflected by the change in the COD value of the electroplating solution, i.e., the faster the COD value of the electroplating solution decreases, the faster the electroplating additives in the electroplating solution are consumed. As shown in Table 2 above, when comparing embodiment 9 and embodiment 10, in which the electroplating cell was provided with a electroplating cell divider, with comparative example 1, embodiment 1 and embodiment 4, in which the electroplating cell is not provided with a electroplating cell divider: in embodiment 9 and embodiment 10, the difference between the COD values of the catholyte before and after electroplating were not exceed 80 mg/L, indicating a small consumption of electroplating additives. In comparative example 1, embodiment 1 and embodiment 4, the difference between the COD values of the electroplating solution before and after electroplating were more than 200 mg/L, indicating a large consumption of electroplating additives. It can be proved that the electroplating cell of the present disclosure provided with an electroplating cell divider can effectively save electroplating additives.
Furthermore, the basic setup of Comparative Example 1 of the prior art was the most similar to that of Embodiment 9 and Embodiment 10 of the present disclosure. However, both Embodiment 9 and Embodiment 10 were superior to Comparative Example 1 in terms of electroplating uniformity, small hole electroplating quality, anode coating condition, and consumption of electroplating additives.
The present disclosure may be outlined in other specific forms that do not contradict the spirit or the main features of the present disclosure. The aforementioned embodiments are the preferred embodiments of the present invention. They do not intend to limit the scope of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An optimized method for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell (5), an electroplating power supply (6), an insoluble anode (1), a cathode (4), and an acid sulfate copper electroplating solution as an electroplating solution, wherein the method comprises following steps:

step 1: providing an insoluble anode (1) made of coated titanium in the form of a mesh or a perforated plate, and then the insoluble anode (1) and the cathode (4) are placed in the electroplating cell; providing at least one liquid outlet pipe/port (2) on a side of the insoluble anode (1) away from the cathode (4), to generate a liquid flow of the electroplating solution by overflow and/or power driven suction at the liquid outlet pipe/port (2); and

step 2: initiating an electroplating process by switching on the electroplating power supply (6), while the electroplating solution flows away due to the overflow and/or the power driven suction at the liquid outlet pipe/port, the electroplating solution in the electroplating cell (5) forms the liquid flow towards the liquid outlet pipe/port (2), and accordingly, adding another electroplating solution to the electroplating cell (5) to maintain a liquid volume in the cell until the electroplating process is completed and the electroplated cathode is removed.

2. The method according to claim 1, wherein at least one liquid ejecting pipe/port (10) is provided on a side of the insoluble anode (1) facing the cathode (4); the liquid ejecting pipe/port (10) connects to an external liquid ejecting pipeline to spray liquid towards the anode; and in conjunction with the liquid outlet pipe/port (2), produces the more stable and more controllable liquid flow in a vicinity of the insoluble anode (1) that flows away from the cathode (4).

3. The method according to claim 2, wherein a gas-liquid separator (8) is further provided, so that a gas-liquid mixture from the electroplating cell (5) is discharged via the liquid outlet pipe/port (2) and a connecting pipe into the gas-liquid separator (8); a gas in the gas-liquid mixture is released inside the gas-liquid separator (8) and a liquid is then diverted back to the electroplating cell (5) for circulation.

4. The method according to claim 3, wherein an electroplating cell divider (11) is provided in the electroplating cell (5), dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone; the electroplating solution in the electroplating anode zone is an anolyte, which is specifically composed of an aqueous solution comprises at least one inorganic acid and/or at least one inorganic salt, or the acid sulfate copper electroplating solution; the electroplating solution in the electroplating cathode zone is the acid sulfate copper electroplating solution; during the electroplating process, the insoluble anode (1) and the cathode (4) are placed separately in the electroplating anode zone and the electroplating cathode zone; the liquid outlet pipe/port (2) and the liquid ejecting pipe/port (10) are located within the electroplating anode zone.

5. The method according to claim 4, wherein the electroplating anode zone is in the form of an anode box (13) inside the electroplating cell (5), dividing the electroplating cell into the electroplating anode zone and the electroplating cathode zone; particularly, the anode box (13) is shaped as a cubic box, in which the insoluble anode (1) is provided; a side of the anode box (13) facing the cathode (4) is the electroplating cell divider (11), making an inner space of the anode box (13) to be the electroplating anode zone, and a space in the electroplating cell (5) outside the anode box (13) to be the electroplating cathode zone; the liquid outlet pipe/port (2) is provided at the anode box (13), specifically in an area inside the anode box (13) or on a wall of the anode box (13) on the side of the insoluble anode (1) away from the cathode (4); furthermore, the liquid ejecting pipe/port (10) is provided in the area inside the anode box (13) between the anode and the nearby wall of the anode box on the side of the insoluble anode (1) facing the cathode (4).

6. The method according to claim 1, wherein a fixed frame (16) is provided at edges of the insoluble anode; the fixed frame (16) is made of material that is insoluble as an anode, heat-resisting, acid-resisting and relatively rigid.

7. The method according to claim 6, wherein a conductor (17) connected to a positive electrode of the electroplating power supply (6) is attached to the insoluble anode (1) on the side away from the cathode (4).

8. The method according to claim 7, wherein the insoluble anode (1) and/or the fixed frame (16) and/or the conductor (17) is provided on its side facing the cathode (4) with a reverse-pulse protective screen (15), and the reverse-pulse protective screen (15) is made of uncoated titanium in the form of a protrusion, or a protruding mesh or bar.

9. The method according to claim 8, wherein when the reverse-pulse protective screen (15) is provided attaching to the insoluble anode (1), the reverse-pulse protective screen (15) is made of uncoated titanium in the form of the protrusion, or the protruding mesh or bar, protruding from the side of the insoluble anode (1) facing the cathode (4) and directly connecting to a titanium substrate of the insoluble anode (1); when the reverse-pulse protective screen (15) is provided with the fixed frame (16) made of uncoated or coated titanium, the reverse-pulse protective screen (15) is connected to either the titanium substrate of the insoluble anode (1) or the titanium of the fixed frame (16), or to both; when the reverse-pulse protective screen (15) is provided on the conductor (17), the reverse-pulse protective screen (15) extends out of a surface of the insoluble anode (1) through the holes of the anode and towards the cathode (4).

10. The method according to claim 9, wherein the protrusion is in any one of the form of a bump, a spike, or a vertical bar; the protruding mesh or bar is a mesh or bar extending towards the cathode with its supporting foot fixed on the side of the insoluble anode (1) and/or the fixed frame (16) and/or the conductor (17) facing the cathode, or a mesh or bar formed by interconnecting an upper part of the protrusions, a plane surface formed by the protruding mesh or bar is parallel or substantially parallel to the surface of the anode (1).

11. An optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell (5), an insoluble anode (1), a cathode (4), and an electroplating power supply (6), wherein:

the electroplating cell is provided with at least one liquid outlet pipe/port (2) on a side of the insoluble anode (1) away from the cathode, to generate a liquid flow in the electroplating cell (5) by overflow and/or power driven suction of an electroplating solution at the liquid outlet pipe/port (2);

the insoluble anode (1) is made of coated titanium in the form of a mesh or a perforated plate;

a positive electrode and a negative electrode of the electroplating power supply (6) are respectively connected to the insoluble anode (1) and the cathode (4) in the electroplating process.

12. The device according to claim 11, wherein the electroplating cell (5) is provided with at least one liquid jet pipe/port (10), the liquid jet pipe/port (10) is located in an area on a side of the insoluble anode (1) facing the cathode (4) and between the anode and the cathode; the liquid ejecting pipe/port (10) connects to an external liquid ejecting pipeline to spray liquid towards the anode (1); the device is provided with a fluid circulating system, which mainly consists of a power driven device and a connecting pipe, with one end connecting to the liquid outlet pipe/port (2) and the other end connecting to the liquid ejecting pipe/port (10); the fluid circulating system is utilized to make the electroplating solution flow away from the liquid outlet pipe/port (2) and return to the electroplating cell (5), forming the liquid flow in the electroplating cell (5) towards the liquid outlet pipe/port (2) located at the anode.

13. The device according to claim 12, wherein the liquid outlet pipe/port (2) is connected to a gas-liquid separator (8) via a connection pipe; the gas-liquid separator (8) is also connected to the electroplating cell (5) via a pump and the connection pipe to form a fluid circulating system, which returns the gas-released liquid back into the electroplating cell (5) for circulation.

14. The device according to claim 13, wherein an electroplating cell divider (11) is provided in the electroplating cell (5), dividing the electroplating cell (5) into an electroplating anode zone and an electroplating cathode zone.

15. The device according to claim 14, wherein an anode box (13) is provided inside the electroplating cell (5), dividing the electroplating cell into the electroplating anode zone and the electroplating cathode zone: the anode box (13) is shaped as a cubic box, in which the insoluble anode (1) is provided; a side of the anode box (13) facing the cathode (4) is the electroplating cell divider (11), making an inner space of the anode box (13) to be the electroplating anode zone, and a space in the electroplating cell outside the anode box to be the electroplating cathode zone; the liquid outlet pipe/port (2) is provided at the anode box (13), specifically in an area inside the anode box (13) or on a wall of the anode box on the side of the insoluble anode (1) away from the cathode (4); furthermore, the liquid ejecting pipe/port (10) is provided inside the anode box (13), specifically in the area inside the anode box (13) between the anode and the nearby wall of the anode box on the side of the insoluble anode (1) facing the cathode (4).

16. The device according to claim 15, wherein an electroplating solution ejecting pipe (14) is provided at a side edge of the anode box on the side facing the cathode, and each electroplating solution ejecting pipe (14) is equipped with a flow regulator to adjust an ejection effect of the electroplating solution towards the cathode.

17. The device according to claim 16, wherein the insoluble anode (1) is provided with a reverse-pulse protective screen (15), the reverse-pulse protective screen (15) is made of uncoated titanium protruding from the side of the insoluble anode (1) facing the cathode (4) and directly connecting to a titanium substrate of the insoluble anode (1); the reverse-pulse protective screen is in any one of the form of a bump, a spike, a vertical bar, or a mesh or bar connected to the protrusions.

18. The device according to claim 17, wherein the insoluble anode (1) is further provided with a fixed frame (16) at its edges.

19. The device according to claim 18, wherein a conductor (17) connected to the positive electrode of the electroplating power supply (6) is attached to the insoluble anode (1) on the side away from the cathode (4).

20. The device according to claim 19, wherein an insoluble anode (1) with the reverse-pulse protective screen (15), the fixed frame (16) and the conductor (17), together with the insoluble anode accessories including the liquid outlet pipe/port (2) and the liquid ejecting pipe/port (10) are provided in the anode box (13) as an anode box assembly.