Electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method and application

Abstract

The invention relates to the technical field of copper plating raw material electrochemical preparation, and discloses an electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method and application, and the preparation method comprises the following steps: preparing an electronic copper plating raw material by synchronous anode electrochemistry, coupling cathode hydrogen evolution reaction to prepare hydrogen, and coupling oxygen reduction reaction to generate electric energy, the high-purity electronic copper plating raw material obtained in the anode chamber through the electrolytic bath with the polymer ion membrane can be used as an electronic copper electroplating high-purity copper ion source or a high-purity accelerator or a high-purity leveling agent, on the other hand, high-purity hydrogen can be obtained through a hydrogen evolution reaction in the cathode chamber, and meanwhile electric energy is efficiently output outwards through a cathode oxygen reduction reaction. The problems that an existing electronic copper plating raw material preparation method is complex, high in cost and poor in controllability and has potential safety hazards are solved, a high-added-value cathode hydrogen product can be obtained with low energy consumption through simple symbiotic electrochemical preparation, / the electronic copper plating raw material is spontaneously produced, and electric energy is generated.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochemical preparation of copper plating raw materials, and in particular relates to a method and application of electrochemical preparation of electronic copper plating raw materials, hydrogen and electric energy symbiosis. Background Art

[0002] Copper metal is widely used in electronic products due to its good electrical and thermal conductivity. Electrodeposition of copper is an important step in realizing chip interconnection and ensuring the operation of electronic products. The conformal electrodeposition of copper metal is inseparable from the electronic copper plating raw materials, including copper source and copper plating additives including accelerators, levelers and inhibitors. With the development of technology, the requirements for chip interconnection size are constantly increasing. In order to ensure the long-term stable operation of the chip during operation, it is necessary to avoid the electronic copper plating raw materials, including copper source, organic impurities in additives, various metals and metal impurities on the quality of electronic products. Controllable preparation of high-purity electronic copper plating raw materials is very important for chip manufacturing.

[0003] In the electronic copper plating process, copper sulfate is often used as a copper ion source. However, low-purity copper sulfate will cause holes or gaps to form during use, seriously affecting the reliability of three-dimensional packaging. Therefore, high-purity copper sulfate is very important for chip packaging, especially for high-tech requirements such as chip Damascus interconnection. At present, the preparation of high-purity copper sulfate mainly includes chemical method and electrochemical method, as shown below:

[0004] Chemical method: CuO+H2SO4→CuSO4+H2O

[0005] Electrochemical method: Cu–2e - →Cu 2+ ,Cu 2+ +SO4 2- →CuSO4

[0006] The former dissolves high-purity copper oxide in a high-purity sulfuric acid solution to obtain high-purity copper sulfate. This method is very convenient, but it has high requirements for raw materials, a long process route, and poor control over the reaction process, so it is rarely used. The electrochemical method oxidizes high-purity metallic copper in a sulfuric acid solution through an electrochemical oxidation method to finally obtain high-purity copper sulfate. This method has become the main method for preparing copper sulfate because of its easy control and high efficiency and low pollution. However, during use, the cathode product hydrogen is only transported to the anode chamber as a gas to stir the solution, which leads to a waste of cathode reaction. In addition, the large solution resistance generated by the large distance between the electrodes of the traditional copper sulfate preparation device leads to additional consumption of electrical energy. Therefore, the traditional copper sulfate preparation technology needs to be improved and developed.

[0007] In addition to copper sulfate, copper methanesulfonate has become an ideal choice for copper ion sources in electronic copper plating in recent years due to its stability, easy recovery and higher copper ion supply. For high-precision chip interconnection, the preparation of high-purity copper methanesulfonate is an important factor in ensuring defect-free conformal metal deposition. However, the preparation of commercial copper methanesulfonate currently mainly relies on chemical methods, as shown below:

[0008] Cu(OH)2+2CH3SO3H→Cu(CH3SO3)2+2H2O

[0009] That is, copper hydroxide is dissolved in a high-purity methanesulfonic acid solution to prepare high-purity copper methanesulfonate. This method has the disadvantages of being difficult to control, time-consuming, and requiring long-term high temperature, which is not conducive to its industrial application and promotion.

[0010] On the other hand, as an important component of copper plating additives, sulfonyl disulfide is often used as an acidic plating accelerator to accelerate the deposition rate of copper ions and effectively refine the grains of the copper plating layer. It is an important component of electronic copper plating and has gained a huge demand for products due to its excellent application effect. However, in actual use, the demand for high-purity accelerators forces companies to purchase imported accelerators at high prices during the production process. The purity can reach more than 98%, while the effective content of domestic accelerators cannot reach more than 90%, which is difficult to meet the use needs. It is urgent to develop a synthesis method for high-purity sulfonyl disulfide copper plating accelerators. At present, there are two main preparation methods for sulfonyl disulfide plating in China, including sodium sulfide method and sodium hydrosulfide method. Taking SPS and SH-110 as examples:

[0011] SPS elemental sulfur method:

[0012]

[0013] SPS sodium hydrosulfide method:

[0014]

[0015] SH-110 elemental sulfur preparation:

[0016]

[0017] SH-110 sodium hydrosulfide preparation method:

[0018]

[0019] Among them, the elemental sulfur method has many side reactions in the first step, which leads to the presence of sulfur compound impurities, affecting the quality of the final accelerator produced. The sodium hydrosulfide method can effectively avoid the presence of sulfur compound impurities and is currently the mainstream accelerator production method in China. However, in its production process, the use of chemical oxidation in the second step of oxidation is uncontrollable, and the traditional hydrogen peroxide oxidation agent will bring safety and stability problems. Replacing it with other oxidants such as potassium permanganate will bring impurity removal problems, making it difficult to obtain high-purity products.

[0020] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0021] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide an electrochemical preparation method and application of electronic copper plating raw materials, hydrogen and electric energy, aiming to solve the problems of high energy consumption, high cost and ineffective utilization of cathode products in the existing electrochemical preparation methods of electronic copper plating raw materials.

[0022] The technical solution of the present invention is as follows:

[0023] A method for preparing an electronic copper plating raw material, hydrogen and electric energy by electrochemical symbiosis, comprising the following steps:

[0024] An electrolyzer / fuel cell is provided, the electrolyzer / fuel cell comprising an electrolyzer, a polymer ion membrane disposed in the middle of the electrolyzer and dividing the electrolyzer into an anode chamber and a cathode chamber, an anode electrode disposed in the anode chamber, a cathode electrode disposed in the cathode chamber, the anode electrode and the cathode electrode being connected to an external power source via an electric wire, the anode chamber being connected to a first storage tank for storing a first electrolyte, and the cathode chamber being connected to a second storage tank for storing a second electrolyte or oxygen;

[0025] When an external power source is turned on, a self-generated electrochemical reduction reaction occurs in the anode chamber and the cathode chamber under the isolation of the polymer ion membrane and the action of an external voltage, wherein the anode electrode or electrolyte in the anode chamber is selectively oxidized, and then the electronic copper plating raw material is obtained through a filtration and purification step, while the electrochemical reduction reaction in the cathode chamber produces high-purity hydrogen used as fuel and electronic special gas, and realizes spontaneous power supply to the outside while producing the electronic copper plating raw material.

[0026] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the electronic copper plating raw material is copper sulfate, the anode electrode is metallic copper, the first electrolyte and the second electrolyte are both sulfuric acid solutions with a purity greater than or equal to 96%, the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold or a compound containing a metal; the polymer ion membrane is a cation exchange membrane.

[0027] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the electronic copper plating raw material is copper methane sulfonate, the anode electrode is metallic copper, the first electrolyte and the second electrolyte are both sodium hydroxide solutions with a purity greater than or equal to 98%, the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold or a compound containing a metal; the polymer ion membrane is a cation exchange membrane.

[0028] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the electronic copper plating raw material is a sulfonyl disulfide copper plating accelerator, the anode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal, and the first electrolyte includes a sodium hydroxide solution, a thiol compound and a thiol sulfonate; the second electrolyte is a sodium hydroxide solution, and the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal; and the polymer ion membrane is an anion exchange membrane.

[0029] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the sulfonyl disulfide copper plating accelerator is a sodium polydisulfide propane sulfonate copper plating accelerator, the mercapto sulfonate is sodium 3-mercaptopropane sulfonate, and the mercapto compound is 2-mercaptothiazoline.

[0030] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodiethane sulfonate, the mercapto sulfonate is sodium 2-mercaptoethane sulfonate, and the mercapto compound is 2-mercaptothiazoline.

[0031] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein, if the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodihexanesulfonate, the mercaptosulfonate is sodium 4-mercaptobutanesulfonate, and the mercapto compound is 2-mercaptothiazoline.

[0032] The electronic copper plating raw material, hydrogen and electric energy symbiotic electrochemical preparation method, wherein the purity of the mercaptosulfonate is greater than or equal to 95%, and the concentration is 10-200g / L; the purity of the mercapto compound is greater than or equal to 99%, and the concentration is 10-200g / L.

[0033] An application of an electronic copper plating raw material, wherein the electronic copper plating raw material prepared by the preparation method of the invention is used in an electroplating copper or chemical copper plating process.

[0034] Beneficial effects: The present invention uses synchronous anode electrochemistry to prepare electronic copper plating raw materials such as high-purity copper sulfate or high-purity copper methanesulfonate or sulfonyl disulfide copper plating accelerators, and couples the cathode hydrogen evolution reaction to produce hydrogen or couples the oxygen reduction reaction to produce electricity. The electronic copper plating value-added product is prepared by anode electrochemical oxidation to replace the anode oxygen evolution reaction, which can greatly reduce the theoretical potential of the anode reaction and achieve low-energy consumption hydrogen production / synchronous electricity generation. The high-purity electronic copper plating raw material obtained in the anode chamber by electrolysis with an ion exchange membrane can be used as a high-purity copper ion source or high-purity accelerator or high-purity leveling agent for electronic copper electroplating. On the other hand, high-purity hydrogen can be obtained by hydrogen evolution reaction in the cathode chamber, and at the same time, the cathode oxygen reduction reaction outputs electricity efficiently. The present invention overcomes the problems of the existing electronic copper plating raw material preparation method being complicated, costly, poor controllability and safety hazards, and can obtain high-value-added cathode hydrogen products with low energy consumption through simple symbiotic electrochemical preparation, spontaneously produce electronic copper plating raw materials and generate electricity. The ultra-high purity copper sulfate or copper methanesulfonate or sulfonyl disulfide copper plating accelerator obtained by the invention can be used in the electroplating copper process for manufacturing chip Damascus interconnection, through silicon via (TSV), through glass via (TGV), redistribution layer (RDL), three-dimensional interconnection bump, chip carrier, printed circuit board (PCB), copper foil, composite copper foil, foam copper and the like, and in the chemical copper plating process for preparing composite copper foil, foam copper and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The present invention shows a flow chart of an electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy.

[0036] Figure 2 This is a schematic diagram of the present invention for preparing electronic copper plating raw materials and hydrogen based on an electrolyzer / fuel cell and realizing self-powered external power supply.

[0037] Figure 3 Another schematic diagram of the present invention is a method of preparing electronic copper plating raw materials based on an electrolytic cell / fuel cell and realizing self-powered external power supply. DETAILED DESCRIPTION

[0038] The present invention provides an electrochemical preparation method and application of electronic copper plating raw materials, hydrogen and electric energy symbiosis. In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0039] Electrochemical oxidation can rely on the control of an external power supply to efficiently control the reaction. Under the premise of using high-purity reactants, it can replace chemical oxidation to safely and controllably prepare high-purity electronic copper plating raw materials. It is an ideal method for preparing electronic copper plating raw materials. In addition, experiments have shown that the electrochemical oxidation of electronic copper plating raw materials has a lower thermodynamic barrier and is more likely to occur than the traditional anode oxygen evolution reaction. Therefore, the electrochemical oxidation preparation of electronic copper plating raw materials is used as the anode reaction to replace the oxygen evolution reaction, and the dual-electrode electrolyzer / fuel cell is formed by coupling the hydrogen evolution reaction / oxygen reduction reaction as the cathode reaction. This can greatly reduce the energy demand of the electrolyzer and spontaneously generate electricity. High-purity electronic copper plating raw materials can be efficiently prepared at the anode end, while high-purity hydrogen can be efficiently prepared at the cathode. At the same time, electronic copper plating raw materials can be spontaneously prepared and powered externally. This is a promising strategy.

[0040] Based on this, the present invention provides an electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy symbiosis, such as Figure 1 As shown, it includes the steps of:

[0041] S100, providing an electrolyzer / fuel cell, the electrolyzer / fuel cell comprising an electrolyzer, a polymer ion membrane disposed in the middle of the electrolyzer and dividing the electrolyzer into an anode chamber and a cathode chamber, an anode electrode disposed in the anode chamber, a cathode electrode disposed in the cathode chamber, the anode electrode and the cathode electrode being connected to an external power source via an electric wire, the anode chamber being connected to a first storage tank for storing a first electrolyte, and the cathode chamber being connected to a second storage tank for storing a second electrolyte or oxygen;

[0042] S200, connecting an external power source, allowing the anode chamber and the cathode chamber to undergo a self-generated electrochemical reduction reaction under the isolation of the polymer ion membrane and the action of an external voltage, wherein the anode electrode or the electrolyte in the anode chamber is selectively oxidized, and then filtered and purified to obtain an electronic copper plating raw material, while the electrochemical reduction reaction in the cathode chamber produces high-purity hydrogen used as a fuel and electronic special gas, and realizes spontaneous power supply to the outside while producing the electronic copper plating raw material.

[0043] Specifically, in the actual operation process, a dual-electrode electrolyzer / fuel cell is used. The electrolyzer is designed with an anode chamber and a cathode chamber. The reactants are dissolved in the electrolyte. The anode electrodes are placed in the electrolyte, and the cathode electrode is placed in the electrolyte or only oxygen is introduced without adding electrolyte. The electronic copper plating raw material-hydrogen / electricity symbiotic electrochemical preparation is carried out under the external direct current / self-generated chemical reaction. Depending on the electrodes and reactants used, it can be used to prepare copper sulfate, copper methanesulfonate or sulfonalkyl disulfide.

[0044] The present invention uses synchronous electro-oxidation to prepare high-purity copper sulfate or copper methanesulfonate or sulfonyl disulfide copper plating accelerator and cathode hydrogen evolution reaction / oxygen reduction reaction, which can not only realize the efficient and controllable preparation of electronic copper plating raw materials, but also greatly reduce the energy consumption of electrolytic hydrogen production / realize external power supply, and effectively eliminate the potential safety hazards caused by the mixing of anode and cathode oxygen and hydrogen in the traditional water electrolysis process. High-purity electronic copper plating raw materials can be directly prepared by the anode reaction of this electrolyzer / fuel cell, which can be directly applied to electronic interconnection after a certain purification, and high-purity hydrogen can be obtained from the cathode of the electrolyzer as an efficient fuel and electronic special gas, or can be coupled with the cathode oxygen reduction reaction to form a fuel cell to output electrical energy externally. The present invention overcomes the problems of complex process, high cost, and difficulty in control of the existing chemical preparation method of electronic copper plating raw materials, and the problems of high energy consumption, high cost, and ineffective utilization of cathode products in the electrochemical preparation method. The present invention overcomes the problem of high thermodynamic barrier of the traditional anode oxygen evolution reaction in the electrolyzer, can obtain high-purity fuel hydrogen at low power input, and realizes the spontaneous production of electronic copper plating raw materials in the fuel cell while powering the external power supply. The method for preparing the electronic copper plating raw material provided by the present invention has simple process and low production cost, can be produced continuously and on a large scale, improves production efficiency, improves production safety and greatly reduces reaction energy consumption, realizes spontaneous preparation of the electronic copper plating raw material and supplies power to the outside.

[0045] In some embodiments, Figure 2 As shown, in the electrochemical preparation process of copper sulfate-hydrogen / electricity symbiosis, an electrolyzer / fuel cell based on a cation exchange membrane is used, the electrolyzer / fuel cell is designed with an anode chamber and a cathode chamber, metal copper is used as the anode electrode, sulfuric acid solution is used as the anode electrolyte, nickel, platinum, palladium, gold metal or alloy or metal compound is used as the cathode hydrogen evolution reaction / oxygen reduction reaction electrode, sulfuric acid is used as the cathode electrolyte, a cation exchange membrane is used to separate the anode and the cathode, and at a certain temperature, electrochemical oxidation is used to dissolve the anode metal copper to generate Cu 2+ , while the cation exchange membrane blocks copper ions from entering the cathode chamber from the anode chamber, avoiding reduction on the cathode. 2+ With SO4 2- Combined with the production of copper sulfate, the subsequent ultra-high purity copper sulfate electroplating solution is obtained by super filtration purification and recrystallization. + Electromigration crosses the ion membrane and generates hydrogen on the cathode surface, which is then output and stored after water-gas separation. For fuel cells, H + Electromigration passes through the ion membrane and an oxygen reduction reaction occurs on the cathode surface to generate H2O. At the same time, the entire fuel cell supplies power to the outside. The high-purity copper sulfate obtained at the anode can be used for electronic copper plating as a copper ion source. The hydrogen generated at the cathode can be used as a green fuel and electronic special gas. The generated electricity can be directly stored and used. The electrode reaction is as follows: Anode: Cu-2e- →Cu 2 + ; Cathode: 2H + +2e - →H2(HER)or O2+4H + +4e - →2H2O(ORR).

[0046] In this embodiment, the anode electrode is a high-purity copper electrode with a purity of ≥99.999%; the concentration range of the sulfuric acid electrolyte is 0.1-10 mol / L, and the purity of the sulfuric acid electrolyte is ≥96%.

[0047] In some embodiments, Figure 3 As shown, in the copper methanesulfonate-hydrogen / electricity symbiotic electrochemical preparation process, an electrolyzer / fuel cell based on a cationic membrane is used. The electrolyzer / fuel cell is designed with an anode chamber and a cathode chamber, and metal copper is used as the anode electrode. A methanesulfonic acid solution is used as the anode electrolyte, and a metal or alloy or metal compound of nickel, platinum, palladium, and gold is used as the cathode hydrogen evolution reaction / oxygen reduction reaction electrode. No electrolyte is added to the cathode chamber, only oxygen is introduced. A cationic membrane is used to separate the anode and the cathode. At a certain temperature, electrochemical oxidation is used to dissolve the anode metal copper to generate Cu 2+ , while the cationic membrane blocks copper ions from entering the cathode chamber from the anode chamber to avoid reduction on the cathode. 2+ With CH3SO3 - Combined to form copper methanesulfonate, followed by ultra-high purity copper methanesulfonate electroplating solution combined with superfiltration purification and recrystallization steps. + Electromigration crosses the ion membrane and an oxygen reduction reaction occurs on the cathode surface to generate H2O. At the same time, the entire fuel cell supplies power to the outside. The high-purity copper methanesulfonate obtained at the anode can be used in electronic copper plating as a copper ion source, and the electricity generated at the cathode can be directly stored and used. The electrode reaction is as follows

[0048] Anode: Cu-2e - →Cu 2+

[0049] Cathode: O2+4H + +4e - →2H2O(ORR).

[0050] In this embodiment, the anode electrode is a high-purity copper electrode with a purity of ≥99.999%; the concentration range of the methanesulfonic acid electrolyte is 0.1-10 mol / L, the purity of the methanesulfonic acid electrolyte is ≥98%; the oxygen is pure oxygen with a purity of ≥99.9%.

[0051] In some embodiments, in the electrochemical preparation process of sulfonyl disulfide copper plating accelerator-hydrogen / electricity symbiosis, an electrolyzer / fuel cell based on an anion exchange membrane is used. The electrolyzer / fuel cell is designed with an anode chamber and a cathode chamber. The anode electrode and the cathode hydrogen evolution reaction / oxygen reduction reaction electrode are both made of metal or alloy or metal compound. The anode uses sodium hydroxide as the electrolyte, and the cathode adds sodium hydroxide as the electrolyte / does not add electrolyte and only oxygen is introduced. The anode and the cathode are separated by an anion exchange membrane, and the thiol compound and the thiol sulfonate are used as the anolyte electrolyte. At a certain temperature, the anode thiol compound and the thiol sulfonate are electrochemically oxidized to convert them into sulfonyl disulfide, and the anion exchange membrane blocks the electrolyte from entering the cathode chamber from the anode chamber. Subsequently, a high-purity sulfonyl disulfide copper plating accelerator is obtained by combining superfiltration purification, recrystallization, decolorization and drying steps. For the electrolytic cell, hydrogen evolution reaction occurs on the cathode surface to generate H2, which is then output and stored after water vapor separation, while OH - Electromigration crosses the ion membrane to the anode to participate in the reaction. For fuel cells, oxygen and water undergo oxygen reduction reaction and produce OH - , the whole fuel cell supplies power to the outside, while OH - Electromigration passes through the ion membrane to the anode to participate in the reaction. The high-purity sulfoalkyl disulfide obtained at the anode can be used as an accelerator for electronic copper plating, and the hydrogen generated at the cathode can be used as a green fuel and electronic special gas / the generated electricity can be directly stored and used. The electrode reaction is as follows:

[0052] When the prepared sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodiethane sulfonate (SES):

[0053] anode:

[0054] Cathode: 2H2O+2e - →H2+2OH - (HER)or O2+2H2O+2e - →4OH - (ORR)

[0055] When the prepared sulfonyl disulfide copper plating accelerator is sodium polydipropane disulfide sulfonate (SPS):

[0056] anode:

[0057] Cathode: 2H2O+2e - →H2+2OH - (HER)or O2+2H2O+2e - →4OH - (ORR)

[0058] When the prepared sulfonyl disulfide copper plating accelerator is 3,3-dithiodihexane sulfonate sodium (SHS):

[0059] anode:

[0060] Cathode: 2H2O+2e - →H2+2OH - (HER)or O2+2H2O+2e - →4OH - (ORR)

[0061] When the prepared sulfonyl disulfide copper plating accelerator is sodium thiazoline disulfide propane sulfonate (SH-110):

[0062] anode:

[0063] Cathode: 2H2O+2e - →H2+2OH - (HER)or O2+2H2O+2e - →4OH - (ORR)

[0064] In this embodiment, if the sulfonyl disulfide copper plating accelerator is a sodium polydisulfide propane sulfonate copper plating accelerator, the mercapto sulfonate is sodium 3-mercaptopropane sulfonate, and the mercapto compound is 2-mercaptothiazoline; if the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodiethane sulfonate, the mercapto sulfonate is sodium 2-mercaptoethane sulfonate, and the mercapto compound is 2-mercaptothiazoline; if the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodihexane sulfonate, the mercapto sulfonate is sodium 4-mercaptobutane sulfonate, and the mercapto compound is 2-mercaptothiazoline. In this embodiment, the purity of the mercaptosulfonate is greater than or equal to 95%, and the concentration is 10-200g / L; the purity of the mercapto compound is greater than or equal to 99%, and the concentration is 10-200g / L; the concentration range of sodium hydroxide in the electrolyte is 0.1-5mol / L; the applied voltage range is 0-4.0V; and the temperature range is 5-90°C.

[0065] In some embodiments, the electronic copper plating raw material prepared by the present invention can be used in the electroplating copper process for the manufacture of chip Damascus interconnection, through silicon via (TSV), through glass via (TGV), redistribution layer (RDL), three-dimensional interconnection bumps, chip carriers, printed circuit boards (PCBs), copper foil, composite copper foil, foam copper, etc., and in the chemical copper plating process for the preparation of composite copper foil, foam copper, etc., but is not limited thereto.

[0066] The present invention will be further explained below by means of specific embodiments:

[0067] Example 1

[0068] A step of electrochemical preparation of copper sulfate-hydrogen symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper sulfate and hydrogen, a double-electrode electrolytic cell is used, and the electrolytic cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode is made of a nickel mesh electrode material loaded with a platinum-carbon catalyst as an electrode. A cationic membrane (DuPont N117) is used to separate the cathode and the anode. The anode and cathode electrolytic cells use 1 mol / L sulfuric acid as the electrolyte, and the sulfuric acid electrolyte is passed to the anode and cathode through a liquid supply system. A DC voltage of 1.5 V is applied at room temperature to achieve electrochemical preparation of copper sulfate-hydrogen symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with SO4 2- Combined to form copper sulfate, and then filtered and recrystallized to obtain ultra-high purity copper sulfate. The hydrogen ions at the cathode are reduced to hydrogen on the electrode surface, and then output together with the solution to obtain high-purity hydrogen through a water-gas separation step. The separated solution continues to be used as an electrolyte. The energy consumption of hydrogen production is reduced by 30%, and the content of each component of the copper sulfate produced is shown in Table 1 below:

[0069] Table 1 Component content of high purity copper sulfate solution

[0070]

[0071] Example 2

[0072] A step of electrochemical preparation of copper sulfate-hydrogen symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper sulfate and hydrogen, a double-electrode electrolytic cell is used, and the electrolytic cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode is made of foam nickel electrode material loaded with platinum carbon as an electrode. A cationic membrane (DuPont N115) is used to separate the cathode and the anode. The anode and cathode electrolytic cells use 1 mol / L sulfuric acid as the electrolyte, and the sulfuric acid electrolyte is passed to the anode and cathode through a liquid supply system. A DC voltage of 1.5V is applied at room temperature to achieve electrochemical preparation of copper sulfate-hydrogen symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with SO4 2- Combined to form copper sulfate, and then filtered and recrystallized to obtain ultra-high purity copper sulfate. The hydrogen ions at the cathode are reduced to hydrogen on the electrode surface, and then output together with the solution to obtain high-purity hydrogen through a water-gas separation step. The separated solution continues to be used as an electrolyte. The energy consumption of hydrogen production is reduced by 28%, and the content of each component of the copper sulfate produced is shown in Table 2 below:

[0073] Table 2 Component content of high purity copper sulfate solution

[0074]

[0075]

[0076] Example 3

[0077] A step of electrochemical preparation of copper sulfate-electricity symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper sulfate and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode uses ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode uses a nickel foam electrode material loaded with platinum carbon as an electrode. A cationic membrane (DuPont N115) is used to separate the cathode and the anode. The anode chamber uses 1 mol / L sulfuric acid as an electrolyte, and the sulfuric acid electrolyte is passed to the anode through a liquid supply system. The cathode chamber does not pass an electrolyte but only pure oxygen. The battery voltage is adjusted to 0.5V at 70°C for electrochemical preparation of copper sulfate-electricity symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with SO4 2- Combined to form copper sulfate, and then filtered and recrystallized to obtain ultra-high purity copper sulfate. The oxygen part of the cathode is converted into water after the oxygen reduction reaction. The solution is blown out of the cathode chamber by the unreacted oxygen and then separated by the water-gas separation device. The separated oxygen continues to be used as a reactant in the cathode chamber. The content of each component of the prepared copper sulfate is shown in Table 3 below:

[0078] Table 3 Component content of high purity copper sulfate solution

[0079]

[0080] Example 4

[0081] A step of electrochemical preparation of copper sulfate-electricity symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper sulfate and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode is made of foamed nickel electrode material loaded with iron-nitrogen co-doped carbon catalyst as an electrode. A cationic membrane (DuPont NR211) is used to separate the cathode and the anode. The anode chamber uses 1 mol / L sulfuric acid as the electrolyte, and the sulfuric acid electrolyte is passed to the anode through the liquid supply system. The cathode chamber does not pass the electrolyte but only pure oxygen. The battery voltage is regulated to 0.5V at 65°C for electrochemical preparation of copper sulfate-electricity symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with SO4 2-Combined to form copper sulfate, and then filtered and recrystallized to obtain ultra-high purity copper sulfate. The oxygen part of the cathode is converted into water after the oxygen reduction reaction. The solution is blown out of the cathode chamber by the unreacted oxygen and then separated by the water-gas separation device. The separated oxygen continues to be used as a reactant in the cathode chamber. The content of each component of the prepared copper sulfate is shown in Table 4 below:

[0082] Table 4 Component content of high purity copper sulfate solution

[0083]

[0084] Example 5

[0085] A step of electrochemical preparation of copper methanesulfonate-hydrogen symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper methanesulfonate and hydrogen, a double-electrode electrolytic cell is used, and the electrolytic cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode uses a nickel mesh electrode material loaded with a platinum-carbon catalyst as an electrode. A cationic membrane (DuPont NR212) is used to separate the cathode and the anode. The anode and cathode electrolytic cells use 1 mol / L methanesulfonic acid as an electrolyte, and the methanesulfonic acid electrolyte is passed to the anode and cathode through a liquid supply system. A DC voltage of 1.5 V is applied at room temperature to achieve electrochemical preparation of methanesulfonic acid-hydrogen symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with CH3SO3 - Combined to form copper methanesulfonate, and then filtered and recrystallized to obtain ultra-high purity copper methanesulfonate. The hydrogen ions at the cathode are reduced to hydrogen on the electrode surface, and after being output together with the solution, high-purity hydrogen is obtained through a water-gas separation step, and the separated solution continues to be used as an electrolyte. The energy consumption of hydrogen production is reduced by 21%, and the content of each component of the copper methanesulfonate is shown in Table 5 below:

[0086] Table 5 Component content of high-purity copper methanesulfonate solution

[0087]

[0088] Example 6

[0089] A step of electrochemical preparation of copper methanesulfonate-hydrogen symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper methanesulfonate and hydrogen, a double-electrode electrolytic cell is used, and the electrolytic cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode is made of foam nickel electrode material loaded with a platinum-carbon catalyst as an electrode. A cationic membrane (DuPont NR115) is used to separate the cathode and the anode. The anode and cathode electrolytic cells use 1 mol / L methanesulfonic acid as an electrolyte, and the methanesulfonic acid electrolyte is passed to the anode and cathode through a liquid supply system. A DC voltage of 1.5 V is applied at room temperature to achieve electrochemical preparation of methanesulfonic acid-hydrogen symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with CH3SO3 - Combined to form copper methanesulfonate, and then filtered and recrystallized to obtain ultra-high purity copper methanesulfonate. The hydrogen ions at the cathode are reduced to hydrogen on the electrode surface, and after being output together with the solution, high-purity hydrogen is obtained through a water-gas separation step, and the separated solution continues to be used as an electrolyte. The energy consumption of hydrogen production is reduced by 27%, and the content of each component of the copper methanesulfonate is shown in Table 6 below:

[0090] Table 6 Component content of high-purity copper methanesulfonate solution

[0091]

[0092] Example 7

[0093] A step of electrochemical preparation of copper sulfate-electricity symbiosis based on ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper methanesulfonate and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity copper metal (purity ≥ 99.999%) as an electrode, and the cathode is made of foam nickel electrode material loaded with platinum carbon as an electrode. A cationic membrane (DuPont N115) is used to separate the cathode and the anode. The anode chamber uses 1 mol / L methanesulfonic acid as an electrolyte, and the methanesulfonic acid electrolyte is passed to the anode through a liquid supply system. The cathode chamber does not pass electrolyte but only pure oxygen. The battery voltage is adjusted to 0.5V at 80°C for electrochemical preparation of copper sulfate-electricity symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with CH3SO3 - Combined to form copper methanesulfonate, and then filtered and recrystallized to obtain ultra-high purity copper methanesulfonate. The oxygen part of the cathode is converted into water after oxygen reduction reaction. The solution is blown out of the cathode chamber by unreacted oxygen and then separated by a water-gas separation device. The separated oxygen continues to be used as a reactant in the cathode chamber. The content of each component of the obtained copper methanesulfonate is shown in Table 7 below:

[0094] Table 7 Component content of high-purity copper methanesulfonate solution

[0095]

[0096] Example 8

[0097] A step of electrochemical preparation of copper sulfate-electricity symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of copper methanesulfonate and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode is made of ultra-high purity metallic copper (purity ≥ 99.999%) as an electrode, and the cathode is made of a foamed nickel electrode material loaded with an iron-nitrogen co-doped carbon catalyst as an electrode. A cationic membrane (DuPont NR212) is used to separate the cathode and the anode. The anode chamber uses 1 mol / L methanesulfonic acid as an electrolyte, and the methanesulfonic acid electrolyte is passed to the anode through a liquid supply system. The cathode chamber does not pass an electrolyte but only pure oxygen. The battery voltage is regulated to 0.5V at 85°C for electrochemical preparation of copper sulfate-electricity symbiosis. The metallic copper at the anode is electrochemically oxidized to generate Cu 2+ , and then with CH3SO3 - Combined to form copper methanesulfonate, and then filtered and recrystallized to obtain ultra-high purity copper methanesulfonate. The oxygen part of the cathode is converted into water after oxygen reduction reaction. The solution is blown out of the cathode chamber by unreacted oxygen and then separated by a water-gas separation device. The separated oxygen continues to be used as a reactant in the cathode chamber. The content of each component of the obtained copper methanesulfonate is shown in Table 8 below:

[0098] Table 8 Component content of high-purity copper methanesulfonate solution

[0099]

[0100] Example 9

[0101] A step of electrochemical preparation of SES-hydrogen symbiosis based on an ion membrane electrochemical method is performed. In the process of electrochemical preparation of SES and hydrogen, a double-electrode electrolyzer is used, and an anode chamber and a cathode chamber are designed in the electrolyzer. The anode uses nickel foam as an electrode, and the cathode uses a nickel mesh electrode material loaded with a platinum carbon catalyst as an electrode. An anion membrane (FAA-3-PK-130) is used to separate the cathode and the anode. The anode and cathode electrolyzers use 1 mol / L sodium hydroxide as an electrolyte, and MES is added to the anode sodium hydroxide electrolyte as an electrolyte. The MES concentration is 19.8 g / L, and the electrolyte is passed to the anode and cathode through a liquid supply system. At room temperature, a DC voltage of 1.2 V is passed to achieve SES-hydrogen symbiosis electrochemical preparation. The MES at the anode is electrochemically oxidized to generate SES, and then the SES product is obtained by filtering and recrystallization purification steps. The hydrogen ions at the cathode are reduced to hydrogen on the electrode surface, and then discharged together with the solution to obtain high-purity hydrogen through a water-gas separation step. The separated solution continues to be used as an electrolyte. The reaction is carried out at a constant voltage of 1.2V for 1 hour, and the SES product is obtained after purification. The purity of SES is 85.3% as measured by HPLC. The energy consumption of hydrogen production is reduced by 35%,

[0102] Example 10

[0103] A step of electrochemical preparation of SES-electricity symbiosis based on ion membrane electrochemical method is performed. In the process of electrochemical preparation of SES and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode uses nickel foam as an electrode, and the cathode uses a nickel foam electrode material loaded with a platinum carbon catalyst as an electrode. An anion membrane (FAB-PK-30) is used to separate the cathode and the anode. The anode uses 1 mol / L sodium hydroxide as an electrolyte, and no electrolyte is added to the cathode chamber. Only pure oxygen is passed through. MES is added to the anode sodium hydroxide electrolyte as an electrolyte. The MES concentration is 39.8g / L, and the electrolyte is passed to the anode through a liquid supply system. The battery voltage is set to 0.6V at 60°C for SES-electricity symbiosis electrochemical preparation. The MES at the anode is electrochemically oxidized to generate SES, and then the SES product is obtained through filtration and recrystallization purification steps. The oxygen in the cathode is converted into water after the oxygen reduction reaction. The solution is blown out of the cathode chamber by the unreacted oxygen and separated by the water-gas separation device. The separated oxygen continues to be used as a reactant in the cathode chamber. The reaction is carried out at a battery voltage of 0.5V for 1 hour, and the SES product is obtained after purification. The purity of SES is 75.4% measured by HPLC. The energy consumption of hydrogen production is reduced by 26%.

[0104] Embodiment 11

[0105] A step of electrochemical preparation of SPS-hydrogen symbiosis based on ion membrane electrochemical method is performed. In the process of electrochemical preparation of SPS and hydrogen, a double-electrode electrolyzer is used, and the electrolyzer is designed with an anode chamber and a cathode chamber. The anode uses nickel foam as an electrode, and the cathode uses a nickel foam electrode material loaded with a platinum carbon catalyst as an electrode. An anion membrane (FAB-PK-30) is used to separate the cathode and the anode. The anode and cathode electrolyzers use 1 mol / L sodium hydroxide as an electrolyte, and MPS is added to the anode sodium hydroxide electrolyte as an electrolyte. The MPS concentration is 39.8 g / L, and the electrolyte is passed to the anode and cathode through a liquid supply system. At room temperature, a DC voltage of 1.5 V is passed to realize the electrochemical preparation of SPS-hydrogen symbiosis. The MPS at the anode is electrochemically oxidized to generate SPS, and then the SPS product is obtained through filtration and recrystallization purification steps. The hydrogen ions at the cathode are reduced to hydrogen gas on the electrode surface, and then discharged together with the solution to obtain high-purity hydrogen gas through a water-gas separation step, and the separated solution continues to be used as an electrolyte. The reaction is carried out at a constant voltage of 1.5V for 3 hours, and the SPS product is obtained after purification. The purity of the SPS is 96.4% as measured by HPLC.

[0106] Example 12

[0107] A step of electrochemical preparation of SPS-electricity symbiosis based on ion membrane electrochemical method is performed. In the process of electrochemical preparation of SPS and external power supply, a dual-electrode fuel cell is used, and the fuel cell is designed with an anode chamber and a cathode chamber. The anode uses nickel foam as an electrode, and the cathode uses nickel foam electrode material loaded with platinum carbon catalyst as an electrode. An anion membrane (FA4-3-PK-30) is used to separate the cathode and the anode. The anode uses 5 mol / L sodium hydroxide as an electrolyte, and no electrolyte is added to the cathode chamber. Only pure oxygen is passed through. MPS is added to the anode sodium hydroxide electrolyte as an electrolyte. The MPS concentration is 39.8 g / L, and the electrolyte is passed to the anode through a liquid supply system. The battery voltage is set to 0.6 V at 85°C for SPS-electricity symbiosis electrochemical preparation. The MPS at the anode is electrochemically oxidized to generate SPS, and then the SPS product is obtained through filtration and recrystallization purification steps. The oxygen in the cathode is converted into water after the oxygen reduction reaction. The solution is blown out of the cathode chamber by the unreacted oxygen and then separated by the water-gas separation device. The separated oxygen is continued to be used as a reactant in the cathode chamber. The reaction is carried out at a battery voltage of 0.6V for 2 hours, and the SPS product is obtained after purification. The purity of the SPS is 98.9% as measured by HPLC.

[0108] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. An electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy symbiosis, It is characterized in that Includes steps: An electrolyzer / fuel cell is provided, the electrolyzer / fuel cell comprising an electrolyzer, a polymer ion membrane disposed in the middle of the electrolyzer and dividing the electrolyzer into an anode chamber and a cathode chamber, an anode electrode disposed in the anode chamber, a cathode electrode disposed in the cathode chamber, the anode electrode and the cathode electrode being connected to an external power source via an electric wire, the anode chamber being connected to a first storage tank for storing a first electrolyte, and the cathode chamber being connected to a second storage tank for storing a second electrolyte or oxygen; When an external power source is turned on, a self-generated electrochemical reduction reaction occurs in the anode chamber and the cathode chamber under the isolation of the polymer ion membrane and the action of an external voltage, wherein the anode electrode or electrolyte in the anode chamber is selectively oxidized, and then the electronic copper plating raw material is obtained through a filtration and purification step, while the electrochemical reduction reaction in the cathode chamber produces high-purity hydrogen used as fuel and electronic special gas, and realizes spontaneous power supply to the outside while producing the electronic copper plating raw material.

2. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy according to claim 1, It is characterized in that If the electronic copper plating raw material is copper sulfate, the anode electrode is metallic copper, the first electrolyte and the second electrolyte are both sulfuric acid solutions with a purity greater than or equal to 96%, the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal; and the polymer ion membrane is a cation exchange membrane.

3. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy according to claim 1, It is characterized in that If the electronic copper plating raw material is copper methanesulfonate, the anode electrode is metallic copper, the first electrolyte and the second electrolyte are both sodium hydroxide solutions with a purity greater than or equal to 98%, the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal; and the polymer ion membrane is a cation exchange membrane.

4. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy symbiosis according to claim 1, It is characterized in that If the electronic copper plating raw material is a sulfonyl disulfide copper plating accelerator, the anode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal, and the first electrolyte includes a sodium hydroxide solution, a thiol compound, and a thiol sulfonate; the second electrolyte is a sodium hydroxide solution, and the cathode electrode is a metal or alloy of nickel, platinum, palladium, gold, or a compound containing a metal; and the polymer ion membrane is an anion exchange membrane.

5. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy according to claim 4, It is characterized in that If the sulfonyl disulfide copper plating accelerator is a sodium polydisulfide propane sulfonate copper plating accelerator, the mercapto sulfonate is sodium 3-mercaptopropane sulfonate, and the mercapto compound is 2-mercaptothiazoline.

6. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy symbiosis according to claim 4, It is characterized in that If the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodiethane sulfonate, the mercapto sulfonate is sodium 2-mercaptoethane sulfonate, and the mercapto compound is 2-mercaptothiazoline.

7. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy according to claim 4, It is characterized in that If the sulfonyl disulfide copper plating accelerator is sodium 3,3-dithiodihexanesulfonate, the mercaptosulfonate is sodium 4-mercaptobutanesulfonate, and the mercapto compound is 2-mercaptothiazoline.

8. The electrochemical preparation method of electronic copper plating raw materials, hydrogen and electric energy symbiosis according to claim 4, It is characterized in that The purity of the mercaptosulfonate is greater than or equal to 95%, and the concentration is 10-200 g / L; the purity of the mercapto compound is greater than or equal to 99%, and the concentration is 10-200 g / L.

9. Application of an electronic copper plating raw material, It is characterized in that The electronic copper plating raw material prepared by any preparation method described in claims 1-8 is used in electroplating copper or chemical copper plating process.

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