A device and method for dynamically regulating metal cations in an inert anode electroplating solution based on cyclic voltammetry

Abstract

The application discloses a kind of based on cyclic voltammetry inert anode plating solution metal cation dynamic regulation device and method, belong to electroplating technical field.This device is based on the structure of anion exchange membrane (AEM) compartment, combined with cyclic voltammetry (CV) quantitative detection technology, by AEM compartment electroplating-electrolytic cell, inert anode plating system, electrolytic cation supplement system, CV concentration quantitative detection system composition.Among them, AEM realizes the selective migration of anion in electroplating chamber and electrolysis chamber, metal cation barrier, CV concentration quantitative detection system establishes the linear correlation between metal cation concentration and reduction peak current to realize the accurate quantification of plating solution ion concentration, electrolytic cation supplement system through controllable dissolution of soluble metal anode synchronously supplements the cation consumed by electroplating.The application solves the problems of continuous attenuation of cation concentration, large pH fluctuation of plating solution, poor plating layer quality and short service life of plating solution in inert anode plating through the synergistic effect of AEM compartment isolation, CV quantitative detection and electrolytic synchronous supplement, realizes the dynamic balance and accurate regulation of metal cation concentration in plating solution, improves the surface quality, mechanical properties and corrosion resistance of plating layer, prolongs the service life of plating solution, and is suitable for industrial production of inert anode plating system such as watt nickel.

Description

Technical Field

[0001] This invention belongs to the field of electroplating technology, specifically relating to a device and method for dynamic control of metal cations in inert anodic electroplating solutions based on cyclic voltammetry, applicable to Ni in inert anodic electroplating systems such as Watt's nickel plating. 2+ It enables quantitative detection and dynamic, precise replenishment of metal cation concentrations, making it particularly suitable for precision electroplating industrial production where stringent requirements exist for coating quality and plating solution stability. Background Technology

[0002] Nickel electroplating (such as Watt's nickel plating) is one of the most widely used electroplating processes in industry. The plating layer possesses excellent corrosion resistance, wear resistance, and adhesion, and is widely used for surface protection of metal substrates. During the electroplating process, the plating solution contains metal cations (such as Ni...) 2+ The concentration stability of cations is the core factor determining the quality of the plating solution. Traditional electroplating processes mainly use soluble metal anodes to replenish cations, but this has significant drawbacks: the dissolution rate of soluble anodes is affected by factors such as current density, temperature, and pH value, and problems such as dissolution that is too fast and produces metal sludge, or dissolution that is too slow and leads to insufficient cation replenishment are likely to occur. In addition, non-uniform dissolution of the anode will change the inter-electrode gap, resulting in uneven electric field distribution and affecting the consistency of the plating thickness. At the same time, the continuous consumption of soluble anodes requires frequent replacement, increasing production costs and downtime. The dissolution process also introduces impurities, reducing the purity of the plating solution.

[0003] Inert anodes (such as platinum-plated titanium foil PTTA) are the preferred anodes for high-precision electroplating due to their advantages such as good chemical stability, no surface deformation, and no sludge generation. They can maintain a uniform inter-electrode electric field, significantly improving the precision of the coating, and do not require frequent replacement, reducing production and maintenance costs. However, inert anodes cannot replenish the metal cations in the plating solution by dissolving them, and Ni... 2+ Continuous reduction deposition at the cathode leads to a rapid decline in the cation concentration of the plating bath, while the inert anode only undergoes the oxygen evolution reaction, generating a large amount of H₂. + This causes a sharp drop in the pH value of the plating solution, disrupting the boric acid pH buffer system and producing Ni(OH)2 precipitate that embeds into the coating, forming defects such as pinholes and pits. In addition, the decay of cation concentration and pH fluctuations lead to a decrease in cathodic polarization, coarsening of coating crystal particles, and a significant reduction in mechanical properties and corrosion resistance.

[0004] Traditional methods for addressing insufficient cations in inert anode electroplating involve the intermittent addition of metal salts. However, this approach struggles to precisely match the real-time cation consumption rate, resulting in fluctuations in plating solution concentration of ±15%. Furthermore, manual operation introduces impurities, and frequent shutdowns for replenishment reduce production efficiency. Some existing ion replenishment technologies utilize mixed active / inert anodes, but these are prone to generating metal sludge that clogs the equipment and cannot achieve precise quantitative and dynamic cation replenishment. Simultaneously, current methods for detecting ion concentration in plating solutions lack rapid and accurate quantitative means, making it difficult to provide real-time feedback on ion concentration changes and thus hindering precise control of cation replenishment.

[0005] To address issues such as cation concentration decay, pH fluctuations, inaccurate concentration detection, and uncontrollable replenishment in inert anode electroplating, there is an urgent need to develop a precise cation control technology that combines quantitative cyclic voltammetry detection with simultaneous electrolytic replenishment. This technology utilizes anion exchange membranes to achieve compartmentalized isolation between electroplating and electrolysis, establishes a quantitative ion concentration detection model using cyclic voltammetry, and enables real-time quantitative monitoring and precise electrolytic replenishment of cations. This maintains the ion balance and pH stability of the plating solution, improves coating quality, and extends the service life of the plating solution. Summary of the Invention

[0006] The purpose of this invention is to provide a device and method for dynamic control of metal cations in inert anode electroplating solutions based on cyclic voltammetry. This invention addresses problems in existing inert anode electroplating systems, such as continuous decay of metal cation concentration, large pH fluctuations in the plating solution, lack of accurate ion concentration detection methods, uncontrollable cation replenishment, and poor coating quality. Through the synergistic effect of compartmentalized anion exchange membrane (AEM), quantitative detection by cyclic voltammetry (CV), and synchronous electrolytic replenishment, the invention achieves real-time quantitative monitoring and dynamic precise replenishment of metal cations in the plating solution. This maintains the ion balance and pH stability of the plating solution, improves the surface quality, mechanical properties, and corrosion resistance of the coating, extends the service life of the plating solution, and provides technical support for the industrial optimization of inert anode electroplating systems.

[0007] A device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry, comprising the following steps:

[0008] S1: The device of this invention consists of five core parts: AEM compartment electroplating-electrolysis cell, inert anode electroplating system, electrolytic cation replenishment system, cyclic voltammetry (CV) concentration quantitative detection system, and plating solution control system;

[0009] S1-1: The AEM compartmentalized electroplating-electrolysis tank uses a gel polystyrene anion exchange membrane (AEM) containing quaternary amine groups to seal and divide the tank into an electroplating chamber and an electrolysis chamber, with an electrode spacing of 30 mm between the two chambers; the AEM relies on the Donnan repulsion mechanism to achieve Ni 2+ With a metal cation rejection rate of ≥99.9%, only Cl is allowed. -SO4 2- The free migration of anions provides a stable current path for the two chambers, while also achieving physical isolation between the electroplating and electrolysis processes, thus preventing electrolysis byproducts from contaminating the electroplating solution.

[0010] S1-2: The inert anode electroplating system uses platinum-titanium (PTTA) sheets as the inert anode and pre-treated pure copper substrate as the cathode, evenly distributed in the electroplating chamber and connected to the positive and negative terminals of the electroplating power supply respectively; the electroplating current density is controlled at 2.5 A / dm³. 2 Watt's nickel plating solution is added to the electroplating chamber to achieve nickel plating electrodeposition on pure copper substrate. The inert anode has no dissolution loss and maintains the long-term stability of the inter-electrode electric field.

[0011] S1-3: The electrolytic cation replenishment system uses pure nickel sheets as the soluble metal anode and graphite electrodes as the inert cathode, evenly distributed within the electrolysis chamber and connected to the positive and negative terminals of the electrolysis power supply, respectively. A 38 g / L KCl solution is added to the electrolysis chamber as the electrolyte, and the electrolysis current density is adjusted to 1.2 A / dm³. 2 Pure nickel sheets undergo an oxidation-dissolution reaction to produce Ni. 2+ Charge balance is achieved through anion migration in the AEM, simultaneously replenishing the Ni consumed in the electroplating chamber. 2+ Furthermore, only hydrogen evolution reaction occurs in the graphite cathode, with no metal ion deposition, and the electrolysis current efficiency is ≥95%.

[0012] S1-4: The cyclic voltammetry (CV) concentration quantitative detection system is the core quantitative detection module, employing a standard three-electrode system: a glassy carbon electrode as the working electrode, a saturated calomel electrode as the reference electrode, and a platinum sheet as the counter electrode; the scan range is set to -2.0V to -1.0V, the scan rate is 100mV / s, and Ni is extracted from -1.6V to -1.4V. 2+ Reduction peak current; by preparing multiple sets of Watt's nickel standard solutions with different dilution ratios, the reduction peak current was measured and linearly fitted to construct a linear fitting model between cation concentration (C) and reduction peak current (Ip), thus realizing the Ni plating solution... 2+ Rapid and accurate quantification of concentration;

[0013] S1-5: The plating solution control system includes an air agitator, a temperature control module, and a pH monitoring module. The air agitator is installed in the plating chamber to achieve uniform mixing of the plating solution, alleviate concentration polarization, remove hydrogen evolution bubbles on the cathode surface, and avoid pinhole defects in the plating layer. The temperature control module precisely maintains the plating solution temperature at 45-50℃. The pH monitoring module monitors the pH value of the plating solution in real time, and offsets 50% of the H+ ions through the pure nickel dissolution reaction of the electrolytic cation replenishment system. + The amount of product generated is adjusted to maintain the pH value within the process range of 3.8-4.5.

[0014] S2: Add 600ml of deionized water to a beaker, heat in a water bath to 50-60℃, slowly add 260g / L NiSO4·6H2O, and mechanically stir until completely dissolved; add 40g / L NiCl2·6H2O, and continue stirring until clear; dissolve 40g / L H3BO3 separately in 200ml of 80℃ hot water, and slowly pour it into the main solution after complete dissolution; add deionized water to make up to 1L, stir continuously for 10min, filter through a 5μm filter, add 5g / L sodium saccharin as a brightener, and adjust the pH to 3.8-4.5. Rinse with deionized water → chemically degrease with alkaline solution at 60-70℃ for 10-15min → rinse with deionized water → pickle with 10% hydrochloric acid → rinse with deionized water, ensuring that the substrate surface is free of oil, oxides, and impurities, and dry for later use. Prepare a 38g / L KCl aqueous solution and add it to the electrolysis chamber to ensure conductivity and compatibility for anion migration;

[0015] S3: Construction of a quantitative detection model for CV concentration. Using the prepared Watt's nickel plating solution as the stock solution, at least 10 sets of standard solutions with different dilution ratios were prepared, and the dilution ratio and Ni were recorded for each set. 2+ Theoretical concentration; using a three-electrode system of a CV concentration quantitative detection system, three CV scans were performed on each standard solution to measure the reduction peak current, and the average value was taken as the peak current value corresponding to that concentration; with Ni 2+ A linear fit was performed with concentration on the x-axis and reduction peak current on the y-axis to obtain the fitting equation Ip=aC+b. The required correlation coefficient R² ≥ 0.98 was specified. This model can infer Ni from the reduction peak current of the unknown plating solution. 2+ Concentration, enabling quantitative detection;

[0016] S4: Turn on the air agitator and temperature control module of the plating solution control system to maintain the plating solution temperature at 45-50℃ and ensure uniform mixing of the plating solution; clamp the pretreated pure copper substrate onto the cathode of the plating chamber, ensuring good contact with the negative terminal of the power supply; turn on the inert anode plating system and adjust the plating current density to 2.5A / dm³. 2 Nickel plating electrodeposition begins; simultaneously, the electrolytic cation replenishment system is activated, and the initial electrolytic current density is adjusted to 1.2 A / dm³. 2 Pure nickel sheet dissolves to form Ni 2+ To replenish cations in the electroplating chamber;

[0017] S5: A CV concentration quantitative detection system is used to perform Ni concentration analysis on the plating bath every 2 hours. 2+ Quantitative concentration detection, calculating real-time concentration based on a fitted model;

[0018] S6: Dynamically adjust the current density of the electrolytic power supply; when Ni is detected... 2+When the concentration decreases, appropriately increasing the electrolytic current density accelerates the dissolution rate of the pure nickel sheet, achieving precise replenishment of cations and ensuring that the Ni concentration remains stable during the 10-hour electroplating process. 2+ Consumption rate should be controlled below 22.7%;

[0019] S7: Monitors the pH value of the electroplating solution throughout the process, and counteracts H+ through the dissolution reaction of the electrolysis system. + Maintain the pH value at 3.8-4.5 to avoid the formation of Ni(OH)2 precipitate;

[0020] The inert anode electroplating solution metal cation dynamic control device based on cyclic voltammetry used in the above method includes: 1-AEM compartment electroplating-electrolytic cell, 2-Anion exchange membrane (AEM), 3-Electroplating power supply, 4-Pure nickel soluble anode, 5-Pure copper cathode substrate, 6-Electroplating chamber, 7-Platinum-plated titanium inert anode, 8-pH monitoring module, 9-CV concentration quantitative detection system, 10-Air stirrer, 11-Temperature control module electrolytic power supply, 12-Graphite cathode, 13-Electrolytic chamber, 14-Electrolytic power supply, 901-Saturated calomel reference electrode, 902-Working electrode, 903-Electrolytic cell, 904-Platinum sheet counter electrode, 905-Electrochemical workstation;

[0021] The entire device is based on an AEM compartment electroplating-electrolysis tank, employing a modular construction approach. Each functional module is independently deployed yet interconnected and controlled. The integrated electroplating and electrolysis chambers are sealed and separated by anion exchange membranes. The electrode spacing between the two chambers is precisely calibrated to ensure uniform electric field distribution and ion migration efficiency. The tank sidewalls are pre-installed with sampling ports and pipeline interfaces to accommodate the process requirements of plating solution circulation, concentration detection, and parameter monitoring. Temperature control and pH monitoring sensors are installed on the outside of the AEM compartment electroplating-electrolysis tank. These sensors penetrate to a preset depth in the plating solution and are treated with anti-deposition insulation to prevent plating layer adhesion from affecting detection accuracy, ensuring real-time and accurate monitoring of plating solution temperature and pH. An air agitator is installed inside the electroplating chamber to efficiently remove hydrogen bubbles from the cathode surface.

[0022] The CV concentration quantitative detection system is the core detection component of this device, and its specific structure and functions are as follows: 1. Three-electrode connection mechanism: The saturated calomel reference electrode 901, working electrode 902, and platinum sheet counter electrode 903 are fixed to the detection bracket by a special electrode clamp. The electrode clamp is insulated and anti-slip, which can precisely adjust the depth and spacing of the electrodes inserted into the plating solution. The front end of the working electrode is mirror polished to ensure the stability of the detection signal. The wires of the three electrodes are all wrapped with shielded wires and connected to an external electrochemical workstation to effectively avoid the deviation of detection data caused by electromagnetic interference. 2. Concentration Quantitative Detection Mechanism: The detection bracket can be flexibly moved to the sampling port of the electroplating room for direct in-situ detection of the electroplating solution without the need for additional sampling and transfer, thus reducing detection errors; the electrochemical workstation has preset scanning parameters and can automatically complete cyclic voltammetry scanning, reduction peak current extraction and data recording. Through a pre-constructed cation concentration-reduction peak current linear fitting model, it can realize rapid quantitative calculation of the cation concentration of the plating solution. The detection data can be transmitted to the electrolysis power supply control terminal in real time, providing data support for dynamic adjustment of current density; 3. Expandable and Optimizable Design: By replacing the working electrode to adapt to different metal cations and optimizing the cyclic voltammetric scanning parameters (scanning range, scan rate), it is possible to achieve accurate quantitative detection of multiple metal cations such as nickel, copper, and tin, adapting to the detection needs of different inert anode electroplating systems; at the same time, multi-channel detection probes can be added to realize the synchronous detection of plating solution concentration at different locations in the electroplating chamber, accurately reflecting the concentration distribution of the plating solution, and further improving the accuracy of cation replenishment; 4. Expandable and Optimizable Design: By designing auxiliary contoured anodes with different internal flow channel structures and installing different types of friction pairs on the anode surface, it is possible to achieve coordinated control of the flow field, mass transfer field, electric field and friction external force field, thereby effectively improving processing quality and efficiency.

[0023] Beneficial effects: The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry provided by this invention have the following core advantages compared with the prior art: 1. Precise quantification and dynamic replenishment of cations: A linear fitting model of metal cation concentration and reduction peak current was constructed based on cyclic voltammetry, with a correlation coefficient ≥0.98, enabling rapid and precise quantitative detection of ion concentration in the plating bath. Combined with dynamic current control of the electrolytic cation replenishment system, precise matching of cation consumption and replenishment was achieved, enabling Ni electroplating in 10 hours... 2+ With a consumption rate of only 22.7%, it fundamentally alleviates the problem of cation concentration decay in inert anode electroplating; 2. Maintaining long-term stability of the plating solution: Utilizing the Donnan repulsion mechanism of AEM to achieve a metal cation rejection rate of ≥99.9%, while simultaneously offsetting 50% of H+ ions through the dissolution reaction of the soluble metal anode via electrolysis. + The amount generated effectively suppresses drastic fluctuations in the pH value of the plating solution, avoids the formation of Ni(OH)2 precipitate, extends the service life of the plating solution, and reduces the cost of plating solution replacement and maintenance. 3. Significantly improves overall coating quality: Through the synergistic effect of AEM compartmentalization, simultaneous electrolysis replenishment, and bath agitation control, electroplating kinetics are optimized, resulting in a smooth and dense coating surface with a roughness Ra≤0.124μm and grain refinement to 9.56nm. The coating exhibits excellent microhardness stability, maintaining a high corrosion potential and low corrosion current even after immersion in 3.5% NaCl solution for 7 days, and the charge transfer resistance is increased to 10489Ω·cm. 2 Its corrosion resistance is significantly better than that of traditional processes; 4. Overcoming the inherent defects of traditional processes: Abandoning the uncontrollable dissolution of traditional soluble anodes and the crude method of manual intermittent replenishment, achieving precise ion control in inert anode electroplating; the AEM compartment structure avoids electrolysis byproducts from contaminating the electroplating solution, air agitation alleviates concentration polarization, removes hydrogen evolution bubbles, eliminates defects such as pinholes and pits in the plating layer, and improves the precision and consistency of the plating layer. 5. High adaptability and easy industrialization: The device has a simple structure, and each module can be flexibly adapted to different inert anode electroplating systems. Different cations can be controlled simply by replacing the soluble anode and optimizing the CV detection parameters. CV quantitative detection and electrolysis current control can be automated and linked without manual intervention, resulting in high production efficiency and suitability for large-scale precision electroplating production in the industrial sector. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the overall structure of the inert anodic electroplating solution metal cation dynamic control device based on cyclic voltammetry of the present invention.

[0025] Figure 2 This is a schematic diagram of the three-electrode cyclic voltammetry test results of the electrochemical workstation of this invention;

[0026] In the diagram, 1-AEM compartment electroplating-electrolysis cell, 2-Anion exchange membrane (AEM), 3-Electroplating power supply, 4-Pure nickel soluble anode, 5-Pure copper cathode substrate, 6-Electroplating chamber, 7-Platinum-plated titanium inert anode, 8-pH monitoring module, 9-CV concentration quantitative detection system, 10-Air stirrer, 11-Temperature control module electrolysis power supply, 12-Graphite cathode, 13-Electrolysis chamber, 14-Electrolysis power supply, 901-Saturated calomel reference electrode, 902-Working electrode, 903-Electrolysis cell, 904-Platinum sheet counter electrode, 905-Electrochemical workstation. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. The present invention uses Watt's nickel inert anode electroplating of Ni 2+ Taking precise control as an example, it is not limited to the specific parameters described in this embodiment. It can be flexibly adjusted according to different electroplating systems and is applicable to the control of metal cations in various inert anode electroplating processes.

[0028] This embodiment uses the above-described apparatus and method to achieve Ni plating in Watt's nickel inert anode electroplating on a pure copper substrate. 2+ Precise quantitative detection and simultaneous replenishment were used to compare the coating quality and plating solution stability of the traditional single inert anode electroplating process (control group) with the controlled process of this invention (experimental group):

[0029] The first step involves device setup and parameter setting, constructing an AEM compartmentalized electroplating-electrolysis cell. The electrode spacing between the electroplating and electrolysis chambers is 30 mm. The AEM is a gel polystyrene film, and Ni... 2+ Retention rate 99.9%; the inert anodic electroplating system uses a 25mm×24mm×1mm platinum-plated titanium sheet as the anode and a 25mm×24mm×1mm pure copper sheet as the cathode, with an electroplating current density of 2.5A / dm³. 2 The electrolytic cation replenishment system uses a 50mm×25mm×1mm pure nickel sheet as the anode and a 50mm×25mm×1mm graphite sheet as the cathode, with an initial electrolytic current density of 1.2A / dm³. 2 The CV concentration quantitative detection system has a scanning range of -2.0V to -1.0V and a scanning rate of 100mV / s; the plating solution control system maintains the electroplating solution temperature at 45-50℃, and the air agitator operates continuously.

[0030] The second step is the preparation of the plating solution. The Watt's nickel plating solution for the electroplating chamber consists of: NiSO4·6H2O 260g / L, NiCl2·6H2O 40g / L, H3BO3 40g / L, sodium saccharin 5g / L, pH=9.5; the electrolyte for the electrolysis chamber is: 38g / L KCl solution, pH=7.0.

[0031] The third step involves constructing a quantitative detection model for CV concentration. Ten groups of Watt's nickel standard solutions with different dilution ratios were prepared, and the Ni concentration in each group was measured. 2+ The peak current was restored, and a linear fitting was performed to obtain the fitting equation: Ip=7.8C+4.28, with a fitting correlation coefficient R2=0.9822, which meets the requirements for quantitative detection.

[0032] The fourth step is simultaneous electroplating with Ni. 2+ Precise replenishment, start the electroplating and electrolysis systems, run synchronously for 10 hours, and check the Ni in the electroplating chamber every 2 hours using the CV system. 2+ Concentration was dynamically adjusted by regulating the electrolytic current density; the control group only had the inert anode electroplating system turned on, with no additional electrolysis.

[0033] The fifth step is post-plating treatment. After electroplating, the workpiece is ultrasonically cleaned with deionized water for 5 minutes and dried with hot air at 80°C to obtain a nickel plating layer.

[0034] Finally, performance testing and result comparison were conducted on the plating solution stability, coating surface morphology, mechanical properties, and corrosion resistance of the experimental and control groups. The results are as follows: Plating solution stability: After 10 hours of electroplating, the Ni in the experimental group... 2+ The consumption rate was only 22.7%, the concentration remained at 77.3% of the initial value, and the pH value remained stable at 3.8-4.5; the control group Ni 2+ The concentration decreased significantly, the pH value dropped below 3.0, and a large amount of Ni(OH)2 precipitate was produced. Surface morphology: The experimental group coating had a smooth and dense surface, Ra = 0.124 μm, with no pinholes or pits, and Ni purity ≥ 98%. The control group coating was rough, Ra = 0.224 μm, with numerous pinholes and pits, and Ni purity dropped below 94%. Mechanical properties: The experimental group coating had an average grain size of 9.56 nm and excellent microhardness stability with no significant decrease. The control group coating had grains coarsened to 13.22 nm, and the microhardness decreased significantly with electroplating time. Corrosion resistance: After immersion in 3.5% NaCl solution for 7 days, the experimental group coating had a corrosion potential Ecorr = -0.458 V and a corrosion current density Icorr = 2.34 μA / cm². 2 Charge transfer resistance Rct = 10489 Ω·cm 2 The corrosion potential of the control group coating was Ecorr = -0.527V, and the corrosion current density was Icorr = 703μA / cm². 2 Rct is only 3640 Ω·cm 2 The corrosion resistance of the experimental group was significantly improved.

[0035] It should be noted in the description of this invention that the above embodiments use Watt's nickel inert anode electroplating of Ni 2+ The adjustment mentioned above does not constitute a limitation on the scope of application of this invention. This invention can be flexibly adapted to various inert anode electroplating systems: the electroplating system can be adapted to inert anode electroplating of other metals such as copper, tin, and chromium, only requiring replacement of the soluble metal anode and the ion characteristic peaks detected by CV, and reconstruction of the concentration-reduction peak current fitting model; the electroplating substrate can be adapted to various metal substrates such as steel, aluminum, and magnesium, only requiring adjustment of the substrate pretreatment process to adapt to the surface characteristics of the substrate; process parameters such as electroplating / electrolysis current density, plating solution temperature, and pH value can be flexibly adjusted according to the needs of different electroplating processes, and the scanning range and rate of CV detection can be optimized according to the reduction characteristics of different cations; industrial expansion can automatically link the CV concentration quantitative detection system with the electrolysis power supply to achieve real-time online detection of ion concentration and automatic control of electrolysis current without manual intervention, adapting to large-scale industrial production. The above adjustments are all within the scope of the technical concept of this invention and do not change the core design of AEM compartment isolation, CV quantitative detection, and synchronous electrolysis supplementation, aiming to reflect the adaptability, flexibility, and industrial application value of this invention.

Claims

1. A device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry, characterized in that, The process includes the following steps: Constructing a compartmentalized electroplating-electrolysis tank divided into an electroplating chamber and an electrolysis chamber by an anion exchange membrane (AEM); adding a plating solution such as Watt's nickel to the electroplating chamber and an electrolyte solution containing the same anions as the plating solution to the electrolysis chamber; pre-treating the electroplating substrate by degreasing, pickling, and cleaning, then clamping it at the cathode end of the electroplating chamber and arranging an inert anode at the anode end of the electroplating chamber to form an inert anode electroplating system and connecting it to the electroplating power supply; arranging a soluble metal anode matching the cations to be replenished at the anode end of the electrolysis chamber and a graphite cathode at the cathode end to form an electrolytic cation replenishment system and connecting it to the electrolysis power supply; using cyclic voltammetry (CV) to determine the reduction peak current of standard electroplating solutions of different concentrations, constructing a linear fitting model of cation concentration-reduction peak current, and establishing a CV concentration quantitative detection system; simultaneously activating the electroplating system and the electrolytic cation replenishment system, and using the CV concentration quantitative detection system to monitor the cation concentration of the plating solution in the electroplating chamber in real time, adjusting the current density of the electrolysis power supply to achieve precise cation replenishment. According to claim 1, a triboelectric-electrolysis assisted jet electrodeposition apparatus and method for small-diameter blind hole parts is characterized in that the pretreatment step of the inner cavity of the small hole includes: using a flap wheel grinding head to grind and polish the inner cavity of the small hole in sequence from small mesh to large mesh, cleaning and then removing oil with alkaline washing solution, then cleaning with acetone, alcohol and deionized water in sequence, and finally drying for later use.

2. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 1, characterized in that, The electroplating substrate is a pure copper substrate. The pretreatment steps are: deionized water rinsing → chemical degreasing with alkaline solution at 60-70℃ for 10-15 minutes → deionized water rinsing → pickling with 10% hydrochloric acid → deionized water rinsing, to ensure that the substrate surface is free of oil, oxides and impurities. According to claim 3, a triboelectric-electrolysis assisted jet electrodeposition apparatus and method for small-diameter blind hole parts is characterized in that the anode frame device adapts to the electrodeposition processing of anodes of different materials by replacing the contoured auxiliary anode; at the same time, by designing different internal flow channel structures of the auxiliary contoured anode and installing different forms of friction pairs on its surface, the flow field, mass transfer field, electric field and friction external force field are coordinated and controlled to improve processing quality and efficiency.

3. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 1, characterized in that, The device mainly includes: an AEM compartment electroplating-electrolysis cell, an inert anode electroplating system, an electrolytic cation replenishment system, and a cyclic voltammetry (CV) concentration quantitative detection system; wherein: the anion exchange membrane of the AEM compartment electroplating-electrolysis cell is a gel polystyrene membrane containing quaternary amine groups, allowing only Cl-... - SO4 2- Anions migrate freely, affecting Ni 2+ The rejection rate of metal cations is ≥99.9%; the inert anode of the inert anode electroplating system is a platinum-plated titanium sheet (PTTA), and the electroplating current density is controlled at 2.5 A / dm³. 2 The electroplating solution temperature was maintained at 45-50℃, and the pH value was controlled at 3.8-4.

5. The soluble metal anode of the electrolytic cation replenishment system was a pure nickel sheet, and the cathode was a graphite electrode. The electrolytic current density was adjusted to 1.2 A / dm³. 2 The current efficiency is ≥95%; the CV concentration quantitative detection system uses a glassy carbon electrode as the working electrode, a saturated calomel electrode as the reference electrode, and a platinum sheet as the counter electrode. The scanning range is -2.0V to -1.0V, the scanning rate is 100mV / s, and it extracts Ni from -1.6V to -1.4V. 2+ The peak current is restored; the plating solution control system is equipped with an air stirrer and a temperature control module to achieve uniform mixing of the plating solution, mitigation of concentration polarization, and temperature stability.

4. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 3, characterized in that, The CV concentration quantitative detection system prepares at least 10 groups of Watt's nickel standard solutions with different dilution factors, measures the reduction peak current of each group, and performs linear fitting to obtain a linear fitting equation between cation concentration (C) and reduction peak current (Ip), with a fitting correlation coefficient R. 2 ≥0.

98. This equation allows for the inverse calculation of cation concentration from the reduction peak current of an unknown plating solution, enabling quantitative detection.

5. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claims 3 and 4, characterized in that, The electrode spacing between the electroplating chamber and the electrolysis chamber of the AEM compartment electroplating-electrolysis tank is 30 mm. The electrolyte solution in the electrolysis chamber is a 38 g / L KCl solution. The Watt nickel plating solution in the electroplating chamber consists of: NiSO4·6H2O 260 g / L, NiCl2·6H2O 40 g / L, H3BO3 40 g / L, and sodium saccharin 5 g / L. When preparing the plating solution, nickel sulfate and nickel chloride are first dissolved in deionized water at 50-60℃, and boric acid is dissolved separately in hot water at 80℃ and then added to the main solution. After making up the volume, the solution is filtered through a 5 μm filter.

6. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 3, characterized in that, The soluble pure nickel anode dissolution reaction of the electrolytic cation replenishment system can offset 50% of the hydrogen ion generation in the inert anode electroplating system, effectively suppressing the rapid drop in pH value of the plating solution and avoiding Ni(OH)2 precipitation and pinhole defects in the plating layer due to pH fluctuations.

7. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 1, characterized in that, During the simultaneous electroplating and electrolysis process, the Ni concentration in the electroplating chamber is monitored in real time using a CV concentration quantitative detection system. 2+ When the concentration begins to decrease, the current density of the electrolytic power supply is dynamically increased to maintain the Ni concentration in the plating solution during the 10-hour electroplating process. 2 + The consumption rate was only 22.7%, and the cation concentration was maintained at more than 77% of the initial concentration.

8. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry according to claim 3, characterized in that, The air agitator of the plating solution control system can remove hydrogen bubbles on the cathode surface, alleviate concentration polarization, improve current efficiency, and at the same time ensure the uniform distribution of cations and additives in the plating solution, avoiding coating thickness deviations caused by uneven local concentrations.

9. The device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry as described in claim 1, characterized in that, The post-treatment steps for the workpiece after electroplating are as follows: ultrasonic cleaning with deionized water for 5 minutes → hot air drying at 80℃. The resulting nickel plating layer has a surface roughness Ra≤0.124μm, improved Vickers hardness stability compared to traditional single electroplating processes, and a charge transfer resistance Rct≥10489Ω·cm. 2 It retains excellent corrosion resistance even after being immersed in a 3.5% NaCl solution for 7 days.

10. A device and method for dynamic control of metal cations in inert anodic electroplating solution based on cyclic voltammetry, as described in claims 1-9, characterized in that, The following methods can be used to dynamically control the cations in inert anodic plating solutions and improve the coating quality: The Donnan repulsion mechanism of AEM is used to achieve efficient retention of metal cations, ensuring stable ion concentration in the electroplating chamber. At the same time, current pathways are formed through anion migration, enabling independent operation of electroplating and electrolysis in separate chambers. A linear fitting model of cation concentration and reduction peak current was constructed based on cyclic voltammetry to achieve rapid and accurate quantitative detection of ion concentration in the plating solution, providing data support for cation replenishment. The soluble metal anode of the electrolytic cation replenishment system can be controlled to dissolve, enabling synchronous and efficient replenishment of cations consumed in electroplating. The electrolytic current efficiency is ≥95%, maintaining the dynamic balance of cations in the plating solution. By using an electrolytic dissolution reaction, some of the hydrogen ions generated during the electroplating process are counteracted, drastic fluctuations in the pH value of the plating solution are suppressed, Ni(OH)2 precipitation and plating defects are avoided, and the service life of the plating solution is extended. The plating bath control system, which combines air agitation and temperature control, alleviates concentration polarization, removes hydrogen evolution bubbles, optimizes electroplating kinetics, and improves the density, uniformity, and mechanical properties of the coating.

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