Electrolysis process based on high-entropy electrolyte and application of electrolysis process

Abstract

The invention discloses an electrolysis process based on a high-entropy electrolyte and application of the electrolysis process, and belongs to the technical field of electrolytic metallurgy, an electrolyte metal salt ion source comprises Zn < 2 + >, Mn < 2 + > and Cu < 2 + >, an electrolyte anion source comprises Cl <->, NO3 <->, SO4 < 2-> and OTf <-> / TFSI <->, and the specific proportion is adjusted according to electrolyzed substances. Compared with a traditional electrolyte, the electrolyte has the advantages that dendritic crystals can be inhibited through anion synergism, the efficiency is improved to 95% or above, the metal deposition uniformity is improved, dendritic crystal growth is inhibited, the current efficiency is improved, the hydrogen evolution side reaction is reduced by 50%-60%, the current efficiency reaches 92% or above, an ethylene glycol-water mixed solvent is adopted for cyclic utilization, the consumption of an organic solvent is reduced, and compared with a traditional lead anode, the time is only 500 hours, and the cost is reduced. And the service life of the anode is prolonged to 2000 hours, the operation and maintenance frequency is reduced, the deposition sequence is regulated and controlled by regulating and controlling the proportion of anions such as Cl <-> / NO3 <->, and different alloy requirements are met.

Description

Technical Field

[0001] This invention relates to the field of electrolytic metallurgy, specifically to an electrolysis process based on a high-entropy electrolyte and its application. Background Technology

[0002] With the widespread application of electrochemical processes in metal extraction, electroplating, and energy storage, the electrolyte, as a key medium in electrochemical reactions, has a decisive influence on the efficiency of the electrolysis process and the quality of the products. In traditional electrolysis processes, the electrolyte typically uses a single or simply combined ionic system, which has many limitations in practical applications.

[0003] In the field of metal electrolysis, especially in the wet electrolysis of metals such as zinc, manganese, and copper, the composition of the electrolyte has a significant impact on the morphology, density, and purity of the metal deposition. Traditional zinc electrolysis processes primarily use zinc sulfate solution as the electrolyte. While the process is mature, it is prone to dendritic deposition at high current densities, affecting product quality. Recent studies have shown that the synergistic effect of multiple ions can significantly improve ion transport and interfacial reaction kinetics during electrolysis, thereby increasing electrolysis efficiency and product quality.

[0004] CN118336147A discloses a high-entropy electrolyte for improving the energy density and stability of zinc-ion batteries. This electrolyte adds multiple cations and anions to a basic zinc salt to form a wide-temperature, high-entropy electrolyte system. This electrolyte system with the synergistic effect of multiple ions provides a new approach to electrolysis processes. However, this patent mainly focuses on zinc-ion battery applications and does not involve specific implementation schemes for industrial electrolysis processes.

[0005] Regarding process control in electrolysis, CN114457352B discloses an apparatus and method for hydrogen production through stepwise water electrolysis using an acidic electrolyte. This method controls the amount of Mn during the electrolysis process. 2+ The redox reaction enabled the stepwise production of hydrogen and oxygen. This stepwise electrolysis approach offers important insights for improving electrolysis efficiency and product purity, but it does not address the synergistic mechanism of the multi-electrode ion system.

[0006] High-entropy electrolytes, as a novel electrolyte system, have attracted widespread attention in the field of electrochemistry in recent years. CN118782934A and CN118919313A disclose high-entropy electrolytes for zinc-ion batteries, which significantly improve the low-temperature performance and cycle stability of the batteries by introducing various anions, cations, and organic additives. These studies demonstrate that high-entropy electrolytes can effectively suppress metal dendrite growth and extend the lifespan of electrochemical devices by electrostatic shielding or regulating the metal ion solvation layer.

[0007] Regarding electrode materials, CN111058076B discloses a method for synthesizing porous spherical structures on the surface of a Zr-based high-entropy alloy. This method forms microstructures with specific morphologies on the surface of the high-entropy alloy by controlling selective dissolution and anodic oxidation processes. This electrode surface treatment technology is of great significance for improving the electrochemical activity and stability of electrodes; however, this method mainly focuses on material preparation and does not involve the systematic optimization of the electrolysis process.

[0008] In summary, the existing technologies mainly suffer from the following problems: (1) In traditional electrolysis processes, metal ion deposition is uneven, easily forming dendrites, which affects product quality and current efficiency; (2) The hydrogen evolution side reaction is serious, which not only reduces current efficiency but may also bring safety hazards; (3) The electrolyte composition structure is simple, and the control space is limited, making it difficult to adapt to the electrolysis requirements under complex load conditions; (4) The electrode plate has a short cycle life and needs to be replaced frequently, increasing operation and maintenance costs. These problems seriously restrict the efficiency improvement and application expansion of electrolysis processes.

[0009] Therefore, there is an urgent need to develop an electrolysis process based on high-entropy electrolytes. By optimizing the electrolyte composition and electrolysis process parameters through the synergistic effect mechanism of multiple ions, the electrolysis process can be made efficient, stable and controllable, while extending the service life of electrodes and reducing operation and maintenance costs. Summary of the Invention

[0010] To address the technical problems of traditional electrolysis processes, such as uneven metal ion deposition leading to dendrite formation, severe hydrogen evolution side reactions reducing current efficiency, limited controllability of electrolyte composition and structure making it difficult to adapt to complex load conditions, and short electrode plate cycle life requiring frequent replacement and increasing maintenance costs, this invention provides an electrolysis process based on a high-entropy electrolyte and its application. This process achieves the technical effects of improving metal deposition uniformity, suppressing dendrite growth, reducing hydrogen evolution side reactions, increasing current efficiency, extending anode life, and enhancing process flexibility. The process is highly flexible and can be adapted to various non-ferrous metal smelting scenarios.

[0011] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0012] An electrolysis process based on a high-entropy electrolyte includes the following steps:

[0013] S1. Preparation of electrolyte: The electrolyte contains the metal cation Zn 2+ Mn 2+ Cu 2+ At least one of them, and the anion Cl - 、NO3 - SO4 2- OTf - or TFSI - At least one of them;

[0014] S2. Pretreatment and electrode assembly: The cathode is surface treated and coated with a corrosion-resistant coating, the anode is treated with a catalytic coating, and the electrodes are assembled in the electrolytic cell;

[0015] S3. Perform multi-stage electrolysis: Under monitoring and feedback regulation, electrolysis is carried out in three stages: initial stage, main electrolysis stage and final treatment stage.

[0016] S4. Stripping and Electrolyte Regeneration: After electrolysis, the deposits are stripped from the cathode, and the electrolyte is purified and its concentration adjusted for recycling.

[0017] Further, the electrolyte preparation method in step S1 is as follows: first, dissolve the main salt ZnSO4·7H2O and Zn(NO3)2 in deionized water, then add LiTFSI and sonicate to eliminate agglomeration, then slowly add ZnCl2 solution to avoid local Cl... - Excessive concentration leads to precipitation. During the process, EMIM-BF4 is added, and after continuous stirring, the mixture is allowed to stand to obtain a homogeneous phase. The mass ratio of ZnSO4·7H2O, Zn(NO3)2, LiTFSI, and ZnCl2 is 80~120:10~20:15~25:5~15; the volume fraction of EMIM-BF4 is 3~8%.

[0018] Furthermore, in the electrolyte prepared in step S1, Zn 2+ Concentration of 80~150 g / L, Cl - Concentration of 10~50 g / L, NO3 - The concentration is 5~30 g / L, the solvent is a water-ethylene glycol mixture with 0.2~0.8 g / L of ammonium polyacrylate added, and the pH value of the electrolyte is maintained in the range of 2.5~5.0.

[0019] Further, in step S2, the cathode is made of stainless steel, aluminum, or graphite, and its surface is coated with a TiO2-Nafion composite coating with a thickness of 15~25 μm; the anode is a titanium-based anode, and its surface is sprayed with a coating having a loading of 1.0~2.0 mg / cm³. 2 The RuO2-IrO2 mixed catalytic coating.

[0020] Furthermore, in step S3, the multi-stage electrolysis specifically involves:

[0021] Initial stage (0-15 minutes): Control the current density to 200~250 A / m 2 The temperature was 30~35℃, the electrolyte flow rate was 1.0~1.5 L / min, and NO3 was monitored. - Concentration changes trigger the fluid replenishment procedure;

[0022] Main electrolysis stage (15-270 minutes): An acidic regulator is automatically injected based on real-time pH to maintain the pH at 3.8 ± 0.2, suppressing the hydrogen evolution side reaction. The current density is gradually reduced over time, decreasing by 3-5 A / m every 20-30 minutes. 2 To compensate for changes in electrolyte conductivity;

[0023] Final treatment (270-300 minutes): Stepwise reduction of current density to 45-55 A / m 2 This promotes crystal annealing and reorganization, thereby increasing the density of the deposited layer.

[0024] Furthermore, in the initial stage, NO3 was monitored by in-situ Raman spectroscopy. - At ~1050 cm -1 The characteristic peak at the point is triggered when the peak intensity decreases by 8-10%, and the peristaltic pump is activated to replenish the electrolyte. During the main electrolysis stage, the pH value is maintained by injecting H3PO4 microemulsion at a flow rate of 0.2-0.6 mL / min.

[0025] Further, the specific operation of step S4 is as follows: the deposited cathode is immersed in an ethanol-glycerol mixture with a volume ratio of 2~4:1, and the deposit is peeled off with the assistance of ultrasonic vibration at 30~50 kHz. After filtering out the detached particles, Zn in the electrolyte is removed by electrodialysis. 2+ And add anionic salts to restore the electrolyte concentration to more than 90% of the initial concentration.

[0026] Furthermore, the electrolysis process takes place inside an electrolytic cell equipped with a pH sensor, an ion concentration sensor, and a peristaltic pump. The pH sensor is used to monitor the pH of the electrolyte in real time, and the ion concentration sensor is used to detect Zn. 2+ Mn 2+ Or anion concentration, the peristaltic pump is used to accurately replenish the electrolyte or regulator based on sensor feedback.

[0027] Furthermore, the inside of the electrolytic cell is sealed with a polytetrafluoroethylene gasket to prevent the evaporation of organic solvents; a magnetic stirrer is also installed inside the cell to control the electrolyte flow rate.

[0028] Furthermore, the electrode is modularly designed and can be cleaned or replaced; for cathodes with a surface roughness greater than Ra0.8 μm, laser cladding technology is used for remanufacturing to restore the integrity of the coating.

[0029] The above process is applicable to the wet electrolysis of metals such as zinc, manganese, and copper.

[0030] The beneficial effects of this invention are as follows:

[0031] This invention uses Cl - 、NO3- OTf - TFSI - The synergistic inhibition of dendrites by multiple anions effectively suppresses dendrite growth during metal deposition, increasing electrolysis efficiency to over 95% compared to traditional single-anion electrolytes and significantly improving the uniformity of metal deposition. Simultaneously, by precisely controlling the electrolyte pH and adding H3PO4 microemulsion, this invention reduces hydrogen evolution side reactions by 50%–60%, achieving a current efficiency of over 92%. The use of an ethylene glycol-water mixed solvent system with recycling not only reduces organic solvent consumption but also extends anode life from 500 hours for traditional lead anodes to 2000 hours, significantly reducing maintenance frequency and costs. Furthermore, this invention regulates Cl... - / NO3 - The ratio can be flexibly adjusted to control the metal deposition sequence, adapting to different alloy requirements. This high degree of process flexibility provides a wider range of applications for electrolysis processes. Attached Figure Description

[0032] Figure 1 Summary table of key technical points for precise electrolyte preparation;

[0033] Figure 2 A comparison table of key process parameters for electrode pretreatment and assembly;

[0034] Figure 3 Table for setting key parameters for the three stages of electrolysis;

[0035] Figure 4 An anion dynamic compensation table for the stripping and cleaning process;

[0036] Figure 5 A table comparing key parameters for the stripping and cleaning process. Detailed Implementation

[0037] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited thereto.

[0038] Example 1

[0039] The specific steps of this electrolysis process are as follows:

[0040] (1) Precise preparation of electrolyte:

[0041] First, dissolve the main salt by placing ZnSO4·7H2O (100 g / L) and Zn(NO3)2 (15 g / L) into an electrolytic cell, then add an appropriate amount of deionized water. Dissolve the main salt in the deionized water and turn on the magnetic stirrer until the main salt is completely dissolved. Then, introduce the anionic additive step by step. First, add LiTFSI (20 g / L), sonicate for 30 minutes to eliminate agglomeration, and then slowly add ZnCl2 solution (10 g / L) dropwise to avoid localized Cl- buildup. - If the concentration is too high, precipitation will occur. During this process, add EEMIM-BF4 (5% by volume), stir continuously for 2 hours, and take the homogeneous phase after standing and separating the layers.

[0042] (2) Electrode pretreatment and assembly:

[0043] The stainless steel cathode (ASTM B266) was sanded, then coated with acetone to remove oil. Finally, a TiO2-Nafion composite coating (20 μm thickness) was applied to the surface of the stainless steel cathode, and then it was dried for later use. The main anode structure was a titanium-based anode, with a RuO2-IrO2 mixture (loading 1.5 mg / cm²) sprayed onto the surface. 2 The electrolytic cell is sintered and formed, and the inside of the electrolytic cell is equipped with a polytetrafluoroethylene gasket to isolate the electrolyte from the external environment and prevent the evaporation of organic solvents.

[0044] (3) Initial stage (0-15 minutes):

[0045] Set the initial current density to 250 A / m 2 The temperature was set at 35°C, and the peristaltic pump was turned on to adjust the flow rate to 1.2 L / min. During this process, NO3 was monitored by in-situ Raman spectroscopy. - Characteristic peak (~1050 cm) -1 When the intensity drops by 10%, the fluid replenishment program is triggered to start the peristaltic pump for replenishment.

[0046] Main electrolysis stage (15-270 minutes):

[0047] Based on the real-time pH (target 3.8 ± 0.2), the H3PO4 microemulsion was automatically injected at a flow rate of 0.5 mL / min to suppress the hydrogen evolution side reaction. The current density was then adjusted to 5 A / m² every 30 minutes. 2 (Decrease) to compensate for changes in electrolyte conductivity.

[0048] Final processing (270-300 minutes):

[0049] Stepwise reduction of current to 50 A / m 2 This promotes crystal annealing and recombination, and increases the density of the deposited layer;

[0050] (4) Peeling and cleaning:

[0051] After deposition, the cathode was immersed in a 3:1 volume ratio ethanol-glycerol mixture, and the metal foil was peeled off with ultrasonic vibration (40 kHz). After filtering out the detached particles, Zn was removed by electrodialysis. 2+ The concentrate is replenished with fresh anionic salt to a concentration of over 90% of the initial concentration, and then laser cladding is performed on cathodes with a surface roughness > Ra 0.8 μm to restore the integrity of the coating.

[0052] During electrolysis, the synergistic effect of multiple anions in the high-entropy electrolyte forms a stable interfacial structure, effectively suppressing dendrite growth. EMIM-BF4, as an organic additive, reduces interfacial tension and improves current efficiency. Throughout the process, real-time monitoring and precise control ensure the uniformity and density of metal deposition, resulting in a metal foil with excellent mechanical properties and surface quality.

[0053] Example 2

[0054] The basic steps of this embodiment, such as precise electrolyte preparation, electrode pretreatment and assembly, staged electrolysis control, and stripping and cleaning, are the same as those described in Embodiment 1.

[0055] The difference in this embodiment lies in the inclusion of a pH sensor, an ion concentration sensor, and a peristaltic pump within the electrolytic cell, forming a closed-loop control system. The pH sensor employs a glass electrode, achieving a measurement accuracy of ±0.01 pH units, enabling real-time monitoring of electrolyte pH changes. The ion concentration sensor utilizes a selective ion electrode, allowing simultaneous detection of Zn. 2 + Mn 2+ Concentration (detection limit 5 mg / L) and major anions such as SO42- 2- Cl - 、NO3 - The concentration (detection limit 10 mg / L) was measured. These sensors acquire data every 5 seconds via a data acquisition module and transmit it to the control unit for analysis.

[0056] The peristaltic pump system comprises three independently controlled pump heads, each specifically designed for the precise replenishment of the electrolyte bulk components, pH adjuster, and specific anion additives. When the pH sensor detects a deviation of the electrolyte pH from the target range (3.8 ± 0.2), the control system automatically activates the corresponding peristaltic pump to precisely add H3PO4 microemulsion or dilute NaOH solution at an adjustable flow rate of 0.2–2.0 mL / min for neutralization and adjustment. Similarly, when the ion concentration sensor detects Zn… 2+ When the concentration is below 95 g / L, the system will initiate a replenishment procedure, adding pre-prepared concentrated Zn. 2+ The solution ensures the stability of the metal ion concentration during electrolysis.

[0057] During electrolysis, the control system establishes an adaptive control algorithm based on sensor feedback data. This algorithm can predict the changing trends of electrolyte components and make timely adjustments, avoiding the product quality instability caused by parameter fluctuations in traditional electrolysis processes. Especially during the main electrolysis stage (15-270 minutes), the system can dynamically adjust the current density according to real-time changes in ion concentration to maintain optimal deposition conditions.

[0058] With this real-time monitoring and precise adjustment system, the electrolysis process in this embodiment can maintain the stability of the electrolyte composition even after long-term operation (more than 72 hours), the surface roughness of the deposited product is reduced by 35%, the grain size distribution is more uniform, and the current efficiency is increased by 12%, which has significant advantages over the traditional electrolysis process.

[0059] Example 3

[0060] The specific steps of this electrolysis process are as follows:

[0061] (1) Precise preparation of electrolyte:

[0062] In this embodiment, the Zn in the electrolyte 2+ The concentration is 120 g / L, Cl - The concentration is 25 g / L, NO3 - The concentration was 15 g / L. The electrolyte preparation process was similar to that described in Example 1, but in this example, a higher concentration of zinc salt was used to achieve the desired Zn concentration. 2+ The concentration was adjusted, and the amounts of ZnCl2 and Zn(NO3)2 added were adjusted to meet specific Cl... - and NO3 - Concentration requirements.

[0063] (2) Electrode pretreatment and assembly:

[0064] The electrode pretreatment and assembly steps are basically carried out in accordance with the method in Example 1. The difference is that this example uses a water-ethylene glycol mixture as a solvent and adds 0.5 g / L of ammonium polyacrylate as a dispersant and stabilizer to the solvent.

[0065] (3) Electrolysis process control:

[0066] The electrolysis process is controlled in three stages, similar to Example 1. This example places particular emphasis on pH control, maintaining the electrolyte pH within the range of 2.5 to 5.0, and adjusting it according to the needs of different electrolysis stages. The initial stage pH is set at 4.5, gradually decreasing to 3.5 during the main electrolysis stage, and further adjusting to 3.0 in the final treatment stage to optimize metal deposition quality and current efficiency.

[0067] (4) Peeling and cleaning:

[0068] The stripping and cleaning steps were basically carried out in accordance with the method in Example 2, but 0.5% citric acid was added to the cleaning solution to better remove impurities from the deposited metal surface.

[0069] The process described in this embodiment is particularly suitable for the wet electrolysis of metals such as zinc, manganese, and copper. By precisely controlling the Zn... 2+ Concentration, Cl - Concentration and NO3 - The concentration, the use of a water-glycol mixed solvent, and the addition of ammonium polyacrylate significantly improved electrolysis efficiency and metal deposition quality. Within a pH range of 2.5–5.0, the hydrolysis behavior and deposition morphology of metal ions could be effectively controlled by adjusting the pH value in stages.

[0070] Experimental results show that the metal foil prepared under this process has higher purity (above 99.95%) and a more uniform grain structure (average grain size 5.2 μm), with surface roughness reduced to below Ra 0.3 μm. Compared with the traditional electrolysis process, the current efficiency is improved by 12%, energy consumption is reduced by 15%, and the mechanical properties of the metal foil are significantly improved, with tensile strength increasing by 20% and ductility increasing by 15%.

[0071] Example 4

[0072] The electrolysis process in this embodiment includes steps such as precise preparation of electrolyte, electrode pretreatment and assembly, staged electrolysis control, and stripping and cleaning, which are basically the same as those described in Embodiment 1.

[0073] In the precise preparation stage of the electrolyte, the main salt was dissolved and the anionic additive was introduced stepwise according to the method of Example 1. The difference is that a magnetic stirrer was set inside the electrolytic cell in this example to ensure that the electrolyte remains uniform throughout the electrolysis process and to control the flow rate to be stable within the range of 1.2 L / min.

[0074] Electrode pretreatment and assembly, initial electrolysis stage, main electrolysis stage, final treatment, and stripping and cleaning steps were all performed according to the method in Example 1.

[0075] By incorporating a magnetic stirrer inside the electrolytic cell and precisely controlling the flow rate within the range of 1.2 L / min, this embodiment achieves thorough mixing and uniform flow of the electrolyte, effectively avoiding localized differences in electrolyte concentration and improving electrolysis efficiency. The use of the magnetic stirrer also promotes uniform ion distribution during electrolysis, reduces concentration polarization, further suppresses dendrite growth, and enhances the quality and uniformity of the metal deposition layer.

[0076] Experimental results show that, using the electrolysis process of this embodiment, the surface roughness of the deposited metal layer is reduced by 15%, the grain size distribution is more uniform, the mechanical strength of the metal foil is increased by 12%, and the current efficiency is improved by 8%. These improvements are mainly attributed to the introduction of a magnetic stirrer and precise control of the flow rate, demonstrating the superiority of this embodiment in high-entropy electrolyte electrolysis processes.

[0077] Example 5

[0078] The specific steps of this electrolysis process are as follows:

[0079] In this embodiment, the electrolysis process employs the same precise electrolyte preparation method, staged electrolysis control, and stripping and cleaning steps as in Example 1.

[0080] Regarding electrode pretreatment and assembly, this embodiment adopts a modular electrode design, as detailed below:

[0081] A variety of cathode materials can be selected, including stainless steel, aluminum, or graphite plates as the substrate. The cathode surface is coated with a TiO2-Nafion composite coating, with the coating thickness precisely controlled at 20 μm. This composite coating structure significantly improves the cathode's corrosion resistance while also enhancing the uniformity of metal deposition and reducing dendrite growth tendency.

[0082] The anode uses a titanium-based coating material with a surface coating of RuO2-IrO2 mixture, and its loading is 1.5 mg / cm³. 2 This noble metal oxide coating exhibits excellent electrocatalytic activity and stability, enabling it to maintain efficient anodic reactions at high current densities while reducing the generation of side reactions.

[0083] The electrodes feature a modular design, facilitating regular cleaning or replacement. This design philosophy allows for timely maintenance based on the electrode surface condition during long-cycle electrolysis, extending electrode lifespan and maintaining stable electrolytic performance. When electrode surface contamination or performance degradation occurs, the electrodes can be quickly disassembled for cleaning or replaced, minimizing production downtime.

Claims

1. An electrolysis process based on a high-entropy electrolyte, characterized in that, Includes the following steps: S1. Preparation of electrolyte: The electrolyte contains the metal cation Zn 2+ Mn 2+ Cu 2+ At least one of them, and the anion Cl - 、NO3 - SO4 2- OTf - or TFSI - At least one of them; S2. Pretreatment and electrode assembly: The cathode is surface treated and coated with a corrosion-resistant coating, the anode is treated with a catalytic coating, and the electrodes are assembled in the electrolytic cell; S3. Perform multi-stage electrolysis: Under monitoring and feedback regulation, electrolysis is carried out in three stages: initial stage, main electrolysis stage and final treatment stage. S4. Stripping and Electrolyte Regeneration: After electrolysis, the deposits are stripped from the cathode, and the electrolyte is purified and its concentration adjusted for recycling.

2. The electrolysis process based on high-entropy electrolyte according to claim 1, characterized in that, The electrolyte preparation method in step S1 is as follows: First, dissolve the main salt ZnSO4·7H2O and Zn(NO3)2 in deionized water, then add LiTFSI and sonicate, then add ZnCl2 solution, and add EMIM-BF4 during the process. After continuous stirring, let it stand to obtain a homogeneous phase. The mass ratio of ZnSO4·7H2O, Zn(NO3)2, LiTFSI and ZnCl2 is 80~120:10~20:15~25:5~15; the volume fraction of EMIM-BF4 is 3~8%.

3. The electrolysis process based on high-entropy electrolyte according to claim 1, characterized in that, In the electrolyte prepared in step S1, Zn 2+ Concentration of 80~150 g / L, Cl - Concentration of 10~50 g / L, NO3 - The concentration is 5~30 g / L, the solvent is a water-ethylene glycol mixture with 0.2~0.8 g / L of ammonium polyacrylate added, and the pH value of the electrolyte is maintained in the range of 2.5~5.

0.

4. The electrolysis process based on high-entropy electrolyte according to claim 1, characterized in that, In step S2, the cathode is made of stainless steel, aluminum, or graphite, and its surface is coated with a TiO2-Nafion composite coating with a thickness of 15-25 μm; the anode is a titanium-based anode, and its surface is sprayed with a coating having a loading of 1.0-2.0 mg / cm³. 2 The RuO2-IrO2 mixed catalytic coating.

5. The electrolysis process based on high-entropy electrolyte according to claim 1, characterized in that, In step S3, the multi-stage electrolysis specifically involves: Initial stage: During the first 15 minutes of electrolysis, control the current density at 200~250 A / m 2 The temperature was 30~35℃, the electrolyte flow rate was 1.0~1.5 L / min, and NO3 was monitored. - Concentration changes trigger the fluid replenishment procedure; Main electrolysis stage: During the 15-270 minutes of electrolysis, an acidic regulator is automatically injected based on the real-time pH to maintain the pH at 3.8±0.2, suppressing the hydrogen evolution side reaction. The current density is gradually reduced over time, decreasing by 3-5 A / m every 20-30 minutes. 2 To compensate for changes in electrolyte conductivity; Final treatment: During the 270-300 minutes of electrolysis, the current density is gradually reduced to 45-55 A / m. 2 This promotes crystal annealing and reorganization, thereby increasing the density of the deposited layer.

6. The electrolysis process based on high-entropy electrolyte according to claim 5, characterized in that, In the initial stage, NO3 was monitored by in-situ Raman spectroscopy. - At ~1050 cm -1 The characteristic peak at the location is triggered when the peak intensity decreases by 8-10%, causing the peristaltic pump to replenish the electrolyte. During the main electrolysis stage, the pH value is maintained by injecting H3PO4 microemulsion at a flow rate of 0.2~0.6 mL / min.

7. The electrolysis process based on high-entropy electrolyte according to claim 1, characterized in that, The specific operation of step S4 is as follows: the deposited cathode is immersed in an ethanol-glycerol mixture with a volume ratio of 2~4:1, and the deposit is peeled off with the assistance of ultrasonic vibration at 30~50 kHz. After filtering out the detached particles, Zn in the electrolyte is removed by electrodialysis. 2+ And add anionic salts to restore the electrolyte concentration to more than 90% of the initial concentration.

8. The electrolysis process based on a high-entropy electrolyte according to any one of claims 1 to 7, characterized in that, The electrolysis process takes place inside an electrolytic cell equipped with a pH sensor, an ion concentration sensor, and a peristaltic pump. The pH sensor is used to monitor the pH of the electrolyte in real time, and the ion concentration sensor is used to detect Zn. 2+ Mn 2+ Or anion concentration, the peristaltic pump is used to accurately replenish the electrolyte or regulator based on sensor feedback.

9. The electrolysis process based on high-entropy electrolyte according to claim 8, characterized in that, The electrolytic cell is sealed with a polytetrafluoroethylene gasket and is equipped with a magnetic stirrer. The electrode is modularly designed. For cathodes with a surface roughness greater than Ra 0.8 μm, laser cladding technology is used for remanufacturing to restore the integrity of the coating.

10. The application of the process according to any one of claims 1 to 9 in the wet electrolysis of at least one of zinc, manganese or copper.

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