Active anode for ionic membrane electrolytic cell and manufacturing method of active anode

Abstract

The invention relates to an active anode for an ionic membrane electrolytic bath and a manufacturing method thereof, and belongs to the technical field of active anodes, the active anode for the ionic membrane electrolytic bath comprises a titanium-based net, the titanium-based net is provided with a coating, the coating is of a rutile structure composed of platinum, ruthenium, iridium and tin, the content of platinum is 2-40 mol%, the content of ruthenium is 5-45 mol%, the content of iridium is 5-45 mol%, and the content of tin is 5-20 mol%. The content of the iridium is 2 mol%-40 mol%, and the content of the tin is 10 mol%-65 mol%. The oxygen evolution potential is high, the catalytic capacity is high, the conductivity is high, and the oxygen evolution side reaction is not prone to occurring; the performance is stable, corrosion resistance is achieved, the service life is long, and the electrode can be continuously used after column recoating after failure; the electrode cost is effectively controlled; and the product quality is improved, the chlorine purity is high, and the oxygen content is low (below 0.8%).

Description

Technical Field

[0002] The invention relates to an active anode for an ion membrane electrolyzer and a manufacturing method thereof, belonging to the technical field of active anodes. Background Art

[0004] The chlor-alkali industry is a basic chemical industry. Currently, the ion membrane method is used to produce alkali, that is, brine is electrolyzed through an ion membrane electrolyzer to produce caustic soda, chlorine, hydrogen, etc.

[0005] Anode reaction 2Cl － -2e － =Cl2↑

[0006] 4OH － -4e － =O2↑+2H2O

[0007] Cathode reaction 2H2O + 2e － =H2↑+2OH －

[0008] At the anode, the dissolved chlorine reacts with the sodium hydroxide that permeates from the cathode.

[0009] 3Cl2+6NaOH=5NaCl +NaClO3+3H2O

[0010] The generated NaClO3 has strong oxidizing properties.

[0011] In chlor-alkali production, salt (NaCl) and electricity are the main costs. For every ton of caustic soda produced, the DC power consumption reaches 2000-2350 kWh. The main factors of power consumption are:

[0012] 1. The structure of the electrolytic cell;

[0013] 2. Chlorine evolution potential of anode;

[0014] 3. Hydrogen evolution potential at cathode.

[0015] SnO2 is an important inorganic functional material. Nano-SnO2 film electrode has unique photoelectric and electrochemical properties, which can further change the performance of titanium-based coatings.

[0016] Iridium dioxide (IrO2) electrode has a high oxygen evolution potential and strong corrosion resistance, and has broad application prospects as an anode material in acidic media. The performance of IrO2 electrode can be improved by adding elements such as Ru, Sn, Ta, Zr, and Co.

[0017] Ruthenium oxide and iridium oxide are the few conductive oxides.

[0018] RuO2 has the following properties:

[0019] 1. The consumption rate is extremely small;

[0020] 2. High current operation has good durability;

[0021] 3. Chlorine overpotential is not affected by other reactions;

[0022] 4. It has ceramic properties and high melting point;

[0023] 5. Strong adhesion to titanium base.

[0024] The following table shows the chlorine precipitation rate R (Cl2) of different electrodes

[0025]

[0026] In chlor-alkali production, the traditional titanium-based ruthenium titanium coating has been tested in production practice and found to have the following defects: short electrode life, high oxygen content in the produced chlorine, which affects the purity of the chlorine and causes a decrease in current efficiency.

[0027] Therefore, it is necessary to increase the oxygen evolution potential of its active coating, reduce the chlorine evolution potential, and increase the electrode life. Summary of the invention

[0029] The technical problem to be solved by the present invention is: in order to overcome the deficiencies of the prior art, an active anode for an ion membrane electrolyzer and a method for making the same are provided to improve the oxygen evolution potential of an electrode active coating, reduce the chlorine evolution potential, and improve the electrode life.

[0030] The technical solution adopted by the present invention to solve the above-mentioned problem is: an active anode for an ion membrane electrolyzer, comprising a titanium-based mesh, on which a coating is arranged, and the coating is a rutile structure composed of platinum, ruthenium, iridium and tin, the content of the platinum is 2 mol% to 40 mol%, the content of the ruthenium is 5% to 45 mol%, the content of the iridium is 2 mol% to 40 mol%, and the content of the tin is 10 mol% to 65 mol%.

[0031] Preferably, the platinum carrier is chloroplatinic acid.

[0032] Preferably, the ruthenium carrier is ruthenium trichloride.

[0033] Preferably, the iridium carrier is iridium tetrachloride.

[0034] Preferably, the tin carrier is tin chloride or organic tin.

[0035] A method for manufacturing an active anode for an ion membrane electrolyzer comprises the following steps:

[0036] Step S1, using TA1 titanium plate expanded mesh as the substrate of the electrode;

[0037] Step S2, processing the substrate web to provide a flat, clean, and rough-surfaced substrate, thereby ensuring that the bonding strength and specific surface area of ​​the coating are maximized;

[0038] Step S3, preparing a coating solution of the compound solution for the anode coating of the ion-exchange membrane electrolyzer according to the formula, and evenly coating the coating solution on the substrate by a multi-pass coating method to form stable multi-metal oxide crystals on the surface of the titanium substrate.

[0039] Preferably, during the production process of the active anode for the ion-exchange membrane electrolyzer, a substrate coating monitoring process is provided, including the following process:

[0040] Step 1: Obtain the image data of the coating after each coating, divide it into grids based on the image data, and obtain the area to be inspected;

[0041] Step 2: Based on the area to be inspected, obtain the thickness value of each area to be inspected, and preliminarily determine whether the coating quality meets the requirements. If an analysis and evaluation signal is generated during the preliminary determination process, determine again whether the coating needs to be adjusted to obtain the operation classification coefficient;

[0042] Step 3: Compare the operation classification coefficient with the corresponding threshold value to generate a signal whether to continue the coating work;

[0043] If the operation classification coefficient is greater than or equal to the operation classification coefficient threshold, a discontinue coating signal is generated; when the discontinue coating signal is obtained, the coating work is restarted;

[0044] If the operation classification coefficient is less than the operation classification coefficient threshold, a continue coating signal is generated; when the continue coating signal is obtained, the coating work is continued on the coating that is currently unevenly coated.

[0045] Preferably, in step 2, the thickness value of each area to be inspected is obtained; if the thickness value of the area to be inspected does not meet the thickness mean range set by the standard process, it means that the area to be inspected does not meet the process requirements, and the area to be inspected is marked as an unqualified area;

[0046] If there are unqualified areas in all the areas to be inspected, an analysis and evaluation signal is generated;

[0047] When the analysis and evaluation signal is obtained, the operational classification coefficient is obtained.

[0048] As a preferred method, the process of obtaining the operation classification coefficient is as follows:

[0049] First, the unqualified area is further divided. If the thickness value of the area to be inspected is less than the minimum value of the thickness mean range set by the standard process, it is marked as a concave unqualified area;

[0050] If the thickness value of the area to be inspected is greater than the maximum value of the thickness mean range set by the standard process, it will be marked as a protruding unqualified area;

[0051] Obtain the thickness values ​​of all protruding unqualified areas, and calculate the total thickness value ZBA of the protruding unqualified areas; obtain the thickness values ​​of all concave unqualified areas, and calculate the total thickness value ZBT of the concave unqualified areas;

[0052] The total thickness value ZBA of the unqualified protruding area and the total thickness value ZBT of the unqualified concave area are calculated by difference to obtain the coating compensation difference, and the coating compensation difference is compared with the coating compensation difference threshold;

[0053] If the coating compensation difference is greater than or equal to the coating compensation difference threshold, a judgment signal is generated;

[0054] When the judgment signal is obtained, the ratio of the proportion of unqualified areas and the ratio of the distribution of unqualified areas are obtained, and the operation classification coefficient XFC is calculated;

[0055] The process of obtaining the ratio of unqualified areas is as follows:

[0056] Counting the number of all protruding unqualified areas and concave unqualified areas, adding the number of all protruding unqualified areas to the number of all concave unqualified areas, and obtaining the total number of unqualified areas;

[0057] Then the total number of unqualified areas and the total number of areas to be inspected are calculated to obtain the ratio of unqualified areas.

[0058] The process of obtaining the distribution ratio of unqualified areas is as follows:

[0059] The inspection area is divided into horizontal and vertical directions, and the horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are calculated. The horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are added together to obtain the unqualified area distribution ratio.

[0060] As a preferred method, the calculation process of the horizontal unqualified area distribution ratio is:

[0061] The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed:

[0062] Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column;

[0063] Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up;

[0064] The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column;

[0065] If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated;

[0066] The number of unqualified signals generated in the column of the area to be inspected is obtained, and the ratio is calculated by dividing the area to be inspected into columns to obtain the horizontal unqualified area distribution ratio;

[0067] The calculation process of the vertical unqualified area distribution ratio is:

[0068] The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed:

[0069] Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column;

[0070] Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up;

[0071] The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column;

[0072] If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated;

[0073] The number of unqualified signals generated in the column of the area to be inspected is obtained, and the number of columns divided by the area to be inspected is calculated to obtain the horizontal unqualified area distribution ratio.

[0074] Compared with the prior art, the advantages of the present invention are:

[0075] 1. High oxygen evolution potential, strong catalytic ability, high conductivity, and not prone to oxygen evolution side reaction;

[0076] 2. Stable performance, corrosion resistance, long service life, the electrode can be re-coated and continued to be used after failure;

[0077] 3. Electrode cost is effectively controlled;

[0078] 4. To improve product quality, the chlorine gas must be of high purity and low oxygen content (below 0.8%). BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 Schematic diagram of the upper surface structure of the titanium-based mesh;

[0081] Figure 2 Schematic diagram of the lower surface structure of the titanium-based mesh;

[0082] Figure 3 This is a first schematic diagram of an active anode coating for an ion-exchange membrane electrolyzer according to the present invention;

[0083] Figure 4 This is a second schematic diagram of an active anode coating for an ion membrane electrolyzer according to the present invention. DETAILED DESCRIPTION

[0085] Example 1

[0086] like Figure 1-4 As shown, an active anode for an ion membrane electrolyzer in this embodiment includes a titanium-based mesh, and a coating is provided on the titanium-based mesh;

[0087] The coating is a stable rutile structure composed of platinum (Pt), ruthenium (Ru), iridium (Ir) and tin (Sn), wherein the content of platinum is 2 mol%, the content of ruthenium is 5%, the content of iridium is 2 mol%, and the content of tin is 10 mol%;

[0088] The carrier of platinum is chloroplatinic acid, the carrier of ruthenium is ruthenium trichloride, the carrier of iridium is iridium tetrachloride, and the carrier of tin is tin chloride, organic tin, etc.;

[0089] Tin-containing electrodes have the characteristics of high oxygen evolution overpotential;

[0090] Sintering Sn-containing electrodes and sintering Sn-Ir-Ru-Pt alloy electrodes not only retain the high oxygen evolution potential of the iridium electrode, but also reduce the electrode chlorine evolution potential and reduce the use of iridium in the anode coating;

[0091] For example, adding chlorides of platinum and iridium to a coating solution containing ruthenium trichloride and tin tetrachloride can prepare a multi-catalytic active component of the coating, which has a low chlorine release potential, a higher oxygen release potential and better resistance to oxygen corrosion.

[0092] The electrocatalytic property of iridium oxide for the generation of chlorine is not outstanding, but its electrochemical activity for oxygen evolution in acidic media is second only to RuO2, and it can maintain a high stability in this medium, showing excellent electrolytic durability; it is generally believed that this is because Ir's oxygen adsorption is reversible, and structurally, IrO2 is a peroxo structure (IrO2+δ, aerobic state) and its catalytic structure will not be destroyed by the influx of oxygen; because iridium oxide itself has good corrosion resistance to oxygen, strong antioxidant capacity, and higher oxygen evolution overpotential than ruthenium, it has been used as an intermediate layer to improve the titanium ruthenium coating formula.

[0093] The electrochemically active surface area of ​​the coating reaches its maximum value when the Ir content is 60 mol%. In the electrical performance test: the volt-ampere capacity of the coating with an Ir content of 3 mol% to 60 mol% increases with the occurrence of oxygen evolution, while that of the 100% IrO2 coating decreases accordingly, indicating that the appropriate addition of IrO2 makes the titanium electrode have better electrolytic durability.

[0094] The addition of SnO2 will significantly change the appearance of the coating and reduce the porosity of the coating. At the same time, with the increase of SnO2 content, the electrochemical behavior of the coating will shift to be dominated by SnO2. When the SnO2 content is 10 mol%~60 mol%, after a strong oxygen release process, the volt-ampere capacity of the coating will be significantly reduced. Excessive addition of SnO2 will reduce the electrocatalytic activity of the coating.

[0095] Deactivation factors of coated titanium anode:

[0096] 1. Dissolution and consumption of oxide coating;

[0097] 2. The coating falls off;

[0098] 3. Passivation of titanium substrate (TiO2 film is formed between titanium-based mesh and coating);

[0099] Requirements for the middle layer: Enhance bonding strength and avoid passivation;

[0100] Middle layer selection direction:

[0101] 1. The middle layer contains metal layers Sn and Pt;

[0102] 2. Metal oxide intermediate layer SnO2, ptO2;

[0103] 3. A mixture of metal and metal oxide (including Sn and Ir intermediate layers).

[0104] A method for manufacturing an active anode for an ion membrane electrolyzer comprises the following steps:

[0105] Step S1, using TA1 titanium plate expanded mesh as the substrate of the electrode;

[0106] Step S2: The substrate web is subjected to high temperature annealing, leveling, sandblasting, pickling, cleaning and other processes to provide a flat, clean, rough-surfaced substrate, thereby ensuring the maximum bonding strength and specific surface area of ​​the coating;

[0107] Step S3, preparing a coating solution of a compound solution for an anode coating of an ion-exchange membrane electrolyzer according to a formula, and uniformly coating the coating solution on the substrate by a multiple-pass coating method. After each coating, drying is performed first, and then partial oxidation is performed at high temperature. The process is repeated multiple times (8 to 12 times) and then sintered to form stable multi-metal oxide crystals on the surface of the titanium substrate.

[0108] Test results of the test product:

[0109] 1. Appearance of anodic coating:

[0110] 2. Chlorine evolution potential test results: 1.07V~1.09V (index: ≤1.13 V, current density 4kA / ㎡, saturated brine, temperature 90℃±1℃, VS SCE);

[0111] 3. Strengthening weight loss test results: <3mg (Indicator: weight loss <6.3mg, 30%WtNaOH solution (CP grade), test piece 10cm 2 , temperature 90℃±1℃, current density 20 kA / ㎡, electrolysis 4 hours);

[0112] 4. Tests in an experimental electrolytic cell device showed that the electrolysis voltage was 20 mV lower than the existing anode; the purity of chlorine was greater than 98.8% (without acid addition process), and the oxygen content was less than 0.6%.

[0113] In summary, by changing the anode coating formula, a stable lattice structure of the anode coating is obtained, and the requirements of lower power consumption, longer service life, and low side reactions in chlor-alkali production are met, and it has the following characteristics:

[0114] 1. High oxygen evolution potential, strong catalytic ability, high conductivity, and not prone to oxygen evolution side reaction;

[0115] 2. Stable performance, corrosion resistance, long service life, the electrode can be re-coated and continued to be used after failure;

[0116] 3. Electrode cost is effectively controlled;

[0117] 4. To improve product quality, the chlorine gas must be of high purity and low oxygen content (below 0.8%).

[0118] Example 2

[0119] The difference from the above-mentioned embodiment 1 is that: an active anode for an ion membrane electrolyzer in this embodiment comprises a titanium-based mesh, and a coating is arranged on the titanium-based mesh;

[0120] The coating is a stable rutile structure composed of platinum (Pt), ruthenium (Ru), iridium (Ir) and tin (Sn), wherein the content of platinum is 20 mol%, the content of ruthenium is 20 mol%, the content of iridium is 20 mol%, and the content of tin is 35 mol%.

[0121] Example 3

[0122] The difference from the above-mentioned embodiment 1 is that: an active anode for an ion membrane electrolyzer in this embodiment comprises a titanium-based mesh, and a coating is arranged on the titanium-based mesh;

[0123] The coating is a stable rutile structure composed of platinum (Pt), ruthenium (Ru), iridium (Ir) and tin (Sn), wherein the content of platinum is 40 mol%, the content of ruthenium is 45 mol%, the content of iridium is 40 mol%, and the content of tin is 65 mol%.

[0124] Example 4

[0125] Based on the above-mentioned Examples 1-3, in the process of manufacturing the active anode for the ion membrane electrolyzer, the quality of the substrate coating also plays a crucial role in the quality of the active anode for the ion membrane electrolyzer; specifically:

[0126] Electrolysis life: The coating amount is one of the factors that directly affect the electrolysis life. If the coating amount is too small, the active components are not enough to complete the electrode reaction at a low potential, and the substrate is easily passivated during the electrolysis process. If the coating amount is too large, although it may delay the passivation of the substrate to a certain extent, it will also increase the cost, reduce the bonding strength between the coatings, and may even affect the electrolysis efficiency;

[0127] Electrolysis efficiency: The thickness of the coating will also affect the electrolysis efficiency. If the coating is too thin, it may lead to uneven current distribution during the electrolysis process, affecting the purity and yield of the electrolysis product. If the coating is too thick, it may increase the energy consumption during the electrolysis process and reduce the electrolysis efficiency.

[0128] Current distribution: The uniformity of the coating directly affects the distribution of current during electrolysis. If the coating is uneven, it may lead to uneven distribution of current on the anode surface, causing local current to be too large or too small, thus affecting the quality and yield of the electrolysis product;

[0129] Electrolysis stability: Coating uniformity also affects the stability of the electrolysis process. Uneven coating may cause potential fluctuations on the anode surface during electrolysis, which in turn affects the stability and consistency of the electrolysis products.

[0130] Based on this, in the process of making active anode for ion membrane electrolyzer, a substrate coating monitoring process is set up specifically, including the following processes:

[0131] Step 1: Obtain the image data of the coating after each coating, divide it into grids based on the image data, and obtain the area to be inspected;

[0132] In some embodiments, a compound solution for an anode coating of an ion-exchange membrane electrolyzer is formulated to form a coating solution, the coating solution is uniformly coated on a substrate, an image of the coating on the substrate after coating is captured by a visual camera, and a plurality of areas to be inspected are obtained by grid-type area division;

[0133] Step 2: Based on the area to be inspected, obtain the thickness value of each area to be inspected, and preliminarily determine whether the coating quality meets the requirements. If an analysis and evaluation signal is generated during the preliminary determination process, determine again whether the coating needs to be adjusted to obtain the operation classification coefficient;

[0134] In some embodiments, the thickness value of each area to be inspected is obtained, and then the thickness value of each area to be inspected is compared with the thickness mean range set by the standard process;

[0135] If the thickness value of the area to be inspected is within the average thickness range set by the standard process, it means that the area to be inspected meets the process requirements, and the area to be inspected is marked as a qualified area;

[0136] If the thickness value of the area to be inspected does not meet the thickness mean range set by the standard process, it means that the area to be inspected does not meet the process requirements, and the area to be inspected is marked as an unqualified area;

[0137] If all the areas to be inspected are qualified areas, it means that the coating quality of this pass meets the requirements for active anode preparation, and the next step of active anode preparation process needs to be carried out. If all the areas to be inspected have unqualified areas, an analysis and evaluation signal is generated;

[0138] When the analysis and evaluation signal is obtained, the operation classification coefficient is obtained;

[0139] Among them, the process of obtaining the operation classification coefficient is:

[0140] First, the unqualified area is further divided. If the thickness value of the area to be inspected is less than the minimum value of the thickness mean range set by the standard process, it is marked as a concave unqualified area;

[0141] If the thickness value of the area to be inspected is greater than the maximum value of the thickness mean range set by the standard process, it will be marked as a protruding unqualified area;

[0142] Get the thickness value of all protruding unqualified areas through the formula , the total thickness value ZBA of the protruding unqualified area is calculated; where i represents the number of protruding unqualified areas;

[0143] Get the thickness values ​​of all unqualified concave areas through the formula , the total thickness value ZBT of the unqualified concave area is calculated; where j represents the number of unqualified concave areas;

[0144] The total thickness value ZBA of the unqualified protruding area and the total thickness value ZBT of the unqualified concave area are calculated by difference to obtain the coating compensation difference, and the coating compensation difference is compared with the coating compensation difference threshold;

[0145] If the coating compensation difference is greater than or equal to the coating compensation difference threshold, it means that the excess amount coated on the protruding unqualified area can be used to repeatedly coat the insufficient amount coated on the concave unqualified area, which may theoretically meet the uniformity of the first coating thickness and meet the process requirements for active anode production, and then a judgment signal is generated;

[0146] If the coating compensation difference is less than the coating compensation difference threshold, it means that the excess amount coated on the protruding unqualified area cannot be used to repeatedly coat the insufficient amount coated on the concave unqualified area. If the uniformity of the coating thickness does not meet the process requirements for the production of active anodes, a re-coating work signal is generated;

[0147] When the judgment signal is obtained, the ratio of the unqualified area proportion and the unqualified area distribution ratio are obtained and marked as ZB and ZF. , the operation classification coefficient XFC is calculated, where a1 and a2 are weight ratio coefficients, a1+a2=1, a1 is 0.42, a2 ​​is 0.28, and the values ​​of a1 and a2 reflect the influence of the proportion of unqualified areas and the distribution ratio of unqualified areas on the operation classification coefficient;

[0148] First, specifically, the process of obtaining the ratio of unqualified areas is as follows:

[0149] Counting the number of all protruding unqualified areas and concave unqualified areas, adding the number of all protruding unqualified areas to the number of all concave unqualified areas, and obtaining the total number of unqualified areas;

[0150] Then the total number of unqualified areas and the total number of areas to be inspected are calculated to obtain the ratio of unqualified areas.

[0151] Second, specifically, the process of obtaining the unqualified area distribution ratio is as follows:

[0152] The quality inspection area is divided into horizontal and vertical directions, and the horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are calculated. The horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are added together to obtain the unqualified area distribution ratio;

[0153] Furthermore, the calculation process of the horizontal unqualified area distribution ratio is:

[0154] The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed:

[0155] Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column;

[0156] Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up;

[0157] The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column;

[0158] If the coating compensation difference of each column is greater than or equal to the coating compensation difference threshold of each column, a qualified signal of the area to be inspected in this column is generated;

[0159] If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated;

[0160] The number of unqualified signals generated in the column of the area to be inspected is obtained, and the ratio is calculated by dividing the area to be inspected into columns to obtain the horizontal unqualified area distribution ratio;

[0161] Furthermore, the calculation process of the vertical unqualified area distribution ratio is:

[0162] The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed:

[0163] Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column;

[0164] Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up;

[0165] The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column;

[0166] If the coating compensation difference of each column is greater than or equal to the coating compensation difference threshold of each column, a qualified signal of the area to be inspected in this column is generated;

[0167] If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated;

[0168] The number of unqualified signals generated in the column of the area to be inspected is obtained, and the ratio is calculated by dividing the area to be inspected into columns to obtain the horizontal unqualified area distribution ratio;

[0169] It should be explained that the operation classification coefficient reflects the following: on the premise that the uniformity of the coating thickness of the current pass meets the process requirements for the production of active anodes in theory, the distribution of the unqualified areas in the horizontal and vertical directions is judged from the number of unqualified areas, so as to comprehensively consider the difficulty of repeating the coating operation on the basis of the currently applied coating to ensure the uniformity of the coating;

[0170] Step 3: Compare the operation classification coefficient with the corresponding threshold value to generate a signal whether to continue the coating work;

[0171] In some embodiments, obtaining an operation classification coefficient, and comparing the operation classification coefficient to a corresponding threshold value;

[0172] If the operation classification coefficient is greater than or equal to the operation classification coefficient threshold, a discontinue coating signal is generated; when the discontinue coating signal is obtained, the currently unevenly coated coating can be scraped off and the coating work can be performed again;

[0173] If the operation classification coefficient is less than the operation classification coefficient threshold, a continue coating signal is generated; when the continue coating signal is obtained, the coating of the current uneven coating is continued, so as to meet the process requirements of the active anode production for the coating layer;

[0174] The technical solution of the embodiment of the present invention is as follows: image data of the coating after each coating pass is obtained, and grid-type division is performed based on the image data to obtain the area to be inspected; based on the area to be inspected, the thickness value of each area to be inspected is obtained to preliminarily determine whether the coating quality meets the requirements. If an analysis and evaluation signal is generated during the preliminary determination process, it is determined again whether the coating needs to be adjusted to obtain an operation classification coefficient; the operation classification coefficient is compared with the corresponding threshold to generate a signal on whether to continue the coating operation; the present invention judges the distribution of unqualified areas in terms of the number and proportion of unqualified areas and the horizontal and vertical directions on the premise that the uniformity of the coating thickness of the coating theoretically meets the process requirements for the production of active anodes, thereby comprehensively considering the difficulty of repeating the coating operation on the basis of the currently coated coating to ensure the uniformity of the coating, which not only realizes real-time monitoring of the coating coated in time, but also realizes better compensation work in the case of unevenness.

[0175] In addition to the above embodiments, the present invention also includes other implementation modes. Any technical solutions formed by equivalent transformation or equivalent replacement should fall within the protection scope of the claims of the present invention.

Claims

1. An active anode for an ion membrane electrolyzer, comprising a titanium-based mesh, wherein a coating is provided on the titanium-based mesh, characterized in that: The coating is a rutile structure composed of platinum, ruthenium, iridium and tin, wherein the content of platinum is 2 mol% to 40 mol%, the content of ruthenium is 5% to 45 mol%, the content of iridium is 2 mol% to 40 mol%, and the content of tin is 10 mol% to 65 mol%.

2. The active anode for an ion-exchange membrane electrolyzer according to claim 1, characterized in that: The platinum carrier is chloroplatinic acid.

3. The active anode for an ion-exchange membrane electrolyzer according to claim 1, characterized in that: The carrier of ruthenium is ruthenium trichloride.

4. The active anode for an ion-exchange membrane electrolyzer according to claim 1, characterized in that: The iridium carrier is iridium tetrachloride.

5. The active anode for an ion-exchange membrane electrolyzer according to claim 1, characterized in that: The tin carrier is tin chloride or organic tin.

6. A method for manufacturing an active anode for an ion-exchange membrane electrolyzer, characterized in that: The steps include: Step S1, using TA1 titanium plate expanded mesh as the substrate of the electrode; Step S2, processing the substrate web to provide a flat, clean, and rough-surfaced substrate, thereby ensuring that the bonding strength and specific surface area of ​​the coating are maximized; Step S3, preparing a coating solution of the compound solution for the anode coating of the ion-exchange membrane electrolyzer according to the formula, and evenly coating the coating solution on the substrate by a multi-pass coating method to form stable multi-metal oxide crystals on the surface of the titanium substrate.

7. The method for manufacturing an active anode for an ion-exchange membrane electrolyzer according to claim 6, characterized in that: In the process of manufacturing active anode for ion membrane electrolyzer, a substrate coating monitoring process is set up, including the following processes: Step 1: Obtain the image data of the coating after each coating, divide it into grids based on the image data, and obtain the area to be inspected; Step 2: Based on the area to be inspected, obtain the thickness value of each area to be inspected, and preliminarily determine whether the coating quality meets the requirements. If an analysis and evaluation signal is generated during the preliminary determination process, determine again whether the coating needs to be adjusted to obtain the operation classification coefficient; Step 3: Compare the operation classification coefficient with the corresponding threshold value to generate a signal whether to continue the coating work; If the operation classification coefficient is greater than or equal to the operation classification coefficient threshold, a discontinue coating signal is generated; when the discontinue coating signal is obtained, the coating work is restarted; If the operation classification coefficient is less than the operation classification coefficient threshold, a continue coating signal is generated; when the continue coating signal is obtained, the coating work is continued on the coating that is currently unevenly coated.

8. The method for manufacturing an active anode for an ion-exchange membrane electrolyzer according to claim 7, characterized in that: In step 2, the thickness value of each area to be inspected is obtained; if the thickness value of the area to be inspected does not meet the thickness mean range set by the standard process, it means that the area to be inspected does not meet the process requirements, and the area to be inspected is marked as an unqualified area; If there are unqualified areas in all the areas to be inspected, an analysis and evaluation signal is generated; When the analysis and evaluation signal is obtained, the operational classification coefficient is obtained.

9. The method for manufacturing an active anode for an ion-exchange membrane electrolyzer according to claim 8, characterized in that: The process of obtaining the operational classification coefficient is: First, the unqualified area is further divided. If the thickness value of the area to be inspected is less than the minimum value of the thickness mean range set by the standard process, it is marked as a concave unqualified area; If the thickness value of the area to be inspected is greater than the maximum value of the thickness mean range set by the standard process, it will be marked as a protruding unqualified area; Obtain the thickness values ​​of all protruding unqualified areas, and calculate the total thickness value ZBA of the protruding unqualified areas; obtain the thickness values ​​of all concave unqualified areas, and calculate the total thickness value ZBT of the concave unqualified areas; The total thickness value ZBA of the unqualified protruding area and the total thickness value ZBT of the unqualified concave area are calculated by difference to obtain the coating compensation difference, and the coating compensation difference is compared with the coating compensation difference threshold; If the coating compensation difference is greater than or equal to the coating compensation difference threshold, a judgment signal is generated; When the judgment signal is obtained, the ratio of the proportion of unqualified areas and the ratio of the distribution of unqualified areas are obtained, and the operation classification coefficient XFC is calculated; The process of obtaining the ratio of unqualified areas is as follows: Counting the number of all protruding unqualified areas and concave unqualified areas, adding the number of all protruding unqualified areas to the number of all concave unqualified areas, and obtaining the total number of unqualified areas; Then the total number of unqualified areas and the total number of areas to be inspected are calculated to obtain the ratio of unqualified areas. The process of obtaining the distribution ratio of unqualified areas is as follows: The inspection area is divided into horizontal and vertical directions, and the horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are calculated. The horizontal unqualified area distribution ratio and the vertical unqualified area distribution ratio are added together to obtain the unqualified area distribution ratio.

10. The method for manufacturing an active anode for an ion-exchange membrane electrolyzer according to claim 9, characterized in that: The calculation process of the horizontal unqualified area distribution ratio is: The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed: Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column; Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up; The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column; If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated; The number of unqualified signals generated in the column of the area to be inspected is obtained, and the ratio is calculated by dividing the area to be inspected into columns to obtain the horizontal unqualified area distribution ratio; The calculation process of the vertical unqualified area distribution ratio is: The area to be inspected is divided horizontally, and then the area to be inspected is divided into m groups of columns, each column includes several areas to be inspected, and the areas to be inspected in each column are analyzed: Obtain the thickness values ​​of all the protruding unqualified areas in each column of the area to be inspected, and sum them up to obtain the total thickness value of the protruding unqualified areas in each column; Obtain the thickness values ​​of all the unqualified concave areas in each column of the area to be inspected, and calculate the total thickness value of the unqualified concave areas in each column by summing them up; The total thickness value of each column of protruding unqualified areas and the total thickness value of each column of recessed unqualified areas are calculated to obtain the coating compensation difference of each column, and the coating compensation difference of each column is compared with the coating compensation difference threshold of each column; If the coating compensation difference of each column is less than the coating compensation difference threshold of each column, an unqualified signal of the area to be inspected in this column is generated; The number of unqualified signals generated in the column of the area to be inspected is obtained, and the number of columns divided by the area to be inspected is calculated to obtain the horizontal unqualified area distribution ratio.

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