Method for evaluating influence of organic additive on service life of titanium anode
By optimizing the coating structure using a constant current testing method and a nano-cerium oxide-zirconia composite coating solution, the signal noise problem caused by the decomposition products of additives in the preparation of electrolytic copper foil was solved, thereby improving the accuracy and stability of anode lifetime evaluation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGXI STANDE ELECTRODE TECH CO LTD
- Filing Date
- 2025-12-31
- Publication Date
- 2026-04-10
AI Technical Summary
In the prior art, the decomposition products of organic additives during the preparation of electrolytic copper foil can easily penetrate into the microcracks of the iridium-coated titanium anode, causing irregular fluctuations in the cell voltage and current density signals, which affects the accuracy and reliability of anode life evaluation.
A constant current testing method was used, combined with a composite coating solution of nano-cerium oxide and nano-zirconia, to optimize the coating structure. The constant current testing method was used to simulate the actual working scenario of the anode to accelerate the failure process. The failure mechanism was analyzed by voltage monitoring, and the coating density was optimized to reduce signal noise.
It significantly improves the accuracy and stability of anode life evaluation, reduces voltage fluctuations and current density deviations, and enhances the accuracy of failure identification and the ability to distinguish the effects of different additive brands/concentrations.
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Figure CN121830757A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of titanium anodes, and particularly relates to a method for evaluating the influence of an organic additive on the service life of a titanium anode. BACKGROUND
[0002] One of the important ways to control performance in the preparation process of electrolytic copper foil is to introduce an additive. By introducing the additive into the electrolyte, the reaction potential of copper deposition can be changed, and the microstructure and morphology of the plating layer are affected. In addition, the synergistic effect of different additives is one of the core elements affecting the service life of the anode. The copper plating additives are all organic additives, which can be basically divided into three types according to the function, including a brightener, a leveling agent and an inhibitor. The brightener is usually a small-molecule sulfur-containing organic substance, represented by polydithiopropyl sulfide (SPS); the leveling agent is usually a nitrogen-containing cationic surfactant, generally a quaternary ammonium salt or a heterocyclic surfactant; and the inhibitor is usually a polyether substance, and the most common one is polyethylene glycol (PEG). Among the three substances, the monomer molecular weight of the brightener is the smallest, and the brightener is also more easily decomposed by the titanium anode, so the brightener is the most researched in the market, and reducing the decomposition of the brightener is a long-term task.
[0003] The influence of the additive on the service life of the anode is throughout the whole electrolytic system, and the core action is to delay or accelerate the anode failure by controlling the electrode structure stability, interface reaction kinetics and degree of side reaction. In the production of electrolytic copper foil, the leveling agent, the brightener and the inhibitor are used as electrolyte additives, and the service life of the anode is indirectly affected by controlling the cathode copper deposition behavior. The oxidation and decomposition behavior of the additive on the anode surface may cause coating corrosion, passivation or impedance rise, and then shorten the service life of the anode. The brightener is the main threat to the service life of the anode due to the sulfur and alkyne alcohol easy to oxidize groups, and the decomposition products of the brightener accelerate the coating failure through acidification, corrosion, adsorption of the insulating layer and other mechanisms; the organic film formed by the adsorption of the brightener may cover the active sites of the anode, so that the oxygen evolution potential is increased, the lattice oxygen loss of the noble metal in the coating is accelerated, and the service life is consumed.
[0004] Based on the above factors, different brands of brighteners are selected, and the concentration gradient is controlled to further explore the specific influence of SPS on the service life of the anode, and a new accelerated service life evaluation system is developed, that is, a method for evaluating the influence of an organic additive SPS on the service life of a titanium anode.
[0005] And in the existing accelerated life test, the micro-cracks generated in the preparation process of iridium series coating titanium anode, usually with a density of about 5 strips / mm2, is a common technical problem. Under high current density test conditions, organic additives (especially SPS) in the electrolyte and their decomposition products easily penetrate into these micro-cracks, triggering local hidden corrosion of the coating, resulting in irregular fluctuations in the tank voltage and current density signals during the test, for example, voltage fluctuations can reach ±0.05V. This noise in the baseline signal can mask the onset of real coating failure, leading to inaccurate determination of the time of appearance of anode passivation criteria, such as voltage rising to 1.5 times the initial value, thereby reducing the sensitivity and reliability of the entire evaluation system in distinguishing different brands or concentrations of additives. SUMMARY
[0006] The purpose of the present application is to develop an evaluation method for the influence of organic additive SPS on the life of titanium anode, which combines pre-processed iridium series coating titanium anode, titanium-based cathode and electrolyte with different additives according to the design to explore the influence of brightener SPS on the life of anode by constant current test method.
[0007] To achieve the above-mentioned purpose, the present application provides the following technical scheme: an evaluation method for the influence of organic additive on the life of titanium anode, comprising the following steps: S1: preparing an iridium series coating titanium anode sample according to the sample preparation process, which includes cutting, sandblasting, annealing, pickling, soaking, coating, high-temperature sintering and cooling; S2: shearing the sample obtained in S1, and then polishing to obtain a surface coating with a fixed area; S3: analyzing the sample obtained in S2 before accelerated life test, including SEM, XRD and electrochemical test, etc.; S4: taking titanium substrate as cathode, polishing it before test to remove surface impurities and oxide layer; S5: preparing a 20% sulfuric acid solution as the base solution of electrolyte, and selecting four different brands of SPS to add corresponding amount of additives in the base solution according to different concentration gradients to configure the electrolyte; S6: placing the cathode and anode treated in steps S3 and S4 in a 1000ml customized container containing electrolyte with different additives, and using a polytetrafluoroethylene fixing nut to ensure that the two electrodes are spaced about 10mm apart; S7: using constant current test method, accelerated life test of anode is carried out by setting high current density, electrolysis is carried out at room temperature, changes of tank voltage with time are recorded, consumption of solution in the container is monitored, and replenishment is added and checked every day; S8: Observe the voltage change, when the titanium anode passivation occurs, the cell voltage rises sharply, which is considered as anode failure, the cell voltage rises to about 1.5 times the initial voltage, according to the total power-on time at this time to calculate the anode strengthening life; S9: After the sample after the life test is washed with deionized water and dried, it is subjected to accelerated life test and analysis, including SEM, XRD and electrochemical test, failure analysis is carried out according to the results, and finally the results are output.
[0008] Preferably, the titanium substrate selected in the above step S4 is a titanium plate, a titanium mesh or a titanium rod, and the specific specification is TA1 or TA2.
[0009] Preferably, the SPS brand selected in the above step S5 is A, B, C or D, and the concentration gradient range is 1-7 mg / L.
[0010] Preferably, in the above step S7, the reason for choosing constant current test method is as follows: The attenuation and failure of anode life are directly related to the electrochemical reaction rate of anode material in essence, and the key driving factor of reaction rate is current density, not voltage. The core reason for choosing constant current test method is that it can accurately simulate the actual working scene of anode, efficiently accelerate the failure process, shorten the test period, and ensure the stability of test results, repeatability and correlation; Most importantly, it is convenient for failure mechanism analysis, and the failure mechanism can be analyzed reversely through voltage monitoring, which has the dual values of "life evaluation" and "failure diagnosis".
[0011] Preferably, in the above step S7, the direct current source is selected as 10A / 36V, and the current density is set as 5A / cm 2 .
[0012] Preferably, in the above step S7, the current density is set as 5A / cm 2 The reason is as follows: In the copper plating industry, the actual working current density of anode is usually low (the conventional acid copper plating anode current density is about 0.5-2A / cm²). 5A / cm² belongs to "moderate overworking condition" current density: it can compress the experimental period to several days or weeks by increasing the current intensity to accelerate the electrochemical reaction rate (such as anode dissolution, side reaction generation) on the surface of anode; It will not cause "over acceleration" due to too high current density, avoid abnormal failure of anode (such as instantaneous ablation, structure disintegration) which is irrelevant to actual working condition, and ensure that the experimental results can reflect the true life law.
[0013] Preferably, the replenishing solution in step S7 is an aqueous solution containing the same concentration of additives, and the same volume of replenishing solution is added at a fixed time every day. For the same batch of samples, two anodes are taken from each group for repeated accelerated life test to reduce experimental error.
[0014] Preferably, the sample preparation process in step S1 specifically includes the following steps: Trimming: the size is limited to 15x20 cm, and the aspect ratio is 1.33:1 to reduce the uneven current distribution caused by edge effects, ensure uniform current density during testing, and avoid local premature failure interference with life determination; Sand blasting: 0.3-0.5mm diamond sand is used, and the surface roughness Ra is ≥4.5μm to increase the adhesion of the coating and delay the peeling of the coating during high-voltage testing of the anode plate; Annealing: using segmented temperature control to reduce the risk of hydrogen embrittlement and thermal stress cracking during high-current testing: 400℃ for 1h to remove hydrogen→600℃ for 2h to eliminate stress→furnace cooling; Pickling: using a mixture of oxalic acid and hydrogen peroxide solution with a concentration of 10%+3%. Compared with conventional single oxalic acid, the use of this mixture can generate a more uniform microporous structure and improve the adhesion of the coating; Soaking: 95℃ for 30min; Coating: using a coating solution to coat the anode mark, and using a customized roller brush to coat the coating solution to form a fixed topography on the anode surface, inhibit crack propagation under high current, and prolong the time to passivation.
[0015] In the present application, to solve the signal noise problem in the background art, the composition of the coating solution in the coating step is optimized. The coating solution contains a complex combination of nano cerium oxide and nano zirconium oxide. The core mechanism is the synergistic filling and structural enhancement effect of the two different particle sizes and properties of nanoparticles: (1) Synergistic filling effect: nano zirconium oxide particles with a particle size of 20-30nm are smaller than the interstitial pores between conventional nano cerium oxide particles and the initial defects of microcracks. During coating and sintering, these smaller zirconium oxide particles can effectively fill the gaps between the cerium oxide particle accumulation and the microcracks on the coating surface, forming a more dense "cerium-zirconium composite coating" structure. After this optimization, the crack density of the coating can be significantly reduced from ≤5 / mm² to ≤3 / mm².
[0016] (2) Interfacial physical barrier effect: this dense coating structure can physically block the SPS molecules and the acidic products (such as SO4 2- , H +) penetration to the inside of the coating. This fundamentally avoids the slight fluctuations in voltage and current signals caused by SPS-induced localized corrosion at the deep cracks, ensuring the stability of the signal baseline throughout the entire accelerated life test process. The voltage fluctuation can be reduced from ±0.05V to within ±0.02V, and the current density deviation can be reduced from ±0.2A / cm² to ±0.08A / cm².
[0017] (3) Failure signal sharpening effect: due to the more uniform overall structure of the coating, when the oxidative decomposition of SPS leads to the deactivation of the active components of the coating, the passivation process of the anode is more synchronized, rather than starting from the cracks and expanding locally. Therefore, when passivation occurs, the resistance of the entire anode surface will show a sharp, uniform jump, which is manifested as a more rapid and steep rise in the cell voltage. The failure response time can be shortened from about 30 minutes to about 10 minutes. This significantly improves the accuracy of anode life endpoint interpretation and the resolution sensitivity of different SPS brands / concentrations.
[0018] High-temperature sintering: inert atmosphere protection sintering, 550℃×10min→480℃×30min, through the protection of inert gas to reduce the oxidation loss of noble metal, to ensure the consistency of the coating conductivity.
[0019] Preferably, in the above sample preparation process, the sandblasting angle is limited to 90°±5°, further improving the uniformity of the surface roughness of the anode plate sample; The crack density of the coating after sintering is limited to ≤5 lines / mm², meeting the SEM detection standard.
[0020] Compared with the prior art, the beneficial effects of the present application are: 1. The present application aims to explore the effects of different additives on anode life, find a best anode life evaluation system, reduce the influence of electrolyte factors on accelerated life, and improve the accuracy and stability of life test results.
[0021] 2. Brightener is the most important in the entire additive system, so in the study of single additive, the brightener (SPS) is chosen as the research object. The minimum SPS concentration and SPS brand that affect the anode life are studied, and a complete accelerated life additive test system is established in the laboratory.
[0022] 3. By specific optimization of the composition of the coating liquid, a nano cerium oxide-zirconium oxide compound system is introduced, and the compactness of the iridium series coating is significantly improved in physical structure by using the synergistic filling effect. This optimization directly addresses and solves the signal baseline noise problem in accelerated life test, which is specifically manifested as: the voltage signal baseline fluctuation is reduced, the current density stability is improved, and the voltage mutation response speed of anode failure is accelerated. These improvements greatly improve the signal-to-noise ratio of the life test data, and the distinguishing ability of different SPS brands (such as C brand with greater impact on life and B brand and D brand with less impact) is more significant and reliable, greatly improving the accuracy, repeatability and reliability of the evaluation method. BRIEF DESCRIPTION OF DRAWINGS
[0023] Fig. 1 A sample preparation process flowchart of a titanium anode in an evaluation method of the influence of an organic additive on the life of a titanium anode according to the present application; Fig. 2 A flowchart of an evaluation method of the influence of an organic additive on the life of a titanium anode according to the present application. DETAILED DESCRIPTION
[0024] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.
[0025] Embodiment 1: with reference to the attached Figs. 1-2 The present application provides a technical solution: an evaluation method of the influence of an organic additive on the life of a titanium anode, comprising the following steps: S1: preparing an iridium series coating titanium anode sample according to a sample preparation process, which includes: cutting: limiting the size to 15x20 cm, with a length-width ratio of 1.33:1, to reduce the uneven current distribution caused by edge effect, ensure uniform current density during testing, and avoid local premature failure interference with life determination; Sand blasting: using 0.3-0.5mm diamond sand, surface roughness Ra≥4.5μm, increasing the adhesion of the coating, delaying the peeling of the coating during high voltage testing of the anode plate, and limiting the sand blasting angle to 90°±5°, further improving the uniformity of the surface roughness of the anode plate sample; Annealing: using stepwise temperature control to reduce the risk of hydrogen embrittlement and thermal stress cracking during high current testing: 400℃ for 1h to remove hydrogen→600℃ for 2h to eliminate stress→furnace cooling; Pickling: using oxalic acid + hydrogen peroxide mixed solution, concentration 10% + 3%, compared with the conventional single oxalic acid, using this mixed solution can generate more uniform microporous structure, improve the coating adhesion; Soaking: 95℃ for 30min; Coating: using coating solution to coat the anode mark, using custom drum brush to coat the coating solution, so that the anode surface forms a fixed morphology, inhibits crack propagation under high current, and prolongs the passivation time; The coating coating adopts an optimized coating solution, and the composition is: 0.5% by mass fraction of nano cerium oxide, 0.2% by mass fraction of nano zirconium oxide (particle size 25nm), and the balance is a mixed solvent of ethanol and deionized water (volume ratio 1:1). Before use, the coating solution is placed in an ultrasonic disperser for 30 minutes at a frequency of 40 kHz to ensure uniform dispersion of nanoparticles and avoid agglomeration. Subsequently, a custom drum brush is used for uniform coating. After subsequent high-temperature sintering, the nano zirconium oxide particles can effectively embed in the micro-pores and cracks of the cerium oxide coating, producing a synergistic filling effect as described in the invention, and finally obtaining a dense composite coating with a crack density ≤5 lines / mm². The optimized coating provides a test interface with more stable electrochemical performance and lower background noise for subsequent accelerated life testing; High-temperature sintering: inert gas protection sintering, 550℃×10min→480℃×30min, by the protection of inert gas to reduce the oxidation loss of noble metal, to ensure the consistency of the coating conductivity, and limit the crack density of the coating after sintering ≤5 lines / mm², to meet the SEM detection standard; Through the above process, the basic life of the manufactured titanium anode sample is improved, the life difference of different SPS brands is amplified, and the sensitivity of the evaluation system is highlighted.
[0026] S2: Shear the sample obtained in S1, and then polish to obtain a surface coating of a fixed area; S3: Perform accelerated life testing before analysis on the sample obtained in S2, including SEM, XRD, and electrochemical testing, etc. S4: Take a titanium plate as the cathode, with a specification of TA1, polish it before testing to remove surface impurities and oxide layers; S5: Prepare a 20% sulfuric acid solution as the electrolyte base solution, and add SPS brightener of brand A to prepare an electrolyte with a final concentration of 1mg / L; S6: Place the cathode and anode treated in steps S3 and S4 in a custom container containing 1000mL of electrolyte with different additives, and use a polytetrafluoroethylene fixed nut to ensure that the two electrodes are spaced about 10mm apart; S7: Accelerated life test of the anode was carried out by using a constant current test method, and a 10A / 36V direct current power supply was used, and the current density was set to 5A / cm 2 The electrolysis was carried out at room temperature, the change of tank voltage with time was recorded, the consumption of solution in the container was monitored, the replenishment liquid was added every day and observed, wherein the replenishment liquid was an aqueous solution containing the same concentration of additives, and the same volume of replenishment liquid was added at a fixed time every day; S8: The voltage change was observed, when the titanium anode was passivated, the tank voltage was sharply increased, which was regarded as anode failure, the tank voltage was increased to about 1.5 times of the initial voltage, and the anode strengthening life was calculated according to the total power-on time at this time; S9: The sample after the life test was rinsed with deionized water and dried, and was analyzed after the accelerated life test, including SEM, XRD and electrochemical test, the failure analysis was carried out according to the results, and finally the results were output.
[0027] Example 2: The difference between this example and example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and A brand SPS brightener is added respectively, and an electrolyte with a final SPS concentration of 3mg / L is prepared.
[0028] Example 3: The difference between this example and example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and A brand SPS brightener is added respectively, and an electrolyte with a final SPS concentration of 5mg / L is prepared.
[0029] Example 4: The difference between this example and example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and A brand SPS brightener is added respectively, and an electrolyte with a final SPS concentration of 7mg / L is prepared.
[0030] Comparative example 1: The difference between this example and example 1 is only that in step S5, no SPS is selected.
[0031] Table 1 is a table of A brand SPS electrolyte with different concentration gradients and test life in examples 1-4 and comparative example 1
[0032] Example 5: The difference between this example and example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and B brand SPS brightener is added respectively, and an electrolyte with a final SPS concentration of 1mg / L is prepared.
[0033] Example 6: The difference between this example and Example 5 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and B brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 3 mg / L.
[0034] Example 7: The difference between this example and Example 1 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and B brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 5 mg / L.
[0035] Example 8: The difference between this example and Example 1 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and B brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 7 mg / L.
[0036] Table 2 is a table of B brand SPS electrolyte with different concentration gradients and test life in Examples 5-8 and Comparative Example 1
[0037] Example 9: The difference between this example and Example 1 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and C brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 1 mg / L.
[0038] Example 10: The difference between this example and Example 5 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and C brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 3 mg / L.
[0039] Example 11: The difference between this example and Example 1 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and C brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 5 mg / L.
[0040] Example 12: The difference between this example and Example 1 is only that in step S5, a sulfuric acid solution with a mass concentration of 20% is prepared as the electrolyte base solution, and C brand SPS brightener is added respectively to prepare electrolyte with a final SPS concentration of 7 mg / L.
[0041] Table 3 is a table of C brand SPS electrolyte with different concentration gradients and test life in Examples 9-12 and Comparative Example 1
[0042] Example 13: The difference between this example and Example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and a C brand SPS brightener is added to prepare an electrolyte with a final SPS concentration of 1 mg / L.
[0043] Example 14: The difference between this example and Example 5 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and a C brand SPS brightener is added to prepare an electrolyte with a final SPS concentration of 3 mg / L.
[0044] Example 15: The difference between this example and Example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and a C brand SPS brightener is added to prepare an electrolyte with a final SPS concentration of 5 mg / L.
[0045] Example 16: The difference between this example and Example 1 is only that in step S5, a 20% sulfuric acid solution is prepared as the electrolyte base solution, and a C brand SPS brightener is added to prepare an electrolyte with a final SPS concentration of 7 mg / L.
[0046] Table 4 is a table of the D brand SPS electrolyte with different concentration gradients and the test life in Examples 13-16 and Comparative Example 1
[0047] Comparative Example 2: The difference between this example and Example 1 is that in step S1, a conventional preparation process is used, and after the temperature is raised in the annealing stage, it is directly held at 600°C for 2 h, and a single oxalic acid is used for acid pickling.
[0048] Comparative Example 3: The difference between this example and Example 1 is that in step S1, a conventional preparation process is used, and the coating solution is not updated in the coating stage, and the coating tool is a roller brush commonly used in the market.
[0049] Table 5 is a table of the A brand SPS electrolyte and the test life in Example 1 and Comparative Examples 1-3
[0050] According to the above tests, compared with the conventional annealing and acid pickling process, the process optimization in this patent can greatly improve the anode life, and the optimization of the coating stage can greatly improve the anode life, which can increase the anode life by 31.34%. The accelerated life of the titanium anode sample after adding the additive decreases, and the anode life gradually decreases with the increase of the concentration of the brightener SPS, which indicates that the titanium anode is greatly affected by the concentration of the additive SPS, and the same concentration of brand B and brand D has similar influence on the anode life, and both have the smallest influence on the anode life, and brand C has the largest influence on the anode life, which can easily reduce the accelerated life of the titanium anode.
[0051] Although the present application has been described in detail with reference to the foregoing embodiments, the technical solutions recorded in the foregoing embodiments can be modified, or some of the technical features can be replaced by equivalent features, by those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for evaluating the effect of an organic additive on the life of a titanium anode, characterized by, The method comprises the following steps: S1: preparing an iridium-based coated titanium anode sample according to a sample preparation process, the sample preparation process of the titanium anode comprising cutting, sand blasting, annealing, pickling, soaking, coating, high-temperature sintering, and cooling; S2: shearing the sample obtained in S1, and then polishing to obtain a surface coating with a fixed area; S3: performing pre-accelerated life test analysis on the sample obtained in S2, including SEM, XRD, and electrochemical test, etc.; S4: taking a titanium substrate as a cathode, and polishing the titanium substrate to remove impurities and an oxide layer on the surface of the titanium substrate; S5: preparing a sulfuric acid solution with a mass concentration of 20% as an electrolyte base solution, and adding SPS brighteners of A, B, C, and D brands to prepare electrolytes with final concentrations of 1 mg / L, 3 mg / L, 5 mg / L, and 7 mg / L of SPS, respectively. 2.S6: placing the cathodes and anodes treated in steps S3 and S4 in a customized container containing 1000 mL of electrolyte with different additives, and using a polytetrafluoroethylene fixing nut to ensure that the two electrodes are spaced apart by about 10 mm; S7: performing accelerated life test on the anode by setting a large current density using a constant current test method, electrolyzing at room temperature, recording the change of tank voltage with time, monitoring the consumption of the solution in the container, adding a replenishing solution every day, and checking; S8: observing the change of voltage, regarding the anode as being invalid when the titanium anode is passivated and the tank voltage sharply rises, and calculating the anode strengthening life according to the total power-on time at this time; S9: rinsing and drying the sample after the life test, performing accelerated life test analysis on the sample, including SEM, XRD, and electrochemical test, performing failure analysis according to the results, and finally outputting the results.
3. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 1, characterized by: The titanium substrate selected in step S4 is a titanium plate, a titanium mesh, or a titanium rod, and the specific specifications are TA1 or TA2.
4. The method for evaluating the influence of an organic additive on the service life of a titanium anode according to claim 1, characterized in that: The SPS brands selected in step S5 are A, B, C, and D, and the concentration gradient range is 1-7 mg / L.
5. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 1, characterized by: During the above step S7, the direct current power source is selected as 10A / 36V, and the current density is set as 5A / cm 2 .
6. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 1, characterized by: The replenishing solution in step S7 is an aqueous solution containing the same concentration of additives, and the same volume of replenishing solution is added at a fixed time every day. For the same batch of samples, two anodes are taken for repeated accelerated life test in each group of experiments to reduce experimental errors.
7. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 1, characterized by: The sample preparation process in step S1 specifically comprises the following steps: Cutting: the size is limited to 15×20 cm, and the length-width ratio is 1.33:1; Sand blasting: 0.3-0.5 mm diamond sand is used, and the surface roughness Ra is greater than or equal to 4.5 μm; Annealing: using segmented temperature control: 400°C for 1 h, 600°C for 2 h, and furnace cooling; Pickling: using a mixture of oxalic acid and hydrogen peroxide solution; Soaking: 95°C for 30 min; Coating: using a coating solution to coat the anode marker, and using a customized roller brush to coat the coating solution, so that a fixed pattern is formed on the surface of the anode; High-temperature sintering: sintering under the protection of inert atmosphere, 550°C×10 min→480°C×30 min.
8. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 6, characterized by: In the above sample preparation process, the sand blasting angle is limited to 90°±5°; The crack density of the coating after sintering is limited to less than or equal to 5 lines / mm².
9. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 6, characterized by: In the coating step, the coating liquid used contains nano cerium oxide and nano zirconium oxide, the mass fraction of the nano cerium oxide ranges from 0.4% to 0.6%, and the mass fraction of the nano zirconium oxide ranges from 0.15% to 0.25%, based on the total mass of the coating liquid.
10. The method for evaluating the effect of an organic additive on the service life of a titanium anode according to claim 8, characterized by: The mass fraction of the nano cerium oxide is 0.5%, and the mass fraction of the nano zirconium oxide is 0.2%; the particle size of the nano zirconium oxide is 20nm to 30nm.