A multilayer PCB titanium anode net and a preparation method thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI JIPING NEW ENERGY TECH CO LTD
- Filing Date
- 2026-05-15
- Publication Date
- 2026-08-07
AI Technical Summary
[0004]然而，现有钛阳极技术在高频脉冲电镀应用中存在以下问题：1.传统“底层-中间层-表层”平面层状复合结构中，各层之间存在明显的物理界面，热膨胀系数差异导致高频脉冲热循环下界面应力集中，易发生层间剥离失效；2.电子传导依赖层间物理接触，高频下存在传导滞后和界面过热，产生“瓶颈效应”，导致能量损耗大、电流响应速度慢；3.涂层耐蚀性不足，在强氧化性电镀液中长期服役时易发生晶间腐蚀，尤其是高频脉冲的周期性电流变化加速了裂纹的萌生与扩展；4.传统镀层均匀性难以保证
本发明以钛网为基材，在其表面依次构建底层、中间层和表层，其中钛网基体通过激光刻蚀与化学蚀刻结合处理，提高与表层的结合力，化学蚀刻时采用草酸与双氧水的混合溶液处理，通过草酸的化学蚀刻作用去除钛基体表面的自然氧化层并形成均匀的麻面结构，同时利用双氧水的氧化性加速蚀刻动力学并抑制氢脆现象，为后续涂层提供理想的机械锚固界面；底层为IrO2-Ta2O3-SnO2纳米晶层，可确保与钛网基体结合牢固，防止钛基体在高频脉冲下生成钝化膜；中间层为高熵氧化物(IrRuTaSnBi)Ox固溶体层，通过高熵效应缓解晶格畸变，阻止裂纹扩展，从而提高涂层的整体耐蚀性；表层的比表面积大，帮助降低真实电流密度，从而适应高频脉冲下的瞬态大电流。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of anode preparation technology and relates to a multilayer titanium anode mesh and its preparation method. Background Technology
[0002] Electrodes are commonly used in electrocatalytic technologies such as electroplating and electrolysis. Among them, high-frequency pulse electroplating technology has become a key process for fine circuit filling and through-hole electroplating in high-end printed circuit board (PCB) manufacturing due to its characteristics of high limiting current density, dense coating, and excellent deep plating capability. In the high-frequency pulse (typically frequency ≥10 kHz, duty cycle can be as low as 10%~30%) operating mode, the anode needs to withstand instantaneous large current and periodic current reverse impact, which places stringent requirements on the conductivity, passivation resistance and mechanical stability of the anode.
[0003] In the prior art, the active coating of titanium anodes mainly adopts noble metal oxide systems, such as iridium or ruthenium, and extends the life by adding components such as tantalum and tin to form binary or ternary solid solutions.
[0004] However, existing titanium anode technology has the following problems in high-frequency pulse electroplating applications: 1. In the traditional planar layered composite structure of "bottom layer-intermediate layer-top layer", there are obvious physical interfaces between the layers. The difference in thermal expansion coefficients leads to stress concentration at the interface under high-frequency pulse thermal cycling, which easily causes interlayer delamination failure; 2. Electron conduction depends on interlayer physical contact. At high frequencies, there is conduction hysteresis and interface overheating, which produces a "bottleneck effect", resulting in large energy loss and slow current response speed; 3. The coating has insufficient corrosion resistance. When it is used for a long time in a strong oxidizing electroplating solution, it is prone to intergranular corrosion. In particular, the periodic current changes of high-frequency pulses accelerate the initiation and propagation of cracks; 4. It is difficult to guarantee the uniformity of traditional coatings.
[0005] Therefore, there is an urgent need to develop a titanium anode to adapt to high-frequency pulse conditions. Summary of the Invention
[0006] The purpose of this invention is to provide a multilayer titanium anode mesh and its preparation method. The anode prepared by this invention has a long lifespan, high TP value, good electroplating uniformity, and is suitable for high-frequency pulse environments.
[0007] The objective of this invention can be achieved through the following technical solutions: A multilayer PCB titanium anode mesh, the PCB titanium anode mesh comprising a titanium mesh substrate, a bottom layer, an intermediate layer and a surface layer arranged sequentially; The intermediate layer comprises titanium tantalum oxide; the intermediate layer is a high-entropy oxide solid solution layer, the chemical formula of the high-entropy oxide is (IrRuTaSnBi)Ox, x=8~12; The surface layer is grown on the surface of the intermediate layer and is a ternary oxide solid solution of (IrTaSn)Ox, x=5~7. The surface of the surface layer has an Ir-rich nanosynaptic structure.
[0008] A method for preparing a multilayer titanium anode mesh according to claim 1, comprising the following steps: S1. Pretreatment of the titanium matrix: The laser-treated titanium mesh was immersed in a mixed solution of 10% oxalic acid and 5% hydrogen peroxide (volume ratio 1:1), treated at 85°C for 30 minutes, removed and rinsed with deionized water until neutral, and then dried in a nitrogen stream. S2, Preparation of the bottom layer: A mixed dispersion of precursors containing chloroiridic acid, tantalum pentachloride, tin tetrachloride, and modified titanium carbide was coated onto the surface of a pretreated titanium mesh. The coating-drying-sintering process was repeated to form the bottom layer. S3. Preparation of the intermediate layer: A high-entropy precursor solution containing Ir, Ru, Ta, Sn, and Bi is coated onto the bottom surface, dried, sintered, and the process is repeated to form a high-entropy oxide solid solution intermediate layer. S4. Preparation of the surface layer: A template-assisted method is used to assemble a polystyrene microsphere template on the surface of the intermediate layer, fill it with a precursor containing Ir, Ta, and Sn, and remove the template by thermal desorption to form the surface layer, thus obtaining the titanium anode mesh.
[0009] As a preferred embodiment of the present invention, the preparation process of the modified titanium carbide in step S2 is as follows: Titanium carbide powder was dispersed in a mixture of tetrabutyl titanate, anhydrous ethanol, glacial acetic acid and deionized water in a volume ratio of (5~7):(50~60):2:1. The mixture was ultrasonically dispersed for 30 min, centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 80℃ for 12 h to obtain mixture A. Mixture A was placed in a tube furnace and heated to 490-510°C at 5°C / min under a hydrogen / argon mixed atmosphere with a hydrogen gas fraction of 5% and held for 1 hour. Then, under an H2 / H2O mixed atmosphere with a hydrogen gas fraction of 5%, the temperature was increased to 900-920°C at 2°C / min and held for 12 hours. The mixture was then naturally cooled to room temperature to obtain the modified titanium carbide.
[0010] As a preferred technical solution of the present invention, in step S2, the mass ratio of chloroiridic acid, tantalum pentachloride, tin tetrachloride and modified titanium carbide in the precursor mixed dispersion is (40~60):(20~40):(10~30):(5~15).
[0011] As a preferred technical solution of the present invention, in step S2, the sintering is carried out under a nitrogen protective atmosphere, the sintering temperature is 450~500℃, the sintering time is 10~20min each time, and the coating-drying-sintering operation is repeated 8~15 times.
[0012] As a preferred technical solution of the present invention, in step S3, Ir, Ru, Ta, Sn and Bi in the high-entropy precursor solution are in equimolar ratio, and the molar percentage of each metal is 15~25%.
[0013] As a preferred technical solution of the present invention, in step S3, citric acid is also added to the high-entropy precursor solution, and the molar ratio of citric acid to total metal ions is (1~2):1.
[0014] As a preferred technical solution of the present invention, in step S3, the sintering temperature is 490~530℃, the heating rate is 5~10℃ / min, the sintering time is 10~20min, and the coating-drying-sintering operation is repeated 5~10 times.
[0015] As a preferred technical solution of the present invention, in step S4, the molar ratio of Ir, Ta and Sn in the precursor containing Ir, Ta and Sn is (50~70):(15~25):(15~25).
[0016] As a preferred embodiment of the present invention, the specific preparation process of step S4 is as follows: Polystyrene microspheres were dispersed in deionized water to form a suspension with a mass fraction of 5-8%. Sodium dodecyl sulfate with a volume fraction of 0.1-0.5% was added. Microsphere templates were assembled on the surface of the titanium mesh treated in step S3 by spin coating. After completion, the microspheres were treated with oxygen plasma for 30-45 seconds at a power of 50W. Chloroiridic acid, tantalum pentachloride, and tin tetrachloride were added to ethylene glycol solvent to form a surface precursor solution. The titanium mesh prepared by the above operation was immersed in the surface precursor solution and deposited by electrophoretic deposition. After deposition, the sample was placed in a muffle furnace and heated to 400-500℃ at a heating rate of 0.5-2℃ / min and held for 30-60 min. Subsequently, the sample was subjected to rapid thermal annealing at 400℃ for 1.5 min.
[0017] This invention introduces modified titanium carbide into the bottom layer and uses a two-stage reduction process to obtain a pure-phase Ti4O7 shell. The bottom layer is gradient sintered under nitrogen protection to prevent Ti4O7 oxidation. The high-entropy intermediate layer achieves molecular-level mixing of five metal ions through citric acid complexation. It can serve as a conductive reinforcement network and is embedded in the three-dimensional micro / nano structure of the titanium mesh matrix through electrophoretic deposition, forming a continuous conductive path extending from the interior of the matrix to the surface. This helps to eliminate the "bottleneck effect" caused by interlayer interface contact in traditional layered structures, improves the electron transport response speed, and thus meets the microsecond-level transient requirements of high-frequency pulses.
[0018] The intermediate layer adopts a pentagonal high-entropy oxide solid solution of (IrRuTaSnBi)Ox. The five metal elements Ir, Ru, Ta, Sn and Bi are prepared in an equimolar ratio to form a high-entropy precursor solution. Citric acid is added as a complexing agent to achieve uniform mixing at the molecular level. After sintering, a single solid solution high-entropy oxide layer of (IrRuTaSnBi)Ox is formed. The lattice distortion caused by the high-entropy effect absorbs the mechanical stress generated by the periodic thermal shock of high-frequency pulses, thereby achieving synergistic optimization of conductivity, corrosion resistance and thermal stability.
[0019] The surface layer grows directly on the surface of the intermediate layer, forming a continuous transition interface without physical delamination issues. Rapid thermal annealing further reduces the oxygen evolution overpotential. A template-assisted method is used to first assemble a regular polystyrene microsphere monolayer template on the surface of the intermediate layer, followed by electrophoretic deposition to fill the precursor. Rate-controlled pyrolysis avoids rapid template decomposition that could damage the nanocone structure.
[0020] The beneficial effects of this invention are: This invention uses a titanium mesh as a substrate, on which a bottom layer, an intermediate layer, and a top layer are sequentially constructed. The titanium mesh substrate is treated with a combination of laser etching and chemical etching to improve its adhesion to the top layer. During chemical etching, a mixed solution of oxalic acid and hydrogen peroxide is used. The natural oxide layer on the surface of the titanium substrate is removed by the chemical etching action of oxalic acid, forming a uniform rough surface structure. At the same time, the oxidizing property of hydrogen peroxide accelerates the etching kinetics and inhibits hydrogen embrittlement, providing an ideal mechanical anchoring interface for subsequent coatings. The bottom layer is an IrO2-Ta2O3-SnO2 nanocrystalline layer, which ensures a strong bond with the titanium mesh substrate and prevents the formation of a passivation film on the titanium substrate under high-frequency pulses. The intermediate layer is a high-entropy oxide (IrRuTaSnBi)Ox solid solution layer, which alleviates lattice distortion and prevents crack propagation through the high-entropy effect, thereby improving the overall corrosion resistance of the coating. The top layer has a large specific surface area, which helps to reduce the actual current density, thus adapting to the transient high current under high-frequency pulses. Detailed Implementation
[0021] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.
[0022] It should be noted that, unless otherwise specified, the present invention does not specifically limit the source of the raw materials used in the following embodiments. Commercially available products or products prepared by conventional preparation methods that are well known to those skilled in the art can be used. Experimental methods that do not specify specific conditions are all conventional methods and conventional conditions well known in the art.
[0023] Example 1
[0024] S1. Pretreatment of the titanium matrix: The laser-treated titanium mesh was immersed in a mixed solution of 10% oxalic acid and 5% hydrogen peroxide (volume ratio 1:1) and treated at 85°C for 30 min. After removal, it was rinsed with deionized water until neutral and dried in a nitrogen stream. The laser power was set to 20 W and the scanning speed to 200 mm / s. S2, Preparation of the bottom layer: Titanium carbide powder was dispersed in a mixture of tetrabutyl titanate, anhydrous ethanol, glacial acetic acid and deionized water in a volume ratio of 6:55:2:1. The mixture was ultrasonically dispersed for 30 min, centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 80 °C for 12 h to obtain mixture A. The solid-liquid ratio of titanium carbide powder to the mixture was 1:30 g / mL. Mixture A was placed in a tube furnace and heated to 500°C at 5°C / min and held for 1 hour in a hydrogen / argon mixed atmosphere with a hydrogen gas fraction of 5%. Then, it was heated to 910°C at 2°C / min and held for 12 hours in a H2 / H2O mixed atmosphere with a hydrogen gas fraction of 5%. The mixture was then naturally cooled to room temperature to obtain the modified titanium carbide. Chloroiridic acid, tantalum pentachloride, and tin tetrachloride were added to a mixed solvent of n-butanol and isopropanol in a volume ratio of 1:1. Then, 5% concentrated hydrochloric acid and 3% polyethylene glycol PEG 400 were added to the mixed solvent to obtain a precursor solution. The total mass ratio of chloroiridic acid, tantalum pentachloride, and tin tetrachloride to the mixed solvent was 1 g: 25 mL. Modified titanium carbide was then added, with the mass ratio of chloroiridic acid, tantalum pentachloride, tin tetrachloride, and modified titanium nitride being 50:30:20:10. After stirring for 2 hours, the mixture was aged for 24 hours to obtain a bottom precursor mixed dispersion. The coating was applied to the surface of the pretreated titanium mesh, dried in an oven at 120°C for 15 minutes, and then sintered under a nitrogen protective atmosphere at a temperature of 480°C for 15 minutes each time. The coating-drying-sintering process was repeated 10 times to obtain the bottom layer. S3. Preparation of the intermediate layer: Ir:Ru:Ta:Sn:Bi were weighed according to the molar ratio (each metal molar percentage 20%), chloroiridic acid, ruthenium trichloride, tantalum pentachloride, tin tetrachloride and bismuth nitrate were weighed respectively. The above metal salts were dissolved in a mixed solvent of ethylene glycol methyl ether and anhydrous ethanol in a volume ratio of 1:1. Citric acid with a molar ratio of 1:1.5 to the total metal ions was added as a complexing agent. The mixture was stirred for 4 hours to obtain a high-entropy oxide precursor solution. The precursor solution was coated on the surface of the titanium mesh with the prepared bottom layer. After sintering, an intermediate layer was obtained. The sintering temperature was 510℃, the heating rate was 8℃ / min, and the sintering time was 15min each time. The coating-drying-sintering operation was repeated 7 times to form the intermediate layer. S4. Preparation of the surface layer: Polystyrene microspheres were dispersed in deionized water to form a suspension with a mass fraction of 7%. Sodium dodecyl sulfate with a volume fraction of 0.4% was added. Microsphere templates were assembled on the surface of the titanium mesh treated in step S3 by spin coating. After completion, the microspheres were treated with oxygen plasma for 35 seconds at a power of 50W. Weigh out chloroiridic acid, tantalum pentachloride, and tin tetrachloride according to an Ir:Ta:Sn molar ratio of 60:20:20. Add chloroiridic acid, tantalum pentachloride, and tin tetrachloride to ethylene glycol solvent to form a surface precursor solution. Immerse the titanium mesh prepared by the above operation into the surface precursor solution and perform electrophoretic deposition at a voltage of 15V for 45s. After deposition, place the sample in a muffle furnace and heat it to 450℃ at a heating rate of 1℃ / min and hold it for 40min. Then, perform rapid thermal annealing at 400℃ for 1.5min to form the surface layer, thus obtaining the PCB titanium anode mesh.
[0025] Example 2
[0026] S1. Pretreatment of the titanium matrix: The laser-treated titanium mesh was immersed in a mixed solution of 10% oxalic acid and 5% hydrogen peroxide (volume ratio 1:1) and treated at 85°C for 30 min. After removal, it was rinsed with deionized water until neutral and dried in a nitrogen stream. The laser power was set to 20 W and the scanning speed to 200 mm / s. S2, Preparation of the bottom layer: Titanium carbide powder was dispersed in a mixture of tetrabutyl titanate, anhydrous ethanol, glacial acetic acid and deionized water in a volume ratio of 5:50:2:1. The mixture was ultrasonically dispersed for 30 min, centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 80 °C for 12 h to obtain mixture A. The solid-liquid ratio of titanium carbide powder to the mixture was 1:30 g / mL. Mixture A was placed in a tube furnace and heated to 490-510°C at 5°C / min under a hydrogen / argon mixed atmosphere with a hydrogen gas fraction of 5% and held for 1 hour. Then, under an H2 / H2O mixed atmosphere with a hydrogen gas fraction of 5%, the temperature was increased to 900°C at 2°C / min and held for 12 hours. The mixture was then naturally cooled to room temperature to obtain the modified titanium carbide. Chloroiridic acid, tantalum pentachloride, and tin tetrachloride were added to a mixed solvent of n-butanol and isopropanol in a volume ratio of 1:1. Then, 5% concentrated hydrochloric acid and 3% polyethylene glycol PEG 400 were added to the mixed solvent to obtain a precursor solution. The total mass ratio of chloroiridic acid, tantalum pentachloride, and tin tetrachloride to the mixed solvent was 1 g: 25 mL. Modified titanium carbide was then added, with the mass ratio of chloroiridic acid, tantalum pentachloride, tin tetrachloride, and modified titanium nitride being 40:20:10:5. After stirring for 2 hours, the mixture was aged for 24 hours to obtain a bottom precursor mixed dispersion. The coating was applied to the surface of the pretreated titanium mesh, dried in an oven at 120°C for 10 minutes, and then sintered. The sintering was carried out under a nitrogen protective atmosphere at a temperature of 450°C for 10 minutes each time. The coating-drying-sintering operation was repeated 8 times to obtain the bottom layer. S3. Preparation of the intermediate layer: Ir:Ru:Ta:Sn:Bi were weighed according to the molar ratio (each metal molar percentage 20%), chloroiridic acid, ruthenium trichloride, tantalum pentachloride, tin tetrachloride and bismuth nitrate were weighed respectively. The above metal salts were dissolved in a mixed solvent of ethylene glycol methyl ether and anhydrous ethanol in a volume ratio of 1:1. Citric acid with a molar ratio of 1:1 to the total metal ions was added as a complexing agent. The mixture was stirred for 4 hours to obtain a high-entropy oxide precursor solution. The precursor solution was coated on the surface of the titanium mesh with the prepared bottom layer. After sintering, an intermediate layer was obtained. The sintering temperature was 490℃, the heating rate was 5℃ / min, and the sintering time was 10min each time. The coating-drying-sintering operation was repeated 5 times to form the intermediate layer. S4. Preparation of the surface layer: Polystyrene microspheres were dispersed in deionized water to form a 5% (w / w) suspension. Sodium dodecyl sulfate (0.1% (v / v)) was added. Microsphere templates were assembled on the surface of the titanium mesh treated in step S3 using a spin-coating method. After completion, the microspheres were treated with oxygen plasma for 30 seconds at a power of 50W. Weigh out chloroiridic acid, tantalum pentachloride, and tin tetrachloride according to an Ir:Ta:Sn molar ratio of 50:15:15. Add the chloroiridic acid, tantalum pentachloride, and tin tetrachloride to ethylene glycol solvent to form a surface precursor solution. Immerse the titanium mesh prepared by the above operation into the surface precursor solution and perform electrophoretic deposition at a voltage of 15V for 45s. After deposition, place the sample in a muffle furnace and heat it to 400℃ at a heating rate of 0.5℃ / min and hold it at that temperature for 30min. Then, perform rapid thermal annealing at 400℃ for 1.5min to form a surface layer, thus obtaining the PCB titanium anode mesh.
[0027] Example 3
[0028] S1. Pretreatment of the titanium matrix: The laser-treated titanium mesh was immersed in a mixed solution of 10% oxalic acid and 5% hydrogen peroxide (volume ratio 1:1) and treated at 85°C for 30 min. After removal, it was rinsed with deionized water until neutral and dried in a nitrogen stream. The laser power was set to 20 W and the scanning speed to 200 mm / s. S2, Preparation of the bottom layer: Titanium carbide powder was dispersed in a mixture of tetrabutyl titanate, anhydrous ethanol, glacial acetic acid and deionized water in a volume ratio of 7:60:2:1. The mixture was ultrasonically dispersed for 30 min, centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 80 °C for 12 h to obtain mixture A. The solid-liquid ratio of titanium carbide powder to the mixture was 1:30 g / mL. Mixture A was placed in a tube furnace and heated to 510°C at 5°C / min and held for 1 hour in a hydrogen / argon mixed atmosphere with a hydrogen gas fraction of 5%. Then, it was heated to 920°C at 2°C / min and held for 12 hours in an H2 / H2O mixed atmosphere with a hydrogen gas fraction of 5%. The mixture was then naturally cooled to room temperature to obtain the modified titanium carbide. Chloroiridic acid, tantalum pentachloride, and tin tetrachloride were added to a mixed solvent of n-butanol and isopropanol in a volume ratio of 1:1. Then, 5% concentrated hydrochloric acid and 3% polyethylene glycol PEG 400 were added to the mixed solvent to obtain a precursor solution. The total mass ratio of chloroiridic acid, tantalum pentachloride, and tin tetrachloride to the mixed solvent was 1 g: 25 mL. Modified titanium carbide was then added, with the mass ratio of chloroiridic acid, tantalum pentachloride, tin tetrachloride, and modified titanium nitride being 60:40:30:15. After stirring for 2 h, the mixture was aged for 24 h to obtain a bottom precursor mixed dispersion. The coating was applied to the surface of the pretreated titanium mesh, dried in an oven at 120°C for 20 minutes, and then sintered under a nitrogen protective atmosphere at a temperature of 500°C for 20 minutes each time. The coating-drying-sintering process was repeated 15 times to obtain the bottom layer. S3. Preparation of the intermediate layer: Ir:Ru:Ta:Sn:Bi were weighed according to the molar ratio (each metal molar percentage 20%), chloroiridic acid, ruthenium trichloride, tantalum pentachloride, tin tetrachloride and bismuth nitrate were weighed respectively. The above metal salts were dissolved in a mixed solvent of ethylene glycol methyl ether and anhydrous ethanol in a volume ratio of 1:1. Citric acid with a molar ratio of 1:2 to the total metal ions was added as a complexing agent. The mixture was stirred for 4 hours to obtain a high-entropy oxide precursor solution. The precursor solution was coated on the surface of the titanium mesh with the prepared bottom layer. After sintering, an intermediate layer was obtained. The sintering temperature was 530℃, the heating rate was 10℃ / min, and the sintering time was 20min each time. The coating-drying-sintering operation was repeated 10 times to form the intermediate layer. S4. Preparation of the surface layer: Polystyrene microspheres were dispersed in deionized water to form a suspension with a mass fraction of 8%. Sodium dodecyl sulfate with a volume fraction of 0.5% was added. Microsphere templates were assembled on the surface of the titanium mesh treated in step S3 by spin coating. After completion, the microspheres were treated with oxygen plasma for 45 seconds at a power of 50W. Weigh out chloroiridic acid, tantalum pentachloride, and tin tetrachloride according to an Ir:Ta:Sn molar ratio of 70:25:25. Add the chloroiridic acid, tantalum pentachloride, and tin tetrachloride to ethylene glycol solvent to form a surface precursor solution. Immerse the titanium mesh prepared by the above operation into the surface precursor solution and perform electrophoretic deposition at a voltage of 15V for 45s. After deposition, place the sample in a muffle furnace and heat it to 500℃ at a heating rate of 2℃ / min and hold it for 60min. Then, perform rapid thermal annealing at 400℃ for 1.5min to form the surface layer, thus obtaining the PCB titanium anode mesh.
[0029] Example 4
[0030] The process is basically the same as in Example 1, except that in step S3 of this example, chloroiridic acid, ruthenium trichloride, tantalum pentachloride, tin tetrachloride and bismuth nitrate are weighed according to the molar ratio of Ir:Ru:Ta:Sn:Bi of 25:25:20:15:15 respectively.
[0031] Example 5
[0032] The process is basically the same as in Example 1, except that in step S4 of this example, a template is assembled using polystyrene microspheres with a diameter of 500 nm, and the electrophoretic deposition voltage is 20V for 60s.
[0033] Comparative Example 1 It is basically the same as Example 1, except that no modified titanium carbide is added to the bottom layer of this comparative example.
[0034] Comparative Example 2 The comparison example is basically the same as Example 1, except that the intermediate layer uses a traditional IrO2-Ta2O5 binary oxide and does not contain a high-entropy design: chloroiridic acid and tantalum pentachloride are weighed according to the Ir:Ta molar ratio of 70:30, dissolved in a mixed solvent of n-butanol and isopropanol, coated and sintered at 500°C, and repeated 5 times to form an IrO2-Ta2O5 intermediate layer.
[0035] Comparative Example 3 It is basically the same as Example 1, except that the surface of this comparative example was not treated with polystyrene microsphere template.
[0036] Comparative Example 4 It is basically the same as Example 1, except that the titanium substrate in this comparative example is not laser etched, but only chemically etched.
[0037] Performance testing: 1. Accelerates lifespan: The sample prepared by cutting a 2cm*2cm sample from the examples and comparative examples was used as the anode, and a titanium plate was used as the cathode. The electrolyte was a 20% (w / w) H2SO4 solution, and electrolysis was performed using a DC power supply with a current density of 5A / cm². -2 When the voltage increases by 5V from the initial voltage, the anode fails, and the cumulative electrolysis time is recorded. 2. High-frequency pulse lifetime: The test conditions were: pulse frequency 20kHz, duty cycle 50%, and current density 10A / dm³. 2 The electrolyte was a 0.5 mol / L sulfuric acid solution, and the temperature was controlled at 50 ± 1℃. During the test, the titanium anode mesh under test was used as the anode, and the stainless steel plate was used as the cathode, with an electrode spacing of 50 mm. The cell voltage was recorded every 24 hours, and the electrolyte was replaced every 72 hours. When the cell voltage rose more than 10V from the initial value, or the area of coating peeling observed by visual observation exceeded 10% of the working area, or the anode potential (vs SCE) remained higher than 2.0V, the anode was considered to have failed. The cumulative electrolysis time was the high-frequency pulse life. Three parallel samples were tested for each group of samples, and the arithmetic mean was taken as the final test result. 2. Deep plating capability (TP value): Electroplating was performed on the anodes prepared by the examples and comparative examples. The electroplating solution temperature was set to 25°C, the current density was set to 4.0 ASD, and the electroplating time was 45 min. At least 10 through holes were sliced and analyzed in each electroplated copper sample to determine its TP value. The TP value was calculated by measuring the ratio of the average thickness of the copper plating layer at the center of the hole to the average thickness of the copper plating layer on the sample surface. The results are shown in the table below: Based on the above data, it can be seen that the titanium anode mesh prepared by the present invention has a long lifespan, high TP value, good electroplating uniformity, and long high-frequency pulse lifespan.
[0038] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A multilayer PCB titanium anode mesh, characterized in that, The PCB titanium anode mesh comprises a titanium mesh substrate, a bottom layer, an intermediate layer, and a surface layer arranged sequentially. The intermediate layer comprises titanium tantalum oxide; the intermediate layer is a high-entropy oxide solid solution layer, the chemical formula of the high-entropy oxide is (IrRuTaSnBi)Ox, x=8~12; The surface layer is grown on the surface of the intermediate layer and is a ternary oxide solid solution of (IrTaSn)Ox, where x = 5~7.
2. A method for preparing a multilayer titanium anode mesh according to claim 1, characterized in that, Includes the following steps: S1. Pretreatment of the titanium matrix: The laser-treated titanium mesh was immersed in a mixed solution of 10% oxalic acid and 5% hydrogen peroxide (volume ratio 1:1), treated at 85°C for 30 minutes, removed and rinsed with deionized water until neutral, and then dried in a nitrogen stream. S2, Preparation of the bottom layer: A mixed dispersion of precursors containing chloroiridic acid, tantalum pentachloride, tin tetrachloride, and modified titanium carbide was coated onto the surface of a pretreated titanium mesh. The coating-drying-sintering process was repeated to form the bottom layer. S3. Preparation of the intermediate layer: A high-entropy precursor solution containing Ir, Ru, Ta, Sn, and Bi is coated onto the bottom surface, dried, sintered, and the process is repeated to form a high-entropy oxide solid solution intermediate layer. S4. Preparation of the surface layer: A template-assisted method is used to assemble a polystyrene microsphere template on the surface of the intermediate layer, fill it with a precursor containing Ir, Ta, and Sn, and remove the template by thermal desorption to form the surface layer, thus obtaining the titanium anode mesh.
3. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S2, the preparation process of the modified titanium carbide is as follows: Titanium carbide powder was dispersed in a mixture of tetrabutyl titanate, anhydrous ethanol, glacial acetic acid and deionized water in a volume ratio of (5~7):(50~60):2:
1. The mixture was ultrasonically dispersed for 30 min, centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 80℃ for 12 h to obtain mixture A. Mixture A was placed in a tube furnace and heated to 490-510°C at 5°C / min under a hydrogen / argon mixed atmosphere with a hydrogen gas fraction of 5% and held for 1 hour. Then, under an H2 / H2O mixed atmosphere with a hydrogen gas fraction of 5%, the temperature was increased to 900-920°C at 2°C / min and held for 12 hours. The mixture was then naturally cooled to room temperature to obtain the modified titanium carbide.
4. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S2, the mass ratio of chloroiridic acid, tantalum pentachloride, tin tetrachloride and modified titanium carbide in the precursor mixed dispersion is (40~60):(20~40):(10~30):(5~15).
5. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S2, the sintering is carried out under a nitrogen protective atmosphere, the sintering temperature is 450~500℃, the sintering time is 10~20min each time, and the coating-drying-sintering operation is repeated 8~15 times.
6. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S3, Ir, Ru, Ta, Sn, and Bi in the high-entropy precursor solution are in equimolar ratio, and the molar percentage of each metal is 15-25%.
7. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S3, citric acid is also added to the high-entropy precursor solution, and the molar ratio of citric acid to total metal ions is (1~2):
1.
8. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S3, the sintering temperature is 490~530℃, the heating rate is 5~10℃ / min, the sintering time is 10~20min, and the coating-drying-sintering operation is repeated 5~10 times.
9. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, In step S4, the molar ratio of Ir, Ta, and Sn in the precursor containing Ir, Ta, and Sn is (50~70):(15~25):(15~25).
10. The method for preparing a multilayer titanium anode mesh according to claim 2, characterized in that, The specific preparation process of step S4 is as follows: Polystyrene microspheres were dispersed in deionized water to form a suspension with a mass fraction of 5-8%. Sodium dodecyl sulfate with a volume fraction of 0.1-0.5% was added. Microsphere templates were assembled on the surface of the titanium mesh treated in step S3 by spin coating. After completion, the microspheres were treated with oxygen plasma for 30-45 seconds at a power of 50W. Chloroiridic acid, tantalum pentachloride, and tin tetrachloride were added to ethylene glycol solvent to form a surface precursor solution. The titanium mesh prepared by the above operation was then immersed in the surface precursor solution and deposited using an electrophoretic deposition process. After deposition, the sample was placed in a muffle furnace and heated to 400-500℃ at a heating rate of 0.5-2℃ / min and held for 30-60 min. Subsequently, the sample was subjected to rapid thermal annealing at 400℃ for 1.5 min.