A process for preparing titanium anodes for electrolytic copper foil

Abstract

This invention discloses a preparation process for titanium anodes used in electrolytic copper foil, relating to the field of anode plate manufacturing technology. In preparing the titanium anode for electrolytic copper foil, porous titanium is pretreated and then reacted sequentially with sodium hydroxide and chloroacetic acid to obtain nanowire titanium dioxide coated porous titanium; an iridium-tantalum pentoxide / titanium anode is prepared by mixing chloroiridium hexahydrate and tantalum ethoxide to form an iridium-tantalum pentoxide coating solution; polypyrrole is polymerized and coated onto graphene oxide to obtain polypyrrole-coated graphene oxide; a composite coating solution is prepared by reacting polypyrrole-coated graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate, followed by reduction with hydrazine hydrate; this composite coating solution is then coated onto the iridium-tantalum pentoxide / titanium anode to obtain the titanium anode for electrolytic copper foil. The titanium anode for electrolytic copper foil prepared by this invention exhibits excellent electrocatalytic performance and service life.

Description

Technical Field

[0001] This invention relates to the field of anode plate manufacturing technology, specifically to a process for preparing titanium anodes for electrolytic copper foil. Background Technology

[0002] Electrolytic copper foil is one of the most important raw materials in the electronics industry, used in the production of copper-clad laminates, printed circuit boards, and the manufacture of lithium-ion batteries. The electrolytic copper foil process involves obtaining plating or deposition layers through electrolysis. This process has many advantages, such as simple and convenient operation and high cleanliness. Currently, printed circuit boards are widely used in the electronics industry for new technologies. In recent years, the rapid development of portable electronic products and the use of lithium-ion batteries in large new energy vehicles have spurred the rapid development of the lithium battery industry, bringing new development and opportunities to electrolytic copper foil, used as the negative electrode material for lithium-ion batteries.

[0003] Since the electrolytic manufacturing of copper foil involves an anodic oxygen evolution reaction in an acidic system, the anodes used in this process are generally titanium anodes coated with oxygen-evolving noble metal oxides. However, traditional titanium anodes for electrolytic copper foil are prone to failure during use due to factors such as chemical damage to the base metal, coating erosion, and coating peeling. With technological advancements and economic development, the performance requirements for titanium anodes used in electrolytic copper foil are becoming increasingly stringent. Therefore, developing a titanium anode for electrolytic copper foil with high electrocatalytic performance and a long service life holds great promise. Summary of the Invention

[0004] The purpose of this invention is to provide a process for preparing titanium anodes for electrolytic copper foil, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A process for preparing a titanium anode for electrolytic copper foil, wherein the process involves preparing an iridium-tantalum coating solution by mixing iridium chloroiridium hexahydrate and tantalum ethoxide, and coating the solution onto porous titanium nanowires coated with titanium dioxide to obtain an iridium dioxide-tantalum pentoxide / titanium anode; and preparing a composite coating solution by mixing nickel-iron layered double hydroxide-reduced graphene oxide polypyrrole composite, and coating the solution onto the iridium dioxide-tantalum pentoxide / titanium anode to obtain the titanium anode for electrolytic copper foil.

[0007] As an optimization, the nanowire titanium dioxide coating porous titanium is prepared by pretreating porous titanium and then reacting it sequentially with sodium hydroxide and chloroacetic acid.

[0008] As an optimization, the nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite is prepared by reacting polypyrrole-coated graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate with hydrazine hydrate for reduction.

[0009] As an optimization, the polypyrrole-coated graphene oxide is prepared by polymerizing and depositing pyrrole onto graphene oxide.

[0010] As an optimization, the preparation process of the titanium anode for electrolytic copper foil includes the following preparation steps:

[0011] (1) Pretreated porous titanium and a 10 mol / L sodium hydroxide aqueous solution are mixed evenly at a mass ratio of 1:30-40, placed in a high-pressure reactor, stirred at 135-145℃ and 300-500 r / min for 13-15 h, filtered, and dried at 5-7 Pa and 50-60℃ for 5-6 h to obtain sodium titanate coated porous titanium; the sodium titanate coated porous titanium is immersed in a 0.1 mol / L hydrogen chloride aqueous solution, stirred at 30-40℃ and 300-500 r / min for 11-13 h, filtered, washed with deionized water 3-5 times, dried at 70-80℃ for 4-6 h, and then sintered at 440-460℃ for 60-70 min to obtain nanowire titanium dioxide coated porous titanium;

[0012] (2) Mix chloroiridium hexahydrate, 13-14% ethanol tantalum aqueous solution, and n-butanol in a mass ratio of 1:(0.2-0.3):(8-10) to prepare an iridium-tantalum coating solution; use a brush coating method to uniformly coat the iridium-tantalum coating solution onto the nanowire titanium dioxide-coated porous titanium to obtain an iridium dioxide-tantalum pentoxide / titanium anode;

[0013] (3) Pyrrole, a 50-60% (w / w) aqueous solution of phosphoric acid, hexaalkyltrimethylammonium bromide, and deionized water are mixed evenly in a mass ratio of 1:(1-1.2):(0.06-0.08):(20-30). Then, graphene oxide with a mass of 0.1-0.2 times that of pyrrole is added. The mixture is ultrasonically dispersed for 1-2 hours, stirred at 14-16°C and 300-500 r / min for 2-3 hours, and then ammonium persulfate with a mass of 0.03-0.05 times that of pyrrole is added. The mixture is stirred and reacted for another 3-4 hours. The mixture is filtered and dried at 50-60°C and 50-7 Pa for 5-6 hours to obtain polypyrrole-coated graphene oxide. The polypyrrole-coated graphene oxide and hexahydrate are then mixed. Nickel chloride, ferric chloride hexahydrate, hydrazine hydrate aqueous solution with a mass fraction of 60-64%, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:(2-2.2):(0.3-0.5):(2-2.2):(3-4):(4-5), and placed in a high-pressure reactor. The mixture was stirred at 115-125℃ and 300-500 r / min for 17-19 h. The temperature was then raised to 155-165℃, and the stirring was continued for 2-3 h. The mixture was filtered, washed 3-5 times with deionized water, and dried at 50-60℃ and 5-7 Pa for 5-6 h to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite.

[0014] (4) A nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite and a hydrochloric acid aqueous solution with a mass fraction of 20-30% were mixed evenly at a mass ratio of 1:(4-6) to prepare a composite coating solution. The composite coating solution was evenly coated on the iridium dioxide-tantalum pentoxide / titanium anode with a brush, dried at 115-125℃ for 10-12 min, cooled to room temperature and then coated 3-5 times. The anode was sintered at 445-455℃ for 60-70 min to obtain a titanium anode for electrolytic copper foil.

[0015] As an optimization, the pretreatment method of the porous titanium in step (1) is as follows: the porous titanium is placed in an ethanol aqueous solution with a mass fraction of 50-60% and mixed evenly, ultrasonically treated for 1-2 hours, filtered, and dried at 5-7 Pa and 50-60℃ for 5-6 hours to obtain the pretreated porous titanium.

[0016] As an optimization, the porous titanium was sourced from the Beijing Nonferrous Metals Research Institute and has dimensions of 60mm × 40mm × 1.4mm.

[0017] As an optimization, the specific operation process of the brush coating method in step (2) is as follows: use a brush to uniformly coat the iridium-tantalum coating liquid onto the porous titanium nanowire titanium dioxide coating, dry at 115-125℃ for 2-3 hours, sinter at 440-460℃ for 20-30 minutes, cool to room temperature and repeat the coating until the iridium content reaches 5-6 g / m2, and obtain the iridium dioxide-tantalum pentoxide / titanium anode.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] In preparing titanium anodes for electrolytic copper foil, the present invention involves pretreating porous titanium and reacting it with sodium hydroxide to obtain sodium titanate-coated porous titanium; reacting the sodium titanate-coated porous titanium with chloroacetic acid to obtain nanowire titanium dioxide-coated porous titanium; preparing an iridium-tantalum coating solution using chloroiridium hexahydrate and tantalum ethoxide and coating it onto the nanowire titanium dioxide-coated porous titanium to obtain an iridium dioxide-tantalum pentoxide / titanium anode; polymerizing pyrrole and coating it onto graphene oxide to obtain polypyrrole-coated graphene oxide; reacting polypyrrole-coated graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate with hydrazine hydrate and reducing them to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite; preparing the nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite into a composite coating solution and coating it onto the iridium dioxide-tantalum pentoxide / titanium anode to obtain a titanium anode for electrolytic copper foil.

[0020] First, porous titanium is pretreated and reacted with sodium hydroxide to obtain sodium titanate-coated porous titanium. Then, the sodium titanate-coated porous titanium is reacted with chloroacetic acid to obtain nanowire titanium dioxide-coated porous titanium. Compared with ordinary titanium-based materials, porous titanium has a high specific surface area and high porosity. A titanium dioxide nanowire film is generated in situ on the porous titanium using a hydrothermal method, further increasing the specific surface area of ​​the porous titanium. The developed specific surface area gives the titanium anode for electrolytic copper foil a large number of reactive centers and a large amount of reactant deposition. The porous titanium serves as both a carrier for the titanium dioxide nanowires and an excellent conductor. The in-situ generation of the titanium dioxide nanowire film on porous titanium effectively avoids the problem of poor film-substrate bonding caused by doping modification, effectively improving the electrocatalytic performance and service life of the titanium anode for electrolytic copper foil.

[0021] Secondly, iridium-tantalum pentoxide / titanium anodes were prepared by mixing iridium chloroiridium acid hexahydrate and tantalum ethoxide to form an iridium-tantalum pentoxide coating solution and coating it onto porous titanium nanowires coated with titanium dioxide. An iridium-tantalum pentoxide oxide coating was then formed on the iridium-tantalum pentoxide / titanium anode. Since the anodic oxygen evolution reaction of electrolytic copper foil is carried out in an acidic system, the iridium-tantalum pentoxide oxide coating remains stable in the acidic solution, making it an ideal coated titanium anode for the oxygen evolution reaction. In this process, iridium dioxide is the electrocatalytic material, and tantalum pentoxide is the stabilizer. Tantalum pentoxide can not only strengthen the cracks on the coating surface and improve the electrocatalytic performance of the titanium anode for electrolytic copper foil, but it can also form a solid solution with iridium dioxide, increasing the stability and service life of the electrode.

[0022] Finally, pyrrole was polymerized and coated onto graphene oxide to prepare polypyrrole-coated graphene oxide; the polypyrrole-coated graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate were reacted and reduced with hydrazine hydrate to prepare a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite; the nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite was formulated into a composite coating solution and coated onto an iridium dioxide-tantalum pentoxide / titanium anode to obtain a titanium anode for electrolytic copper foil; both reduced graphene oxide and polypyrrole have high conductivity and can quickly provide electrons, accelerating the mass transfer and charge transport of the titanium anode for electrolytic copper foil in the oxygen evolution reaction, thus improving the electrocatalytic performance of the titanium anode for electrolytic copper foil; nickel and iron have good stability in acidic media, and the layered structure of the iron and nickel-containing layered hydroxide has a large specific surface area, providing a large number of active sites for the oxygen evolution reaction, which can further improve the electrocatalytic performance of the titanium anode for electrolytic copper foil. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1

[0025] A process for preparing a titanium anode for electrolytic copper foil, the process comprising the following steps:

[0026] (1) Porous titanium was mixed evenly in a 50% ethanol aqueous solution, ultrasonically treated for 1 h, filtered, and dried at 5 Pa and 50 °C for 6 h to obtain pretreated porous titanium; the pretreated porous titanium and a 10 mol / L sodium hydroxide aqueous solution were mixed evenly at a mass ratio of 1:30, placed in a high-pressure reactor, stirred at 135 °C and 300 r / min for 15 h, filtered, and dried at 5 Pa and 50 °C for 6 h to obtain sodium titanate coated porous titanium; the sodium titanate coated porous titanium was immersed in a 0.1 mol / L hydrogen chloride aqueous solution, stirred at 30 °C and 300 r / min for 13 h, filtered, washed three times with deionized water, dried at 70 °C for 6 h, and then sintered at 440 °C for 70 min to obtain nanowire titanium dioxide coated porous titanium;

[0027] (2) Mix chloroiridium hexahydrate, 13% ethanol tantalum aqueous solution and n-butanol in a mass ratio of 1:0.2:8 to prepare iridium-tantalum coating solution; use a brush to evenly coat the iridium-tantalum coating solution onto the nanowire titanium dioxide coated porous titanium, dry at 115℃ for 3h, sinter at 440℃ for 30min, cool to room temperature and repeat coating until the iridium content reaches 5g / m2 to obtain iridium dioxide-tantalum pentoxide / titanium anode;

[0028] (3) Pyrrole, a 50% (w / w) aqueous solution of phosphoric acid, hexaalkyltrimethylammonium bromide, and deionized water were mixed evenly in a mass ratio of 1:1:0.06:20. Then, graphene oxide with a mass of 0.1 times that of pyrrole was added, and the mixture was ultrasonically dispersed for 1 hour. The mixture was stirred at 14°C and 300 r / min for 3 hours. Ammonium persulfate with a mass of 0.03 times that of pyrrole was added, and the mixture was stirred and reacted for another 4 hours. The mixture was filtered and dried at 50°C and 5 Pa for 6 hours to obtain polypyrrole-coated graphene oxide. Nickel chloride hexahydrate, ferric chloride hexahydrate, 60% hydrazine hydrate aqueous solution, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2:0.3:2:3:4 and placed in a high-pressure reactor. The mixture was stirred at 115℃ and 300 r / min for 19 h, then heated to 155℃ and stirred for another 3 h. The mixture was filtered, washed three times with deionized water, and dried at 50℃ and 5 Pa for 6 h to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite.

[0029] (4) The nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite and the hydrochloric acid aqueous solution with a mass fraction of 20% were mixed evenly at a mass ratio of 1:4 to prepare a composite coating solution; the composite coating solution was evenly coated on the iridium dioxide-tantalum pentoxide / titanium anode with a brush, dried at 115℃ for 12min, cooled to room temperature and then coated 3 times, and sintered at 445℃ for 70min to obtain the titanium anode for electrolytic copper foil.

[0030] Example 2

[0031] A process for preparing a titanium anode for electrolytic copper foil, the process comprising the following steps:

[0032] (1) Porous titanium was mixed evenly in a 55% ethanol aqueous solution, ultrasonically treated for 1.5 h, filtered, and dried at 6 Pa and 55 °C for 5.5 h to obtain pretreated porous titanium; the pretreated porous titanium and a 10 mol / L sodium hydroxide aqueous solution were mixed evenly at a mass ratio of 1:35, placed in a high-pressure reactor, stirred at 140 °C and 400 r / min for 14 h, filtered, and dried at 6 Pa and 55 °C for 5.5 h to obtain sodium titanate coated porous titanium; the sodium titanate coated porous titanium was immersed in a 0.1 mol / L hydrogen chloride aqueous solution, stirred at 35 °C and 400 r / min for 12 h, filtered, washed 4 times with deionized water, dried at 75 °C for 5 h, and then sintered at 450 °C for 65 min to obtain nanowire titanium dioxide coated porous titanium;

[0033] (2) Iridium chloroiridium hexahydrate, 13.5% ethanol tantalum aqueous solution, and n-butanol were mixed evenly in a mass ratio of 1:0.25:9 to prepare an iridium-tantalum coating solution. The iridium-tantalum coating solution was evenly coated on the nanowire titanium dioxide-coated porous titanium with a brush, dried at 120℃ for 2.5h, sintered at 450℃ for 25min, cooled to room temperature and then coated again until the iridium content reached 5.5g / m2, thus obtaining an iridium dioxide-tantalum pentoxide / titanium anode.

[0034] (3) Pyrrole, a 55% aqueous solution of phosphoric acid, hexaalkyltrimethylammonium bromide, and deionized water were mixed evenly in a mass ratio of 1:1.1:0.07:25. Then, graphene oxide with a mass ratio of 0.15 times that of pyrrole was added, and the mixture was ultrasonically dispersed for 1.5 h. The mixture was then stirred at 15 °C and 400 r / min for 2.5 h. Ammonium persulfate with a mass ratio of 0.04 times that of pyrrole was added, and the mixture was stirred and reacted for another 3.5 h. The mixture was filtered and dried at 6 Pa and 55 °C for 5.5 h to obtain polypyrrole-coated graphene oxide. The polypyrrole-coated graphene oxide and hexaalkyltrimethylammonium bromide were then mixed evenly in a mass ratio of 1:1.1:0.07:25. Nickel chloride hydrate, ferric chloride hexahydrate, hydrazine hydrate aqueous solution with a mass fraction of 62%, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2.1:0.4:2.1:3.5:4.5 and placed in a high-pressure reactor. The mixture was stirred at 120℃ and 400 r / min for 18 h, then heated to 160℃ and stirred for another 2.5 h. The mixture was filtered, washed four times with deionized water, and dried at 6 Pa and 55℃ for 5.5 h to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite.

[0035] (4) The nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite and the hydrochloric acid aqueous solution with a mass fraction of 25% were mixed evenly at a mass ratio of 1:5 to prepare a composite coating solution; the composite coating solution was evenly coated on the iridium dioxide-tantalum pentoxide / titanium anode with a brush, dried at 120℃ for 11 min, cooled to room temperature and then coated 4 times, and sintered at 440℃ for 65 min to obtain the titanium anode for electrolytic copper foil.

[0036] Example 3

[0037] A process for preparing a titanium anode for electrolytic copper foil, the process comprising the following steps:

[0038] (1) Porous titanium was mixed evenly in a 60% ethanol aqueous solution, ultrasonically treated for 2 h, filtered, and dried at 7 Pa and 60 °C for 5 h to obtain pretreated porous titanium; the pretreated porous titanium and a 10 mol / L sodium hydroxide aqueous solution were mixed evenly at a mass ratio of 1:40, placed in a high-pressure reactor, stirred at 145 °C and 500 r / min for 13 h, filtered, and dried at 7 Pa and 60 °C for 5 h to obtain sodium titanate coated porous titanium; the sodium titanate coated porous titanium was immersed in a 0.1 mol / L hydrogen chloride aqueous solution, stirred at 40 °C and 500 r / min for 11 h, filtered, washed 5 times with deionized water, dried at 80 °C for 4 h, and then sintered at 460 °C for 60 min to obtain nanowire titanium dioxide coated porous titanium;

[0039] (2) Mix chloroiridium hexahydrate, 14% ethanol tantalum aqueous solution, and n-butanol in a mass ratio of 1:0.3:10 to prepare an iridium-tantalum coating solution; use a brush to evenly coat the iridium-tantalum coating solution onto the nanowire titanium dioxide-coated porous titanium, dry at 125℃ for 2h, sinter at 460℃ for 20min, cool to room temperature and repeat the coating until the iridium content reaches 6g / m2 to obtain an iridium dioxide-tantalum pentoxide / titanium anode;

[0040] (3) Pyrrole, a 60% (w / w) aqueous solution of phosphoric acid, hexaalkyltrimethylammonium bromide, and deionized water were mixed evenly in a mass ratio of 1:1.2:0.08:30. Then, 0.2 times the mass of pyrrole and graphene oxide were added. The mixture was ultrasonically dispersed for 2 hours, stirred at 16°C and 500 r / min for 2 hours, and then 0.05 times the mass of pyrrole and ammonium persulfate were added. The mixture was stirred and reacted for another 3 hours. The mixture was filtered and dried at 7 Pa and 60°C for 5 hours to obtain polypyrrole-coated graphene oxide. The polypyrrole-coated graphene oxide and hexaalkyltrimethylammonium bromide were then mixed evenly in a mass ratio of 1:1.2:0.08:30. Nickel chloride hydrate, ferric chloride hexahydrate, hydrazine hydrate aqueous solution with a mass fraction of 64%, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2.2:0.5:2.2:4:5 and placed in a high-pressure reactor. The mixture was stirred at 125℃ and 500 r / min for 17 h, then heated to 165℃ and stirred for another 2 h. The mixture was filtered, washed 5 times with deionized water, and dried at 7 Pa and 60℃ for 5 h to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite.

[0041] (4) The nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite and the hydrochloric acid aqueous solution with a mass fraction of 30% were mixed evenly at a mass ratio of 1:6 to prepare a composite coating solution; the composite coating solution was evenly coated on the iridium dioxide-tantalum pentoxide / titanium anode with a brush, dried at 125℃ for 10 min, cooled to room temperature and then coated 5 times, and sintered at 455℃ for 60 min to obtain the titanium anode for electrolytic copper foil.

[0042] Comparative Example 1

[0043] The difference between the preparation process of the titanium anode for electrolytic copper foil in Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is modified as follows: iridium-tantalum hexahydrate, 13.5% tantalum ethoxide aqueous solution, and n-butanol are mixed evenly at a mass ratio of 1:0.25:9 to prepare an iridium-tantalum coating solution; the iridium-tantalum coating solution is evenly coated onto porous titanium with a brush, dried at 120°C for 2.5 h, sintered at 450°C for 25 min, cooled to room temperature, and the coating is repeated until the iridium content reaches 5.5 g / m², thus obtaining an iridium dioxide-tantalum pentoxide / titanium anode. The remaining steps are the same as in Example 2.

[0044] Comparative Example 2

[0045] The difference between the preparation process of the titanium anode for electrolytic copper foil in Comparative Example 2 and Example 2 lies in step (2). Step (2) is modified as follows: iridium chlorohydrate and n-butanol are mixed evenly at a mass ratio of 1:9 to prepare a coating solution; the coating solution is evenly coated onto the porous titanium nanowire titanium dioxide coating with a brush, dried at 120°C for 2.5 h, sintered at 450°C for 25 min, cooled to room temperature, and the coating process is repeated until the iridium content reaches 5.5 g / m², thus obtaining the iridium dioxide titanium anode. The remaining steps are the same as in Example 2.

[0046] Comparative Example 3

[0047] The preparation process of the titanium anode for electrolytic copper foil in Comparative Example 3 differs from that in Example 2 only in step (3). Step (3) is modified as follows: graphene oxide, nickel chloride hexahydrate, ferric chloride hexahydrate, 60% hydrazine hydrate aqueous solution, deionized water, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:2:0.3:2:3:4 and placed in a high-pressure reactor. The mixture is stirred at 115°C and 300 r / min for 19 h, then heated to 155°C and stirred for another 3 h. The mixture is then filtered, washed three times with deionized water, and dried at 50°C and 5 Pa for 6 h to obtain the nickel-iron layered double hydroxide reduced graphene oxide composite. The remaining steps are the same as in Example 2.

[0048] Comparative Example 4

[0049] The preparation process of the titanium anode for electrolytic copper foil in Comparative Example 4 differs from that in Example 2 only in step (3). Step (3) is modified as follows: pyrrole, a 50% (w / w) aqueous solution of phosphoric acid, hexaalkyltrimethylammonium bromide, and deionized water are mixed evenly in a mass ratio of 1:1:0.06:20. Then, graphene oxide with a mass of 0.1 times that of pyrrole is added, and the mixture is ultrasonically dispersed for 1 hour. The mixture is then stirred at 14°C and 300 r / min for 3 hours. Finally, ammonium persulfate with a mass of 0.03 times that of pyrrole is added, and the mixture is stirred and reacted for another 4 hours. The mixture was filtered and dried at 5 Pa and 50 °C for 6 h to obtain polypyrrole-coated graphene oxide. The polypyrrole-coated graphene oxide, a 60% (w / w) aqueous solution of hydrazine hydrate, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2:3:4 and placed in a high-pressure reactor. The mixture was stirred at 115 °C and 300 r / min for 19 h, then heated to 155 °C and stirred for another 3 h. The mixture was filtered, washed three times with deionized water, and dried at 5 Pa and 50 °C for 6 h to obtain reduced graphene oxide. The remaining steps were the same as in Example 2.

[0050] Test Example 1

[0051] Electrocatalytic performance testing

[0052] Test method: A typical three-electrode system was used in a glass electrolytic cell, with a titanium anode for electrolytic copper foil as the working electrode, a platinum wire as the auxiliary electrode, and a saturated calomel electrode as the reference electrode. Measurements were performed at room temperature in a 1 mol / L sulfuric acid aqueous solution using a CHI660D electrochemical workstation. The linear voltammetry scan voltage was 0.4 V, and the scan rate was 10 mV / s. -1 The results are shown in Table 1.

[0053] Table 1

[0054]

[0055] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Table 1 reveals that the titanium anode for electrolytic copper foil prepared in this invention exhibits excellent electrocatalytic performance.

[0056] By comparison, the volt-ampere charge capacity of Examples 1-3 is greater than that of Comparative Example 1, indicating that sodium titanate-coated porous titanium is prepared by reacting pretreated porous titanium with sodium hydroxide; and nanowire titanium dioxide-coated porous titanium is prepared by reacting sodium titanate-coated porous titanium with chloroacetic acid. Compared with ordinary titanium-based materials, porous titanium has a high specific surface area and high porosity. The in-situ generation of titanium dioxide nanowire films on porous titanium via hydrothermal method further increases the specific surface area of ​​porous titanium. The developed specific surface area gives the titanium anode for electrolytic copper foil more reactive centers and a larger amount of reactant adsorption. Porous titanium serves as both a carrier for titanium dioxide nanowires and an excellent conductor. The in-situ generation of titanium dioxide nanowire films on porous titanium effectively avoids the problem of poor film-substrate bonding caused by doping modification, and effectively improves the electrocatalytic performance of titanium anodes for electrolytic copper foil.

[0057] By comparison, the volt-ampere charge capacity of Examples 1-3 is greater than that of Comparative Example 2, indicating that the iridium-tantalum pentoxide / titanium anode is prepared by preparing an iridium-tantalum coating solution with iridium chloroiridium acid hexahydrate and tantalum ethoxide and coating it onto porous titanium nanowires coated with titanium dioxide. An iridium-tantalum pentoxide oxide coating is formed on the iridium-tantalum pentoxide / titanium anode. The anodic oxygen evolution reaction of copper foil is carried out in an acidic system. The iridium-tantalum pentoxide oxide coating can remain stable in the acidic solution and is a relatively ideal coated titanium anode for the oxygen evolution reaction. Among them, iridium dioxide is the electrocatalytic material and tantalum pentoxide is the stabilizer. Tantalum pentoxide can strengthen the cracks on the coating surface and improve the electrocatalytic performance of the titanium anode for electrolytic copper foil.

[0058] By comparison, the volt-ampere charge capacities of Examples 1-3 are greater than those of Comparative Examples 3-4, indicating that polypyrrole-coated graphene oxide is prepared by polymerizing pyrrole and coating it onto graphene oxide; a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite is prepared by reacting polypyrrole-coated graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate with hydrazine hydrate; the nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite is formulated into a composite coating solution and coated onto iridium dioxide-tantalum pentoxide. A titanium anode for electrolytic copper foil was fabricated on a titanium anode. Reduced graphene oxide and polypyrrole both have high conductivity and can quickly provide electrons, accelerating mass transfer and charge transport in the oxygen evolution reaction of the titanium anode for electrolytic copper foil, thus improving the electrocatalytic performance of the titanium anode for electrolytic copper foil. Nickel and iron have good stability in acidic media, and the layered structure of layered hydroxides containing iron and nickel has a large specific surface area, providing a large number of active sites for the oxygen evolution reaction, which can further improve the electrocatalytic performance of the titanium anode for electrolytic copper foil.

[0059] Test Example 2

[0060] Service life test

[0061] Test method: The service life of the examples and comparative examples was determined by standard accelerated corrosion test. The accelerated corrosion test was carried out at 30°C in a 1 mol / L sulfuric acid aqueous electrolyte, with a cathode current density of 2 A / m. 2 In the comparative example, the distance between the electrode and the cathode was 2 cm. The change in cell pressure was monitored in real time. When the cell pressure rose rapidly, the electrode was considered to have failed. The time when the electrode failed was the enhanced electrolysis life. The results are shown in Table 2.

[0062] Table 2

[0063] Enhanced electrolysis life (h) Enhanced electrolysis life (h) Example 1 863.45 Comparative Example 1 445.67 Example 2 875.21 Comparative Example 2 358.78 Example 3 860.55 Comparative Example 3 664.66 Comparative Example 4 862.98

[0064] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Table 2 reveals that the titanium anode for electrolytic copper foil prepared in this invention has a good service life.

[0065] By comparison, the enhanced electrolysis life of Examples 1-3 is greater than that of Comparative Example 1, indicating that sodium titanate-coated porous titanium is prepared by reacting pretreated porous titanium with sodium hydroxide; and nanowire titanium dioxide-coated porous titanium is prepared by reacting sodium titanate-coated porous titanium with chloroacetic acid. Compared with ordinary titanium-based materials, porous titanium has a high specific surface area and high porosity. The in-situ generation of titanium dioxide nanowire films on porous titanium via hydrothermal method further increases the specific surface area of ​​porous titanium. The developed specific surface area gives the titanium anode for electrolytic copper foil more reactive centers and a larger amount of reactant adsorption. Porous titanium serves as both a carrier for titanium dioxide nanowires and an excellent conductor. The in-situ generation of titanium dioxide nanowire films on porous titanium effectively avoids the problem of poor film-substrate bonding caused by doping modification, effectively improving the service life of titanium anodes for electrolytic copper foil.

[0066] By comparison, the enhanced electrolysis life of Examples 1-3 is greater than that of Comparative Example 2, indicating that the iridium-tantalum pentoxide / titanium anode is prepared by preparing an iridium-tantalum coating solution with iridium chloroiridium acid hexahydrate and tantalum ethoxide and coating it onto porous titanium nanowires coated with titanium dioxide. An iridium-tantalum pentoxide oxide coating is formed on the iridium-tantalum pentoxide / titanium anode. The electrolysis of copper foil is carried out in an acidic system for the anodic oxygen evolution reaction. The iridium-tantalum pentoxide oxide coating can remain stable in the acidic solution, making it a more ideal coated titanium anode for the oxygen evolution reaction. Among them, iridium dioxide is the electrocatalytic material and tantalum pentoxide is the stabilizer. Tantalum pentoxide can not only strengthen the cracks on the coating surface and improve the electrocatalytic performance of the titanium anode for electrolysis of copper foil, but also form a solid solution with iridium dioxide, increasing the stability and service life of the electrode.

[0067] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A process for preparing a titanium anode for electrolytic copper foil, characterized in that, The preparation process of the titanium anode for electrolytic copper foil involves preparing an iridium-tantalum coating solution by mixing iridium chloroiridium hexahydrate and tantalum ethoxide, and coating it onto porous titanium nanowires coated with titanium dioxide to obtain an iridium dioxide-tantalum pentoxide / titanium anode; preparing a composite coating solution by mixing nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite, and coating it onto the iridium dioxide-tantalum pentoxide / titanium anode to obtain the titanium anode for electrolytic copper foil; The nanowire titanium dioxide coating porous titanium is prepared by pretreating porous titanium and reacting it sequentially with an aqueous solution of sodium hydroxide and hydrogen chloride. The nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite is prepared by reacting polypyrrole with graphene oxide, nickel chloride hexahydrate, and ferric chloride hexahydrate, followed by reduction with hydrazine hydrate. The polypyrrole-coated graphene oxide is prepared by polymerizing and depositing pyrrole onto graphene oxide.

2. The preparation process of a titanium anode for electrolytic copper foil according to claim 1, characterized in that, The preparation process of the titanium anode for electrolytic copper foil includes the following steps: (1) Pretreated porous titanium and sodium hydroxide aqueous solution with a concentration of 10 mol / L are mixed evenly at a mass ratio of 1:30~40, placed in a high-pressure reactor, stirred at 135~145℃ and 300~500 r / min for 13~15 h, filtered, and dried at 5~7 Pa and 50~60℃ for 5~6 h to obtain sodium titanate coated porous titanium; Sodium titanate-coated porous titanium was immersed in a 0.1 mol / L aqueous solution of hydrogen chloride and stirred at 30-40°C and 300-500 r / min for 11-13 h. After filtration, it was washed 3-5 times with deionized water, dried at 70-80°C for 4-6 h, and then sintered at 440-460°C for 60-70 min to obtain nanowire titanium dioxide-coated porous titanium. (2) Mix chloroiridium hexahydrate, 13-14% ethanol tantalum aqueous solution and n-butanol in a mass ratio of 1:(0.2-0.3):(8-10) to prepare an iridium-tantalum coating solution; use a brush coating method to uniformly coat the iridium-tantalum coating solution onto the nanowire titanium dioxide-coated porous titanium to obtain an iridium dioxide-tantalum pentoxide / titanium anode; (3) Pyrrole, a 50-60% phosphoric acid aqueous solution, hexaalkyltrimethylammonium bromide, and deionized water are mixed evenly in a mass ratio of 1:(1-1.2):(0.06-0.08):(20-30). Then, graphene oxide with a mass of 0.1-0.2 times that of pyrrole is added. The mixture is ultrasonically dispersed for 1-2 hours and stirred at 14-16℃ and 300-500 r / min for 2-3 hours. Ammonium persulfate with a mass of 0.03-0.05 times that of pyrrole is added, and the mixture is stirred for another 3-4 hours. The mixture is filtered and dried at 50-60℃ and 5-7 Pa for 5-6 hours to obtain polypyrrole-coated graphene oxide. The polypyrrole-coated graphene oxide and hexahydrate are then mixed. Nickel chloride, ferric chloride hexahydrate, hydrazine hydrate aqueous solution with a mass fraction of 60-64%, deionized water, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:(2-2.2):(0.3-0.5):(2-2.2):(3-4):(4-5), and placed in a high-pressure reactor. The mixture was stirred at 115-125℃ and 300-500 r / min for 17-19 h. The temperature was then raised to 155-165℃, and the stirring was continued for 2-3 h. The mixture was filtered, washed 3-5 times with deionized water, and dried at 50-60℃ and 5-7 Pa for 5-6 h to obtain a nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite. (4) Mix the nickel-iron layered double hydroxide reduced graphene oxide polypyrrole composite and the hydrochloric acid aqueous solution with a mass fraction of 20-30% at a mass ratio of 1:(4-6) to prepare a composite coating solution; use a brush to evenly coat the composite coating solution onto the iridium dioxide-tantalum pentoxide / titanium anode, dry at 115-125℃ for 10-12 min, cool to room temperature and repeat the coating 3-5 times, and sinter at 445-455℃ for 60-70 min to obtain the titanium anode for electrolytic copper foil.

3. The preparation process of a titanium anode for electrolytic copper foil according to claim 2, characterized in that, The pretreated porous titanium in step (1) is prepared by mixing the porous titanium in an ethanol aqueous solution with a mass fraction of 50-60%, ultrasonically treating it for 1-2 hours, filtering it, and drying it at 5-7 Pa and 50-60 °C for 5-6 hours to obtain the pretreated porous titanium.

4. The preparation process of a titanium anode for electrolytic copper foil according to claim 3, characterized in that, The porous titanium has dimensions of 60mm × 40mm × 1.4mm.

5. The preparation process of a titanium anode for electrolytic copper foil according to claim 2, characterized in that, The specific operation process of the brush coating method in step (2) is as follows: the iridium-tantalum coating solution is evenly coated onto the porous titanium nanowire titanium dioxide coating with a brush, dried at 115~125℃ for 2~3 hours, sintered at 440~460℃ for 20~30 minutes, cooled to room temperature and then the coating is repeated until the iridium content reaches 5~6 g / m 2 An iridium dioxide-tantalum pentoxide / titanium anode was prepared.

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