CN113755902B - Titanium anode plate and preparation method and application thereof - Google Patents

Titanium anode plate and preparation method and application thereof Download PDF

Info

Publication number
CN113755902B
CN113755902B CN202111164561.1A CN202111164561A CN113755902B CN 113755902 B CN113755902 B CN 113755902B CN 202111164561 A CN202111164561 A CN 202111164561A CN 113755902 B CN113755902 B CN 113755902B
Authority
CN
China
Prior art keywords
titanium
titanium plate
plate
acid
rare metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111164561.1A
Other languages
Chinese (zh)
Other versions
CN113755902A (en
Inventor
姚力军
郭廷宏
潘杰
王学泽
章晨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Chuangzhi Ultrapure New Material Co ltd
Original Assignee
Ningbo Chuangzhi Ultrapure New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Chuangzhi Ultrapure New Material Co ltd filed Critical Ningbo Chuangzhi Ultrapure New Material Co ltd
Priority to CN202111164561.1A priority Critical patent/CN113755902B/en
Publication of CN113755902A publication Critical patent/CN113755902A/en
Application granted granted Critical
Publication of CN113755902B publication Critical patent/CN113755902B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention relates to a titanium anode plate and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) annealing the titanium plate to obtain an annealed titanium plate; (2) Polishing the annealed titanium plate obtained in the step (1), and pickling to obtain a pickled titanium plate; (3) Acid etching the acid-washed titanium plate obtained in the step (2) to obtain a pretreated titanium plate; (4) And (4) uniformly coating a rare metal coating solution on the pretreated titanium plate obtained in the step (3), and drying and roasting to obtain the titanium anode plate. The invention improves the shape stability and consistency by annealing the titanium plate, increases the binding force of the coating by soaking the titanium plate in acid pickling before acid etching, improves the uniformity of surface coating, and prepares the anode plate with electrolytic stability, thereby ensuring the purity of electrolysis.

Description

Titanium anode plate and preparation method and application thereof
Technical Field
The invention belongs to the field of anode plates, relates to a preparation method of a titanium anode plate, and particularly relates to the titanium anode plate and the preparation method and application thereof.
Background
With the rapid development of vlsi, the size of semiconductor chips has been reduced to nanometer level, and the conventional aluminum and aluminum alloy interconnection lines have not been able to meet the requirements of vlsi process. Compared with aluminum, copper has higher electromigration resistance and higher conductivity, and particularly, an ultra-high purity copper plate with the purity of more than 6N has important significance for reducing the resistance of a chip interconnection line and improving the operation speed of the chip interconnection line. However, below the 28nm process node, the electromigration problem of the ultra-high pure copper is serious, and the electromigration can be effectively reduced by adding trace manganese element into the ultra-high pure copper to form a self-diffusion barrier layer. The extraction method of the metal manganese mainly adopts an electrolytic method, an anode plate is important equipment in the electrolytic manganese production process, and the preparation of the anode plate which is beneficial to electrolyzing high-purity manganese is a key technology in the semiconductor process.
CN101285201A discloses an electrolytic manganese anode plate and a production method thereof, which is prepared by mixing, pressing and molding graphite powder, glass or kaolin, silver powder, tin powder, lead powder, borax and water and carbonizing at high temperature. The anode plate is made of graphite as a main material and other auxiliary materials, and has the advantages of low production cost, long service life, small anode mud amount, high electric efficiency, good oxidation resistance, corrosion resistance and mechanical strength, and can improve the yield of electrolytic manganese and reduce the production cost of the electrolytic manganese.
CN 105755509A discloses an electrolytic manganese anode plate and a manufacturing method thereof, the anode plate comprises the following components by mass percent: 0.08 to 0.12 percent of silver, 2 to 4 percent of tin, 1 to 3 percent of stibium, 0.02 to 0.04 percent of lanthanide series mixed rare earth and the balance of lead. The manufacturing method of the anode plate comprises the following steps: smelting silver-tin intermediate alloy and lanthanide series mixed rare earth-lead intermediate alloy; smelting an alloy; and casting the smelted alloy into a rough plate, and carrying out rolling, shearing and punching treatment. The electrolytic manganese anode plate has the advantages of simple manufacturing process, low manufacturing cost, high mechanical property of the anode plate, long service life, reduced oxygen evolution potential, reduced cell pressure and reduced production energy consumption.
CN 107419296A discloses a preparation method of a fence type anode plate for electrolytic manganese with high conductivity and long service life, which comprises five steps of carrying out aluminum substrate surface treatment, preparing an aluminum-based lead alloy high-conductivity composite anode rod, carrying out aluminum-based lead alloy high-conductivity composite anode rod surface lead alloy grain boundary treatment, assembling the fence type anode plate and preparing a nano polyaniline anticorrosive layer on the anode plate surface. The fence type anode plate for the electrolytic manganese with high conductivity and long service life, which is prepared, has good conductivity and strong corrosion resistance, can effectively solve the problems of low current efficiency, high anode corrosion rate and the like in the wet electrolytic manganese process, greatly prolongs the service life of the anode plate, and obviously reduces the production cost.
The anode plates for preparing manganese are disclosed in the prior art, and the performance of the anode plates is improved, but CN101285201A adopts graphite electrolysis, because the graphite electrolysis is easy to expand and fall off in the electrolysis, the purity of the electrolytic manganese is reduced. The anode plates disclosed in CN 105755509A and CN 107419296A are made of lead alloy, and have the advantages of high production cost, short service life, short slag removal period in the production process, large resistance, high power consumption, poor mechanical strength, easy deformation, easy deposition and precipitation of divalent lead ions in the electrolysis process, and reduction of purity of electrolytic manganese.
Therefore, how to overcome the defects of the traditional graphite and lead alloy anode plate, the anode plate capable of improving the purity of the electrolytic manganese is prepared under the condition of not introducing new impurities, and the problems of improving the current efficiency and reducing the energy consumption are urgently needed to be solved.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a titanium anode plate and a preparation method and application thereof. According to the preparation method, the titanium anode plate with high current efficiency, low energy consumption and high electrolytic purity is prepared by annealing the titanium plate, pickling and soaking and coating a single rare metal coating on the surface layer of the titanium plate.
In a first aspect, the present invention provides a method for preparing a titanium anode plate, wherein the method comprises the following steps:
(1) Annealing the titanium plate to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and pickling to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) to obtain a pretreated titanium plate;
(4) And (4) uniformly coating a rare metal coating solution on the pretreated titanium plate obtained in the step (3), and drying and roasting to obtain the titanium anode plate.
According to the invention, the annealing treatment in the step (1) can eliminate residual stress in the titanium plate, and the shape stability and consistency of the titanium plate are improved. Through the acid washing in the step (2), the microporous structure on the surface of the titanium plate is increased, so that the binding force between the titanium plate and the coating is increased, the uniformity of surface coating is improved, the coating is effectively prevented from falling off in the electrolytic process, and the finally obtained titanium anode plate has high electrolytic purity.
Preferably, the annealing treatment in step (1) is carried out at a temperature of 500 to 600 ℃, for example 500 ℃,520 ℃, 550 ℃, 570 ℃ or 600 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably 540 to 580 ℃.
Preferably, the annealing treatment time in step (1) is 15-60min, such as 15min, 20min, 30min, 35min, 40min or 60min, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 30-40min.
Preferably, the pickling solution used in the pickling in the step (2) comprises hydrochloric acid and/or nitric acid.
Preferably, the pickling solution has a mass concentration of 5 to 10%, for example 5%, 6%, 7%, 8%, 9% or 10%, but not limited to the values recited, and other values not recited within the numerical range are equally applicable.
Preferably, the acid washing time in step (2) is 4-10h, such as 4h, 6h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the acid etching temperature in step (3) is 90-120 ℃, for example, it may be 90 ℃,100 ℃,105 ℃,110 ℃ or 120 ℃, but it is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the acid etching time in step (3) is 2-4h, such as 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the solution used for acid etching in step (3) is oxalic acid with a mass concentration of 5-15%, such as 5%, 7%, 10%, 12% or 15%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the rare metal coating solution of step (4) comprises a binder, water and a rare metal salt.
Preferably, the mass ratio of the binder, water and rare metal salt is (30-40): (3-7): 1, and may be, for example, 30.
Preferably, the binder comprises any one of, or a combination of at least two of, an ethylene glycol polyester, a propylene glycol polyester, or a pentaerythritol polyester, typical but non-limiting combinations including combinations of ethylene glycol polyester and propylene glycol polyester, ethylene glycol polyester and pentaerythritol polyester, propylene glycol polyester and pentaerythritol polyester, or ethylene glycol polyester, propylene glycol polyester and pentaerythritol polyester.
Preferably, the rare metal salt comprises any one of ruthenium salt, iridium salt or rhodium salt or a combination of at least two of them, typical but non-limiting combinations include ruthenium salt and iridium salt, iridium salt and rhodium salt, ruthenium salt and rhodium salt, or ruthenium salt, iridium salt and rhodium salt, preferably ruthenium salt.
The ruthenium salt of the present invention includes, but is not limited to, ruthenium trichloride, ruthenium iodide or ruthenium acetate.
The iridium salts include, but are not limited to, iridium trichloride, iridium iodide, or iridium acetate.
Rhodium salts of the present invention include, but are not limited to, rhodium trichloride, rhodium iodide, or rhodium acetate.
The rare metal ruthenium, iridium or rhodium adopted in the coating has the advantages of high catalytic activity, low working voltage, low energy consumption and the like, and the prepared titanium anode plate has low energy consumption and high current efficiency. Meanwhile, rare metals such as ruthenium, iridium or rhodium have strong corrosion resistance and are not easy to fall off in the electrolytic process, so that the electrolytic purity of the titanium anode plate is improved.
Preferably, the mass of the rare metal-containing coating solution of step (4) is 5 to 9wt% of the mass of the titanium plate, and may be, for example, 5wt%, 6wt%, 7wt%, 8wt%, or 9wt%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the drying in step (4) is 90-120 ℃, for example, 90 ℃,100 ℃,105 ℃,110 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying time in step (4) is 15-20min, such as 15min, 16min, 17min, 18min, 19min or 20min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the calcination in step (4) is 480 to 560 ℃, and may be, for example, 480 ℃,500 ℃,520 ℃,540 ℃ or 560 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the calcination time in step (4) is 15-20min, such as 15min, 16min, 17min, 18min, 19min or 20min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the titanium plate in the step (1) is a titanium plate with a grid.
Preferably, the length of the grid is 80-120mm, for example 80mm, 90mm, 100mm, 110mm or 120mm, the width is 15-25mm, for example 15mm, 17mm, 20mm, 22mm or 25mm, the spacing of the grid is 5-10mm, for example 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, but not limited to the values listed, other values not listed within the numerical range are equally applicable.
Preferably, the titanium plate of step (1) has an opening ratio of 40-50%, for example, 40%, 42%, 44%, 46%, 48% or 50%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
The grid size provided by the invention is used for adjusting a certain opening ratio, keeping proper mechanical strength and meeting certain aesthetic requirements. When the aperture ratio of the titanium plate is more than 50%, the current density of the titanium plate is too high, the yield of the manganese metal is high, and the growth of the nodular dendritic crystal is caused; when the aperture ratio of the titanium plate is less than 40%, the current density of the titanium plate is small, and the prepared manganese can not grow into a complete and compact plate.
Preferably, the thickness of the titanium plate in the step (1) is 5 to 10mm, for example 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, but is not limited to the values listed, and other values in the range of values not listed are equally applicable, preferably 6.5 to 8.5mm.
As a preferred technical solution of the first aspect, the preparation method comprises the following steps:
(1) Annealing the titanium plate at 500-600 ℃ for 15-60min to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and pickling for 4-10h to obtain a pickled titanium plate; the pickling solution for pickling comprises any one or a combination of at least two of hydrochloric acid, nitric acid or chromic acid, and the mass concentration is 5-10%;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 2-4h by using oxalic acid with the mass fraction of 5-15% at the temperature of 90-120 ℃ to obtain a pretreated titanium plate;
(4) Uniformly coating a rare metal coating solution on the pretreated titanium plate obtained in the step (3), drying at 90-120 ℃ for 15-20min, and roasting at 480-560 ℃ for 15-20min to obtain the titanium anode plate; the rare metal coating solution accounts for 5-9wt% of the titanium plate and comprises a binder, water and a rare metal salt in a mass ratio of (30-40): 3-7): 1.
In a second aspect, the invention provides a titanium anode plate obtained by the preparation method of the first aspect.
Preferably, the surface of the titanium anode plate is coated with a rare metal coating, the mass of the rare metal coating is 0.2-0.8wt% of the mass of the titanium plate, for example, 0.2wt%, 0.5wt%, 0.6wt%, 0.7wt%, or 0.8wt%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the rare metal coating has a thickness of 1.5-2.5 μm, which may be, for example, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm or 2.5 μm, but is not limited to the recited values, and other values in the range of values not recited are equally applicable.
In a third aspect, the invention provides a use of the titanium anode plate of the second aspect for the electrolytic preparation of manganese.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the shape stability and consistency of the titanium plate are improved by annealing the titanium plate, the binding force between the titanium plate and the coating is increased by pickling and soaking the titanium plate before acid etching, the coating uniformity of the rare metal coating is improved, and the prepared titanium anode plate has electrolytic stability, so that the purity of manganese obtained when the titanium anode plate is used for electrolysis is ensured.
(2) The rare metal adopted in the coating provided by the invention has high catalytic activity, low energy consumption and strong corrosion resistance, is beneficial to reducing the energy consumption of the titanium anode plate during electrolysis, improves the current efficiency during electrolysis, and further ensures the purity of manganese obtained by the titanium anode plate during electrolysis.
(3) According to the invention, the current efficiency is improved and the electrolysis energy consumption is reduced by controlling the size of the grids, the distance between the grids and the aperture ratio of the titanium plate.
Drawings
Fig. 1 is a schematic structural diagram of a titanium anode plate provided by the invention.
Wherein, 1-titanium anode plate and 2-grid.
Detailed Description
The invention is further described in detail by the embodiments with reference to the drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
The embodiment provides a preparation method of a titanium anode plate, which comprises the following steps:
(1) Annealing the titanium plate at 560 ℃ for 35min to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and then pickling for 7 hours by using hydrochloric acid with the mass concentration of 7% to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 3 hours by oxalic acid with the mass fraction of 10% at 105 ℃ to obtain a pre-treated titanium plate;
(4) Uniformly coating a rare metal coating solution with the mass being 7wt% of that of the titanium plate on the pretreated titanium plate obtained in the step (3), drying at 105 ℃ for 18min, and roasting at 520 ℃ for 18min to obtain the titanium anode plate; the rare metal coating solution comprises ethylene glycol polyester (MEG, the beneficial chemical industry of the atrazine) and water and ruthenium trichloride in a mass ratio of 38.
The titanium plate (see fig. 1) in the step (1) is provided with grids, the length of each grid is 100mm, the width of each grid is 20mm, the space between every two grids is 9mm, and the opening rate is 45%.
The surface of the obtained titanium anode plate is coated with a rare metal coating with the thickness of 2 mu m, and the mass of the coating is 0.5wt% of that of the titanium plate.
Example 2
The embodiment provides a preparation method of a titanium anode plate, which comprises the following steps:
(1) Annealing the titanium plate at 540 ℃ for 40min to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and pickling for 8 hours by nitric acid with the mass concentration of 6% to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) by oxalic acid with the mass fraction of 7% for 3.5 hours at the temperature of 100 ℃ to obtain a pre-treated titanium plate;
(4) Uniformly coating a rare metal coating solution with the mass being 6wt% of that of the titanium plate on the pre-treated titanium plate obtained in the step (3), drying at 100 ℃ for 19min, and roasting at 500 ℃ for 19min to obtain the titanium anode plate; the rare metal coating solution comprises propylene glycol polyester (PGI, chongdong Chichen chemical industry), water and iridium trichloride in a mass ratio of 38.
The titanium plate in the step (1) is provided with grids, the length of each grid is 90mm, the width of each grid is 22mm, the space between every two grids is 6mm, and the opening rate is 48%.
The surface of the obtained titanium anode plate is coated with a rare metal coating with the thickness of 2.2 mu m, and the mass of the coating is 0.3wt% of the mass of the titanium plate.
Example 3
The embodiment provides a preparation method of a titanium anode plate, which comprises the following steps:
(1) Annealing the titanium plate for 30min at 580 ℃ to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and then pickling for 6 hours by using nitric acid with the mass concentration of 8% to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 2.5 hours by oxalic acid with the mass fraction of 12% at the temperature of 110 ℃ to obtain a pre-treated titanium plate;
(4) Uniformly coating a rare metal coating solution with the mass being 8wt% of that of the titanium plate on the pretreated titanium plate obtained in the step (3), drying at 110 ℃ for 1695in, and roasting at 540 ℃ for 16min to obtain the titanium anode plate; the rare metal coating solution comprises pentaerythritol polyester (PETS-1, good faith in the Jiaxing and environment-friendly), water and rhodium trichloride in a mass ratio of 38.
The titanium plate in the step (1) is provided with grids, the length of each grid is 110mm, the width of each grid is 18mm, the space between every two grids is 9mm, and the opening rate is 42%.
The surface of the obtained titanium anode plate is coated with a rare metal coating with the thickness of 1.8 mu m, and the mass of the coating is 0.7wt% of the mass of the titanium plate.
Example 4
The embodiment provides a preparation method of a titanium anode plate, which comprises the following steps:
(1) Annealing the titanium plate at 500 ℃ for 60min to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and then pickling for 10 hours by using hydrochloric acid with the mass concentration of 5% to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 4 hours by oxalic acid with the mass fraction of 5% at 90 ℃ to obtain a pre-treated titanium plate;
(4) Uniformly coating a rare metal coating solution with the mass being 5wt% of that of the titanium plate on the pretreated titanium plate obtained in the step (3), drying at 90 ℃ for 20min, and roasting at 480 ℃ for 20min to obtain the titanium anode plate; the rare metal coating solution comprises ethylene glycol polyester (MEG, the beneficial chemical industry of the atrazine) and water, wherein the weight ratio of the ethylene glycol polyester to the water to the rare metal salt is 40.
The titanium plate in the step (1) is provided with grids, the length of each grid is 80mm, the width of each grid is 25mm, the space between every two grids is 5mm, and the opening rate is 40%.
The surface of the obtained titanium anode plate is coated with a rare metal coating with the thickness of 2.5 mu m, and the mass of the coating is 0.2wt% of the mass of the titanium plate.
Example 5
The embodiment provides a preparation method of a titanium anode plate, which comprises the following steps:
(1) Annealing the titanium plate for 15min at the temperature of 600 ℃ to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and then pickling for 4 hours by using hydrochloric acid with the mass concentration of 10% to obtain a pickled titanium plate;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 2 hours by using oxalic acid with the mass fraction of 15% at 120 ℃ to obtain a pre-treated titanium plate;
(4) Uniformly coating a rare metal coating solution with the mass being 9wt% of that of the titanium plate on the pretreated titanium plate obtained in the step (3), drying at 120 ℃ for 15min, and roasting at 560 ℃ for 15min to obtain the titanium anode plate; the rare metal coating solution comprises 30wt% of iridium trichloride, 40wt% of ruthenium trichloride and 30wt% of rhodium trichloride, and is characterized in that the mass ratio of ethylene glycol polyester (MEG, the north river Fengbeneficial chemical industry), water and rare metal salt is as follows.
The titanium plate in the step (1) is provided with grids, the length of each grid is 120mm, the width of each grid is 15mm, the space between every two grids is 10mm, and the opening rate is 50%.
The surface of the obtained titanium anode plate is coated with a rare metal coating with the thickness of 1.5 mu m, and the mass of the coating is 0.8wt% of the mass of the titanium plate.
Example 6
This example provides a method for producing a titanium anode plate, which is the same as in example 1 except that the rare metal salt is substituted for ruthenium trichloride and the like in step (4).
The rare metal salt is composed of 15wt% of iridium trichloride, 75wt% of ruthenium trichloride, 8.5wt% of tantalum pentachloride and 1.5wt% of lanthanum trichloride.
Example 7
This example provides a method for producing a titanium anode plate, which is the same as in example 1 except that the rare metal salt is substituted for ruthenium trichloride and the like in step (4).
The rare metal salt consists of 15wt% of iridium trichloride, 75wt% of ruthenium trichloride, 8.5wt% of cerium trichloride and 1.5wt% of lanthanum trichloride.
Example 8
This example provides a method for producing a titanium anode plate, which is the same as in example 1 except that the rare metal salt is substituted for ruthenium trichloride and the like in step (4).
The rare metal salt consists of 15wt% of iridium trichloride, 75wt% of ruthenium trichloride, 8.5wt% of rhodium trichloride and 1.5wt% of lanthanum trichloride.
Example 9
This example provides a method for preparing a titanium anode plate, which is the same as that of example 1 except that the opening ratio of the titanium plate in step (1) is 35%.
Example 10
This example provides a method for preparing a titanium anode plate, which is the same as that of example 1 except that the opening ratio of the titanium plate in step (1) is 55%.
Comparative example 1
This comparative example provides a method of manufacturing an anode plate, which was the same as in example 1 except that the titanium plate in step (1) was replaced with a graphite plate.
The graphite plate is provided with grids, the length of each grid is 100mm, the width of each grid is 20mm, and the space between every two grids is 9mm.
Comparative example 2
This comparative example provides a method for producing an anode plate, which was the same as in example 1 except that the titanium plate was replaced with a lead plate in step (1).
The lead plate is provided with grids, the length of each grid is 100mm, the width of each grid is 20mm, and the space between every two grids is 9mm.
The titanium anode plates of examples 1 to 10 and comparative examples 1 to 2 were welded to titanium conductive rods to obtain an electrolytic anode plate as an anode, and the titanium plate was used as a cathode, and electrolysis was carried out in a manganese chloride-ammonium chloride system solution at a current density of 200 to 400A/m 2 The electrolytic time was 12 hours, the electrolytic manganese purity was measured by a glow discharge mass spectrometer, and the electrolytic manganese purity (N), the current efficiency (%) and the energy consumption (kW · h/kg) were measured, and the results are shown in table 1.
TABLE 1
Test number Purity of electrolytic manganese (N) Current efficiency (%) Energy consumption (kW h/kg)
Example 1 5N 80.2 7.3
Example 2 4N8 77.4 7.8
Example 3 4N8 78.2 7.9
Example 4 4N5 74.4 8.0
Example 5 4N5 74.7 8.0
Example 6 3N7 71.7 8.2
Example 7 3N9 70.2 8.4
Example 8 3N8 71.3 8.3
Example 9 3N 65.1％ 8.1
Example 10 3N 64.2％ 8.0
Comparative example 1 3N 67.3 8.8
Comparative example 2 3N 64.6 9.5
The following conclusions are drawn from table 1:
(1) From examples 1 to 5, the method for preparing the titanium anode plate is improved by soaking the titanium plate in acid pickling before the annealing treatment and the acid etching of the titanium plate, and the titanium anode plate with high electrolytic purity, high current efficiency and low energy consumption is prepared by controlling the type and the content of rare metals in the coating.
(2) It can be seen from the comparison between examples 6-8 and example 1 that when the rare metal species and content in the titanium anode plate are not within the preferred range provided by the present invention, the electrolytic purity of the prepared titanium anode plate is increased, the current efficiency is reduced and the energy consumption is increased, which indicates that the rare metal coating provided by the present invention is an important process parameter for preparing the titanium anode plate, and is helpful for preparing the titanium anode plate with high electrolytic purity, high current efficiency and low energy consumption.
(3) It can be seen from the comparison between examples 9 and 10 and example 1 that when the opening ratio of the titanium plate is greater than 50% or less than 40%, the electrolytic purity of the prepared titanium anode plate is increased, the current efficiency is reduced, and the energy consumption is increased, which indicates that the annealing treatment temperature provided by the invention is an important process parameter for preparing the titanium anode plate, and is beneficial to preparing the titanium anode plate with high electrolytic purity, high current efficiency and low energy consumption.
(4) As can be seen from comparison of comparative examples 1 and 2 with example 1, when a graphite plate or a lead plate is used, the prepared anode plate has increased electrolytic purity, reduced current efficiency and increased energy consumption, which indicates that the titanium anode plate provided by the present invention is helpful for achieving high electrolytic purity, high current efficiency and low energy consumption in the electrolysis process.
In conclusion, the invention improves the preparation method of the titanium anode plate by carrying out annealing treatment on the titanium plate and carrying out acid pickling and soaking on the titanium plate before acid etching, and prepares the titanium anode plate with high electrolytic purity, high current efficiency and low energy consumption by controlling the type and the content of rare metals in the coating.
The applicant states that the technical scheme of the invention is described by the embodiment, but the invention is not limited to the technical scheme, namely the invention is not meant to rely on the characteristics to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected agents of the present invention, additions of auxiliary agents, selection of specific means, etc., are within the scope and disclosure of the present invention.

Claims (23)

1. A preparation method of a titanium anode plate for preparing manganese through electrolysis is characterized by comprising the following steps:
(1) Annealing the titanium plate at 500-600 ℃ to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and carrying out acid washing by using acid washing liquid of any one or a combination of at least two of hydrochloric acid and/or nitric acid or chromic acid to obtain an acid-washed titanium plate;
(3) Carrying out acid etching on the acid-washed titanium plate obtained in the step (2) by oxalic acid with the mass concentration of 5-15% to obtain a pretreated titanium plate;
(4) Uniformly coating a rare metal coating solution on the pretreated titanium plate obtained in the step (3), and drying and roasting to obtain the titanium anode plate; the mass of the rare metal coating solution is 5-9wt% of that of the titanium plate; the rare metal coating solution comprises a binder, water and a rare metal salt; the mass ratio of the adhesive, the water and the rare metal salt is (30-40) to (3-7) to 1; the rare metal salt comprises any one or combination of at least two of ruthenium salt, iridium salt or rhodium salt;
the titanium plate in the step (1) is a titanium plate with a grid; the opening rate of the titanium plate is 40-50%.
2. The method according to claim 1, wherein the temperature of the annealing treatment in the step (1) is 540 to 580 ℃.
3. The method according to claim 1, wherein the annealing treatment of step (1) is carried out for 15 to 60min.
4. The method according to claim 3, wherein the annealing treatment of step (1) is carried out for 30 to 40min.
5. The method according to claim 1, wherein the pickling solution used in the pickling in step (2) comprises hydrochloric acid and/or nitric acid.
6. The production method according to claim 1, wherein the acid wash has a mass concentration of 5 to 10%.
7. The method according to claim 1, wherein the acid washing time in step (2) is 4-10 hours.
8. The method according to claim 1, wherein the acid etching temperature in the step (3) is 90 to 120 ℃.
9. The method according to claim 1, wherein the acid etching in step (3) is carried out for 2 to 4 hours.
10. The method according to claim 1, wherein the mass ratio of the binder, water and rare metal salt is (35-38): (4-6): 1.
11. The method of claim 1, wherein the binder comprises any one of or a combination of at least two of ethylene glycol polyester, propylene glycol polyester, or pentaerythritol polyester.
12. The production method according to claim 1, wherein the rare metal salt is a ruthenium salt.
13. The method according to claim 1, wherein the temperature of the drying in the step (4) is 90 to 120 ℃.
14. The method according to claim 1, wherein the drying time in step (4) is 15-20min.
15. The method according to claim 1, wherein the temperature of the calcination in the step (4) is 480-560 ℃.
16. The method according to claim 1, wherein the roasting time in the step (4) is 15-20min.
17. The method of claim 1, wherein the length of the grids is 80-120mm, the width is 15-25mm, and the spacing of the grids is 5-10mm.
18. The method according to claim 1, wherein the thickness of the titanium plate of step (1) is 5 to 10mm.
19. The method according to claim 1, wherein the thickness of the titanium plate of the step (1) is 6.5 to 8.5mm.
20. The method of claim 1, comprising the steps of:
(1) Annealing the titanium plate at 500-600 ℃ for 15-60min to obtain an annealed titanium plate;
(2) Polishing the annealed titanium plate obtained in the step (1), and pickling for 4-10h to obtain a pickled titanium plate; the pickling solution for pickling comprises any one or a combination of at least two of hydrochloric acid, nitric acid or chromic acid, and the mass concentration is 5-10%;
(3) Acid etching the acid-washed titanium plate obtained in the step (2) for 2-4h by using oxalic acid with the mass fraction of 5-15% at the temperature of 90-120 ℃ to obtain a pretreated titanium plate;
(4) Uniformly coating a rare metal coating solution on the pretreated titanium plate obtained in the step (3), drying at 90-120 ℃ for 15-20min, and roasting at 480-560 ℃ for 15-20min to obtain the titanium anode plate; the rare metal coating solution accounts for 5-9wt% of the titanium plate, and comprises a binder, water and a rare metal salt, wherein the binder, the water and the rare metal salt are in a mass ratio of (30-40): 3-7): 1.
21. A titanium anode plate obtained by the method of any one of claims 1 to 20.
22. The titanium anode plate of claim 21, wherein the surface of the titanium anode plate is coated with a rare metal coating, the mass of the rare metal coating being 0.2-0.8wt% of the mass of the titanium plate.
23. The titanium anode plate of claim 22, wherein the rare metal coating has a thickness of 1.5-2.5 μ ι η.
CN202111164561.1A 2021-09-30 2021-09-30 Titanium anode plate and preparation method and application thereof Active CN113755902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111164561.1A CN113755902B (en) 2021-09-30 2021-09-30 Titanium anode plate and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111164561.1A CN113755902B (en) 2021-09-30 2021-09-30 Titanium anode plate and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113755902A CN113755902A (en) 2021-12-07
CN113755902B true CN113755902B (en) 2023-04-07

Family

ID=78798743

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111164561.1A Active CN113755902B (en) 2021-09-30 2021-09-30 Titanium anode plate and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113755902B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW214570B (en) * 1989-06-30 1993-10-11 Eltech Systems Corp
EP2390385B1 (en) * 2010-05-25 2015-05-06 Permelec Electrode Ltd. Anode for electrolysis and manufacturing method thereof
CN103668342B (en) * 2013-11-29 2016-03-09 中南大学 A kind of manganese electrolysis titanium based composite anode and preparation method
CN106119849A (en) * 2016-06-29 2016-11-16 苏州吉岛电极科技有限公司 Anode titanium plate Front-coating mirror front surface pretreatment etch method
CN106835192B (en) * 2017-02-02 2018-12-21 桂林理工大学 A kind of preparation method of electrolytic manganese dioxide titanium substrate anode surface composite coating
CN109989075B (en) * 2019-05-10 2019-11-22 建滔（连州）铜箔有限公司 A kind of back coating technique producing electrolytic copper foil titanium anode plate

Also Published As

Publication number Publication date
CN113755902A (en) 2021-12-07

Similar Documents

Publication Publication Date Title
CN103205780A (en) Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode
CN111926349B (en) Composite anode for hydrometallurgy and preparation method and application thereof
CA2783302C (en) Metal electrowinning anode and electrowinning method
CN113668010B (en) Oxygen evolution anode for industrial electrolysis and preparation method thereof
CN111634982B (en) Preparation method of anode material for efficient phenol wastewater degradation
CN109680301B (en) Anode plate for zinc electrolysis and preparation method thereof
JP5686455B2 (en) Method for producing anode for oxygen generation for high load resistance
CN102797017A (en) Method for preparing high-purity metallic silver
CN104313652A (en) Preparation method of aluminum-based multiphase inert composite anode material
CN113755902B (en) Titanium anode plate and preparation method and application thereof
CN113716658B (en) Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure
Li et al. Electrochemical properties of powder-pressed Pb–Ag–PbO2 anodes
CN110980890A (en) Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof
CN103572331B (en) The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode
CN104846417A (en) Method for preparing Ni/CeO2 composite hydrogen evolution electrode
CN114164419B (en) Method for preparing platinum active layer on anode plate by thermal decomposition method
CN102443822B (en) Gradient functional inert anode material used for zinc electrodeposition and its preparation method
CN115626693B (en) Lead-antimony coated titanium anode plate with intermediate layer and preparation method and application thereof
CN102560561A (en) DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof
CN115287737A (en) Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof
CN111607805B (en) High-life anode material
CN111763979B (en) Preparation method of long-life anode material
CN113293411B (en) Gradient composite lead dioxide anode plate and preparation method and application thereof
CN114808041A (en) Preparation and activation regeneration method of Pb-based pseudomorphic stable anode for manganese electrodeposition
CN109537000B (en) Stainless steel based beta-PbO2-MnO2-CeO2-ZrO2Preparation method of inert composite anode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant