CN114196979B - Method for preparing coating titanium electrode by electrostatic spinning method - Google Patents
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Abstract
The invention belongs to the technical field of inorganic materials, and discloses a method for preparing a coated titanium electrode by an electrostatic spinning method. Firstly, preparing a metal salt solution containing a spinning auxiliary agent as a spinning solution, injecting the spinning solution into an injector, putting the treated titanium sheet on a receiving device to serve as a receiving plate, and carrying out electrostatic spinning; placing the electrode obtained by spinning in a muffle furnace for annealing to obtain a coated titanium electrode; the coating component of the prepared coating titanium electrode is RuO 2 ‑TiO 2 Or RuO 2 ‑TiO 2 ‑SnO 2 Or RuO 2 ‑TiO 2 ‑IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the coating can be regulated and controlled, the coating is complete and continuous, and the coating has a nanometer microstructure. The invention has simple process equipment, strong operability and full utilization of spinning solution, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a method for preparing a coating titanium electrode by an electrostatic spinning method, and belongs to the technical field of inorganic materials.
Background
The coated titanium electrode is the most widely used chlorine evolution electrode at present, and has wide application in chlor-alkali industry and water treatment industry. The titanium electrode coating has the advantages of corrosion resistance and good stability, and can sterilize and disinfect water body through electrochemical chlorine separation. However, the current preparation methods of coated titanium electrodes are mainly brush method and dip-coating method. The brush method and the dipping and pulling method need to be repeatedly coated, dried and calcined for many times, the preparation is time-consuming, and the dipping and pulling method is insufficient in utilization of the coating liquid, so that the loss and the waste of the coating liquid are caused. Thus, there is a need to develop new methods of preparing coated titanium electrodes.
The electrostatic spinning method is to inject spinning solution into an injector, and the injector is slowly pushed by a push pump of an electrostatic spinning machine, so that the spinning solution gradually drops out of the injector, and small liquid drops are formed at a needle connected with the injector; the small liquid drops form a Taylor cone under the action of positive high pressure, and the material with the nanometer microstructure is formed on the receiving plate through stretching and quick volatilization of the solvent. In the electrostatic spinning process, the spinning solution is gradually pushed out drop by drop in the injector, so that electrostatic spinning is fully performed, and the loss and waste of the spinning solution are avoided.
Disclosure of Invention
The invention provides a method for preparing a coated titanium electrode by adopting an electrostatic spinning method, which has the advantages of short preparation time and full utilization of coating liquid, and the prepared electrode has adjustable thickness of an active coating, is complete and continuous and has a micro-nano structure.
The following terms are referred to in the present invention, and the meanings are explained as follows:
polyvinylpyrrolidone: PVP for short, weight average molecular weight mw=1300000;
polyethylene oxide: PEO for short, weight average molecular weight mw= 500000 ～ 1000000;
spinning receiving distance: distance of spinning needle to receiving device.
The technical scheme of the invention is as follows:
a method for preparing a coating titanium electrode by an electrostatic spinning method is characterized in that a high molecular spinning auxiliary agent PVP or PEO is added into a spinning solution precursor to enable the spinning solution to have certain viscosity; placing the spinning solution in an injector, placing the treated titanium sheet on a receiving tray horizontally to serve as a receiving substrate, and carrying out electrostatic spinning; the coating titanium electrode with different active coating components can be prepared by regulating and controlling the composition of the spinning solution; the appearance of the coating is controlled by regulating and controlling the spinning voltage, the heating temperature of the receiving substrate, the propelling speed and the spinning receiving distance, and the binding force between the coating and the titanium sheet is controlled; the thickness of the coating is controlled by regulating and controlling the spinning time; the coating titanium electrode prepared by the electrostatic spinning method has the characteristics of full utilization of spinning solution, continuous and complete coating, adjustable coating thickness and coating.
The method for preparing the coating titanium electrode by the electrostatic spinning method comprises the following steps:
1. pretreatment of a titanium sheet substrate: sequentially placing titanium sheets into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 10-20min, heating the cleaned titanium sheets to micro boiling for 1-2h in oxalic acid solution with the mass fraction of 10-15%, performing acid etching, cleaning the titanium sheets subjected to acid etching by using deionized water, and then placing the cleaned titanium sheets into absolute ethyl alcohol for storage for later use;
2. spinning machinePreparing a silk solution, namely adding a certain amount of spinning auxiliary PVP or PEO into ethanol, heating to 50-70 ℃, and then performing ultrasonic dispersion for 20-40min to obtain a solution A; an amount of tetrabutyl titanate (C) 16 H 36 O 4 Ti), ruthenium trichloride (RuCl) 3 ·xH 2 O), or tetrabutyl titanate (C) 16 H 36 O 4 Ti), ruthenium trichloride (RuCl) 3 ·xH 2 O), stannous chloride dihydrate (SnCl) 2 ·2H 2 O), or tetrabutyl titanate (C) 16 H 36 O 4 Ti), ruthenium trichloride (RuCl) 3 ·xH 2 O), chloroiridium acid (H) 2 IrCl 6 ·6H 2 Adding O) into absolute ethyl alcohol, and uniformly stirring to obtain a solution B with the total metal concentration of 0.1-0.3 mol/L; mixing the solution A and the solution B according to the volume ratio of 1:1, uniformly stirring, and standing for 8-12h to obtain spinning solution C;
3. and (3) electrostatic spinning: sucking the spinning solution in step (2) by a disposable injector, putting the spinning solution into a propelling pump of an electrostatic spinning machine, putting the titanium sheet treated in step (1) on a receiving tray horizontally to serve as a receiving substrate, and carrying out electrostatic spinning to obtain a precursor electrode after spinning;
4. annealing: and (3) placing the precursor electrode after spinning in the step (3) in a muffle furnace for annealing under the air atmosphere, wherein the heating rate is 5-10 ℃/min, the annealing temperature is 400-550 ℃, the heat preservation time is 1-2h, and taking out after naturally cooling to room temperature in the furnace to obtain the coating titanium electrode prepared by the electrostatic spinning method.
According to the method of the invention, it is preferred that:
in the step (2), the spinning auxiliary agent in the solution A is polyvinylpyrrolidone (PVP) or polyethylene oxide (PEO), and the addition amount of the spinning auxiliary agent is 0.2-3% of the total weight of the solution A.
In the step (2), the total concentration of the metal in the solution B is the total concentration of Ti and Ru, or the total concentration of Ti, ru and Sn, or the total concentration of Ti, ru and Ir; the molar ratio of the titanium alloy to the titanium alloy is Ti, ru=7:3, or Ti, ru, sn=7:2 (0.5-1), or Ti, ru, ir=7:2 (0.5-1).
In the step (5), the process conditions of the electrostatic spinning are as follows: the positive high pressure is 8-16kV, the injection speed is 0.1-1mm/min, the heating temperature of the receiving disc is 220-270 ℃, the spinning receiving distance is 8-15cm, and the spinning time is 0.5-1h.
The invention can obtain the RuO active coating by regulating and controlling the composition of the spinning solution 2 -TiO 2 Or RuO 2 -TiO 2 -SnO 2 Or RuO 2 -TiO 2 -IrO 2 A coated titanium electrode of (a); the thickness of the coating can be adjusted within the range of 0.1-30 mu m by adjusting the spinning time. The coating is complete and continuous and has a nano microstructure.
Drawings
FIG. 1 is an optical photograph of an electrode of example 1;
FIG. 2 is an SEM photograph of an electrode in example 1;
FIG. 3 is XRD results for the electrode of example 1;
FIG. 4 shows the results of electrode LSV in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments and descriptions of the present invention are provided for the purpose of illustration and are not intended to be limiting.
Example 1
(1) Pretreatment of a titanium sheet substrate: titanium sheet (2X 4 cm) 2 ) Performing sand blasting/sand paper polishing, then sequentially placing the titanium sheets into acetone, absolute ethyl alcohol and deionized water for 20min ultrasonic cleaning, heating the cleaned titanium sheets to micro boiling for 2h in oxalic acid solution with the mass fraction of 10%, performing acid etching, washing the titanium sheets subjected to acid etching treatment by using deionized water, and then placing the titanium sheets into the absolute ethyl alcohol for storage for later use;
(2) Preparing spinning solution, namely adding 0.03g of spinning auxiliary PVP into 3mL of absolute ethyl alcohol to obtain solution A; 214 mu L of tetrabutyl titanate and 56mg of ruthenium trichloride are added into 1.5mL of absolute ethyl alcohol, and the mixture is stirred uniformly to obtain a solution B with the total metal concentration of 0.3 mol/L; mixing and stirring the solution A and the solution B uniformly, and standing for 8 hours to obtain spinning solution C;
(3) And (3) electrostatic spinning: injecting the spinning solution C in the step (2) into a disposable injector, putting the disposable injector into a propelling pump of an electrostatic spinning machine, putting the titanium sheet treated in the step (1) on a receiving tray horizontally to serve as a receiving substrate, setting positive high voltage of 16kV, and the pushing speed of 1mm/min, heating the receiving substrate to 250 ℃, and carrying out electrostatic spinning for 1h at a spinning receiving distance of 15cm to obtain a precursor electrode after spinning;
(4) Annealing: annealing the precursor electrode after spinning in the step (3) in a muffle furnace under the air atmosphere, wherein the heating rate is 5 ℃/min, the annealing temperature is 450 ℃, the heat preservation time is 1h, and taking out after naturally cooling to room temperature in the furnace to obtain the RuO prepared by an electrostatic spinning method 2 -TiO 2 Coating a titanium electrode;
(5) Electrode chlorine evolution potential test: the three-electrode reaction system is adopted, the working electrode is the electrode manufactured in the step (4), and the working area of the electrode immersed in the electrolyte is 6cm 2 The counter electrode is a platinum wire, the reference electrode is Ag/AgCl, the electrolyte is 5mol/L sodium chloride, the volume of the electrolyte is 100mL, and the electrode chlorine evolution potential is 1.34V vs Ag/AgCl after the test in an LSV mode in an electrochemical workstation.
Example 2
As described in example 1, except that:
in the step (2), preparing spinning solution; adding 0.09g of spinning auxiliary PEO into 3mL of absolute ethyl alcohol to obtain a solution A; mixing the solution A and the solution B in equal volume, uniformly stirring, and standing for 10 hours to obtain spinning solution C;
in the step (3), setting positive high voltage of 14kV, the injection speed of 0.5mm/min, the heating temperature of a receiving substrate of 230 ℃, the receiving distance of spinning of 12cm and the spinning time of 1h;
in the step (5), the chlorine evolution potential is 1.33V;
steps (1) and (4) are the same as in example 1.
Example 3
As described in example 1, except that:
in the step (2), 143 mu L of tetrabutyl titanate, 24.9mg of ruthenium trichloride and 11.3mg of stannous chloride dihydrate are added into 1.5mL of absolute ethyl alcohol, and the mixture is stirred uniformly to obtain a solution B with the total metal concentration of 0.3 mol/L; mixing the solution A and the solution B in equal volume, uniformly stirring, and standing for 10 hours to obtain spinning solution C;
in the step (4), the heating rate is 10 ℃/min, the annealing temperature is 500 ℃, the heat preservation time is 1h, and the annealing is naturally cooled in a furnace toTaking out after room temperature to obtain RuO prepared by an electrostatic spinning method 2 -TiO 2 -SnO 2 Coating a titanium electrode;
in the step (5), the chlorine evolution potential is 1.35V;
steps (1) and (3) are the same as in example 1.
Example 4
As described in example 1, except that:
in the step (2), the spinning solution is prepared as follows: adding 0.06g of spinning auxiliary PVP into 3mL of absolute ethyl alcohol to obtain a solution A; 71.5 mu L of tetrabutyl titanate, 12.5mg of ruthenium trichloride and 12.2mL of chloroiridic acid are added into 1.5mL of absolute ethyl alcohol, and the mixture is stirred uniformly to obtain a solution B with the total metal concentration of 0.1 mol/L; mixing the solution A and the solution B in equal volume, uniformly stirring, and standing for 12 hours to obtain spinning solution C;
in the step (4), the heating rate is 5 ℃/min, the annealing temperature is 480 ℃, the heat preservation time is 1h, and the RuO prepared by the electrostatic spinning method is obtained after the RuO is naturally cooled to the room temperature in a furnace and then taken out 2 -TiO 2 -IrO 2 Coating a titanium electrode;
the chlorine evolution potential in the step (5) is 1.35V;
steps (1) and (3) are the same as in example 1.
Claims (3)
1. A method for preparing a coated titanium electrode by an electrostatic spinning method comprises the following steps:
(1) Pretreatment of a titanium sheet substrate: sequentially placing titanium sheets into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 10-20min, heating the cleaned titanium sheets to micro boiling for 1-2h in oxalic acid solution with the mass fraction of 10-15%, performing acid etching, cleaning the titanium sheets subjected to acid etching by using deionized water, and then placing the cleaned titanium sheets into absolute ethyl alcohol for storage for later use;
(2) Preparing a spinning solution: adding a certain amount of spinning auxiliary agent PVP or polyethylene oxide PEO into ethanol to obtain a solution A, wherein the addition amount of the spinning auxiliary agent PVP or PEO is 0.2-3% of the total weight of the solution A; adding a certain amount of tetrabutyl titanate, ruthenium trichloride, or tetrabutyl titanate, ruthenium trichloride, stannous chloride dihydrate, or tetrabutyl titanate, ruthenium trichloride and chloroiridium acid into absolute ethyl alcohol, and uniformly stirring to obtain a solution B with the total metal concentration of 0.1-0.3 mol/L; the total concentration of the metal in the solution B is the total concentration of Ti and Ru, or the total concentration of Ti, ru and Sn, or the total concentration of Ti, ru and Ir; the molar ratio of the titanium alloy to the titanium alloy is Ti, ru=7:3, or Ti, ru, sn=7:2 (0.5-1), or Ti, ru, ir=7:2 (0.5-1); mixing the solution A and the solution B according to the volume ratio of 1:1, uniformly stirring, and standing for 8-12h to obtain spinning solution C;
(3) And (3) electrostatic spinning: injecting the spinning solution C in the step (2) into a disposable injector, putting the disposable injector into a propelling pump of an electrostatic spinning machine, horizontally placing the titanium sheet treated in the step (1) on a receiving tray to serve as a receiving substrate, and carrying out electrostatic spinning to obtain a precursor electrode after spinning; the process conditions of the electrostatic spinning are as follows: the positive high pressure is 8-16kV, the injection speed is 0.1-1mm/min, the heating temperature of a receiving disc is 220-270 ℃, the spinning receiving distance is 8-15cm, and the spinning time is 0.5-1h;
(4) Annealing: annealing the precursor electrode after spinning in the step (3) in a muffle furnace under the air atmosphere, wherein the heating rate is 5-10 ℃/min, the annealing temperature is 400-550 ℃, the heat preservation time is 1-2h, and taking out the precursor electrode after naturally cooling to room temperature in the furnace to obtain the coating titanium electrode prepared by an electrostatic spinning method; the coating thickness of the coated titanium electrode is adjustable within the range of 0.1-30 mu m.
2. The method of claim 1, wherein in step (2), after adding ethanol to PVP or PEO, the mixture is first heated to 50-70 ℃ and then ultrasonically dispersed for 20-40min to obtain solution a.
3. The method according to claim 1, wherein the titanium electrode has a coating composition of RuO 2 -TiO 2 Or RuO 2 -TiO 2 -SnO 2 Or RuO 2 -TiO 2 -IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The coating is complete and continuous and has a nano microstructure.
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| JPS54125197A (en) * | 1978-03-24 | 1979-09-28 | Berumeretsuku Denkiyoku Kk | Electrolytic electrode and its manufacture |
| CN101922016A (en) * | 2009-06-09 | 2010-12-22 | 明达实业(厦门)有限公司 | Titanium electrode for chlorine generator and preparation method thereof |
| CN107398268A (en) * | 2017-07-19 | 2017-11-28 | 中国科学院生态环境研究中心 | A kind of preparation method of manganese oxide carbon nano-fiber catalytic membrane |
| IT201800006544A1 (en) * | 2018-06-21 | 2019-12-21 | ANODE FOR ELECTROLYTIC EVOLUTION OF CHLORINE |
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