CN103741165A - Active coating layer embedded in ruthenium-titanium oxide and preparation method of active coating layer - Google Patents
Active coating layer embedded in ruthenium-titanium oxide and preparation method of active coating layer Download PDFInfo
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Abstract
The invention discloses an active coating layer embedded in a ruthenium-titanium oxide and a preparation method of the active coating layer. The active coating layer takes an iridium-tantalum oxide as the subject, wherein the ruthenium-titanium oxide is embedded. Nanometer ruthenium-titanium oxide powder with dimension within 15 nm is obtained through the control of sintering temperature, is mixed in an iridium-tantalum oxide precursor for heating and curing, and is oxidized, sintered and annealed in a 530 DEG C of box-type furnace to obtain an embedded iridium-tantalum oxide active coating layer. The active material has oxygen evolution and chlorine evolution functions, so that the comprehensive activity of the iridium-tantalum oxide active coating layer is prominently improved, and the practicability is stronger. The preparation method has the characteristics of simplicity, convenience, strong operability and high cost performance.
Description
Technical field
The electrode materials field that the invention belongs to Applied Electrochemistry and energy industry, relates to a kind of material with high electrocatalysis characteristic and preparation method thereof.Concrete Application Areas comprises electrochemistry parts and the devices such as acid electrolytic solution, weak brine electrolysis, organic solution electrolysis, cathodic protection, electrochemical sensor.Suitablely especially be used as the activated coating of electrode materials in analysing electrolyzer chlorine, oxygen are two.
Background technology
Active electrode is parts crucial in electrochemical industry, and nineteen sixty-five Beer develops ruthenium dioxide coated anode first, has opened up anode material of new generation, the existence of activated coating give this class anode high analyse chlorine activity.Through large quantity research, in activated coating, with RuO
2+ TiO
2the binary oxide being composited has more superior over-all properties, is to analyse the industrial coated material the most generally adopting of chlorine.People recognize gradually, and ruthenium dioxide coating is not adapted at analysing in the occasion of oxygen and applies.Vercesi in 1991 etc. have proposed to adopt iridium base oxide can realize the demand of oxygen evolution reaction, have succeeded in developing IrO later
2+ Ta
2o
5composite oxides anode material, this material can be applicable to more harsh electrolytic condition, and has higher oxygen evolution activity.At present, analyse chlorine and analyse oxygen electrode and become topmost two class gassing active electrode materials in electrochemical industry.Along with industrial expansion, the expansion of Application Areas, the complexity of environment for use, the traditionally single Cl that analyses
2, analyse O
2day by day highlight by the limitation of anode.As in electrometallurgy field, the electrolytic acid aqueous solution and perchlorate are produced, more situation is to exist containing oxygen and chlorine-containing compound in electrolytic solution, makes electrolytic environments more harsh, and therefore electrode materials is also subject to more acid test.For this reason, research and development oxygen chlorine pair is analysed electrode materials very important practical significance.For the activated coating of development of new, this research team is round TiO
2+ RuO
2and IrO
2+ Ta
2o
5conduct in-depth research, obtained certain achievement, as in 91 volumes of the < < U.S. in 2008 the pottery > > of association journal with " Phase Structure and Microstructure of a Nanoscale TiO
2-RuO
2-IrO
2-Ta
2o
5anode Coating on Titanium " for topic, disclosed a kind of TiO
2+ RuO
2+ IrO
2+ Ta
2o
5the technology of preparing of activated coating; In Chinese patent 200810072273.1, propose the patent of invention that adopts the activity of alternating structure " to there is the preparation method of the titanium anode of alternating structure coating ", obtained patent for invention.These coatings play obvious effect in the solidity to corrosion of improving titanium anode.Recently, the research of this research group is found to adopt the method that embeds ruthenium titanium oxide, at IrO
2-Ta
2o
5in coating oxidation thing, add RuO
2-TiO
2the method of oxide nanocrystalline, improves IrO
2+ Ta
2o
5analyse chlorine characteristic, prepare a kind of iridium tantalum active anode coating of damascene structures of novel ruthenium titanium oxide, can obtain the characteristic of simultaneously analysing oxygen and analyse chlorine, thereby can obtain efficient oxygen, the two activated coating electrode materialss of analysing of chlorine.
Summary of the invention
The object of this invention is to provide a kind of activated coating that embeds ruthenium titanium oxide and preparation method thereof, thereby obtain the high reactivity electrode materials that has stronger pervasive effect.
Thinking of the present invention is in original iridium tantalum pentoxide activated coating, utilizes embedded technology in this coating, to add ruthenium titanium oxide, to improve iridium tantalum pentoxide, can analyse at the same time oxygen and analyse and in chlorine occasion, have more superior activity.This thinking is to be respectively analysing chlorine and analysing two the most frequently used class active electrode materials of oxygen of generally acknowledging at present based on iridium tantalum pentoxide and ruthenium titanium oxide.Along with growing industrial expansion, the expansion of Application Areas, the complexity of environment for use, the traditionally single Cl that analyses
2, analyse O
2day by day highlight by the limitation of anode.In order to adapt to this variation, this team has proposed to adopt and embedded ruthenium titanium oxide in iridium tantalum pentoxide activated coating, make electrode under arms in process, except the oxygen evolution reaction of iridium tantalum pentoxide, exposedly at surperficial ruthenium titanium oxide, can analyse chlorine reaction, the effective active of the electrode of enhancing.This oxygen, chlorine pair are analysed electrode materials and are had very important practical significance.
Principle of operation of the present invention adds the nano level ruthenium titanium of part active oxidation composition granule exactly in iridium tantalum pentoxide presoma.Described damascene structures is to come from the effect that adopts the insert of about < 15 nm of particle diameter to add, thereby obtained, has the similar structure of matrix material.Pass through again ruthenium titanium oxide nanoscale and the ratio control with iridium tantalum pentoxide, can obtain analysing oxygen and analysing the performance of chlorine of needing.Because the dosage of insert produces obviously impact to the internal organizational structure of active material, add very little, embed interface increasing amount limited, the active effect improving is limited.Add too much, the interface accounting of embedding is too high, affects the associativity of active material, and corrosion resisting property is had a negative impact.By the optimum dosage of mole total of the active substance of design, be 18～22 mol%.
Core technology take the nanocrystalline iridium tantalum activating oxide coating as insert of ruthenium titanium oxide prepared by employing embedding inlay technique of the present invention comprises, (1) first prepares ruthenium titanium oxide, and it has suitable nanoscale; (2) mix with the presoma of iridium tantalum activating oxide, on common deposition and titanium base material; (3) thermal treatment of the iridium tantalum pentoxide coating that contains ruthenium titanium oxide embedded structure.
Preparation method of the present invention mainly comprises following four steps:
(1) preparation of ruthenium titanium oxide slurries: with RuCl
3and TiCl
3for source material, in Ru: Ti ratio takes each source material, and the two is mixed, and obtains ruthenium titanium oxide active slurry;
(2) sintering of ruthenium titanium oxide nanoparticles preparation: extract ruthenium titanium oxide active slurry, after being heating and curing, then oxidation and sinter, acquisition has the insert of the ruthenium titanium oxide of nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, take in proportion each source material, the two is mixed, obtain active slurry;
(4) preparation of activated coating: ruthenium titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on titanium base material; after being heating and curing; oxidation and sinter, finally annealing, obtains the iridium tantalum pentoxide active coated Ti that embeds ruthenium titanium oxide.
Remarkable advantage of the present invention is:
(1) the present invention has effectively utilized the principle of the increase crystal boundary ratio of nanotechnology and matrix material, by embedding grammar, imports a large amount of damascene structures.Increased the number of channels of proton, thereby the activity of electrode materials is improved.
(2) due to by the nano-powder of the fine dimension of the dispersion that has of preparation in advance, after embedding, make the crystal miniaturization of final ruthenium titanium oxide, increased the density in active centre, thereby the actual bearer current density at electrode activity center is declined, thereby the activity of electrode materials is improved.
(3) owing to adding the nano level ruthenium titanium of part active oxidation composition granule in iridium tantalum pentoxide presoma.Can be by the ratio control of ruthenium titanium oxide and iridium tantalum pentoxide, can obtain analysing oxygen and analysing the performance of chlorine of needing.Because coating of the present invention is take iridium tantalum pentoxide as main, so the activity of its gassing is mainly to analyse oxygen, less important is to analyse chlorine.
(4) the present invention, owing to having adopted traditional ruthenium titanium oxide active slurry to solidify in advance, disperses, the method for refinement, and the making of raw material and storage are all easy to.Added in iridium tantalum active slurry, can be prepared electrode materials by traditional technology.Therefore technique is simple, easily goes, and does not totally make tooling cost increase.Owing to improving the performance of electrode materials, make the cost performance of electrode product be able to obvious improvement.
Accompanying drawing explanation
Fig. 1 is transmission electron microscopy (TEM) photo of ruthenium titanium oxide insert.
Embodiment
The concrete preparation process of the iridium tantalum pentoxide with original position embedded structure of the present invention is as follows:
(1) preparation of ruthenium titanium oxide slurries: with RuCl
3and TiCl
3for source material, in Ru: the Ti mol ratio ratio of 3: 7 takes each source material, and is dissolved in respectively butanols, concentration is controlled at 0.3 mol/L left and right, after each source material fully dissolves, the two is mixed, and obtains ruthenium titanium oxide active slurry;
(2) sintering of ruthenium titanium oxide nanoparticles preparation: quantitatively extract ruthenium titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 395 ℃, come out of the stove cooling, after grinding, obtain the insert of the ruthenium titanium oxide with nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, in Ir: the Ta mol ratio ratio of 7: 3 takes each source material, and is dissolved in respectively butanols, concentration is controlled at 0.1 mol/L left and right, after each source material fully dissolves, the two is mixed, and obtains active slurry;
(4) preparation of activated coating: 15 ~ 25 mol% that press mole total amount of active substance extract the iridium tantalum active slurry of ruthenium titanium oxide nano-powder and 85 ~ 75mol%, ruthenium titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material of etching, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 530 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 10-15 time, finally 530 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium titanium oxide.
The present invention has obtained the iridium tantalum pentoxide active titanium anode that has embedded ruthenium titanium oxide nanostructure by above-mentioned enforcement.Research shows, the increasing of the refinement of crystal grain and crystal boundary, effectively improve activating oxide active centre density, improve the conductive capability of dispersion state and proton, to such an extent as to activity is improved.Because the present invention analyses oxygen and analyses the activity of chlorine having the iridium tantalum pentoxide active material that embeds ruthenium titanium oxide structure, having had simultaneously.Carry out contrast experiment with traditional iridium tantalum pentoxide active material of preparing under equal conditions, result shows that the over-all properties of the iridium tantalum pentoxide active material with ruthenium titanium oxide embedded structure is improved significantly.Table 1 is the analysing oxygen and analysing chlorine performance under parallel laboratory test condition without iridium tantalum pentoxide active material embedded structure and that have embedded structure.Can clearly find out, the titanium anode of embedded structure is suitable with the oxygen evolution potential of traditional titanium anode in the performance of analysing oxygen, but its current potential of analysing chlorine obviously reduces.This fully shows, has the iridium tantalum pentoxide active material that embeds ruthenium titanium oxide nanostructure and has good oxygen, the two performances of analysing of chlorine.
Below describe two examples of implementation of the present invention in detail, but the present invention is not only limited to this.
Embodiment 1
Adding the preparation of the iridium tantalum activating oxide covering electrodes material of 18mol% insert carries out according to the following steps:
(1) preparation of ruthenium titanium oxide slurries: with RuCl
3and TiCl
3for source material, in Ru: the Ti mol ratio ratio of 3: 7 takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.25 mol/L, after each source material fully dissolves, the two is mixed, and obtains ruthenium titanium oxide active slurry;
(2) sintering of ruthenium titanium oxide nanoparticles preparation: quantitatively extract ruthenium titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 395 ℃, come out of the stove cooling, after grinding, obtain and there is the insert that nanoscale is the ruthenium titanium oxide of 14 nm.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, in Ir: the Ta mol ratio ratio of 7: 3 takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.15 mol/L, after each source material fully dissolves, the two is mixed, and obtains active slurry;
(4) preparation of activated coating: 18 mol% that press mole total amount of active substance extract the iridium tantalum active slurry of ruthenium titanium oxide nano-powder and 78mol%, ruthenium titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material after the 1 hour cleaning-drying of 10% oxalic acid etching that seethes with excitement, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 530 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 12 times, finally 530 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium titanium oxide.It is analysed oxygen and analyses chlorine performance and is shown in Table 1.
Embodiment 2
Adding the preparation of the iridium tantalum activating oxide covering electrodes material of 22% insert carries out according to the following steps:
(1) preparation of ruthenium titanium oxide slurries: with RuCl
3and TiCl
3for source material, in Ru: the Ti mol ratio ratio of 7: 3 takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.35 mol/L, after each source material fully dissolves, the two is mixed, and obtains ruthenium titanium oxide active slurry;
(2) sintering of ruthenium titanium oxide nanoparticles preparation: quantitatively extract ruthenium titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 385 ℃, come out of the stove cooling, after grinding, obtain and there is the insert that nanoscale nanoscale is the ruthenium titanium oxide of 13 nm.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, in Ir: the Ta mol ratio ratio of 7: 3 takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.15 mol/L, after each source material fully dissolves, the two is mixed, and obtains active slurry;
(4) preparation of activated coating: 15 ~ 25 mol% that press mole total amount of active substance extract the iridium tantalum active slurry of ruthenium titanium oxide nano-powder and 85 ~ 75mol%, ruthenium titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material after the 1 hour cleaning-drying of 10% oxalic acid etching that seethes with excitement, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 530 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 15 times, finally 530 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium titanium oxide.It is analysed oxygen and analyses chlorine performance and is shown in Table 1.
Table 1 has the electrochemical properties of the iridium tantalum pentoxide titanium anode that embeds ruthenium titanium oxide structure
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. an activated coating that embeds ruthenium titanium oxide, is characterized in that: described activated coating is take iridium tantalum pentoxide as main body, has wherein embedded ruthenium titanium oxide.
2. the activated coating of embedding ruthenium titanium oxide according to claim 1, is characterized in that: in described ruthenium titanium oxide, the mol ratio of Ru and Ti is 3:7.
3. the activated coating of embedding ruthenium titanium oxide according to claim 1, is characterized in that: in described iridium tantalum pentoxide, the mol ratio of Ir and Ta is 7:3.
4. the activated coating of embedding ruthenium titanium oxide according to claim 1, is characterized in that: in described activated coating, the mol ratio of Ir and Ru is 75 ~ 85:15 ~ 25.
5. the activated coating of embedding ruthenium titanium oxide according to claim 1, is characterized in that: the particle diameter of described ruthenium titanium oxide is less than 15nm.
6. a method of preparing the activated coating of embedding ruthenium titanium oxide as claimed in claim 1, is characterized in that: comprise the following steps:
(1) preparation of ruthenium titanium oxide active slurry: with RuCl
3and TiCl
3for source material, by the mol ratio of Ru and Ti, be to take each source material at 7: 3, and be dissolved in respectively butanols, after each source material fully dissolves, the two is mixed, obtain ruthenium titanium oxide active slurry;
(2) sintering of ruthenium titanium oxide nanoparticles: extract ruthenium titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 395 ℃, comes out of the stove cooling, after grinding, obtains ruthenium titanium oxide nanoparticles;
(3) preparation of iridium tantalum pentoxide active slurry: with H
2irCl
6and TaCl
5for source material, by Ir and Ta mol ratio, be to take each source material at 7: 3, and be dissolved in respectively butanols, after each source material fully dissolves, the two is mixed, obtain iridium tantalum pentoxide active slurry;
(4) preparation of activated coating: take ruthenium titanium oxide nanoparticles by 15 ~ 25% of mole total amount of active substance, by 85 ~ 75% of mole total amount of active substance, take iridium tantalum pentoxide active slurry, ruthenium titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material of etching, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 530 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 10-15 time, finally 530 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium titanium oxide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988530A (en) * | 2015-08-12 | 2015-10-21 | 海南金海浆纸业有限公司 | Composite coating electrode and preparing method thereof and electrolytic cell |
| CN108048870A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium Si composite oxide and preparation method thereof |
| CN108048869A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium hafnium composite oxides and preparation method thereof |
| CN108048895A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium zirconium mixed oxide and preparation method thereof |
| CN110438527A (en) * | 2019-08-05 | 2019-11-12 | 上海氯碱化工股份有限公司 | The preparation method of the transient metal doped anode containing ruthenium coating |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073497A (en) * | 1993-06-22 | 1995-01-06 | Daiso Co Ltd | Oxygen generating electrode |
| CN101235513A (en) * | 2007-11-14 | 2008-08-06 | 福州大学 | Coating titanium anode |
| CN101435084A (en) * | 2008-12-04 | 2009-05-20 | 福州大学 | Titanium anode with coating having alternate laminated structure and preparation thereof |
| CN102029152A (en) * | 2010-11-30 | 2011-04-27 | 福州大学 | Ru-Zr-Ti ternary oxide active material and preparation method thereof |
| CN102220600A (en) * | 2011-05-31 | 2011-10-19 | 福州大学 | Iridium tantalum activating oxide having in situ embedded structure and preparation method thereof |
-
2014
- 2014-01-26 CN CN201410037120.9A patent/CN103741165B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073497A (en) * | 1993-06-22 | 1995-01-06 | Daiso Co Ltd | Oxygen generating electrode |
| CN101235513A (en) * | 2007-11-14 | 2008-08-06 | 福州大学 | Coating titanium anode |
| CN101435084A (en) * | 2008-12-04 | 2009-05-20 | 福州大学 | Titanium anode with coating having alternate laminated structure and preparation thereof |
| CN102029152A (en) * | 2010-11-30 | 2011-04-27 | 福州大学 | Ru-Zr-Ti ternary oxide active material and preparation method thereof |
| CN102220600A (en) * | 2011-05-31 | 2011-10-19 | 福州大学 | Iridium tantalum activating oxide having in situ embedded structure and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHEN YONG-YI 等: ""Phase Structure and Microstructure of a Nanoscale TiO2-RuO2-IrO2-Ta2O5 Anode Coating on Titanium"", 《J.AM.CERAM.SOC.》, vol. 91, no. 12, 15 December 2008 (2008-12-15), XP055153819, DOI: doi:10.1111/j.1551-2916.2008.02808.x * |
| 陈永毅等，: ""析氯析氧组合涂层钛阳极的研究"", 《稀有金属材料与工程》, vol. 38, no. 7, 15 July 2009 (2009-07-15), pages 1215 - 1218 * |
| 颜琦等: ""嵌入式RuO2 - TiO2 - IrO2/Ti氧化物电极的制备"", 《福建师范大学学报(自然科学版)》, vol. 29, no. 5, 20 September 2013 (2013-09-20) * |
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| CN104988530A (en) * | 2015-08-12 | 2015-10-21 | 海南金海浆纸业有限公司 | Composite coating electrode and preparing method thereof and electrolytic cell |
| CN104988530B (en) * | 2015-08-12 | 2018-01-26 | 海南金海浆纸业有限公司 | A kind of composite coating anode and preparation method thereof and electrolytic cell |
| CN108048870A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium Si composite oxide and preparation method thereof |
| CN108048869A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium hafnium composite oxides and preparation method thereof |
| CN108048895A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium zirconium mixed oxide and preparation method thereof |
| CN108048895B (en) * | 2017-12-20 | 2019-12-17 | 福州大学 | nickel-based active electrode material embedded with ruthenium-zirconium composite oxide and preparation method thereof |
| CN108048870B (en) * | 2017-12-20 | 2019-12-17 | 福州大学 | Nickel-based active electrode material embedded with ruthenium-silicon composite oxide and preparation method thereof |
| CN110438527A (en) * | 2019-08-05 | 2019-11-12 | 上海氯碱化工股份有限公司 | The preparation method of the transient metal doped anode containing ruthenium coating |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
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