CN1772955A - Mixed metal oxide electrode and its making process - Google Patents
Mixed metal oxide electrode and its making process Download PDFInfo
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- CN1772955A CN1772955A CN 200510104253 CN200510104253A CN1772955A CN 1772955 A CN1772955 A CN 1772955A CN 200510104253 CN200510104253 CN 200510104253 CN 200510104253 A CN200510104253 A CN 200510104253A CN 1772955 A CN1772955 A CN 1772955A
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Abstract
The mixed metal oxide electrode features the metal substrate with one intermediate layer coated via physical and/or chemical process and one mixed metal oxide coating formed through painting, several times of thermal decomposition and sintering on the intermediate layer. The metal substrate is made of Ti, Ta, Nb, Zr, W, Al or stainless steel; and the intermediate layer is one or several of nitride, boride or carbide of Ti, Ta and Nb. The mixed metal oxide electrode has the advantages of high electric catalytic activity, high electric conductivity, high anode oxidation resistance, long service life and low production cost.
Description
Technical field
The present invention relates to mixed metal oxide electrode that a kind of Electrochemical Engineering uses and preparation method thereof, particularly relate to a kind of mixed metal oxide electrode that contains the middle layer and preparation method thereof.
Background technology
Electrochemical industry and electrometallurgy industry all be unable to do without electrode, and selection of electrode materials is very important.The dynamic index of the structural shape of the direction of electrode process and kinetics, electrode and electrolyzer and electric cell life, maintenance cost and labor force's consumption and technological process etc. all depends on the structure of electrode and used material to a great extent, especially when carrying out electrode type and electric groove structure design, all wearing quality, electroconductibility, electro catalytic activity and the power consumption value with electrode materials has confidential relation, and the novel electrode material of constantly developing superior performance receives very big concern all the time.
As electrode matrix, its surface-coated is the activated coating of main ingredient with the platinum group metal oxide to existing coated titanium electrode with metal titanium.Coated titanium electrode claims metal anode again, is commonly referred to as DSA both at home and abroad.Henry Beer at first discloses the electro catalytic activity of metal oxide to people, obtain the ruthenium oxide coatings patent in South Africa in nineteen sixty-five, and has announced titanium base mixed oxidization ruthenium coating patent in 1967 in Belgium.After this, Vittorio de Nora has been put to industrialization to the invention of H.Beer.Relevant scholar thinks that the invention of DSA is to the electrochemical field epoch-making contribution, is one of invention the most great in 20th century electrochemistry.About theoretical investigation and the existing a lot of report of invention of DSA, its purpose is the electrocatalysis characteristic and the work-ing life of improving electrode nothing more than at present.There are two aspects in the life-span that influences coated titanium electrode: one is the active dissolution of Catalytic Layer, and another is that the oxidation of titanium matrix causes blunt.The active dissolution of Catalytic Layer can be controlled on component, proportioning and the sintering process of Catalytic Layer.And the oxidation of relevant inhibition titanium matrix causes the blunt electrode failure that causes, and relevant document once proposed to adopt tantalum as the middle layer, but a fatal shortcoming of this method is that to make the cost of electrode too high, and has lost using value.Also there is document to point out, by increasing the brushing number of times of Catalytic Layer, increase the thickness of Catalytic Layer, the oxidation that reduces the titanium matrix causes the blunt time, but this has improved the manufacturing cost of electrode undoubtedly greatly, and the raising in counter electrode life-span also is limited from final effect.Therefore, how under the prerequisite of the electrocatalysis characteristic that guarantees electrode, the novel electrode of developing low-cost, high life becomes the key issue that electrochemical industry is badly in need of solving at present.
Summary of the invention
The purpose of this invention is to provide a kind of mixed metal oxide electrode and preparation method thereof, it can solve the above-mentioned problems in the prior art.
A kind of mixed metal oxide electrode is characterized in that having a metallic matrix, in last coating one deck middle layer, applies mixed metal oxide coating on the middle layer; Described metallic matrix is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel, and described middle layer is the nitride of titanium or tantalum or niobium or in boride or the carbide one or more.
The preparation method of above-mentioned mixed metal oxide electrode is characterized in that on metallic matrix by physics or/and chemical process applies a middle layer, the mixed metal oxide coating that then applies on the middle layer again and form by thermolysis sintering repeatedly; Described metallic matrix is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel, and described middle layer is the nitride of titanium or tantalum or niobium or in boride or the carbide one or more.
Electrode of the present invention has the electro catalytic activity height, conducts electricity very well, and anti-anodic oxidation performance is strong, long service life, the advantage that production cost is low.
Description of drawings
Accompanying drawing 1. is the structural representation that the titanium base mixed metal oxide coating in titanium nitride middle layer is arranged.
Accompanying drawing 2. is for there being and not having the electrocatalysis characteristic design sketch relatively of the titanium base mixed metal oxide electrode in titanium nitride middle layer.
Accompanying drawing 3. is for there being and not having the accelerated life test comparison diagram as a result of the titanium base mixed metal oxide electrode in titanium nitride middle layer.
Embodiment
The structure of mixed metal oxide electrode of the present invention as shown in Figure 1, it is to apply a middle layer 2 on metallic matrix 1, applies mixed metal oxide coating 3 on middle layer 2; Described metallic matrix 1 is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel, and described middle layer 2 is the nitride of titanium or tantalum or niobium or in boride or the carbide one or more.Metallic matrix 1 is the matrix through degreasing and acid etching.The thickness in middle layer 2 is in 0.1 μ m～20 mu m ranges.
During preparation, on metallic matrix 1 by physics or/and the method for chemistry applies a middle layer 2, the mixed metal oxide coating 3 that then on middle layer 2, applies again and form by thermolysis sintering repeatedly; Multiple physics can be adopted or/and the method for chemistry prepares in middle layer 2, and these methods comprise ionitriding, ion implantation, thermospray, physical vapor deposition, chemical vapour deposition, plasma auxiliary chemical vapor deposition.Mixed metal oxide coating 3 has a kind of active ingredient at least and has at least a kind of inert component to mix to be formed, and this active ingredient is platinum metals or its oxide compound, inert component right and wrong platinum metals or its oxide compound.The thermolysis preparation process of mixed metal oxide coating 3 is that the precursor compound with active ingredient and inert component is blended in wiring solution-forming in the organic solvent, the method of this solution by spraying, roller coating or brushing is coated on the middle layer 2, drying then, at high temperature carry out sintering again, repeat above-mentioned coating procedure at least three times afterwards again.The sintering temperature of high-temperature sintering process is 400～560 ℃.
During concrete operations, at first industrially pure titanium TA2 is cleaned with metal cleaner, or in 10% (weight percentage) NaOH aqueous solution, the titanium plate is carried out electrolytic degreasing as negative electrode, then in 10% oxalic acid aqueous solution, handle 2～3h down little boiling, water is rinsed well again, places standby.Containing under the situation of titanium nitride layer, the method for employing ion plating plates the titanium nitride layer of the about 1 μ m of a bed thickness at above-mentioned titanium matrix.
Mixed metal oxide coating 3 is selected the iridium tantalum mixed oxide coatings that oxygen electrode uses of analysing of industrial widespread use, and it typically applies mother liquor and is: H
2IrCl
6XH
2O (being dissolved in the hydrochloric acid)+TaCl
5(being dissolved in the ethanol) mixing solutions, wherein the Ir/Ta mol ratio is 7: 6, being diluted to the metal total concn with concentrated hydrochloric acid again is 0.2mol/L.With soft woollen goods brush pen above-mentioned solution is coated on respectively and contains and not contain on the above-mentioned titanium matrix in TiN middle layer 2, after in 120 ℃ of baking ovens, drying 6～15min, place cabinet-type electric furnace sintering 10min under 400～560 ℃ of differing tempss, after taking out air cooling, repeat above-mentioned steps 10 times, under this sintering temperature, annealed one hour for the last time.Thereby make respectively under 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃ and 560 ℃ of sintering temperatures, contain and each 9 at the titanium base iridium tantalum mixed oxide electrode that does not contain the TiN middle layer.
Electrode of the present invention has been carried out result that electrocatalysis characteristic estimates as shown in Figure 2.The electrocatalysis characteristic evaluation is to adopt constant potential in+1.4V (with respect to saturated calomel electrode) in the 0.5mol/L aqueous sulfuric acid, measures its anodic current density.This anodic current density value is big more, shows that catalytic performance is high more.As can see from Figure 2, it is very approaching with the current density of the electrode that does not contain TiN middle layer 2 to contain the electrode in TiN middle layer 2, shows that the electrocatalysis characteristic that introducing TiN middle layer 2 does not have counter electrode brings negative impact.
Electrode of the present invention has been carried out result that reinforcing life estimates as shown in Figure 3.In the 1mol/L aqueous sulfuric acid, adopt the continuous current method, control current density is 2A/cm
2, measure its groove and press over time.When groove voltage rise high-amplitude surpasses 5V, think that promptly electrode lost efficacy.As can be seen from Figure 3, the electrode reinforcing life time of containing the TiN middle layer is general all greater than the electrode that does not contain the TiN middle layer, and especially sintering temperature is 460 ℃ a electrode, and its reinforcing life is not contain about 2 times of TiN middle layer.
TiN belongs to the metallic bond pottery, have the conductivity more much higher than titanium, its solidity to corrosion is similar to titanium, good anti-anodic oxidation performance is also arranged, and in anode oxidation process, still keep very high conductivity, and the anode oxide film that is unlikely to resemble titanium is nonconducting, just because of its these characteristics, certainly will be able to slow down the blunt phenomenon of causing of titanium matrix to it as the middle layer and take place, thus the work-ing life of improving electrode.And the manufacturing cost of TiN is very cheap, can produce in batches, can satisfy industrial production requirement.
Other metallic matrix of the present invention (tantalum, niobium, zirconium, tungsten, aluminium or stainless steel) has similar character to above-mentioned titanium matrix, described other middle layer (boride of titanium or carbide, in the nitride of tantalum or niobium or boride or the carbide one or more) also has similar character with above-mentioned TiN, realize that with them the prepared electrode of the present invention also has same functional effect, just tired no longer one by one stating here.
The novel electrode that utilizes preparation method of the present invention to obtain can be widely used in chlor-alkali, water electrolysis, sewage disposal, organism electrosynthesis, electrodialysis and the galvanic deposit industry, both can be used as anode and has used, and also can be used as negative electrode and uses.
Claims (7)
1. a mixed metal oxide electrode is characterized in that having a metallic matrix (1), goes up at metallic matrix (1) and applies a middle layer (2), and (2) are gone up and applied mixed metal oxide coating (3) in the middle layer; Described metallic matrix (1) is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel, and described middle layer (2) are the nitride of titanium or tantalum or niobium or in boride or the carbide one or more.
2. electrode according to claim 1 is characterized in that described metallic matrix (1) is the matrix through degreasing and acid etching.
3. electrode according to claim 1, the thickness that it is characterized in that described middle layer (2) are 0.1 μ m～20 μ m.
4. electrode according to claim 1, it is characterized in that described mixed metal oxide coating (3) has a kind of active ingredient at least and has at least a kind of inert component to mix composition, this active ingredient is platinum metals or its oxide compound, inert component right and wrong platinum metals or its oxide compound.
5. the preparation method of the described mixed metal oxide electrode of claim 1, it is characterized in that going up by physics or/and chemical process applies a middle layer (2) at metallic matrix (1), then again in the middle layer (2) go up the mixed metal oxide coating (3) that applies and form by thermolysis sintering repeatedly; Described metallic matrix (1) is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel, and described middle layer (2) are the nitride of titanium or tantalum or niobium or in boride or the carbide one or more.
6. preparation method according to claim 5 is characterized in that the physics in described preparation middle layer (2) or/and chemical process comprises ionitriding, ion implantation, thermospray, physical vapor deposition, chemical vapour deposition, plasma auxiliary chemical vapor deposition.
7. preparation method according to claim 5, it is characterized in that described thermolysis sintering is that precursor compound with active ingredient and inert component is blended in wiring solution-forming in the organic solvent, this solution is coated on the metallic matrix (1) by spraying, roller coating or brushing, drying then, at high temperature carry out sintering again, sintering temperature is 400～560 ℃.
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| CN 200510104253 CN1772955A (en) | 2005-10-12 | 2005-10-12 | Mixed metal oxide electrode and its making process |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016632B (en) * | 2006-12-22 | 2010-11-24 | 扬州大学 | Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method |
| CN101567269B (en) * | 2009-06-05 | 2011-01-05 | 中南大学 | Coating and thermal decomposition process for preparing RuO* electrode material of super-capacitor |
| CN101528985B (en) * | 2006-10-16 | 2011-06-22 | 德诺拉工业有限公司 | Anode for electrolysis |
| CN101490301B (en) * | 2006-07-14 | 2012-05-30 | 丹佛斯公司 | Method for treating titanium objects with a surface layer of mixed tantalum and titanium oxides |
| CN103345958A (en) * | 2013-06-07 | 2013-10-09 | 河北工业大学 | Composite electrode material containing reactive plasma spraying nanometer TiN middle layer and preparation method thereof |
| CN104591342A (en) * | 2014-11-10 | 2015-05-06 | 牛军峰 | Preparation method of Ti/Ebonex/PbO2 electrode for sewage deep-treatment |
| CN104846399A (en) * | 2015-05-29 | 2015-08-19 | 华北水利水电大学 | Titanium-base TiNx/TiO2-RuO2 nano coating anode |
| CN104947143A (en) * | 2015-05-29 | 2015-09-30 | 华北水利水电大学 | Titanium-based TiNx/TiO2-RuO2 coating anode |
| CN104988535A (en) * | 2015-05-22 | 2015-10-21 | 东南大学 | Mixed metal oxide coating electrode and preparation method thereof |
| CN108026649A (en) * | 2015-09-25 | 2018-05-11 | 阿克苏诺贝尔化学品国际有限公司 | Electrode |
| CN109225195A (en) * | 2018-10-15 | 2019-01-18 | 吉林大学 | Nano transition metal boride catalyst and its application in terms of electro-catalysis water-splitting hydrogen manufacturing |
| WO2020215770A1 (en) * | 2019-04-26 | 2020-10-29 | 无锡小天鹅电器有限公司 | Electrolysis electrode and preparation method therefor, electrolysis apparatus, and clothing treatment device |
| CN112609206A (en) * | 2020-11-26 | 2021-04-06 | 中氢能源科技(广东)有限公司 | Anode barrier layer for PEM electrolytic hydrogen production device and preparation method thereof |
| CN113929188A (en) * | 2020-06-29 | 2022-01-14 | 佛山市顺德区美的饮水机制造有限公司 | Electrode structure, purification structure and electrode preparation method |
-
2005
- 2005-10-12 CN CN 200510104253 patent/CN1772955A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490301B (en) * | 2006-07-14 | 2012-05-30 | 丹佛斯公司 | Method for treating titanium objects with a surface layer of mixed tantalum and titanium oxides |
| CN101528985B (en) * | 2006-10-16 | 2011-06-22 | 德诺拉工业有限公司 | Anode for electrolysis |
| CN101016632B (en) * | 2006-12-22 | 2010-11-24 | 扬州大学 | Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method |
| CN101567269B (en) * | 2009-06-05 | 2011-01-05 | 中南大学 | Coating and thermal decomposition process for preparing RuO* electrode material of super-capacitor |
| CN103345958A (en) * | 2013-06-07 | 2013-10-09 | 河北工业大学 | Composite electrode material containing reactive plasma spraying nanometer TiN middle layer and preparation method thereof |
| CN104591342A (en) * | 2014-11-10 | 2015-05-06 | 牛军峰 | Preparation method of Ti/Ebonex/PbO2 electrode for sewage deep-treatment |
| CN104591342B (en) * | 2014-11-10 | 2017-04-05 | 牛军峰 | For the Ti/Ebonex/PbO of advanced treatment of wastewater2The preparation method of electrode |
| CN104988535A (en) * | 2015-05-22 | 2015-10-21 | 东南大学 | Mixed metal oxide coating electrode and preparation method thereof |
| CN104947143A (en) * | 2015-05-29 | 2015-09-30 | 华北水利水电大学 | Titanium-based TiNx/TiO2-RuO2 coating anode |
| CN104846399A (en) * | 2015-05-29 | 2015-08-19 | 华北水利水电大学 | Titanium-base TiNx/TiO2-RuO2 nano coating anode |
| CN104846399B (en) * | 2015-05-29 | 2018-05-29 | 华北水利水电大学 | A kind of titanium-based TiNx/TiO2-RuO2Nano coating anode |
| CN108026649A (en) * | 2015-09-25 | 2018-05-11 | 阿克苏诺贝尔化学品国际有限公司 | Electrode |
| CN109225195A (en) * | 2018-10-15 | 2019-01-18 | 吉林大学 | Nano transition metal boride catalyst and its application in terms of electro-catalysis water-splitting hydrogen manufacturing |
| CN109225195B (en) * | 2018-10-15 | 2021-09-28 | 吉林大学 | Nano transition metal boride catalyst and application thereof in aspect of hydrogen production by electrocatalytic water cracking |
| WO2020215770A1 (en) * | 2019-04-26 | 2020-10-29 | 无锡小天鹅电器有限公司 | Electrolysis electrode and preparation method therefor, electrolysis apparatus, and clothing treatment device |
| CN113929188A (en) * | 2020-06-29 | 2022-01-14 | 佛山市顺德区美的饮水机制造有限公司 | Electrode structure, purification structure and electrode preparation method |
| CN112609206A (en) * | 2020-11-26 | 2021-04-06 | 中氢能源科技(广东)有限公司 | Anode barrier layer for PEM electrolytic hydrogen production device and preparation method thereof |
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