CN101343749A - Metallic oxide coating electrode and manufacture method thereof - Google Patents
Metallic oxide coating electrode and manufacture method thereof Download PDFInfo
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- CN101343749A CN101343749A CNA2008101391492A CN200810139149A CN101343749A CN 101343749 A CN101343749 A CN 101343749A CN A2008101391492 A CNA2008101391492 A CN A2008101391492A CN 200810139149 A CN200810139149 A CN 200810139149A CN 101343749 A CN101343749 A CN 101343749A
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- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- -1 platinum group metal compound Chemical class 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 13
- 239000011858 nanopowder Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical compound [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 claims description 4
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 238000007761 roller coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
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- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a metal oxide coating electrode, which comprises a metal base body and a metal oxide coating. The metal oxide coating electrode is characterized in that an intermediate layer is arranged between the metal base body and the metal oxide coating; the intermediate layer is coated on the metal base body, and the metal oxide coating is coated on the intermediate layer; the intermediate layer is the product which is obtained from the intermediate layer coating fluid manufactured from the nanometer powder of the titanium based ceramal compound soaked in the platinum group metal compound solution, coated on the metal base body, dried, oxidized and pyrolyzed. The invention also discloses a metal oxide coating electrode preparation method. The invention has the advantages that the precious metal consumption is less, the electric catalyzing activity is high, the electric conductivity is good, the anode oxidation resistance is strong, the service life is long, the manufacture is simple, and the production cost is low.
Description
Technical field
The present invention relates to a kind of metal oxide electrode and preparation method thereof, especially relate to a kind of metallic oxide coating electrode that is provided with the middle layer and preparation method thereof, belong to the Electrochemical Engineering field.
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 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.Application number is to disclose a kind of SnO in 2006101441469 the Chinese patent application
2/ IrO
2-Ta
2O
5-SnO
2/ Ti electrode, to disclose a kind of titanium among the CN 03133317 be matrix, be coated with PbO
2Or SeO
2Electrode, above-mentioned electrode all exists manufacturing cost higher except that the scope of application is narrower, the problem that electrode life is short.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
Technical problem to be solved by this invention is, at the deficiencies in the prior art, a kind of long-service-life metal oxide coating electrode that the middle layer is set and preparation method thereof is provided, under the prerequisite of the electrocatalysis characteristic that guarantees electrode, reduces the electrode manufacturing cost, improve electrode life.
Metallic oxide coating electrode of the present invention, its technical scheme of taking are that it comprises metallic matrix and coating of metal oxides, especially between metallic matrix and coating of metal oxides, also is provided with the middle layer; The middle layer is coated on the metallic matrix, and coating of metal oxides is coated on the middle layer; Described metallic matrix is by a kind of the making in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless material, and process degreasing and acid etching; Described middle layer is that the nano-powder with the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds makes middle layer coating liquid, and is coated on the metallic matrix, and drying, the heat of oxidation are decomposed the product that obtains.
Above-mentioned electrode, its described middle layer is made of jointly titanium oxide and platinum metals or platinum group metal oxide.
Above-mentioned electrode, the mol ratio of platinum metals and titanium metal atom is 50: 1～1: 20 in its described middle layer coating liquid, preferred 10: 1～1: 10.
Above-mentioned electrode, its described titanium-based metal ceramic compound are selected from one or more in boride, carbide, nitride, carbon nitrogen thing, oxygen nitrogen thing, oxygen boron thing and the oxygen carbon thing of titanium; Its described platinum metals is one or more among Ru, Rh, Pd, Os, Ir or the Pt.
Above-mentioned electrode, its described heat of oxidation is decomposed, and is to carry out under 350-650 ℃ of temperature after middle layer coating liquid drying.
The preparation method of above-mentioned metallic oxide coating electrode, comprise following content: on electrode metal matrix, apply middle layer coating liquid through degreasing and acid etching processing, prepare the middle layer by dry, oxidation pyrolysated method, then on the middle layer, prepare coating of metal oxides again; Its material of described metallic matrix is selected from a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel; Described middle layer is by the middle layer coating liquid that is coated on the metallic matrix, and drying, heat of oxidation decomposition obtain, and coating liquid in middle layer is made by the nano-powder of the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds.
Above-mentioned preparation method, its described middle layer is that the nano-powder that will contain the solution impregnation titanium-based metal ceramic compound of platinum group metal compounds forms middle layer coating liquid, again this middle layer coating liquid is coated on the metallic matrix by spraying, roller coating or brushing, in drying after 350-650 ℃ implement the heat of oxidation and decompose and be prepared from.
The novel electrode that utilizes preparation method of the present invention to obtain can be widely used in the Electrochemical Engineering such as chlor-alkali, water electrolysis, fuel cell, sewage disposal, organism electrosynthesis, electrodialysis and galvanic deposit, both can be used as anode and used, and also can be used as negative electrode and use.Using electrode that preparation method of the present invention obtains, to have a noble metal dosage low, and the electro catalytic activity height conducts electricity very well, and anti-anodic oxidation performance is strong, long service life, make simple and easy, the advantage that production cost is low.
Description of drawings
The present invention is described in more detail below in conjunction with specific embodiment and accompanying drawing thereof.
Fig. 1 is the structural representation of metal oxide electrode of the present invention;
Fig. 2 is the middle layer Ir of differing temps roasting: the Ti mol ratio is 1: 1 Ti/IrO
2-TiO
2/ IrO
2The XRD figure spectrum of coated electrode;
Fig. 3 is the Ti/IrO with different mol ratio iridium titanium middle layer of 450 ℃ of roastings
2-TiO
2/ IrO
2The XRD figure spectrum of coated electrode;
Fig. 4 is the Ti/IrO with different mol ratio iridium titanium middle layer of 450 ℃ of roastings
2-TiO
2/ IrO
2Coated electrode and Ti/IrO
2The polarization curve of coated electrode in the 0.5mol/L aqueous sulfuric acid;
Fig. 5 is the Ti/IrO with different mol ratio iridium titanium middle layer of 450 ℃ of roastings
2-TiO
2/ IrO
2Coated electrode and Ti/IrO
2The groove of coated electrode is pressed curve over time.
Embodiment
The structure of metal oxide electrode of the present invention as shown in Figure 1, it is to apply a middle layer 2, coated metal oxide coating 3 on middle layer 2 on metallic matrix 1; Described metallic matrix 1 is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel; Described middle layer 2 is that the nano-powder with the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds makes middle layer coating liquid, and is coated on the metallic matrix, and drying, the heat of oxidation are decomposed the product that obtains.Metallic matrix 1 is handled through degreasing and acid etching.Middle layer 2 is that the nano-powder that contains the solution impregnation titanium-based metal ceramic compound of platinum group metal compounds forms middle layer coating liquid, and be coated on the metallic matrix 1, dry back is implemented heat of oxidation decomposition and is obtained by titanium oxide and platinum metals or the common product of forming of platinum group metal oxide under 350-650 ℃ of temperature, the titanium-based metal ceramic compound nano-powder that is wherein adopted is selected from the boride of titanium, carbide, nitride, carbon nitrogen thing, oxygen nitrogen thing, in oxygen boron thing and the oxygen carbon thing one or more, described platinum metals is Ru, Rh, Pd, Os, among Ir or the Pt one or more, and the mol ratio of platinum metals and titanium is 50 in the middle layer coating liquid: 1-1: 20, be preferably 10: 1-1: 10.
During preparation, on metallic matrix 1, apply the middle layer coating liquid of forming by the nano-powder of the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds, prepare middle layer 2 by dry, oxidation pyrolysated method, then on middle layer 2, prepare coating of metal oxides 3 again; Middle layer 2 is that the nano-powder that will contain the solution impregnation titanium-based metal ceramic compound of platinum group metal compounds forms middle layer coating liquid, again this middle layer coating liquid is coated on the metallic matrix 1 by spraying, roller coating or brushing, in drying after 350-650 ℃ implement the heat of oxidation and decompose and be prepared from.
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.The preparation in middle layer, with chloro-iridic acid, propyl carbinol and concentrated hydrochloric acid mix by 1: 10: 1 volume ratio, get the TiN nano-powder formation middle layer coating liquid of this mixed solution of 2 ml with propyl carbinol dilution back dipping different mass, its Ir: the Ti mol ratio was respectively 49: 1,9: 1,1: 1, (respectively use a at 1: 5, b, c, d represents, e represents there is not the middle layer), ultrasonic 1 h mixes, then, on above-mentioned titanium matrix, evenly apply above-mentioned coating liquid with soft woollen goods brush pen, oven dry 10 min in 120 ℃ baking oven, be placed in the cabinet-type electric furnace under predetermined temperature the heat of oxidation again and decompose 15 min, heat of oxidation decomposition temperature is respectively 350,400,450 and 500 ℃, repetitive coatings, dry, the heat of oxidation is decomposed 1 time, thereby obtains the different IrO that form of oxidation pyrolysated under the differing temps
2-TiO
2The middle layer.
Coating of metal oxides 3 is selected the iridium oxide coating that oxygen electrode uses of analysing of industrial widespread use, and it typically applies liquid and is: H
2IrCl
6XH
2O (being dissolved in the hydrochloric acid)+alcohol mixed solution, 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 IrO
2-TiO
2On the above-mentioned titanium matrix in middle layer 2, in 120 ℃ of baking ovens, behind the oven dry 10min, place cabinet-type electric furnace sintering 10min under 350～500 ℃ 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, contain and do not contain IrO thereby make
2-TiO
2The titanium base iridium oxide electrode in middle layer.
Electrode of the present invention has been carried out phase composite to be analyzed as shown in Figures 2 and 3.Fig. 2 is the middle layer Ir of differing temps roasting: the Ti mol ratio is 1: 1 Ti/IrO
2-TiO
2/ IrO
2The XRD figure spectrum of coated electrode.Except the diffraction peak of observing matrix Ti, also exist IrO among Fig. 2
2Diffraction peak, do not see tangible TiO
2Diffraction peak exists, and IrO is described
2With TiO
2Form with sosoloid exists.By purer IrO
2All there are certain skew in 2 θ and the d value of (rutile crystal type) and coating, have further proved the existence of sosoloid.In the time of 350 ℃, do not observe tangible IrO
2Diffraction peak, this is because the muriate of Ir has been decomposed to form thin crystalline substance or amorphous under this temperature.When temperature reached 400 ℃, IrO had appearred
2(110) and (101) face diffraction peak, along with the rising of temperature, IrO
2Degree of crystallinity improves, and the intensity at peak is strengthened gradually, IrO in the time of 450 ℃
2Crystallization is just more complete.The Ti/IrO of the middle layer iridium titanium different mol ratio of roasting when Fig. 3 is 450 ℃
2-TiO
2/ IrO
2The XRD figure spectrum of coated electrode.As can be seen from Figure 3, along with TiO in the middle layer
2The rising of content, IrO
2With TiO
2Solutionizing increases, IrO
2Degree of crystallinity improves, and peak intensity increases.
Electrode of the present invention has been carried out result that electrocatalysis characteristic estimates as shown in Figure 4.Fig. 4 is for having compared the Ti/IrO of the middle layer iridium titanium different mol ratio of 450 ℃ of roastings by polarization curve in the 0.5mol/L aqueous sulfuric acid
2-TiO
2/ IrO
2Coated electrode and the Ti/IrO that does not contain the middle layer
2Analyse the oxygen electro catalytic activity.As can be seen from Figure 4, along with TiO in the middle layer
2The rising of content, polarization curve moves to right, and analyses the oxygen electro catalytic activity and increases.Ti/IrO
2-TiO
2/ IrO
2The oxygen activity of analysing of coated electrode approaches Ti/IrO
2Electrode shows Ti/IrO
2Electrode is introduced IrO
2-TiO
2Still kept electro catalytic activity preferably behind the middle layer.
Electrode of the present invention has been carried out result that reinforcing life estimates as shown in Figure 5.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.Fig. 5 is the Ti/IrO of the middle layer iridium titanium different mol ratio of 450 ℃ of roastings
2-TiO
2/ IrO
2With Ti/IrO
2The groove of coated electrode is pressed curve over time.Along with TiO in the middle layer
2The rising of content analyses the oxygen life-span to be increased to 122 h, Ti/IrO by 33 h
2-TiO
2/ IrO
2The oxygen life-span of analysing of coating prolongs.With Ti/IrO
2Electrode is compared (20 h), introduces the middle layer rear stability and obviously strengthens.
The present invention does not do qualification to coating of metal oxides 3, can be any known coating of metal oxides by any known preparation method's preparation.
Other metallic matrix of the present invention (tantalum, niobium, zirconium, tungsten, aluminium or stainless steel) has similar character to above-mentioned titanium matrix, other titanium-based metal ceramic compound described in the middle layer (boride of titanium, carbide, nitride, carbon nitrogen thing, oxygen nitrogen thing, oxygen boron thing and oxygen carbon thing) also has similar character with above-mentioned TiN, and other platinum metals described in the middle layer (Ru, Rh, Pd, Os or Pt) can play the effect close with above-mentioned Ir, realizes that with them the prepared electrode of the present invention also has same functional effect.
The above; it only is preferred embodiment of the present invention; can not be understood that it is that the present invention is done any pro forma restriction; any one of ordinary skill in the art; in not breaking through the scope of technical scheme disclosed in this invention; the equivalence techniques displacement that the part that the innovative technology that utilizes the present invention to disclose has been done is changed or modified all drops in protection scope of the present invention.
The novel electrode that utilizes preparation method of the present invention to obtain can be widely used in the Electrochemical Engineering such as chlor-alkali, water electrolysis, fuel cell, sewage disposal, organism electrosynthesis, electrodialysis and galvanic deposit, both can be used as anode and used, and also can be used as negative electrode and use.
Claims (9)
1. a metallic oxide coating electrode comprises metallic matrix and coating of metal oxides, it is characterized in that: between described metallic matrix (1) and coating of metal oxides (3), be provided with middle layer (2); Middle layer (2) is coated on the metallic matrix (1), and coating of metal oxides (3) is coated on the middle layer (2); Described metallic matrix (1) is by a kind of the making in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless material, and process degreasing and acid etching processing; Described middle layer (2) is that the nano-powder with the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds makes middle layer coating liquid, and is coated on the metallic matrix (1), and drying, the heat of oxidation are decomposed the product that obtains.
2. electrode according to claim 1 is characterized in that: described titanium-based metal ceramic compound nano-powder is selected from one or more in boride, carbide, nitride, carbon nitrogen thing, oxygen nitrogen thing, oxygen boron thing and the oxygen carbon thing of titanium.
3. electrode according to claim 2 is characterized in that: described platinum metals is one or more among Ru, Rh, Pd, Os, Ir or the Pt.
4. electrode according to claim 3 is characterized in that: in the described middle layer coating liquid, the mol ratio of platinum metals and titanium is 50: 1-1: 20.
5. electrode according to claim 4 is characterized in that: the described heat of oxidation is decomposed, and is to carry out under 350-650 ℃ of temperature after described middle layer coating liquid drying.
6. electrode according to claim 5 is characterized in that: in described middle layer coating liquid, the mol ratio of platinum metals atom and titanium atom is 10: 1～1: 10.
7. electrode according to claim 1 is characterized in that: described middle layer (2) are made of jointly titanium oxide and platinum metals or platinum group metal oxide.
8. the preparation method of each described metallic oxide coating electrode of claim 1 to 7, comprise following content: going up coating middle layer coating liquid through the electrode metal matrix (1) of degreasing and acid etching processing, by dry, heat of oxidation decomposition preparation middle layer (2); Then (2) upward prepare coating of metal oxides (3) in the middle layer again; Wherein: described metallic matrix (1) is a kind of in titanium, tantalum, niobium, zirconium, tungsten, aluminium or the stainless steel; Described middle layer (2) is by the middle layer coating liquid that is coated on the metallic matrix (1), and drying, heat of oxidation decomposition obtain, and coating liquid in middle layer is made by the nano-powder of the solution impregnation titanium-based metal ceramic compound that contains platinum group metal compounds.
9. preparation method according to claim 8 is characterized in that: described middle layer (2) are the middle layer to be applied liquid be coated on the metallic matrix (1) by spraying, roller coating or brushing, in drying after 350-650 ℃ implement the heat of oxidation and decompose and be prepared from.
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