CN104947143A - Titanium-based TiNx/TiO2-RuO2 coating anode - Google Patents
Titanium-based TiNx/TiO2-RuO2 coating anode Download PDFInfo
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- CN104947143A CN104947143A CN201510285951.2A CN201510285951A CN104947143A CN 104947143 A CN104947143 A CN 104947143A CN 201510285951 A CN201510285951 A CN 201510285951A CN 104947143 A CN104947143 A CN 104947143A
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- tinx
- tio
- ruo
- titanium base
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Abstract
The invention belongs to the technical field of insoluble anode preparation in electrochemistry industry, and concretely relates to a titanium-based TiNx/TiO2-RuO2 coating anode. The anode comprised a titanium matrix positioned at inner part, a TiNx interface layer positioned at intermediate part, and a TiO2-RuO2 coating positioned at external part; the TiNx interface layer is prepared by performing an ion nitriding processing method on the titanium matrix; and the TiO2-RuO2 coating is obtained by a thermal decomposition method. According to the anode, the thickness of the TiNx intermediate layer can reach 50-200mum, the TiNx intermediate layer has excellent conductive performance, heat conduction performance and corrosion resistance; surface crack of the TiO2-RuO2 coating is fine, no penetrability crack is generated, so that the TiO2-RuO2 coating has larger reaction surface area, can provide more electrochemical reaction places, can effectively increase the anode stability, prolong the service life of the anode, and has good popularization and application value in the electrochemistry field.
Description
Technical field
The invention belongs to insoluble anode preparing technical field in electrochemical industry, be specifically related to a kind of titanium base TiNx/TiO
2-RuO
2coated anode.
Background technology
Anode is parts crucial in electrochemical industry, is generally divided into soluble anode and insoluble anode.Wherein soluble anode is applied the earliest is graphite anode and lead anode.Anode is different according to the gas of separating out, and can be divided into again and analyses chlorine anode and analyse oxygen anodes.Graphite anode belongs to analyses chlorine anode, and alloy lead anode belongs to analyses oxygen anodes.
Along with industry and scientific and technical development, traditional anode material more and more shows its limitation.Solidity to corrosion as graphite anode be not very desirable, intensity is not high yet; The electrocatalysis characteristic of platinum anode is bad, expensive.This just impels people to research and develop electrocatalysis characteristic is higher, service life is longer anode.
The appearance of titanium-based oxide coating insoluble anode brings rapid development to the development of electrochemical industry.And along with the fast development of industrial application, at present, Ti/TiO
2-RuO
2coated anode is widely used in the fields such as chlorine industry, electroplating industry, Industrial Wastewater Treatment, photochemical catalysis.
But, under high overpotential, electrolytic solution by the tiny crack in coating and substrate contact, thus Ti matrix surface oxidizable generation poorly conductive and loose TiO
2layer, makes bath voltage sharply raise in several hours and cause disbonding, especially overpotential higher to analyse the requirement of antianode under oxygen environment more harsh.Thus also need to improve to improve its electro catalytic activity, service life and stability to Ti base oxide coated anode in actual use.In general, the inefficacy of Ti anode or inactivation mainly contain two kinds of forms, first coating shedding, and its major cause is considered to coating binding force loosely, think in addition to weaken matrix due to Sauerstoffatom and be coated with caused by the bonding force of interlayer; Another kind of failure mode is passivation, its mechanism Useful active center disappearance opinion and matrix oxidation opinion are explained, Ti can be described as be oxidized in the heat-processed prepared and when carrying out electrochemical catalysis in the electrolyte, generate and comparatively loosen and the stable TiO of poorly conductive
2layer.Therefore how to postpone Titanium base oxidation, passivation, how to strengthen coating structure and be obtain stable electrical catalytic activity and long-life research emphasis for oxide coating anode at present with the bonding force of matrix.
Summary of the invention
The object of the invention is to provide a kind of titanium base TiNx/TiO
2-RuO
2coated anode, has carried out nitriding treatment for titanium base matrix surface in this anode, thus at titanium base and TiO
2-RuO
2be coated with interlayer and form middle layer TiNx, under this middle layer effectively can stop noble potential, titanium base is oxidized or passivation phenomenon generation; TiO in this anode simultaneously
2-RuO
2coating adopts thermal decomposition method to be prepared from.
The technical solution used in the present invention is as follows.
A kind of titanium base TiNx/ TiO
2-RuO
2coated anode, comprises and is positioned at inner titanium base, is positioned at middle TiNx middle layer, is positioned at outside TiO
2-RuO
2coating;
Described TiNx middle layer obtains by titanium base is carried out ionitriding process;
Described TiO
2-RuO
2coating is prepared by thermal decomposition method.
Described titanium base TiNx/ TiO
2-RuO
2coated anode, the mol ratio of Ru and Ti is 3:7, TiO
2-RuO
2coating comprises 10 layers.
Described titanium base TiNx/ TiO
2-RuO
2coated anode, TiNx intermediate layer thickness is 50 ~ 200 μm.
Described titanium base TiNx/ TiO
2-RuO
2the preparation method of coated anode, specifically comprises the following steps:
(1) matrix process, carries out sandblasting by Titanium base, is specially, and uses 40 ~ 100 object corundum sands to carry out sandblasting under the pressure of 0.2 ~ 0.5MPa; Such as, under 0.5MPa pressure 40 orders etc. under 60 orders, 0.2MPa pressure under 80 orders, 0.3MPa pressure under 100 orders, 0.4MPa pressure;
(2) acid etching, after after sandblasting in step (1), matrix tap water cleans up repeatedly, soak in acetone with sand grains and the greasy dirt on ultrasonic cleaning removing surface, process clean titanium base at acidic solution acid etching, then totally preserve with deionized water rinsing for subsequent use in ethanol; Dry before using;
Described acidic solution to be massfraction be 10% oxalic acid solution, acid etching is titanium base etch 1h in 90 ~ 97 DEG C of micro-oxalic acid solutions boiled;
(3) nitriding treatment, described nitriding treatment adopts ion nitriding method to carry out nitriding treatment to titanium base after acid etching in step (2), preparation TiNx middle layer, concrete as, the Ls-450 type metallic glow ion cementation vacuum oven of Nanjing special warfare branch office of morning twilight group is adopted to carry out ionitriding process to titanium base
Treating processes is, is dried by titanium base after acid etching in step (2) and is placed in metallic glow ion cementation vacuum oven, be evacuated to highest attainable vacuum; Add working gas in proportion in stove, regulate operating supply voltage and working current to heat up after reaching operating air pressure, be incubated after specified temperature and ion nitriding is carried out to titanium base; Insulation to the specified time, the cooling of slow regulating voltage, to be cooled to powered-down after room temperature, after taking out nitriding treatment, titanium base is for subsequent use;
In ionitriding treating processes, concrete technology parameter setting is as follows, working gas: hydrogen and nitrogen, nitrogen hydrogen ratio, 1 ~ 3:10; Treatment temp: 700 ~ 900 DEG C; Stove internal gas pressure: 150Pa; Conduction ratio: 45; Operating voltage: 700 ~ 800V; Working current: 50 ~ 100A; Treatment time: 8 ~ 15h;
(4) TiO
2-RuO
2prepared by coating, described TiO
2-RuO
2coating adopts thermal decomposition method preparation, and wherein the mol ratio of Ru and Ti is 3:7; Concrete preparation method is as follows,
A, by RuCl
3and Ti (C
4h
9o)
4according to the ratio of mol ratio Ru:Ti=3:7, add propyl carbinol;
B, with banister brush equably by the brushing of steps A gained mixing solutions on pretreated Ti matrix;
C, by the Ti matrix of step B gained brushing mixing solutions dry 10 ~ 20min at 120 ~ 160 DEG C in chamber type electric resistance furnace, then proceed to 450 ~ 550 DEG C of oxidation 10 ~ 20min in box-type furnace, air cooling of finally coming out of the stove;
D, repeating step B, C 10 times, for the last time 450 ~ 550 DEG C of anneal oxidation 30 ~ 120 min in box-type furnace, final obtained coating comprises the TiO of 10 layers
2-RuO
2coating.
Technical characteristics of the present invention is, by adopting ion nitriding method to prepare TiNx middle layer, then adopts thermal decomposition method to prepare multilayer TiO
2-RuO
2coating.Titanium base TiNx/ TiO provided by the present invention
2-RuO
2coated anode, wherein TiNx intermediate layer thickness can reach 50 ~ 200 μm, has excellent conduction, heat conductivility and solidity to corrosion; At this on the Titanium base of nitriding treatment, compared to the anode not carrying out nitriding treatment, TiO
2-RuO
2the surface crack of coating is more tiny, thus larger reaction table area, can provide more electrochemical reaction place; And what is more important, after nitriding treatment, TiO
2-RuO
2coating does not find penetrating crack, thus effectively can improve the stability of anode, extends the service life of anode.Comprehensive, the present invention prepares TiNx middle layer by ionitriding technique, enhances electrochemical reaction activity, effectively raise stability and the service life of anode, especially service life, can extend anode life more than 1 times, thus have good application value in electrochemical field.
Accompanying drawing explanation
Fig. 1 is anode surface scanning electron microscope pattern prepared by different methods, wherein: (a) is titanium base TiNx/TiO after embodiment ionitriding process
2-RuO
2coated anode; B common titanium base TiO that () is the non-nitriding treatment of comparative example
2-RuO
2coated anode;
Fig. 2 is that different methods prepares TiO
2-RuO
2coated anode volt-ampere electric charge;
Fig. 3 is that different methods prepares TiO
2-RuO
2the coated anode life-span.
Embodiment
Below in conjunction with embodiment, explanation is further explained to the application.
Embodiment
The titanium base TiNx/TiO that the present embodiment provides
2-RuO
2coated anode, comprises and is positioned at inner titanium base, is positioned at middle TiNx middle layer, is positioned at outside TiO
2-RuO
2coating;
Described TiNx middle layer obtains by titanium base is carried out ionitriding process;
Described TiO
2-RuO
2coating is prepared by thermal decomposition method method;
Described matrix adopts TA2 titanium.
Described titanium base TiNx/TiO
2-RuO
2coated anode, the mol ratio of Ru and Ti is 3:7, TiO
2-RuO
2coating comprises 10 layers.
Described titanium base TiNx/ TiO
2-RuO
2coated anode, TiNx intermediate layer thickness is 50 ~ 200 μm.
Described titanium base TiNx/ TiO
2-RuO
2the preparation method of coated anode, specifically comprises the following steps:
(1) matrix process, carries out sandblasting by Titanium base, is specially, and uses 40 ~ 100 object corundum sands to carry out sandblasting under the pressure of 0.2 ~ 0.5MPa;
For ease of processing use further, by after sandblasting, the thin slice of titanium plate cut growth × wide × thick=10mm × 10mm × 1.5mm can be used.
(2) acid etching, after after sandblasting in step (1), titanium base tap water cleans up repeatedly, soak in acetone with sand grains and the greasy dirt on ultrasonic cleaning removing surface, process clean titanium base massfraction be 10% be heated to micro-oxalic acid solution etch 1h boiled, then totally preserve for subsequent use in ethanol with deionized water rinsing; Dry before using.
(3) nitriding treatment, described nitriding treatment adopts ion nitriding method to carry out nitriding treatment to titanium base after acid etching in step (2), preparation TiNx middle layer, concrete as, the Ls-450 type metallic glow ion cementation vacuum oven of Nanjing special warfare branch office of morning twilight group is adopted to carry out ionitriding process to titanium base
Treating processes is, is dried by titanium base after acid etching in step (2) and is placed in metallic glow ion cementation vacuum oven, be evacuated to highest attainable vacuum; Add working gas in proportion in stove, regulate operating supply voltage and working current to heat up after reaching operating air pressure, be incubated after specified temperature and ion nitriding is carried out to titanium base; Insulation to the specified time, the cooling of slow regulating voltage, to be cooled to powered-down after room temperature, after taking out nitriding treatment, titanium base is for subsequent use;
In ionitriding treating processes, concrete technology parameter setting is as follows, working gas: hydrogen and nitrogen, nitrogen hydrogen ratio, 1 ~ 3:10; Treatment temp: 700 ~ 900 DEG C; Stove internal gas pressure: 150Pa; Conduction ratio: 45; Operating voltage: 700 ~ 800V; Working current: 50 ~ 100A; Treatment time: 8 ~ 15h.
(4) TiO
2-RuO
2prepared by coating, described TiO
2-RuO
2coating adopts thermal decomposition method preparation, and wherein the mol ratio of Ru and Ti is 3:7; Concrete preparation method is as follows,
A, by RuCl
3and Ti (C
4h
9o)
4according to the ratio of mol ratio Ru:Ti=3:7, add propyl carbinol;
B, with banister brush equably by the brushing of steps A gained mixing solutions on pretreated Ti matrix;
C, by the Ti matrix of step B gained brushing mixing solutions dry 10 ~ 20min at 120 ~ 160 DEG C in chamber type electric resistance furnace, then proceed to 450 ~ 550 DEG C of oxidation 10 ~ 20min in box-type furnace, air cooling of finally coming out of the stove;
D, repeating step B, C 10 times, for the last time 450 ~ 550 DEG C of anneal oxidation 30-120 min in box-type furnace, final obtained coating comprises the TiO of 10 layers
2-RuO
2coating.
comparative example
For specifically evaluating titanium base TiNx/ TiO provided by the present invention
2-RuO
2the performance such as electroconductibility, work-ing life of coated anode, contriver adopts and has prepared anode comparative example with embodiment similar approach, briefly introduces as follows.
comparative example:anode prepared by comparative example belongs to common titanium base TiO
2-RuO
2coated anode, the same embodiment of preparation method, but do not comprise step (3) nitriding treatment, namely comparative example is compared with the application, TiO
2-RuO
2coating production is identical, but titanium base does not carry out nitriding treatment, does not comprise TiNx middle layer.
Carry out scanning electron microscope detection (German LEO S-360 type scanning electronic microscope, magnification is 5000 times) to the anode prepared by embodiment, comparative example, result as shown in Figure 1.Wherein Fig. 1 (a) is that the application provides titanium base TiNx/ TiO
2-RuO
2coated anode, Fig. 1 (b) is that comparative example provides titanium base TiO
2-RuO
2coated anode.Result shows, the TiO that the application provides
2-RuO
2coatingsurface crackle is tiny, without penetrating crack, thus has larger reaction table area, can provide more electrochemical reaction place, and effectively can improve the stability of anode, extends the service life of anode.Further experiment detects and shows (result as shown in Figure 2 and Figure 3), compared to comparative example, the application can improve electro catalytic activity 50%, can extend anode service life more than 1 times, thus the titanium base TiNx/TiO2-RuO2 coated anode of ionitriding treatment process provided by the present invention has good application value at electrochemical industry.
Claims (7)
1. a titanium base TiNx/TiO
2-RuO
2coated anode, is characterized in that, this anode comprises the titanium base being positioned at inside, is positioned at middle TiNx middle layer, is positioned at outside TiO
2-RuO
2coating;
Described TiNx middle layer obtains by titanium base is carried out ionitriding process;
Described TiO
2-RuO
2coating is prepared by thermal decomposition method.
2. titanium base TiNx/TiO as claimed in claim 1
2-RuO
2coated anode, is characterized in that, the mol ratio of Ru and Ti is 3:7, TiO
2-RuO
2coating comprises 10 layers.
3. titanium base TiNx/TiO as claimed in claim 1
2-RuO
2coated anode, is characterized in that, TiNx intermediate layer thickness is 50 ~ 200 μm.
4. titanium base TiNx/TiO described in claim 1
2-RuO
2the preparation method of coated anode, is characterized in that, the method comprises the following steps:
(1) matrix process, carries out sandblasting by Titanium base, is specially, and uses 40 ~ 100 object corundum sands to carry out sandblasting under the pressure of 0.2 ~ 0.5MPa;
(2) acid etching, after being cleaned up by the Titanium base after sandblasting in step (1), at acidic solution acid etching, then rinses well for subsequent use;
(3) nitriding treatment, described nitriding treatment adopts ion nitriding method to carry out nitriding treatment to titanium base after acid etching in step (2), preparation TiNx middle layer,
(4) TiO
2-RuO
2prepared by coating, described TiO
2-RuO
2coating adopts thermal decomposition method preparation.
5. titanium base TiNx/ TiO as claimed in claim 4
2-RuO
2the preparation method of coated anode, is characterized in that, acidic solution described in step (2) to be massfraction be 10% oxalic acid solution, acid etching is titanium base etch 1h in 90 ~ 97 DEG C of oxalic acid solutions.
6. titanium base TiNx/ TiO as claimed in claim 4
2-RuO
2the preparation method of coated anode, is characterized in that, step (3) intermediate ion nitriding adopts the Ls-450 type metallic glow ion cementation vacuum oven of Nanjing special warfare branch office of morning twilight group to carry out ionitriding process to titanium base, and treating processes is:
Titanium base after acid etching in step (2) is dried and is placed in metallic glow ion cementation vacuum oven, be evacuated to highest attainable vacuum; Add working gas in proportion in stove, regulate operating supply voltage and working current to heat up after reaching operating air pressure, be incubated after specified temperature and ion nitriding is carried out to titanium base; Insulation to the specified time, the cooling of slow regulating voltage, to be cooled to powered-down after room temperature, after taking out nitriding treatment, titanium base is for subsequent use;
In ionitriding treating processes, concrete technology parameter setting is as follows, working gas: hydrogen and nitrogen, nitrogen hydrogen ratio, 1 ~ 3:10; Treatment temp: 700 ~ 900 DEG C; Stove internal gas pressure: 150Pa; Conduction ratio: 45; Operating voltage: 700 ~ 800V; Working current: 50 ~ 100A; Treatment time: 8 ~ 15h.
7. titanium base TiNx/TiO as claimed in claim 4
2-RuO
2the preparation method of coated anode, is characterized in that, TiO in step (4)
2-RuO
2in coating, the mol ratio of Ru and Ti is 3:7, and thermal decomposition method prepares TiO
2-RuO
2coating concrete steps are:
A, by RuCl
3and Ti (C
4h
9o)
4according to the ratio of mol ratio Ru:Ti=3:7, add propyl carbinol;
B, with banister brush equably by the brushing of steps A gained mixing solutions in step (3) on the Ti matrix of nitriding treatment;
C, by the Ti matrix of step B gained brushing mixing solutions dry 10 ~ 20min at 120 ~ 160 DEG C in chamber type electric resistance furnace, then proceed to 450 ~ 550 DEG C of oxidation 10 ~ 20min in box-type furnace, air cooling of finally coming out of the stove;
D, repeating step B, C 10 times, for the last time 450 ~ 550 DEG C of anneal oxidation 30-120 min in box-type furnace, final obtained coating comprises the TiO of 10 layers
2-RuO
2coating.
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|---|---|---|---|
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|---|---|---|---|
| CN201510285951.2A CN104947143A (en) | 2015-05-29 | 2015-05-29 | Titanium-based TiNx/TiO2-RuO2 coating anode |
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|---|---|---|---|---|
| CN1772955A (en) * | 2005-10-12 | 2006-05-17 | 中国海洋大学 | Mixed metal oxide electrode and its making process |
| CN103805996A (en) * | 2014-01-16 | 2014-05-21 | 中国科学院金属研究所 | Composite treating method for nitriding surface of metal material after coating |
| CN103952660A (en) * | 2014-05-16 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | Composite material with a nitride film as well as preparation method and application of composite material |
| CN104505259A (en) * | 2014-12-18 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Counter electrode of dye-sensitized solar cell |
-
2015
- 2015-05-29 CN CN201510285951.2A patent/CN104947143A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772955A (en) * | 2005-10-12 | 2006-05-17 | 中国海洋大学 | Mixed metal oxide electrode and its making process |
| CN103805996A (en) * | 2014-01-16 | 2014-05-21 | 中国科学院金属研究所 | Composite treating method for nitriding surface of metal material after coating |
| CN103952660A (en) * | 2014-05-16 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | Composite material with a nitride film as well as preparation method and application of composite material |
| CN104505259A (en) * | 2014-12-18 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Counter electrode of dye-sensitized solar cell |
Non-Patent Citations (3)
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|---|
| YANZHENWEI,ECT.: ""Effect of Different Shapes of the Titanium Based IrO2-TaO5 coatings Anode on Electrochemical Properties"", 《RARE METAL MATERIAL AND ENGINEERING》 * |
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Application publication date: 20150930 |