CN102677092B - Preparation method of titanium anode - Google Patents
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- 239000010936 titanium Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 10
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 25
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- -1 alkyl silicate Chemical compound 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- ZHLKXBJTJHRTTE-UHFFFAOYSA-N Chlorobenside Chemical group C1=CC(Cl)=CC=C1CSC1=CC=C(Cl)C=C1 ZHLKXBJTJHRTTE-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 239000002120 nanofilm Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 17
- 229910001069 Ti alloy Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of a titanium anode, wherein the preparation method is capable of improving electrochemical property of the anode. The preparation method comprises the following steps: at first, depositing a layer of inert porous oxide nano film on a metal Ti substrate, and then coating an active oxide (such as iridium dioxide and ruthenium dioxide) on the surface of the film through a hot decomposition method. The inert porous oxide nano film is obtained by depositing precursor aqueous solution such as SiO2, TiO2 or ZrO2 on the surface of a metal through an electro-deposition method. According to an inert porous oxide nano middle layer provided by the invention, the number of electrochemical active points on a subsequent active oxide coating is remarkably improved, and the electro-catalytic property of the titanium anode is improved. The middle layer of the titanium anode provided by the invention has the advantages of many types, low cost of the preparation method and simple process.
Description
Technical field
The present invention relates to the preparation method of anode material, particularly relate to a kind of preparation method of Ni―Ti anode.
Background technology
Electrochemical industry anode material is the parts of most critical, this is because: anode material is the place of anodic reaction, requires there is high electrochemical activity to the anodic reaction of institute's catalysis, namely will have low anode potential from saves energy.Anodic reaction is that oxygen occurs or the electrochemical industry of analysing chlorine reaction is in the great majority, and the former is as the smelting of common water electrolysis, non-ferrous metal and surface of steel plate protective plating (zinc-plated, zinc-plated etc.) etc., and latter is common chlorine industry.At present for above-mentioned electrochemical industry, mainly use the noble metallic oxide anode (also known as insoluble anode or dimensional stability anode, DSA) in the coating of Ti metal base surface.Analyse oxygen and analyse the metal oxide containing precious metals active component that chlorine electrochemical industry generally uses and be respectively iridium dioxide (IrO
2) and ruthenium dioxide (RuO
2).
The energy problem that modern society occurs, require that electrolytic industry significantly reduces energy consumption, the improvement of antianode material is the key point realizing above-mentioned requirements, namely requires that the Ti anode of current industrial application has higher electrochemical activity.For this reason, research and development have been carried out around the following aspects both at home and abroad: the improvement of (1) active oxidation nitride layer: basic ideas are other constituent elements that adulterate in active coating.The most successful example of this respect develops IrO
2+ Ta
2o
5composite oxide coating is the bulk composition of analysing oxygen DSA commercial at present.(2) improvement in preparation method: the work that this respect does comprises the solution chemistry (as adopted sol-gel technique etc.) improving the heat decomposition temperature of oxide compound and heat treating regime, improvement presoma.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of simple, low cost, there is the preparation method of the Ni―Ti anode of high electrochemical activity.
The object of the invention is to be achieved through the following technical solutions:
The preparation method of Ni―Ti anode comprises the steps:
1) Titanium base is after mechanical sandblasting roughened, put into oil removing 10min at alkaline degreasing liquid 30 ~ 50 DEG C, in the oxalic acid aqueous solution of boiling, pickling 5 ~ 30min removes descaling again, finally use tap water successively, after washed with de-ionized water, quick hot blast drying, places 5 ~ 24h in loft drier, stand-by;
2) precursor solution preparation: add 50 ~ 100mL dehydrated alcohol, 50 ~ 100mL water, 1 ~ 10mL precursor, HCl adjusts pH to 2.0 ~ 6.0, and stirred at ambient temperature 2 ~ 48h is stand-by;
3) in three slot electrodes, add the precursor solution prepared, using Titanium base as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, controlling potential is at-0.5 ~-3.0V, depositing time is 30s ~ 2000s, with 40 ~ 150 DEG C of oven dry after deionized water rinsing, obtains inertia nano-oxide film;
4) at above-mentioned galvanic deposit inertia nano-oxide film surface-coated active oxide coatings, by pyrolysis technique, toast at 350-550 DEG C, decompose, and repeatedly, obtain Ni―Ti anode.
Described inertia nano-oxide film is SiO
2, TiO
2or ZrO
2film.
The precursor of described indifferent oxide is: alkyl silicate, alkyl titanate or zirconic acid alkyl ester.
Described active oxidation nitride layer is iridium dioxide, ruthenium dioxide or its composite oxides.
The precursor of described active oxidation nitride layer is chloracid or the villaumite of iridium or ruthenium.
Described Novel Titanium anode is used for analysing oxygen or analysing chlorine reaction in electrochemical industry.
The invention has the beneficial effects as follows: silica membrane has nano-porous structure, after this film pre-treatment, significantly improve vesicular structure and the electrochemical activity of the active oxide coatings of subsequent coated; In addition, electro-deposition techniques is adopted can to prepare roughness and the larger silicon dioxide film of porousness, more obvious to the facilitation effect of Ni―Ti anode performance.
Accompanying drawing explanation
Fig. 1 (a) is the IrO of directly coating on titanium plate
2the surface topography of active coating, display coating is very fine and close;
Fig. 1 (b) is for first to deposit one deck Nano-meter SiO_2 by electro-deposition techniques on titanium plate surface
2after film, then apply IrO
2the surface topography of active coating, display coating is coarse, porous.
Fig. 2 is that Ni―Ti anode is at 0.5 M H
2sO
4what record in the aqueous solution analyses oxygen polarization curve.(1) be the IrO of directly coating on titanium plate
2anode (Ti/IrO
2); (2) be at the first galvanic deposit one deck SiO in titanium plate surface
2after film, then apply the IrO obtained
2anode (Ti/SiO
2/ IrO
2).Display combined electrode has higher analyses oxygen electrochemical activity.
Embodiment
The preparation method of Ni―Ti anode comprises the steps:
1) Titanium base is after mechanical sandblasting roughened, put into oil removing 10min at alkaline degreasing liquid 30 ~ 50 DEG C, in the oxalic acid aqueous solution of boiling, pickling 5 ~ 30min removes descaling again, finally use tap water successively, after washed with de-ionized water, quick hot blast drying, places 5 ~ 24h in loft drier, stand-by;
2) precursor solution preparation: add 50 ~ 100mL dehydrated alcohol, 50 ~ 100mL water, 1 ~ 10mL precursor, HCl adjusts pH to 2.0 ~ 6.0, and stirred at ambient temperature 2 ~ 48h is stand-by;
3) in three slot electrodes, add the precursor solution prepared, using Titanium base as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, controlling potential is at-0.5 ~-3.0V, depositing time is 30s ~ 2000s, with 40 ~ 150 DEG C of oven dry after deionized water rinsing, obtains inertia nano-oxide film;
4) at above-mentioned galvanic deposit inertia nano-oxide film surface-coated active oxide coatings, by pyrolysis technique, toast at 350-550 DEG C, decompose, and repeatedly, obtain Ni―Ti anode.
Described inertia nano-oxide film is SiO
2, TiO
2, ZrO
2, PbO
2, SnO
2, Co
2o
3, CuO or ZnO film.The precursor of described indifferent oxide is: alkyl silicate, alkyl titanate or zirconic acid alkyl ester.Described active oxidation nitride layer is iridium dioxide, ruthenium dioxide or its composite oxides.The precursor of described active oxidation nitride layer is chloracid or the villaumite of iridium or ruthenium.
Described Ni―Ti anode is used for analysing oxygen or analysing chlorine reaction in electrochemical industry.
Because electro-deposition techniques to have the requirement of degree of cleaning to specimen surface, therefore, first require to carry out oil removing pre-treatment to titanium alloy (TA1) matrix surface.
Titanium alloy substrate, after mechanical sandblasting roughened, puts into oil removing 10min at alkaline degreasing liquid 30 DEG C, then in the oxalic acid aqueous solution of boiling pickling 30 min except descaling, finally use tap water successively, after washed with de-ionized water, use hot blast drying fast, in loft drier, place 24h stand-by.
Embodiment 1
In beaker, add 50 mL dehydrated alcohols, 50 mL water, 1 mL tetraethoxy (TEOS) successively, HCl adjusts about pH to 3.0, and h is stand-by for stirred at ambient temperature 2.In three slot electrodes, add the precursor solution prepared, using TA1 as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, and controlling potential, at-0.5 V, deposits after terminating, with 40 DEG C of oven dry after deionized water rinsing, obtain the Nano-meter SiO_2 of different thickness by changing depositing time
2film.The SiO in galvanic deposit
2the TA1 external coating of nano-oxide film is containing 0.2M H
2irCl
6ethanol/Virahol (volume ratio 1:1) solution, at 450 DEG C, toast 10 min, repeatedly, toast 1 h at the same temperature for the last time, obtain active titanium anode.Coat number of times by adjustment, control final active IrO
2the adhesion amount of oxide skin is ~ 10 g/m
2.
Conventional Ti/IrO
2anode surface densification, smooth (see accompanying drawing 1a); And through galvanic deposit SiO
2the IrO applied after pre-treatment
2coated anode (Ti/SiO
2/ IrO
2) but show pattern (see accompanying drawing 1b) that is coarse, porous.
The oxygen evolution activity of Ni―Ti anode adopts polarization curve to test, and used test solution is 0.5 M H
2sO
4the aqueous solution.Result shows, and the existence of galvanic deposit silicon dioxide intermediate layer significantly improves the electro catalytic activity of Ni―Ti anode (see accompanying drawing 2).For more intuitively illustrating, in table 1, list the SiO prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current.
The SiO that table 1 is prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current (getting the current value under 1.4 V)
Electrodeposition time (s) | Analyse oxygen electric current (mA/cm 2) |
0 | 7.4 |
300 | 10.1 |
600 | 12.3 |
1000 | 13.9 |
1500 | 16.3 |
2000 | 14.2 |
Embodiment 2
In beaker, add 100 mL dehydrated alcohols, 100 mL water, 10 mL tetraethoxys (TEOS) successively, HCl adjusts about pH to 3.0, and h is stand-by for stirred at ambient temperature 48.In three slot electrodes, add the precursor solution prepared, using TA1 as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, and controlling potential, at-3.0 V, deposits after terminating, with 40 DEG C of oven dry after deionized water rinsing, obtain the Nano-meter SiO_2 of different thickness by changing depositing time
2film.The SiO in galvanic deposit
2the TA1 external coating of nano-oxide film is containing 0.2M H
2irCl
6ethanol/Virahol (volume ratio 1:1) solution, at 450 DEG C, toast 10 min, repeatedly, toast 1 h at the same temperature for the last time, obtain active titanium anode.Coat number of times by adjustment, control final active IrO
2the adhesion amount of oxide skin is ~ 10 g/m
2.
With embodiment 1, at 0.5 M H
2sO
4polarization curve is adopted to test its electro catalytic activity in the aqueous solution.For more intuitively illustrating, in table 2, list the SiO prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current.
The SiO that table 2 is prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current (getting the current value under 1.4 V)
Electrodeposition time (s) | Analyse oxygen electric current (mA/cm 2) |
0 | 7.4 |
100 | 11.2 |
300 | 13.8 |
500 | 14.9 |
1000 | 16.8 |
1500 | 13.6 |
Embodiment 3
In beaker, add 50 mL dehydrated alcohols, 50 mL water, 3 mL tetraethoxys (TEOS) successively, HCl adjusts about pH to 3.0, and h is stand-by for stirred at ambient temperature 24.In three slot electrodes, add the precursor solution prepared, using TA1 as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, and controlling potential, at-2.0 V, deposits after terminating, with 40 DEG C of oven dry after deionized water rinsing, obtain the Nano-meter SiO_2 of different thickness by changing depositing time
2film.The SiO in galvanic deposit
2the TA1 external coating of nano-oxide film is containing 0.2 M H
2irCl
6ethanol/Virahol (volume ratio 1:1) solution, at 450 DEG C, toast 10 min, repeatedly, toast 1 h at the same temperature for the last time, obtain active titanium anode.Coat number of times by adjustment, control final active IrO
2the adhesion amount of oxide skin is ~ 10 g/m
2.
With embodiment 1, at 0.5 M H
2sO
4polarization curve is adopted to test its electro catalytic activity in the aqueous solution.For more intuitively illustrating, in table 3, list the SiO prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current.
The SiO that table 3 is prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current (getting the current value under 1.4 V)
Electrodeposition time (s) | Analyse oxygen electric current (mA/cm 2) |
0 | 7.4 |
100 | 9.2 |
300 | 12.3 |
500 | 13.5 |
1000 | 15.7 |
1500 | 16.4 |
Embodiment 4
In beaker, add 50 mL dehydrated alcohols, 50 mL water, 1 mL tetraethoxy (TEOS) successively, HCl adjusts about pH to 3.0, and h is stand-by for stirred at ambient temperature 2.In three slot electrodes, add the precursor solution prepared, using TA1 as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, and controlling potential, at-2.0 V, deposits after terminating, with 40 DEG C of oven dry after deionized water rinsing, obtain the Nano-meter SiO_2 of different thickness by changing depositing time
2film.Change follow-up active oxidation nitride layer, by IrO
2change RuO into
2, used coats solution for containing 0.2M RuCl
3ethanol/water (volume ratio 1:1) solution.Heat decomposition temperature is to coat process similar to embodiment 1.
Table 4 lists the SiO prepared with different electrodeposition time
2layer is the Ti/RuO of pretreatment layer
2anode is respectively at 0.5M H
2sO
4and the anodic current in 1.0M NaCl solution.
The SiO that table 4 is prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current (getting the current value under 1.4V)
Embodiment 5
Concrete implementation step is similar to Example 1, by inertia nano oxide layer by SiO
2change ZrO into
2.Corresponding ZrO
2the process for preparation of precursor be: 50mL dehydrated alcohol and deionized water and hydrochloric acid mixed solution are slowly added 50mL tetrabutyl zirconate (C while stirring
16h
36o
4zr) with the mixed solution of dehydrated alcohol, in total solution, each mol ratio is tetrabutyl zirconate: dehydrated alcohol: H
2o:HCl=1:1:15:0.3, regulates pH=3.0, stirs 30min, ultrasonic 15min.In three slot electrodes, add the precursor solution prepared, using TA1 as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, and controlling potential, at-2.0V, deposits after terminating, with 40 DEG C of oven dry after deionized water rinsing, obtain the nanometer ZrO of different thickness by changing depositing time
2film.。Subsequent thermal decomposes coating IrO
2the process of active coating is identical with embodiment 1.The ZrO prepared with different electrodeposition time is listed in table 5
2layer is that the Ni―Ti anode of pretreatment layer is at 0.5M H
2sO
4in analyse oxygen electric current.
The ZrO that table 5 is prepared with different electrodeposition time
2layer for pretreatment layer Ni―Ti anode analyse oxygen electric current (getting the current value under 1.4V)
Electrodeposition time (s) | Analyse oxygen electric current (mA/cm 2) |
0 | 7.4 |
100 | 11.2 |
300 | 12.9 |
500 | 14.5 |
1000 | 17.2 |
1500 | 16.7 |
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (3)
1. a preparation method for Ni―Ti anode, is characterized in that comprising the steps:
1) Titanium base is after mechanical sandblasting roughened, put into oil removing 10min at alkaline degreasing liquid 30 ~ 50 DEG C, in the oxalic acid aqueous solution of boiling, pickling 5 ~ 30min removes descaling again, finally use tap water successively, after washed with de-ionized water, quick hot blast drying, places 5 ~ 24h in loft drier, stand-by;
2) precursor solution preparation: add 50 ~ 100mL dehydrated alcohol, 50 ~ 100mL water, 1 ~ 10mL precursor, HCl adjusts pH to 2.0 ~ 6.0, and stirred at ambient temperature 2 ~ 48h is stand-by;
3) in three slot electrodes, add the precursor solution prepared, using Titanium base as working electrode, Ag/AgCl is as reference electrode, platinum is to electrode, controlling potential is at-0.5 ~-3.0V, depositing time is 30s ~ 2000s, with 40 ~ 150 DEG C of oven dry after deionized water rinsing, obtains inertia nano-oxide film;
4) at above-mentioned galvanic deposit inertia nano-oxide film surface-coated active oxide coatings, by pyrolysis technique, toast at 350 ~ 550 DEG C, decompose, and repeatedly, obtain Ni―Ti anode;
Wherein, described inertia nano-oxide film is SiO
2film, described precursor is alkyl silicate.
2. the preparation method of a kind of Ni―Ti anode according to claim 1, is characterized in that described active oxidation nitride layer is iridium dioxide, ruthenium dioxide or its composite oxides.
3. the preparation method of a kind of Ni―Ti anode according to claim 1, is characterized in that the precursor of described active oxidation nitride layer is chloracid or the villaumite of iridium or ruthenium.
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