CN109594066A - A kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia - Google Patents
A kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia Download PDFInfo
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- CN109594066A CN109594066A CN201811552023.8A CN201811552023A CN109594066A CN 109594066 A CN109594066 A CN 109594066A CN 201811552023 A CN201811552023 A CN 201811552023A CN 109594066 A CN109594066 A CN 109594066A
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- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 239000010936 titanium Substances 0.000 title claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 206010058490 Hyperoxia Diseases 0.000 title description 8
- 230000000222 hyperoxic effect Effects 0.000 title description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000005488 sandblasting Methods 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- -1 isopropyl ester Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000001462 antimony Chemical class 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 1
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 15
- 239000012530 fluid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
本发明提供一种高氧超纳米晶钛阳极涂层的制备方法，涉及涂层技术领域。本发明包括以下步骤：（1）钛基板的处理，对钛基板依次进行喷砂、酸洗；（2）溶胶的制备，按重量分计将10‑15份三氯化钌、4‑6份H2IrCl6、41‑60份钛酸丁酯溶解于有机溶剂中，混合均匀后添加含有锡盐的纳米分散液，混合均匀后得到溶胶；（3）将溶胶均匀涂覆于经步骤（1）处理的钛基板，在420‑450℃进行烧结。本发明的阳极涂层能够增强阳极在低浓度氯化钠溶液中电解的使用寿命，有效阻碍氧气穿过涂层将电极钝化，从而提高其抗氧化能力，延长使用寿命，同时提高电极的导电性能。The invention provides a preparation method of a high-oxygen super-nanocrystalline titanium anode coating, and relates to the technical field of coatings. The present invention includes the following steps: (1) treatment of titanium substrate, sandblasting and pickling are performed on the titanium substrate in sequence; (2) preparation of sol, 10-15 parts of ruthenium trichloride, 4-6 parts of ruthenium trichloride by weight Dissolving H 2 IrCl 6 and 41-60 parts of butyl titanate in an organic solvent, adding a nano-dispersion containing tin salt after mixing uniformly, and mixing uniformly to obtain a sol; (3) uniformly coating the sol on the sol after step (1 ) treated titanium substrates and sintered at 420‑450°C. The anode coating of the invention can enhance the service life of the anode electrolysis in a low-concentration sodium chloride solution, effectively prevent oxygen from passing through the coating to passivate the electrode, thereby improving its anti-oxidation ability, prolonging the service life, and improving the conductivity of the electrode at the same time. performance.
Description
Technical field
The present invention relates to coating technology fields, and in particular to a kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia.
Background technique
The electrode material that earliest electrochemical industry uses is artificial graphite.After the advent of metal oxide containing precious metals in 1967, graphite
Electrode is gradually replaced by it.It currently as the noble metal oxide electrodes with typical meaning is made using Ru-Ti oxide
For the anode of admiring of active coating.In order to be improved the performance of electrode, scientific research personnel has carried out many-sided effort, dispersion activity
Center is the effective way for improving electrode material performance.Anode of admiring with seed layer in the prior art, is due to seed layer
Using making forming core and the growth of follow-up coating, then so as to improve the institutional framework on activation surface layer.
When electrode uses after a certain period of time, due to Ru02Coating surface active sites are by the impurity in indissoluble species or electrolyte
The gas generated in occupied and electrolytic process declines the true area of electrode constantly the souring of coating, analyses chlorine
Overpotential increases, and chlorine oxygen potential difference further decreases, and then the selectivity of electrode is caused to decline.And along with oxygen evolution reaction
It carries out, forms TiO between Ti matrix and coating interface2Passivating film causes coating resistance to increase, and further makes Ru0, coating activity
It reduces.
Layer protecting film is often applied on anode material in the prior art, to protect anode material, while increasing conduction
Performance.Usually electrolysis is electrolysis saturated salt solution；And it is electrolysed 3% weak brine, this has resulted in being more easier that side reaction, institute occurs
It is higher with the requirement to electrode.So-called side reaction is exactly electrolysis water, and anode generates oxygen, and cathode generates hydrogen.If it is full
And saline solution, then anode mainly generates chlorine.And when generating oxygen, oxygen passes through painting layer gap and enters electrode titanium-based body surface
Face can make electrode Titanium base surface that oxidation occur and generate titanium oxide, and titanium oxide is non-conductive, and electrode passivation is made to fail, and shortens electrode
Service life, the service life that same coated electrode is electrolysed in high concentration saline solution is 6-8, and electric in weak brine
The service life of solution is only 2-3, and anode material in the prior art can not use for a long time in weak brine.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of super nanocrystalline titanium anode coating of hyperoxia, it can be in Titanium base
Upper coating forms the coating of nanocrystalline structure, hinders oxygen to enter electrode, guard electrode, reinforcing life can be of about 260h, quite
It can reach in the service life being electrolysed in weak brine 6 years.
The present invention is a kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia, comprising the following steps:
(1) processing of titanium-base successively carries out sandblasting, pickling to titanium-base；
(2) 10-15 parts of mass concentrations are the ruthenium trichloride of 35-40%, 4-6 parts of mass concentrations by the preparation of colloidal sol, parts by weights meter
For the H of 30-35%2IrCl6, 41-60 parts of butyl titanates be dissolved in organic solvent, after mixing, be added in parts by weight
The 5-10 parts of nano dispersion fluids containing pink salt obtain colloidal sol after mixing, include also antimonic salt, cobalt salt in nano dispersion fluid, receive
The mass concentration of rice dispersion liquid is 25-35%；
Ruthenium trichloride is first dissolved in mass fraction be 36% hydrochloric acid in, then again with H2IrCl6, butyl titanate, organic solvent
Mixing, organic solvent can for n-butanol, isopropyl ester mixed solution, n-butanol, isopropanol volume ratio be 0.8-1.2:1,
The additive amount of organic solvent is 2-3 times of butyl titanate, by weight can be 80-180 parts.
(3) colloidal sol is evenly applied to the titanium-base handled through step (1), is sintered at 420-450 DEG C, 15-
20min, 470 DEG C of annealing 1h.
It should be made annealing treatment after sintering, a period of time is kept the temperature usually at 470 DEG C, the internal stress for forming sintering
It releases, use for a long time is prevented to be cracked with rear film.
(4) step (2), (3) are repeated 25-30 times.
Binding force of the matrix after blasting treatment between oxide coating increases, and anode life significantly improves, pickling energy
Enough remove the impurity of substrate surface, organic matter etc..
The thickness of anodic coating is about 15um, and butyl titanate forms titanium oxide during sintering, can be with titanium-base
In conjunction with ratio it is stronger, coating is not easily to fall off, and the insertion of Titanium dioxide nanoparticle can be such that the active area of coating significantly improves.
H2IrCl6It can be oxidized to IrO when sintering, IrO, which is added in ruthenium series oxide coating, can change gas
Deposition potential, have very big improvement for the oxide anode service life and performance of preparation.This is because Ir oxide structure
It is a kind of peroxidating structure, the infiltration of oxygen cannot make its destruction, and overpotential for oxygen evolution is high compared with ruthenium element, the corrosion resistant of iridium dioxide
Corrosion can be good, and oxidative resistance is strong, in addition, the electric conductivity of anode, electro catalytic activity can be improved, while oxygen evolution potential mentions
The precipitation ratio of height, oxygen is reduced, in addition, oxygen atom is reversible in the adsorption and desorption process of iridium, this is aoxidized for improving
Object anode life plays an important role.Ruthenium trichloride solid should be first dissolved in hydrochloric acid, can guarantee its good dispersibility,
Organic solvent should be pre-configured with completion when mixing, then successively by ruthenium trichloride, H2IrCl6, butyl titanate is dissolved in
In organic solvent, compound organic solvent more has reason the dissolution of each substance, dispersion.
Nano dispersion fluid can improve the dispersibility of various particles in colloidal sol when forming colloidal sol, burn in oxidation
Nanocrystal is capable of forming during knot, crystal grain refinement makes the microstructure for the coating to be formed is finer and close can hinder oxygen
Passing through for gas, prevents passivated electrodes；In addition, the tin oxide formed during oxidation can be in the electric conductivity for improving electrode.
Anodic coating of the invention can enhance service life of the anode in low concentration sodium chloride solution, effectively obstruction oxygen
Gas passes through coating and electrode passivation to improve its oxidation resistance, prolongs the service life, while improving the electric conductivity of electrode
Energy.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
Embodiment one
The present invention is a kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia, comprising the following steps:
(1) processing of titanium-base successively carries out sandblasting, pickling to titanium-base；
(2) preparation of colloidal sol, ruthenium trichloride that 10 parts of mass concentrations are 35% by parts by weights meter, 4 parts of mass concentrations are 30%
H2IrCl6, 41 parts of butyl titanate, 36 parts of n-butanols, 44 parts of isopropanols are added 5 parts in parts by weight and contain after mixing
The nano dispersion fluid of pink salt, obtains colloidal sol after mixing, also includes antimonic salt, cobalt salt in nano dispersion fluid, nano dispersion fluid
Mass concentration is 25%；
Ruthenium trichloride is first dissolved in mass fraction be 36% hydrochloric acid in, then again with H2IrCl6, butyl titanate, organic solvent
Mixing；
(3) colloidal sol is evenly applied to the titanium-base handled through step (1), is sintered at 420 DEG C, 15min, 470 DEG C of annealing
1h；
(4) step (2), (3) 25 times are repeated.
Embodiment two
The present invention is a kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia, comprising the following steps:
(1) processing of titanium-base successively carries out sandblasting, pickling to titanium-base；
(2) preparation of colloidal sol, ruthenium trichloride that 15 parts of mass concentrations are 37% by parts by weights meter, 6 parts of mass concentrations are 34%
H2IrCl6, 60 parts of butyl titanate, 90 parts of n-butanols, 90 parts of isopropanols are added 10 parts in parts by weight and contain after mixing
The nano dispersion fluid of pink salt, obtains colloidal sol after mixing, also includes antimonic salt, cobalt salt in nano dispersion fluid, nano dispersion fluid
Mass concentration is 32%；
Ruthenium trichloride is first dissolved in mass fraction be 36% hydrochloric acid in, then again with H2IrCl6, butyl titanate, organic solvent
Mixing；
(3) colloidal sol is evenly applied to the titanium-base handled through step (1), is sintered at 450 DEG C, 20min, 470 DEG C of annealing
1h；
(4) step (2), (3) 30 times are repeated.
Embodiment three
The present invention is a kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia, comprising the following steps:
(1) processing of titanium-base successively carries out sandblasting, pickling to titanium-base；
(2) preparation of colloidal sol, ruthenium trichloride that 12 parts of mass concentrations are 40% by parts by weights meter, 5 parts of mass concentrations are 35%
H2IrCl6, 50 parts of butyl titanate, 53 parts of n-butanols, 45 parts of isopropanols are added 8 parts in parts by weight and contain after mixing
The nano dispersion fluid of pink salt, obtains colloidal sol after mixing, also includes antimonic salt, cobalt salt in nano dispersion fluid, nano dispersion fluid
Mass concentration is 35%；
Ruthenium trichloride is first dissolved in mass fraction be 36% hydrochloric acid in, then again with H2IrCl6, butyl titanate, organic solvent
Mixing；
(3) colloidal sol is evenly applied to the titanium-base handled through step (1), is sintered at 430 DEG C, 18min, 470 DEG C of annealing
1h；
(4) step (2), (3) 27 times are repeated.
The electrode for being coated with the coating prepared in embodiment one to three is subjected to reinforcing life test, reinforcing life test is
The accelerated life test method that anode is electrolysed under high current density in sulfuric acid solution, by testing different subject anodes identical dense
It spends, in the sulfuric acid solution of temperature, the out-of-service time of the electrode reinforcing life test to work under identical current density, than less
With the service life of electrode.Concrete operations are as follows: (1) by 1.0N H2SO4Solution pours into beaker, and fixed installation electrolysis anode and cathode is simultaneously complete
The very effective working position of total flooding yin-yang；(2) after liquid temperature to be electrolysed rises to 40 DEG C, power on and to adjust Faradaic current close
Degree is 20000A/m2, and maintain its constant during the test, aperiodically added in electrolytic process a certain amount of distilled water and
H2SO4To maintain electrolyte liquid level and concentration；(3) every 48 hour record once electrolytic time, Faradaic current, bath voltage value；
(4) bath voltage starts to stop test when rapid substantial increase；(5) from experiment is started to bath voltage substantial increase
When the electrolysis time accumulated be known as being tested the reinforcing life test failure time of electrode.The area of this test electrode is
10.0cm2。
Be coated with the electrode of one to three kind of coating of embodiment out-of-service time be 285h, 300h, 295h, it is higher than national standard
Many out, anodic coating is able to extend the service life of electrode.
By the anode electrode for being coated with embodiment coating be sent to " chemical industry chlor-alkali chlorine products quality surveillance inspection center " into
Row detection, the number of report are as follows: YJ-2018-015, testing result are as follows:
Meet state in the anode electrode material for being coated with this coating of chemical industry chlor-alkali chlorine products quality surveillance inspection center detection
Border standard, and reinforcing life 285h, more than the 40h of requirement.
Anodic coating of the invention can enhance service life of the anode in low concentration sodium chloride solution, effectively obstruction oxygen
Gas passes through coating and electrode passivation to improve its oxidation resistance, prolongs the service life, while improving the electric conductivity of electrode
Energy.
The present invention is not limited to above-mentioned specific embodiment, and the invention may be variously modified and varied.All foundations
Technical spirit of the invention should be included in the present invention to embodiment of above any modification, equivalent replacement, improvement and so on
Protection scope.
Claims (10)
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| CN111850600A (en) * | 2020-07-17 | 2020-10-30 | 西安怡速安智能科技有限公司 | Formula of anode coating for removing peculiar smell of electrochemical electrode |
| CN111850601A (en) * | 2020-07-17 | 2020-10-30 | 西安怡速安智能科技有限公司 | Novel electrode processing technology and equipment |
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