CN117987674A - Titanium-based electrode and preparation method thereof - Google Patents
Titanium-based electrode and preparation method thereof Download PDFInfo
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- CN117987674A CN117987674A CN202410122984.4A CN202410122984A CN117987674A CN 117987674 A CN117987674 A CN 117987674A CN 202410122984 A CN202410122984 A CN 202410122984A CN 117987674 A CN117987674 A CN 117987674A
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- 239000010936 titanium Substances 0.000 title claims abstract description 104
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 32
- 230000008018 melting Effects 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 30
- -1 titanium tantalum iridium platinum Chemical compound 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 230000001680 brushing effect Effects 0.000 claims abstract description 17
- 239000011247 coating layer Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- 238000003723 Smelting Methods 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005530 etching Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 7
- 238000000861 blow drying Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- WJEPRGMTKJDNFO-UHFFFAOYSA-N platinum tantalum titanium Chemical compound [Ti][Ta][Pt] WJEPRGMTKJDNFO-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910001362 Ta alloys Inorganic materials 0.000 description 4
- VONLASUMRVUZLY-UHFFFAOYSA-N [Ir].[Ti].[Ta] Chemical compound [Ir].[Ti].[Ta] VONLASUMRVUZLY-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 4
- 229910000575 Ir alloy Inorganic materials 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 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
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention discloses a titanium-based electrode and a preparation method thereof, and belongs to the technical field of electrode materials. The preparation method of the titanium-based electrode comprises the following steps: obtaining titanium tantalum iridium platinum alloy by adopting an arc melting method; the titanium tantalum iridium platinum alloy is processed into wires or sheets through plastic processing, vacuum heat treatment and surface treatment are carried out, then steps of dipping or brushing mixed solution, drying and calcining are repeated for 5-10 times, a coating layer is formed on the surface of the alloy, and finally the titanium-based electrode is obtained after calcining for 10 minutes at 510 ℃; the mixed solution is a mixed solution containing Ti, ta, ir, pt metal ions. The titanium-based electrode has strong stripping resistance and longer service life, and can be applied to chlor-alkali industry, electrocatalysis, electrode materials and the like in the electrochemical field.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a titanium-based electrode and a preparation method thereof.
Background
The advent of the titanium-based noble metal oxide electrode of Beers invented in 1968 ended the graphite electrode age over 70 years. The electrode is composed of titanium as a matrix and a conductive noble metal oxide active coating coated on the titanium, and is a composite electrode which is mainly used for an anode. The titanium-based noble metal oxide anode is the most studied electrode material for organic wastewater treatment at present because of the excellent electrochemical performance, and mainly comprises titanium-based iridium (Ti/IrO 2) and titanium-based ruthenium (Ti/RuO 2). The valve metal that can be used as the anode substrate is mainly titanium, niobium, tantalum, etc., but titanium and titanium alloy having relatively high cost performance are often used as the substrate due to the cost.
The main preparation methods of the most important noble metal oxide coating in the electrode material at present mainly comprise a thermal decomposition method, a sol-gel method, an electrochemical deposition method, a laser pulse deposition method, sputtering, a spray high-temperature decomposition method and the like. The thermal decomposition method is used in industry more, and the method mainly comprises the steps of coating a salt solution containing noble metals with fixed components on a titanium plate, drying and baking for multiple times, and finally sintering at high temperature to prepare the electrode.
A great deal of researches show that the service life of the electrode is influenced, besides the quality of the coating and the use of a matrix are also related, the currently used base material is mainly pure titanium, and after the surface of the titanium matrix is exposed after the coating is peeled off in the later period of use of the electrode, the titanium is easy to anodize to generate a compact titanium oxide layer, so that the voltage of the electrode is increased, and the electrode is further invalid. Therefore, in order to improve the life of the electrode, it is necessary to search for electrode substrates and coatings of different elemental species and compositions, and to investigate the influence of chlorine evolution, oxygen evolution performance, and electrode life on the electrode. Therefore, the development of the electrode formed by developing a special electrode matrix and a coating has certain practical significance and application value.
Disclosure of Invention
In view of the above drawbacks of the prior art, the present invention provides a titanium-based electrode and a method for preparing the same.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by weight: ta 0.1-8%, ir 0.01-3.0%, pt 0.05-0.1%, and Ti the rest;
(2) Plastic processing titanium tantalum iridium platinum alloy into wires or sheets, and then carrying out vacuum heat treatment;
(3) Carrying out surface treatment on the alloy subjected to vacuum heat treatment, then repeatedly dipping or brushing a mixed solution, drying and calcining for 5-10 times to form a coating layer on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain a titanium-based electrode;
the mixed solution is a mixed solution containing Ti, ta, ir, pt metal ions.
As a preferred embodiment of the present invention, the temperature of the vacuum heat treatment in the step (2) is 900℃for 1 to 10 hours.
As a preferred embodiment of the invention, the molar ratio of the metal ions Ir to Ta to Pt to Ti in the mixed solution is 1:10:4.9:40060, 30:86:1:3620, 6.3:107:1:4655 or 1:1.07:30.43:3943.
As a preferred embodiment of the present invention, in the step (3), the surface treatment specifically includes: the alloy is corroded by aqua regia, then is corroded by HNO 3 and HF mixed acid with the volume ratio of 1:1 after being washed by water, and finally is put into absolute ethyl alcohol for standby.
As a preferred embodiment of the present invention, in the step (3), the time of impregnation is 1 to 5 minutes; the coating amount is 5-10 times, and the thickness of the coating layer is 10-20 micrometers.
As a preferred embodiment of the present invention, in the step (3), the calcination temperature is 510℃and the time is 10 minutes.
As a preferred embodiment of the present invention, the arc melting process comprises the steps of: putting the alloy raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00-1.1 atm for smelting, smelting current is 100-200A, smelting time is 20-40 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-iridium-platinum alloy.
The invention also discloses a titanium-based electrode prepared by the preparation method of the titanium-based electrode, which comprises a substrate and a surface coating, wherein the substrate is titanium tantalum-iridium-platinum alloy, and the surface coating is a mixture of Ti oxide, ta oxide, ir oxide and Pt oxide.
Compared with the prior art, the invention has the beneficial effects that: the substrate of the titanium-based electrode is titanium tantalum iridium platinum alloy, and the surface coating of the substrate is Ti oxide, ta oxide, ir oxide and Pt oxide. On one hand, the bonding force between the substrate and the surface coating is strong, and the phenomenon of stripping of the electrode coating is not easy to occur. On the other hand, the surface coating of the pure titanium substrate is stripped after the titanium-based electrode is used for a long time, the substrate is exposed to generate anodic oxidation and voltage rise to cause the passivation failure of the electrode, and after the titanium tantalum iridium platinum alloy substrate is exposed, the anodic oxidation mainly generates Ti, ta, ir and Pt oxides to form a novel metal oxide coating, so that the electrode failure caused by the voltage rise can be avoided, and the service life of the electrode is greatly prolonged.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by mass: ta is: 0.1%, ir is: 0.01%, pt is: 0.05% and the balance Ti; the arc melting method comprises the following steps: and (3) putting the Ti metal, ta metal, ir metal and Pt metal raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00 atmospheric pressure for smelting, wherein smelting current is 200A, smelting time is 20 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-platinum alloy.
(2) The titanium tantalum iridium platinum alloy is drawn into wires, and then vacuum heat treatment is carried out for 1 hour in vacuum at 900 ℃ to obtain wires with the diameter of 0.1mm for the electrodes.
(3) Etching the wire with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, etching with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti being 1:10:4.9:40060; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 10 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Example 2
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by mass: ta is: 8%, ir is: 3%, pt is: 0.1% and the balance Ti; the arc melting method comprises the following steps: and (3) putting the Ti metal, ta metal, ir metal and Pt metal raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.1 atmosphere for smelting, wherein smelting current is 100A, smelting time is 40 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-platinum alloy.
(2) And drawing the titanium tantalum iridium platinum alloy into a wire, and then carrying out vacuum heat treatment in vacuum at 900 ℃ for 5 hours to obtain the wire with the diameter of 1mm for the electrode.
(3) Cutting the wire into 10cm long wire, corroding with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, corroding with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti being 30:86:1:3620; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 20 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Example 3
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by mass: ta is: 8%, ir is: 0.5%, pt is: 0.08%, the balance being Ti; the arc melting method comprises the following steps: and (3) putting the Ti metal, ta metal, ir metal and Pt metal raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00 atmospheric pressure for smelting, wherein the smelting current is 150A, the smelting time is 30 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-platinum alloy.
(2) And drawing titanium tantalum iridium platinum alloy into wires, and then carrying out vacuum heat treatment in vacuum at 900 ℃ for 10 hours to obtain wires with the diameter of 2mm for the electrodes.
(3) Cutting the wire into 10cm long wire, corroding with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, corroding with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti of 6.3:107:1:4655; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 15 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Example 4
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by mass: ta is: 0.1%, ir is: 3%, pt is: 0.1% and the balance Ti; the arc melting method comprises the following steps: and (3) putting the Ti metal, ta metal, ir metal and Pt metal raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00 atmospheric pressure for smelting, wherein smelting current is 200A, smelting time is 20 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-platinum alloy.
(2) And drawing the titanium tantalum iridium platinum alloy into a wire, and then carrying out vacuum heat treatment in vacuum at 900 ℃ for 5 hours to obtain the wire with the diameter of 5mm for the electrode.
(3) Cutting the wires into wires with the length of 8cm, corroding the wires by using aqua regia (HNO 3: HCl=1:3), cleaning the wires by using deionized water, corroding the wires by using HNO 3 and HF mixed acid (volume ratio is 1:1), and finally putting the wires cleaned by using deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti being 1:1.07:30.43:3943; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a 10-micrometer rear coating layer on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Comparative example 1
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Pure titanium was drawn into a wire, and then vacuum heat treatment was performed at 900 ℃ for 1 hour in vacuum to obtain a wire with a diameter of 0.1mm for an electrode.
(2) Etching the wire with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, etching with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(3) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti being 1:10:4.9:40060; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(4) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 10 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Comparative example 2
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal and Ir metal, adopting an arc melting method, and obtaining titanium tantalum iridium alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by mass: ta is: 0.1%, ir is: 0.01%, the balance being Ti; the arc melting method comprises the following steps: and (3) putting the Ti metal, the Ta metal and the Ir metal raw materials which are prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with the pressure of 1.00 atmospheric pressure for smelting, wherein the smelting current is 200A, the smelting time is 20 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-iridium alloy.
(2) The titanium tantalum iridium alloy is processed into a wire rod through plastic processing, and then vacuum heat treatment is carried out for 1 hour in vacuum at 900 ℃ to obtain the wire rod with the diameter of 0.1mm for the electrode.
(3) Etching the wire with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, etching with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of compounds with the molar ratio of Ir to Ta to Pt to Ti being 1:10:4.9:40060; the metal ions of Ir ion, ta ion, pt ion and Ti are respectively chloroiridium acid, tantalum pentachloride, chloroplatinic acid and tetrabutyl titanate.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 10 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Comparative example 3
A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal and Ta metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum alloy comprises the following components in percentage by mass: ta is: 0.1% and the balance Ti; the arc melting method comprises the following steps: putting the Ti metal and Ta metal raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00 atmospheres for smelting, wherein the smelting current is 200A, the smelting time is 20 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum alloy.
(2) The titanium tantalum alloy was subjected to plastic working to obtain a wire, and then subjected to vacuum heat treatment at 900℃for 1 hour in vacuum to obtain a wire having a diameter of 0.1mm for an electrode.
(3) Etching the wire with aqua regia (HNO 3: HCl=1:3), cleaning with deionized water, etching with HNO 3 and HF mixed acid (volume ratio is 1:1), and finally placing the wire cleaned with deionized water into absolute ethyl alcohol for standby.
(4) Preparing a mixed solution of a compound with a molar ratio of Ir to Pt metal ions of 1:4.9; ir ion and Pt ion are respectively chloroiridium acid and chloroplatinic acid as raw materials.
(5) Taking out the wire from absolute ethyl alcohol, blow-drying, brushing the mixed solution, forming a thin layer of the solution on the surface of the wire, then performing rotary drying, calcining for 5 minutes in the atmosphere at 390 ℃, repeating the steps of brushing the mixed solution, drying and calcining for 10 times, forming a coating layer with the thickness of 10 micrometers on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain the titanium-based electrode.
Effect example
The anode life-enhancing test failure time was measured for the electrodes prepared in examples 1 to 4 and comparative examples 1 to 3, and the measured electrode-enhancing electrolytic life is shown in Table 1.
The experimental method comprises the following steps: using the electrodes prepared in examples 1 to 4 and comparative examples 1 to 3 as anodes of sodium hypochlorite generators, sodium hypochlorite solutions were prepared in 3 to 5% wt sodium chloride solution systems, potential difference of chlorine evolution and oxygen evolution, whether or not a coating falling phenomenon was found after electrolysis for 30 hours, and the like were shown in Table 1.
The anode life strengthening test failure time measurement was performed on the titanium-based electrodes prepared in examples 1 to 4 and comparative examples 1 to 3 with reference to the test requirements and conditions concerning the anode life strengthening test failure time in the national standard "GB 12176-90 sodium hypochlorite generator". In the test process, 0.5mol/L H 2SO4 solution is used as electrolyte, the current density of an electrode is 2000A/m 2, the electrolysis temperature is 50 ℃, and the voltage and time are recorded. When the voltage rises rapidly, the electrode is considered to be invalid, and the electrolytic reaction time is counted to strengthen the electrolytic life.
TABLE 1
As can be seen from Table 1, the electrodes prepared in comparative examples 1 to 3 have lower potential difference for chlorine and oxygen evolution, overall shorter life of enhanced electrolysis, and the coating layer has a peeling condition after electrolysis for 30 hours, wherein in comparative example 1, the Ti substrate is exposed after the coating layer is peeled off, so that the anode oxidation causes rapid passivation of the electrode; in comparative example 2, the electrode potential was significantly fluctuated due to anodic oxidation of the electrode surface as the coating was peeled off during use due to the lack of Ir and Pt ions in the matrix, and the electrode was oxidized and passivated rapidly after the coating was peeled off. The electrode prepared in comparative example 3 was inferior to the examples in performance mainly because titanium was lacking in the coating layer, titanium oxide was difficult to form during calcination, and only simple mechanical bonding with the substrate was possible, so that peeling easily occurred during electrolysis, and problems of fluctuation and instability of electrode potential occurred. The present invention also explores the use of the same elements for the electrode matrix and the oxide of the surface: for example, the substrate is titanium tantalum alloy, and the surface coating is a mixture of titanium oxide and tantalum oxide; the substrate is tantalum iridium titanium alloy, and the surface coating is a mixture of iridium oxide, titanium oxide and tantalum oxide; the substrate is titanium tantalum platinum alloy, the surface coating is a mixture of platinum oxide, titanium oxide and tantalum oxide, etc., and titanium, tantalum, platinum and iridium are found to have synergistic effects, and the lack of one of them can reduce the performance and life of the electrode. The lack of iridium and platinum elements in the alloy substrate or the surface coating can lead to the rise of oxygen evolution potential and the reduction of service life, and the oxygen evolution potential of the electrode can be reduced only when titanium, tantalum, platinum and iridium in the spinous process and the surface coating coexist, so that the chlorine evolution performance and the service life of the electrode are improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing a titanium-based electrode, comprising the steps of:
(1) Mixing Ti metal, ta metal, ir metal and Pt metal, adopting an arc melting method, and obtaining titanium tantalum iridium platinum alloy by controlling a melting atmosphere and a method of repeated melting; the titanium tantalum iridium platinum alloy comprises the following components in percentage by weight: ta 0.1-8%, ir 0.01-3.0%, pt 0.05-0.1%, and Ti the rest;
(2) Plastic processing titanium tantalum iridium platinum alloy into wires or sheets, and then carrying out vacuum heat treatment;
(3) Carrying out surface treatment on the alloy subjected to vacuum heat treatment, then repeatedly dipping or brushing a mixed solution, drying and calcining for 5-10 times to form a coating layer on the surface of the alloy, and finally calcining for 10 minutes at 510 ℃ to obtain a titanium-based electrode;
the mixed solution is a mixed solution containing Ti, ta, ir, pt metal ions.
2. The method for producing a titanium-based electrode according to claim 1, wherein the temperature of the vacuum heat treatment in the step (2) is 900 ℃ for 1 to 10 hours.
3. The method for preparing a titanium-based electrode according to claim 1, wherein the molar ratio of metal ions Ir to Ta to Pt to Ti in the mixed solution is 1:10:4.9:40060, 30:86:1:3620, 6.3:107:1:4655 or 1:1.07:30.43:3943.
4. The method for producing a titanium-based electrode according to claim 1, wherein in the step (3), the surface treatment specifically comprises: the alloy is corroded by aqua regia, then is corroded by mixed acid of HNO 3 and HF with the volume ratio of 1:1 after being washed by water, and finally is put into absolute ethyl alcohol for standby.
5. The method for producing a titanium-based electrode according to claim 1, wherein in the step (3), the time of impregnation is 1 to 5 minutes; the coating amount is 5-10 times, and the thickness of the coating layer is 10-20 micrometers.
6. The method for producing a titanium-based electrode according to claim 1, wherein in the step (3), the calcination temperature is 510 ℃ for 10 minutes.
7. The method for producing a titanium-based electrode according to claim 1, wherein the arc melting method comprises the steps of: putting the alloy raw materials prepared in proportion into an electric arc furnace, pre-pumping vacuum degree is less than 1 multiplied by 10 -1 Pa, then charging high-purity argon with pressure of 1.00-1.1 atm for smelting, smelting current is 100-200A, smelting time is 20-40 seconds, and repeatedly smelting for 4 times to obtain the button-shaped titanium-tantalum-iridium-platinum alloy.
8. A titanium-based electrode produced by the production method of a titanium-based electrode as claimed in any one of claims 1 to 7.
9. The titanium-based electrode of claim 8, wherein the titanium-based electrode comprises a substrate and a surface coating, the substrate being titanium tantalum iridium platinum alloy, the surface coating being a mixture of Ti oxide, ta oxide, ir oxide, and Pt oxide.
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