CN113755873A - Cathode for seawater electrolysis and preparation method thereof - Google Patents
Cathode for seawater electrolysis and preparation method thereof Download PDFInfo
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- CN113755873A CN113755873A CN202111072648.6A CN202111072648A CN113755873A CN 113755873 A CN113755873 A CN 113755873A CN 202111072648 A CN202111072648 A CN 202111072648A CN 113755873 A CN113755873 A CN 113755873A
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- 239000013535 sea water Substances 0.000 title claims abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 108
- 239000011248 coating agent Substances 0.000 claims abstract description 105
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000010936 titanium Substances 0.000 claims abstract description 87
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 150000002909 rare earth metal compounds Chemical class 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 22
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 5
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007517 polishing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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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
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention aims to provide a cathode for seawater electrolysis and a preparation method thereof, namely, a cathode coating solution is coated on the surface of a pretreated titanium plate, and after step-by-step thermal oxidation treatment, the weight increase of metal oxide of the titanium plate reaches 0.1-5g/m2Thus obtaining the cathode; the cathode coating liquid is one or more of rare earth metal compound or valve type metal compound solution. The cathode prepared by the method can delay the scaling condition on the surface of the cathode, reduce the reaction voltage between the cathode and the anode, prolong the acid washing period of the electrode and reduce the energy consumption.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly provides a cathode for seawater electrolysis and a preparation method thereof.
Background
The seawater electrolysis chlorine production is a widely applied technical means for preventing marine organism pollution. By direct current electrolysis of seawater to produce ClO-And the system kills microorganisms in seawater and can effectively prolong the service life of pipelines and operation equipment in seawater. Method for preparing sodium hypochlorite by electrolyzing seawaterIn the process, a titanium coating anode is generally used as an anode and a titanium plate is used as a cathode. Since the seawater contains Ca in addition to sodium chloride2+、Mg2+And metal ion impurities are generated, and scale-like substances are formed and continuously deposited on the cathode in the electrolytic process, so that the catalytic performance of the electrode is influenced.
To reduce the deposition of impurities, the cathode is typically polished to provide a smooth "mirror" surface on the rough surface of the cathode, thereby reducing the surface area of the substrate and the Ca content2+、Mg2+The binding force of the metal ion dirt-like substance makes the dirt-like substance difficult to be firmly adsorbed on the surface of the cathode, and part of the dirt-like substance can be washed away by flowing seawater. However, the treatment method increases the reaction voltage between the cathode and the anode, and the use of the polishing cathode can only delay the deposition of the scale on the surface of the cathode, and the scale on the surface of the electrode still needs to be removed by adopting a regular acid washing method, so as to maintain the normal operation of the electrolysis process.
The rare earth metal is a general name of 17 elements of scandium, yttrium and lanthanide in IIIB group of the periodic table, and in the heat treatment, the rare earth metal has the functions of purifying and activating the surface of the metal material and the surrounding medium thereof, promoting the decomposition of the penetrating agent and the diffusion of atoms, further changing the property of the metal surface and increasing the bonding force of the matrix and the active layer.
Titanium and titanium alloys are electrically conductive when used as cathodes in brine and are immediately electrically non-conductive when used as anodes, and because of their "valve-like" properties, such metals are often referred to as valve-type metals, and metals with similar properties also include tantalum, tantalum alloys, zirconium alloys, niobium and niobium alloys, and the application of the above valve-type metals and their compounds in the preparation of cathode materials has certain exploratory properties.
On the basis of the existing cathode preparation process of seawater electrolysis, the preparation of the cathode which can delay surface scaling, prolong the acid washing period of the electrode and reduce the reaction voltage by combining the relevant properties of rare earth metal and valve metal has certain significance.
Disclosure of Invention
The invention aims to provide a cathode for seawater electrolysis and a preparation method thereof, and the cathode prepared by the method can delay the scaling on the surface of the cathode, reduce the reaction voltage between the cathode and the anode, prolong the acid washing period of the electrode and reduce the energy consumption.
The technical scheme of the invention is as follows:
a cathode for seawater electrolysis, which is characterized in that: coating a cathode coating solution on the surface of the pretreated titanium plate, and performing step-by-step thermal oxidation treatment until the weight increase of the metal oxide of the titanium plate reaches 0.1-5g/m2Thus obtaining the cathode.
The cathode coating liquid is a rare earth metal compound solution and/or a valve type metal compound solution.
The invention also provides a preparation method of the cathode for seawater electrolysis, which is characterized by comprising the following specific steps:
1) pretreating the titanium plate;
2) uniformly coating the cathode coating liquid on the working surface of the titanium plate to be coated;
3) and step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180 ℃ for 10-30 minutes, then sintering at 200-2Thus obtaining the cathode.
As a preferred technical scheme:
in the step 1), the pretreatment of the titanium plate comprises the following steps: and polishing the titanium plate.
The polishing process comprises the following steps: polishing the two sides of the titanium plate to ensure that the surface of the titanium plate is a flat mirror surface, sequentially using alkali liquor and absolute ethyl alcohol to remove oil from the titanium plate after polishing, then using distilled water to clean the titanium plate, drying the titanium plate in a constant-temperature drying oven at 100 ℃, and cooling the titanium plate for later use.
In the step 2), the cathode coating solution is as follows: 0.05-1g/L cerium chloride, 0.05-0.5g/L praseodymium chloride, 0.2-2g/L lanthanum chloride, 1.0-10.0g/L titanium trichloride, 0.35-5.0g/L tantalum pentachloride, 0.2-4.0g/L zirconium tetrachloride and 0.3-5.0g/L niobium pentachloride. Wherein, organic solvent (such as n-butyl alcohol, absolute ethyl alcohol and the like) is added into the cathode coating liquid containing tantalum pentachloride and/or niobium pentachloride.
The cathodic coating liquid used is further preferably: 0.1-0.5g/L cerium chloride, 0.075-0.2g/L praseodymium chloride, 0.25-1.0g/L lanthanum chloride, 1.5-6.0g/L titanium trichloride, 0.5-4.0g/L tantalum pentachloride, 0.25-3.0g/L zirconium tetrachloride and 0.5-3.0g/L niobium pentachloride.
The cathode coating liquid for the first coating is a rare earth metal compound solution.
In step 3): the step thermal oxidation treatment is three-six thermal oxidation treatment, the cathode coating liquid used in each thermal oxidation treatment is the same or different, and the cathode coating liquid is coated for 1-10 times in each thermal oxidation treatment.
Drawings
Figure 1 shows the voltage of a seawater electrolysis cell as a function of time.
Detailed Description
A preparation method of a cathode for seawater electrolysis comprises the following specific steps:
1) and (3) pretreating the titanium plate:
2) uniformly coating the cathode coating liquid on the working surface of the titanium plate to be coated;
3) and step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180 ℃ for 10-30 minutes, then sintering at 200-700 ℃ for 15-90 minutes, taking out after sintering, cooling to room temperature, and repeating the coating, drying and sintering processes until the weight of the metal oxide of the titanium plate is increased to 0.1-5g/m2Thus obtaining the cathode.
Example 1
Pretreatment of the titanium plate:
firstly, polishing the two sides of a titanium plate by using a grinding wheel and a polishing wheel in sequence, then removing oil from the titanium plate by using alkali liquor and absolute ethyl alcohol in sequence, then cleaning the titanium plate by using distilled water, drying the titanium plate in a constant-temperature drying box at 100 ℃, and cooling the titanium plate to determine one side as a surface to be coated.
Preparing and coating a cathode coating solution:
coating the first coating liquid on a pretreated titanium plate by using 0.3g/L cerium chloride solution, drying at 150 ℃ for 10 minutes, taking out, and thermally oxidizing at 450 ℃ for 30 minutes;
coating the second coating liquid on the titanium plate coated with the first coating liquid by using a 2g/L titanium trichloride solution, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 500 ℃ for 30 minutes, and repeating the process for 5 times;
coating the coating liquid 3g/L of titanium trichloride and 1g/L of tantalum pentachloride mixed solution of n-butyl alcohol on the titanium plate coated with the coating liquid II, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 520 ℃ for 30 minutes, and repeating the process for 6 times;
coating the fourth coating liquid on the titanium plate coated with the third coating liquid by using an absolute ethyl alcohol mixed solution of 5g/L titanium trichloride, 1.5g/L zirconium tetrachloride and 1g/L niobium pentachloride, drying for 10 minutes at 150 ℃, taking out, thermally oxidizing for 30 minutes at 530 ℃, and repeating the process for 6 times before final treatment;
the final coating liquid is No. four coating liquid, the coating process is unchanged, the coating liquid is dried for 10 minutes at 150 ℃, and the coating liquid is taken out and thermally oxidized for 90 minutes at 550 ℃. The increment of the metal oxide on the titanium plate reaches 0.4 +/-0.01 g/m2And obtaining the required cathode.
Example 2
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating a cathode coating solution:
coating the first coating liquid on a pretreated titanium plate, drying the titanium plate at 150 ℃ for 10 minutes, taking out the titanium plate, and thermally oxidizing the titanium plate at 450 ℃ for 30 minutes, wherein the first coating liquid is a mixed solution containing 0.2g/L of cerium chloride and 0.1g/L of praseodymium chloride;
coating the second coating liquid on the titanium plate coated with the first coating liquid by using a 3g/L titanium trichloride solution, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 500 ℃ for 30 minutes, and repeating the process for 5 times;
coating the coating liquid 3.5g/L of titanium trichloride and 1g/L of zirconium tetrachloride on the titanium plate coated with the coating liquid II, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 520 ℃ for 30 minutes, and repeating the process for 6 times;
coating the fourth coating liquid on the titanium plate coated with the third coating liquid by using an absolute ethyl alcohol mixed solution of 4g/L titanium trichloride, 1g/L zirconium tetrachloride and 1.5g/L niobium pentachloride, drying for 10 minutes at 150 ℃, taking out, thermally oxidizing for 30 minutes at 530 ℃, and repeating the process for 7 times before final treatment;
the final coating liquid is No. four coating liquid, the coating process is unchanged, the coating liquid is dried for 10 minutes at 150 ℃, and the coating liquid is taken out and thermally oxidized for 90 minutes at 550 ℃. The increment of the metal oxide on the titanium plate reaches 0.4 +/-0.01 g/m2And obtaining the required cathode.
Example 3
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating a cathode coating solution:
coating the first coating liquid on a pretreated titanium plate, drying the titanium plate at 150 ℃ for 10 minutes, taking out the titanium plate, and thermally oxidizing the titanium plate at 450 ℃ for 30 minutes, wherein the first coating liquid is a mixed solution containing 0.25g/L of cerium chloride and 0.5g/L of lanthanum chloride;
coating the second coating liquid on the titanium plate coated with the first coating liquid by using a 3g/L titanium trichloride solution, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 500 ℃ for 30 minutes, and repeating the process for 5 times;
coating the coating liquid III on the titanium plate coated with the coating liquid II, drying the titanium plate at 150 ℃ for 10 minutes, taking out the titanium plate, thermally oxidizing the titanium plate at 520 ℃ for 30 minutes, and repeating the process for 8 times;
coating the fourth coating liquid on the titanium plate coated with the third coating liquid, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 530 ℃ for 30 minutes, and repeating the process for 9 times before finishing;
the final coating solution is No. four coating solution, and is prepared by drying at 150 deg.C for 10 min, taking out, and heating with oxygen at 550 deg.CTake 90 minutes. The increment of the metal oxide on the titanium plate finally reaches 0.6 +/-0.02 g/m2And obtaining the required cathode.
Example 4
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating a cathode coating solution:
coating the first coating liquid on a pretreated titanium plate by using a cerium chloride solution of 0.25g/L, drying at 150 ℃ for 10 minutes, taking out, and thermally oxidizing at 450 ℃ for 30 minutes;
coating the second coating liquid on the titanium plate coated with the first coating liquid, drying for 10 minutes at 150 ℃, taking out, thermally oxidizing for 30 minutes at 500 ℃, and repeating the process for 5 times;
coating the third coating liquid on the titanium plate coated with the second coating liquid by using a titanium trichloride solution of 2.5g/L, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 520 ℃ for 30 minutes, and repeating the process for 6 times;
coating the coating liquid on the titanium plate coated with the coating liquid III by using a mixed solution of 3g/L titanium trichloride and 2.0g/L tantalum pentachloride and n-butyl alcohol, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 530 ℃ for 30 minutes, and repeating the process for 6 times;
coating the fifth coating liquid on the titanium plate coated with the fourth coating liquid by using a 4g/L titanium trichloride solution, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 550 ℃ for 30 minutes, and repeating the process for 4 times before final treatment;
the final coating solution is No. five coating solution, the coating process is unchanged, the coating solution is dried at 150 ℃ for 10 minutes, and the coating solution is taken out and thermally oxidized at 550 ℃ for 90 minutes. The increment of the metal oxide on the titanium plate finally reaches 0.6 +/-0.02 g/m2And obtaining the required cathode.
Comparative example 1
And (3) polishing the two sides of the titanium plate by using a grinding wheel and a polishing wheel in sequence, then removing oil from the titanium plate by using alkali liquor and absolute ethyl alcohol in sequence, then cleaning the titanium plate by using distilled water, drying the titanium plate in a constant-temperature drying box at 100 ℃, and cooling the titanium plate to finish the preparation.
Comparative example 2
Sequentially removing oil from the titanium plate by using alkali liquor and absolute ethyl alcohol, cleaning the titanium plate by using distilled water, drying the titanium plate in a constant-temperature drying box at 100 ℃, and cooling the titanium plate to finish the preparation.
Seawater electrolysis experiment parameters:
total salinity of about 3.5%, natural seawater containing 2.5% NaCl, 1500A/m225 ± 1 ℃, pole pitch: 2 mm.
The electrolytic cell assembly mode:
six titanium anodes with the same preparation process and coating components are prepared, wherein four anodes and the cathodes prepared in examples 1-4 respectively form an electrolytic cell, the other two anodes and the cathodes in comparative examples 1 and 2 respectively form an electrolytic cell, the six groups of electrolytic cells are connected in series for supplying power for electrolysis, and the change condition of the cell voltage is recorded.
The examples and comparative examples prepared as described above were tested according to the above test methods, and the following results were obtained:
as shown in FIG. 1, in the seawater electrolysis experiment, the cell voltages of examples 1-4 and comparative examples 1-2 increased substantially linearly, the rising rate of comparative example 2 was the greatest, examples 1-4 were much smaller than comparative example 2, and comparative example 1 was slightly larger than examples 1-4.
As can be seen from comparison of cell voltage rising rates of comparative example 1 and comparative example 2, Ca can be reduced by the polishing treatment2+、Mg2+Binding force between the metal ion scale and the surface of the cathode delays scaling of the cathode; by comparing the cell voltages of comparative example 1 and examples 1 to 4, it is known that the catalytic activity of the cathode can be improved and the reaction voltage can be reduced by preparing the cathode catalytic coating on the surface of the polished substrate.
The cathode reaction surface was visually observed, and examples 1 to 4 hardly deposited Ca-containing particles2+、Mg2+Plasma scale, a small amount of scale was found at some points in comparative example 1, and some areas in comparative example 2 had some amount of plate scale.
As can be seen from FIG. 1, the initial cell voltage of comparative example 2 is in a lower state, but in the presence ofWith Ca2+、Mg2+The cell voltage growth rate in the electrolysis of plasma metal ions in seawater was significantly greater than that of comparative example 1 and examples 1 to 4, because the surface of comparative example 2 had a certain roughness and contained Ca2+、Mg2+The scale of the metal ions is easier to deposit on the surface of the cathode prepared in the comparative example 2 and is tightly combined, the scale removing capability of flowing seawater on the surface of the cathode is limited, the scale is continuously accumulated along with the long-term electrolysis, the cell voltage is rapidly increased along with the continuous accumulation of the scale, and the advantage of low cell voltage in the initial electrolysis gradually does not exist along with the long-term electrolysis.
In seawater electrolysis, the cell voltage of examples 1 to 4 is increased slowly compared with comparative examples 1 to 2, and the advantages of impurity deposition resistance and catalytic performance are obviously better than those of comparative examples 1 to 2 as long-term electrolysis is carried out.
In seawater electrolysis, after the base body is polished, although the bath voltage is higher, the formation of scale-like substances on the surface of a cathode can be delayed, the pickling period is prolonged, and the bath voltage of the reaction can be reduced and the energy consumption can be reduced by preparing a catalytic coating on the polished titanium base body as the cathode. Comprehensively considering, in the process of preparing chlorine by electrolyzing seawater for a long time, the preparation of the catalytic coating on the polished titanium substrate as the cathode is an effective means for delaying scaling and reducing energy consumption.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Moreover, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Claims (10)
1. A cathode for seawater electrolysis, which is characterized in that: coating a cathode coating solution on the surface of the pretreated titanium plate, and performing step-by-step thermal oxidation treatment until the weight increase of the metal oxide of the titanium plate reaches 0.1-5g/m2I.e. byThe cathode is prepared.
2. The cathode for seawater electrolysis according to claim 1, wherein: the cathode coating liquid is a rare earth metal compound solution and/or a valve type metal compound solution.
3. A method for preparing a cathode for seawater electrolysis according to claim 1, comprising the following steps:
1) pretreating the titanium plate;
2) uniformly coating the cathode coating liquid on the working surface of the titanium plate to be coated;
3) and step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180 ℃ for 10-30 minutes, then sintering at 200-700 ℃ for 15-90 minutes, taking out after sintering, cooling to room temperature, and repeating the coating, drying and sintering processes until the weight of the metal oxide of the titanium plate is increased to 0.1-5g/m2Thus obtaining the cathode.
4. The method for preparing a cathode for seawater electrolysis according to claim 3, wherein the pretreatment of the titanium plate in step 1) is: and polishing the titanium plate.
5. The method for preparing a cathode for seawater electrolysis according to claim 4, wherein the polishing process comprises: polishing the two sides of the titanium plate to ensure that the surface of the titanium plate is a flat mirror surface, sequentially using alkali liquor and absolute ethyl alcohol to remove oil from the titanium plate after polishing, then using distilled water to clean the titanium plate, drying the titanium plate in a constant-temperature drying oven at 100 ℃, and cooling the titanium plate for later use.
6. The method for preparing a cathode for seawater electrolysis according to claim 3, wherein the cathode coating solution used in the steps 2) and 3) is: 0.05-1g/L cerium chloride, 0.05-0.5g/L praseodymium chloride, 0.2-2g/L lanthanum chloride, 1.0-10.0g/L titanium trichloride, 0.35-5.0g/L tantalum pentachloride, 0.2-4.0g/L zirconium tetrachloride and 0.3-5.0g/L niobium pentachloride.
7. The method for preparing a cathode for seawater electrolysis according to claim 3 or 6, wherein the cathode coating solution used in the steps 2) and 3) is: 0.1-0.5g/L cerium chloride, 0.075-0.2g/L praseodymium chloride, 0.25-1.0g/L lanthanum chloride, 1.5-6.0g/L titanium trichloride, 0.5-4.0g/L tantalum pentachloride, 0.25-3.0g/L zirconium tetrachloride and 0.5-3.0g/L niobium pentachloride.
8. The method for preparing a cathode for seawater electrolysis according to claim 3, wherein: the cathode coating liquid for the first coating is a rare earth metal compound solution.
9. The method for preparing a cathode for seawater electrolysis according to claim 3, wherein in step 3): the step thermal oxidation treatment is three-six thermal oxidation treatment, the cathode coating liquid used in each thermal oxidation treatment is the same or different, and the cathode coating liquid is coated for 1-10 times in each thermal oxidation treatment.
10. The method for preparing a cathode for seawater electrolysis according to claim 3, wherein in step 3): the thermal oxidation temperature is 400-590 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4037032A (en) * | 1976-05-05 | 1977-07-19 | Diamond Shamrock Technologies S.A. | Electric storage battery with valve metal electrodes |
| CN101016632A (en) * | 2006-12-22 | 2007-08-15 | 扬州大学 | Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method |
| CN108070877A (en) * | 2017-11-09 | 2018-05-25 | 江苏安凯特科技股份有限公司 | It is a kind of for cathode of electrolysis production and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4037032A (en) * | 1976-05-05 | 1977-07-19 | Diamond Shamrock Technologies S.A. | Electric storage battery with valve metal electrodes |
| CN101016632A (en) * | 2006-12-22 | 2007-08-15 | 扬州大学 | Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method |
| CN108070877A (en) * | 2017-11-09 | 2018-05-25 | 江苏安凯特科技股份有限公司 | It is a kind of for cathode of electrolysis production and preparation method thereof |
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